JPS6024463B2 - Processing methods for silver halide photographic materials - Google Patents
Processing methods for silver halide photographic materialsInfo
- Publication number
- JPS6024463B2 JPS6024463B2 JP5180377A JP5180377A JPS6024463B2 JP S6024463 B2 JPS6024463 B2 JP S6024463B2 JP 5180377 A JP5180377 A JP 5180377A JP 5180377 A JP5180377 A JP 5180377A JP S6024463 B2 JPS6024463 B2 JP S6024463B2
- Authority
- JP
- Japan
- Prior art keywords
- fixing
- processing
- photographic
- silver
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 silver halide Chemical class 0.000 title claims description 87
- 239000004332 silver Substances 0.000 title claims description 84
- 229910052709 silver Inorganic materials 0.000 title claims description 84
- 239000000463 material Substances 0.000 title claims description 75
- 238000003672 processing method Methods 0.000 title description 17
- 238000012545 processing Methods 0.000 claims description 115
- 238000000034 method Methods 0.000 claims description 76
- 229920000642 polymer Polymers 0.000 claims description 45
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 18
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 18
- 239000007844 bleaching agent Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 238000004061 bleaching Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000008280 blood Substances 0.000 claims 1
- 210000004369 blood Anatomy 0.000 claims 1
- 239000000243 solution Substances 0.000 description 87
- 238000011161 development Methods 0.000 description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 41
- 239000003795 chemical substances by application Substances 0.000 description 41
- 238000011282 treatment Methods 0.000 description 32
- 108010010803 Gelatin Proteins 0.000 description 28
- 239000000975 dye Substances 0.000 description 28
- 239000008273 gelatin Substances 0.000 description 28
- 229920000159 gelatin Polymers 0.000 description 28
- 235000019322 gelatine Nutrition 0.000 description 28
- 235000011852 gelatine desserts Nutrition 0.000 description 28
- 238000005406 washing Methods 0.000 description 26
- 229920001577 copolymer Polymers 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 16
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 14
- 229910052736 halogen Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 238000012805 post-processing Methods 0.000 description 10
- 238000005562 fading Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 206010016256 fatigue Diseases 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 5
- 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 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 229910021612 Silver iodide Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229940045105 silver iodide Drugs 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 150000003567 thiocyanates Chemical class 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- RHUVFRWZKMEWNS-UHFFFAOYSA-M silver thiocyanate Chemical compound [Ag+].[S-]C#N RHUVFRWZKMEWNS-UHFFFAOYSA-M 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process 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
- 238000002474 experimental method Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 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 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-UHFFFAOYSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZKGIQGUWLGYKMA-UHFFFAOYSA-N 1,2-bis(ethenylsulfonyl)ethane Chemical compound C=CS(=O)(=O)CCS(=O)(=O)C=C ZKGIQGUWLGYKMA-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical group O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 1
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 241000282461 Canis lupus Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001269524 Dura Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RDQPFJUFZUMIHX-UHFFFAOYSA-N O.S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1.S(=O)(=O)(O)O.S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1.O Chemical compound O.S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1.S(=O)(=O)(O)O.S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1.O RDQPFJUFZUMIHX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241001125048 Sardina Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- QLGLKGKYKXRALK-UHFFFAOYSA-N [Na].CC=C Chemical group [Na].CC=C QLGLKGKYKXRALK-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 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 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- XIZCERNACVABPM-UHFFFAOYSA-N cyclohexane;sodium Chemical compound [Na].C1CCCCC1 XIZCERNACVABPM-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- ZWDZJRRQSXLOQR-UHFFFAOYSA-N n-butyl-n-phenylacetamide Chemical compound CCCCN(C(C)=O)C1=CC=CC=C1 ZWDZJRRQSXLOQR-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 210000001747 pupil Anatomy 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- YARHBRUWMYJLHY-UHFFFAOYSA-Q triazanium;iron(3+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YARHBRUWMYJLHY-UHFFFAOYSA-Q 0.000 description 1
- DCXPBOFGQPCWJY-UHFFFAOYSA-N trisodium;iron(3+);hexacyanide Chemical compound [Na+].[Na+].[Na+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCXPBOFGQPCWJY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
Description
本発明は、定着館を有する写真用処理浴で処理する工程
を含むハロゲン化銀写真材料の処理方法に関し、とくに
チオシアン酸イオンを定着剤として用いる写真材料の処
理方法に関する。
更に詳しくは、定着効率および写真用処理俗が所謂漂白
定着格である場合は漂白定着効率が優れ、たとえ被処理
写真材料が高線量のハロゲン化銀写真材料であっても、
仕上り写真材料の不透明化がみられない優れた銀画像ま
たはカラー色素画像を得ることができ、かつ定着館を有
する写真用処理液を銀の回収を行ない再生使用するにあ
たっても定着能の劣化がみられない写真材料の処理方法
に関する。一般に露光したハロゲン化線写真感光材料を
現像処理して銀画像またはカラー色素画像を得るには、
現像処理工程後に定着処理が施こされる。すなわち、ハ
ロゲン化銀写真感光材料が黒白用の場合には、現像処理
工程によって銀像を得、その後定着処理によって未露光
のハロゲン化銀を溶解除去し、銀画像のみを感光材料に
記録する。一方、ハロゲン化銀写真感光材料がカラー用
の場合には、ボジにあっては第１現像処理をし、ネガに
あってはそのまま発色現像処理工程によって現像された
銀像を酸化剤（漂白剤）によって漂白し、可溶性銀塩に
変え次いで定着処理で全ての可溶性銀塩を溶解除去する
ことにより、カラー色素画像を感光材料に記録すること
が一般的である。このような漂白と定着とを別個の処理
工程で行なう方式に対し、迅速処理化、省力化を目的と
して処理工程をより簡略化し、漂白と定着とを同時に一
工程で完了させる漂白定着と称される処理方式も採用さ
れている。これらの脱銀工程に用いられるハロゲン化銀
定着剤としては、チオ硫酸塩、チオシアン酸塩、ハロゲ
ン塩、チオ尿素、チオグリコール、チオール化合物等が
知られているが、実際の写真処理においては銀錯塩の安
定性、価格等の点でほとんどの場合、チオ硫酸塩が用い
られる。
いずれを用いるにしても定着処理では残存する銀塩が定
着液成分であるチオ硫酸ナトリウム等のハロゲン化繊と
反応して可溶性鏡塩を形成する化合物によって溶解除去
される。たとえば定着液成分としてチオ硫酸ナトリウム
を用いた場合の反応例は次の通りとされている。ＡｇＸ
十ｎ（ＮＨ４）交２０３→Ａｇ
（Ｓ２０３）ｎｅ（２ｎ‐１）十かＮＨ４由十Ｘｅ（た
だし、ｎは２または３、Ｘはハロゲンを示す。
）この反応例にみられる如く、定着液はハロゲン化銀写
真感光材料を定着処理していくに従って銭錯塩とハロゲ
ンイオンが蓄積すると共に定着剤の効能成分が減少して
いく。
これに伴い定着効率は次第に低下し、そのまま定着処理
を続けると遂には疲労現象が現われて使用に供し得なく
なる。そこでこの疲労定着液を賦活させるために適当量
の新しい定着液（再生剤あるいは補充剤）を補充すると
共に疲労定着液をオーバーフローとして外部に排出させ
る方式が採用されているが、このオーバーフロー液をそ
のまま廃棄することは、銀その他の貴重な成分が含まれ
ていることから資源保護に逆行し、経済的にも極めて不
利であるし、かつ環境汚染の観点からも好ましいことで
はないので、その処理廃液は完全に無害化するための処
理を講じなければならない。この点、以前まではオーバ
ーフロー定着液中の銀イオンを回収したのちに廃棄処分
することが多く行なわれてきたが、最近では更に進んで
銀回収後の定着液をも再生反覆使用するようになってき
た。
例えば、銀の回収法として最も有利に用いられている電
気分解方法によって銀の回収を行なった場合、銀イオン
に結合していたチオ硫酸イオンも再び遊離イオンとなる
ため定着液はその定着能を回復するが、この電解反応に
よりチオ硫酸イオンが減少し、さらには空気酸化あるい
は処理時における所謂キャリィオーバ一等によってもチ
オ硫酸イオンは減少するので、オーバーフローしない程
度の液量で定着液成分を維持できる濃度を有する新しい
定着液（再生剤あるいは補充剤）を補充しながら再生反
覆使用しているのが一般的である。しかし、斯かる補充
方式により定着液の反復使用を行っても、使用頻度が多
くなるのに従って遊離チオ硫酸イオン濃度が充分に高い
のにも拘らず定着性能が次第に変化して定着速度が低下
してしまい、遂には定着不良を生じるようになる。その
原因は被処理感光材料の乳剤届中に含まれる溶解性成分
が定着液中に溶出し、定着阻害成分が蓄積してくる事に
よるものとされている。この解決策として定着促進剤を
添加して定着力を向上させる方法や定着阻害成分とされ
ているハロゲンイオンを除去する方法等が提案されてい
る。すなわち、前者の例としては侍公昭４５−３５７払
号公報記載のィオウ化合物による定着促進、または侍公
昭碑−３９１７３号公報記載のポリエチレングリコール
系化合物による定着促進法等があるが、いずれも定着阻
害成分とされているハロゲンイオン等の蓄積による定着
不良に対しての根本的解決策としては未だ不充分であっ
て再生反覆使用を繰返すうちに最後には定着不良等を起
こす欠点がある。従って、このハロゲンイオンの蓄積収
赦濃度を低下させるためにオーバーフロー定着液の一部
を廃棄しながら再生反覆使用しているのが現状であって
、公害上の問題および不経済性の点を解決するに至って
いない。一方、後者の例としては米国特許公告Ｂ−３９
１５０９号公報、侍公昭４３一３０１６７号公報等に記
載されたハロゲンイオンを除去する技術があり、定着力
向上に効果を挙げているが、いずれもが複雑な構造の装
置を必要とし設備投資の費用および運転コストが高い等
の欠点がある。いずれにしても、定着剤として多用され
ているチオ硫酸塩は、環境汚染のおそれが強く、公害防
止の点で重大な欠点を有しているといえる。
一方、上記チオ硫酸塩以外の定着剤として知られている
ハロゲン塩は、銀錯塩の安定性が低いため、次の水洗工
程等で定着剤濃度が低くなると銀鈴塩の分解が起こり、
ハロゲン銀として彼処理写真材料の乳剤層中に残存し、
ネガフィルムまたはポジフィルム等を処理する際には仕
上りフィルムが不透明となる等の欠点があるので、それ
単独ではほとんど実用化されていないのが現状である。
この欠点を補うために一定量以上のチオ硫酸塩を共存せ
しめればよいことを本発明者は知ったが、このようなチ
オ硫酸塩の使用童は、通常０．２モル／そ程度も必要で
あり、前述のように線の回収を行ないながら反覆使用す
るに際し、一部分をオーバーフローとして廃棄すると、
生物学的酸素要求量（ＢＯＤ）および化学的酸素要求量
（ＣＯＤ）を満たすことができず、環境汚染の虜れがあ
るし、さらにチオ硫酸塩はそれ自身還元剤であるため定
着剤が酸化分解をうけやすく、再生反覆使用上極めて不
利益な結果を生じる。さらにまた、定着能と共に漂白館
を有する漂白定着液の定着剤成分として上記チオ硫酸塩
をチオシアン酸塩またはハロゲン塩と共存せしめると、
チオ硫酸塩はそれ自身が還元剤であるし、このチオ硫酸
塩の保恒剤として必要となる亜硫酸塩もまた還元剤であ
ることから、漂白定着液の酸化還元電位が大幅に卑とな
り、共存する酸化剤酸化力が損われ、当該液の再生反覆
使用が困難になる欠点を生じる。斯かるチオ硫酸塩によ
る弊害は、それ単独で漂白定着液の定着剤成分として用
いた場合にも同様に生じる問題であって、この点でもテ
オ硫酸塩を含まない定着液または漂白定着液による写真
材料の実用的な処理方法の開発が強く要望されているの
が現状である。本発明者は種々研究を行いチオ硫酸塩を
用いないハロゲン化銀写真材料の処理方法として臭素イ
オンおよびヨウ素イオンを定着剤として用いかつ実用的
な定着処理もしくは漂白定着処理技術を開発し、これら
を持願昭５１−５５５１１号および特顔昭５１−４職７
５号明細書としてすでに提案した。
しかしながらこのハロゲンイオンを定着剤とする技術で
は水洗工程での不透明化現象は防止出来るものの、仕上
りフィルム中に透明な銀錆塩が多量に存在し仕上りフィ
ルムの銀画像もしくはカラー色素画像の安定性が悪くな
るという欠点がみし、だされた。仕上りフィルムに残存
する透明な銀鈴塩は水洗時間の延長等によっても容易に
洗出されるものではない事が判った。本発明は叙上の点
に着目して成されたものであって、本発明の第１の目的
は、生物学的酸素要求量（ＢＯＤ）および化学的酸素要
求量（ＣＯＤ）負荷が低く、かつ毒性が低くて環境汚染
防止の要請に適合したハロゲン化銀写真材料の処理方法
を提供することである。
本発明の第２の目的は、定着効率または漂白定着効率が
優れ、たとえ被処理写真材料が高銀量のハロゲン化銀写
真材料であっても、仕上り写真材料の不透明化がみられ
ない優れた狼画像またはカラー色素画像を得ることがで
きるハロゲン化銀写真材料の処理方法を提供することで
ある。
本発明の第３の目的は、被処理感光材料の乳剤層等から
溶出し蓄積する定着阻害成分の影響を受けず、定着液ま
たは漂白定着液を再生反覆使用するに際しても、定着館
または漂白定着能の劣化がなく使用頻度を増大すること
ができるハロゲン化繊写真材料の処理方法を提供するこ
とである。
本発明の第４の目的は、定着能のほかに漂白館を併せ有
する漂白定着液を用いる写真材料の処理方法においては
、液の酸化還元電位を卑にならしめず、共存する漂白剤
（酸化剤）の酸化能力を充分に発揮させることができる
ハロゲン化銀写真材料の処理方法を提供することである
。本発明の第５の目的は、仕上り写真材料を長期に保存
しても銀画像やカラー色素画像の劣化や変色のない保存
安定性の優れた銀画像やカラー色素画像を得ることが出
来るというハロゲン化銀写真材料の処理方法を提供する
事である。
本発明者は少くとも０．２モル／そのチオシアン酸イオ
ンを含む定着館を有する写真用処理格で処理する工程を
含むハロゲン化銀写真材料の処理方法において、前記写
真用処理格および／またはその後処理裕中に、分子構造
中にピロリドン核単位を有する重合体を含有せしめる事
によって前記目的が達成される事を見出した。
本発明によるピロリドン核単位を有する重合体もしは共
重合体を臭素イオン、ヨウ素イオンおよび／またはチオ
シアン酸イオン等それぞれを定着剤とする定着液に添加
もしくは後格に添加せしめ処理すると水洗工程でのハロ
ゲン化銀鍵イオンもしくはチオシアン酸銀錆イオンの分
解による白濁不透明化を防止出来る事を以前に見出した
事は前記した通りである。
しかしながら種々実験の結果定着剤として臭素イオンも
しくはヨウ素イオンを用いた場合には仕上りフィルムは
透明であってもフィルム中に透明な銭鍵イオンが残存す
る事が判明しこの残存銀が多い程仕上がった写真材料の
銀画像や色素画像が保存により変色したり退色したりす
る事を確認した。一方定着剤として本発明によるチオシ
アン酸塩を用いかつピロリドン核単位を有する重合体、
もしくは共重合体を添加するかあるいは重合体、共重合
体を後格に添加し処理すると、仕上がった写真材料が透
明となるばかりでなく、残存銀量もほとんど皆無であり
かつ仕上がった写真材料の銀画像もしくは色素画像の保
存による変色及び退色が非常に少く良好である事を見出
した。
すなわち本発明に係る写真材料の処理方法は、前記の如
き欠点を有し実用的でない定着剤であるチオシアン酸イ
オンを特定の量以上で使用すると共に前述の如き諸欠点
を有するチオ硫酸塩を共存せしめる事なく特定のピロリ
ドン核を有する重合体もしくは共重合体と組み合せる事
により前記目的を達成したものである。
本発明において、定着能を有する写真用処理俗で処理す
る工程とは、定着能を有する処理液にはアミノボリカル
ポン酸金属錆塩、赤血塩、第２鉄塩等の漂白剤（酸化剤
）を含有し漂白館を併せ有する漂白定着液と、漂白能を
有しない通常の定着液とがあるが、この漂白定着液また
は定着液を使用した格によって写真材料を処理する工程
、すなわち漂白定着工程と定着工程の両者を含めたもの
を指称する。
従って、本発明の定着館を有する写真用処理格には、単
なる定着格、酸性定着格、硬膜定着格、漂白定着裕等が
その代表例として含まれ、その他定着館を有するもので
あればあらゆる写真用処理格が含まれる。斯かる定着能
を有する写真用処理格による写真材料の処理は単一な処
理であってもよいし、何段かに分割して別の処理工程で
行ってもよく、例えばハロゲン化銀カラー写真材料の処
理の如く第１定着処理後に漂白し、再度定着処理する場
合も含まれる。本発明の定着能を有する写真用処理格に
含有せしめられる定着剤としてのチオシアン酸イオンは
、可溶性のチオシアン酸塩によって該液に供給されるこ
のチオシアン酸イオンを該処理液に含有せしめるために
用いられる代表的なチオシアン酸化合物としては、チオ
シアン酸ナトリウム、チオシアン酸カリウム、チオシア
ン酸アンモニウム等がある。
この他可溶性のチオシアン酸化合物であれば無機塩、有
機塩等を問わずあらゆるものが使用出来る。とくに望ま
しくは被処理写真材料のゼラチン層への拡散速度が高い
アンモニウム塩およびカリウム塩が有効である。これら
のチオシアン酸化合物は単独でまたは２種以上を適宜組
み合せて使用することができるが、２種のチオシアン酸
塩を粗合せて用いるときは、チオシァン酸塩の総濃度が
前記濃度を満たしていることを要する。このチオシアン
酸塩の含有量は、処理液の定着性を附与する量で少なく
ても０．２モル／そのチオシアン酸イオンを含有する量
であるが、６５モルノクム久上では折出し、処理液が白
濁して使用に供し得ない。本発明において用いられる分
子構造中にピロリドン核単位を有する重合体（以下、単
に本発明の重合体または本発明に用いる重合体という。
）は、重合体の主鏡または側鎖をピロリドン核で任意の
位置に任意の数だけ置換した重合性重合体のすべてが含
まれ、その単独重合体であってもよいし２種以上の共重
合成分を重合した共重合体であってもよい。後者の場合
には、分子構造中にピロリドン核単位を有する共重合体
成分としてのポリマーが、該共重合成分としてのポリマ
ーと共重合する分子構造中にピロリドン核単位を有しな
い他のポリマーと共重合せしめて得た共重合体中に、２
０％以上含まれることが望ましく、とくに３０％以上含
まれることが好ましい。なお、分子構造中にピロリドン
核単位を有する共重合成分としてのポリマーと共重合す
る分子構造中にピロリドン核単位を有しない他のポリマ
ーとしては、親水性の英重合体を得られるものであれば
いかなるものも用いることができる。本発明に用いられ
る重合体の代表的具体例を挙げると下記のものが含まれ
る。
〔１〕ポリーＮ−ビニルー２−ピロリドン（＊注１）〔
２〕ポリーＮ一（２−アクリロイルオキシ）エチル−１
ーピロリドン〔３〕ポリーＮーグリシジル−２ーピロリ
ドン〔４〕ポリーＮーアリルー２−ピロリドン〔５〕ポ
リ−Ｎ，ＮージメチルーＮ一〔３（１ーピロリドニル）
一２ーヒドロキシ〕プロピルーアミンーＮ′ーアクリ。
イルイミン〔６）コポリーＮービニルー２−ピロリドン
／Ｎーアクリロイルモルホリン（モル比４２：斑）〔７
〕コポリーＮ−ビニルー２ーピロリドン／Ｎーアクリロ
イルピベリジン（モル比３５：６５）〔８〕ポリーＮ−
ビニルー２−ピロリドン／Ｎーメタクリロイルー２ーメ
チルイミダゾール（モル比５５：４５）The present invention relates to a method for processing a silver halide photographic material which includes processing in a photographic processing bath having a fixing chamber, and more particularly to a method for processing a photographic material using thiocyanate ions as a fixing agent. More specifically, when the fixing efficiency and photographic processing are so-called bleach-fixing standards, the bleach-fixing efficiency is excellent, even if the photographic material to be processed is a high-dose silver halide photographic material.
It is possible to obtain excellent silver images or color dye images that do not cause opacity of the finished photographic material, and there is no deterioration in fixing ability even when the photographic processing solution with a fixing chamber is recycled and used after recovering the silver. Concerning methods for processing photographic materials that cannot be used. Generally, to obtain a silver image or a color dye image by developing a halogenated photosensitive material exposed to light,
A fixing process is performed after the development process. That is, when the silver halide photographic light-sensitive material is for black and white use, a silver image is obtained by a development process, and then unexposed silver halide is dissolved and removed by a fixing process, and only the silver image is recorded on the light-sensitive material. On the other hand, when the silver halide photographic light-sensitive material is for color use, the positive is subjected to the first development process, and the negative is developed as it is in the color development process. ), it is common to record color dye images on light-sensitive materials by bleaching them to soluble silver salts and then dissolving and removing all the soluble silver salts in a fixing process. In contrast to this type of method in which bleaching and fixing are performed in separate processing steps, a method called bleach-fixing is a method that simplifies the processing steps and completes bleaching and fixing simultaneously in one step for the purpose of speeding up processing and saving labor. A processing method has also been adopted. As silver halide fixing agents used in these desilvering processes, thiosulfates, thiocyanates, halogen salts, thioureas, thioglycols, thiol compounds, etc. are known, but in actual photographic processing, silver In most cases, thiosulfates are used because of the stability, cost, etc. of complex salts. Regardless of which method is used, in the fixing process, the remaining silver salt is dissolved and removed by a fixing solution component such as sodium thiosulfate, a compound that reacts with halogenated synthetic fibers to form a soluble mirror salt. For example, a reaction example using sodium thiosulfate as a fixer component is as follows. AgX
10n(NH4)X203→Ag (S203)ne(2n-1)10 or NH4Xe (However, n is 2 or 3, and X represents a halogen.) As seen in this reaction example, the fixer As silver halide photographic light-sensitive materials are fixed, complex salts and halogen ions accumulate, and the effective components of the fixing agent decrease. As a result, the fixing efficiency gradually decreases, and if the fixing process is continued as it is, a fatigue phenomenon will eventually appear and the device will become unusable. Therefore, in order to activate this fatigued fixer, a method has been adopted in which an appropriate amount of new fixer (regenerant or replenisher) is replenished and the fatigued fixer is discharged outside as an overflow. Discarding the treated waste liquid goes against resource conservation as it contains silver and other valuable components, is extremely disadvantageous economically, and is not desirable from the perspective of environmental pollution. must take steps to completely render it harmless. In this regard, in the past, the silver ions in the overflow fixer were often collected and then disposed of, but recently, the fixer after recovering the silver has also been recycled and used repeatedly. It's here. For example, when silver is recovered by electrolysis, which is the most advantageous method for silver recovery, the thiosulfate ions that were bound to the silver ions become free ions again, so the fixing solution loses its fixing ability. However, this electrolytic reaction reduces thiosulfate ions, and thiosulfate ions also decrease due to air oxidation or so-called carryover during processing, so it is necessary to maintain the fixer components at a level that does not overflow. Generally, the fixing solution is regenerated and used repeatedly while being replenished with a new fixing solution (regenerating agent or replenisher) having the desired concentration. However, even if the fixer is used repeatedly by such a replenishment method, the fixing performance gradually changes and the fixing speed decreases as the frequency of use increases, even though the free thiosulfate ion concentration is sufficiently high. This will eventually lead to poor fixing. The cause is said to be that soluble components contained in the emulsion of the photosensitive material to be processed are eluted into the fixing solution, and fixing-inhibiting components accumulate. As a solution to this problem, methods have been proposed such as adding a fixing accelerator to improve fixing power and removing halogen ions, which are considered to be fixing inhibiting components. That is, examples of the former include methods for promoting fixation using sulfur compounds as described in Samurai Publication No. 45-357, and methods for promoting fixation using polyethylene glycol compounds as described in Samurai Publication No. 39173, but both methods inhibit fixation. It is still insufficient as a fundamental solution to the problem of poor fixing due to the accumulation of halogen ions, etc., which are components, and there is a drawback that poor fixing will eventually occur after repeated recycling and use. Therefore, in order to reduce the accumulated concentration of halogen ions, a part of the overflow fixer is discarded and reused repeatedly, which solves the pollution problem and uneconomical problem. I haven't reached the point where I can. On the other hand, as an example of the latter, U.S. Patent Publication B-39
There are technologies for removing halogen ions described in Publication No. 1509 and Samurai Publication No. 43-30167, etc., which are effective in improving fixing power, but all of them require devices with complex structures and require large capital investments. There are disadvantages such as high cost and operating costs. In any case, thiosulfate, which is frequently used as a fixing agent, is highly likely to pollute the environment and can be said to have a serious drawback in terms of pollution prevention. On the other hand, in the case of halogen salts known as fixing agents other than the above-mentioned thiosulfates, the stability of silver complex salts is low, so when the fixing agent concentration becomes low in the next water washing step, decomposition of the silver salt occurs.
Silver halogen remains in the emulsion layer of processed photographic materials,
When processing negative or positive films, etc., there are drawbacks such as the finished film becoming opaque, so at present it is hardly put to practical use on its own.
The inventor has learned that it is sufficient to coexist a certain amount of thiosulfate in order to compensate for this drawback, but children who use such thiosulfate usually need about 0.2 mol/about Therefore, when the wire is recycled and used repeatedly as mentioned above, if a portion is discarded as overflow,
Biological oxygen demand (BOD) and chemical oxygen demand (COD) cannot be met, resulting in environmental pollution, and since thiosulfate itself is a reducing agent, it can cause oxidation of the fixing agent. It is susceptible to decomposition and causes extremely disadvantageous results in recycling and repeated use. Furthermore, when the above-mentioned thiosulfate is made to coexist with a thiocyanate or a halogen salt as a fixing agent component of a bleach-fix solution having a bleaching capacity as well as a fixing ability,
Thiosulfate itself is a reducing agent, and sulfite, which is necessary as a preservative for thiosulfate, is also a reducing agent, so the redox potential of the bleach-fix solution becomes significantly base, and coexistence is reduced. The oxidizing power of the oxidizing agent is impaired, resulting in the disadvantage that it becomes difficult to recycle and use the liquid repeatedly. These problems caused by thiosulfate also occur when it is used alone as a fixing agent component in a bleach-fix solution, and in this respect, it is also a problem that occurs when using a fixing solution or a bleach-fix solution that does not contain thiosulfate. At present, there is a strong demand for the development of practical processing methods for materials. The present inventor has conducted various studies and developed practical fixing or bleach-fixing techniques using bromide ions and iodine ions as fixing agents as a processing method for silver halide photographic materials that does not use thiosulfate. Holding petition No. 51-55511 and special face No. 7 of 1972
It has already been proposed as Specification No. 5. However, although this technology using halogen ions as a fixing agent can prevent the opacity phenomenon during the water washing process, the presence of a large amount of transparent silver rust salts in the finished film may affect the stability of the silver image or color dye image on the finished film. The drawback was that it would get worse, so it was released. It was found that the transparent silver salt remaining on the finished film was not easily washed out even by extending the washing time. The present invention has been made with attention to the above points, and the first object of the present invention is to reduce biological oxygen demand (BOD) and chemical oxygen demand (COD) loads, Another object of the present invention is to provide a method for processing silver halide photographic materials that has low toxicity and meets the requirements for preventing environmental pollution. A second object of the present invention is to provide an excellent wolf image with excellent fixing efficiency or bleach-fixing efficiency, and in which the finished photographic material does not become opaque even if the photographic material to be processed is a silver halide photographic material with a high silver content. Alternatively, it is an object of the present invention to provide a method for processing silver halide photographic materials by which color dye images can be obtained. A third object of the present invention is to avoid the influence of fixing-inhibiting components that are eluted and accumulated from the emulsion layer of the photosensitive material to be processed, and to provide a solution that can be used in a fixing house or bleach-fixer even when the fixer or bleach-fixer is recycled and used repeatedly. It is an object of the present invention to provide a method for processing halogenated synthetic fiber photographic materials, which can increase the frequency of use without deteriorating performance. A fourth object of the present invention is to avoid making the oxidation-reduction potential of the solution base in a method for processing photographic materials using a bleach-fix solution that has not only a fixing ability but also a bleaching agent. An object of the present invention is to provide a method for processing a silver halide photographic material that can fully utilize the oxidizing ability of a silver halide agent. A fifth object of the present invention is to obtain silver images and color dye images with excellent storage stability that do not cause deterioration or discoloration of silver images or color dye images even when the finished photographic material is stored for a long period of time. The object of the present invention is to provide a method for processing silver oxide photographic materials. The present inventor has proposed a method for processing a silver halide photographic material comprising the step of processing in a photographic processing tank having a fixing chamber containing at least 0.2 mol/thiocyanate ion. It has been found that the above object can be achieved by incorporating a polymer having a pyrrolidone core unit in its molecular structure during the treatment. When the polymer or copolymer having a pyrrolidone core unit according to the present invention is added or added to a fixing solution containing bromide ion, iodine ion, and/or thiocyanate ion as a fixing agent, it can be treated with As mentioned above, it was previously discovered that cloudiness and opacity due to decomposition of silver halide key ions or silver thiocyanate rust ions can be prevented. However, as a result of various experiments, it was found that when bromide ions or iodine ions were used as a fixing agent, transparent Zenki ions remained in the film even if the finished film was transparent, and the more this residual silver, the better the finish. It has been confirmed that silver images and dye images in photographic materials change color or fade due to storage. On the other hand, a polymer using a thiocyanate according to the invention as a fixing agent and having a pyrrolidone core unit,
Alternatively, if a copolymer is added or a polymer or copolymer is added to the post-processing process, the finished photographic material will not only become transparent, but will also have almost no residual silver content and will have a very low residual silver content. It has been found that the silver image or the dye image has very little discoloration or fading during storage and is good. In other words, the method for processing photographic materials according to the present invention uses thiocyanate ion, which is an impractical fixing agent with the above-mentioned drawbacks, in a certain amount or more, and also uses thiosulfate, which has the above-mentioned drawbacks, in coexistence. The above object has been achieved by combining it with a polymer or copolymer having a specific pyrrolidone nucleus without any interference. In the present invention, the process of processing with a photographic processing solution having fixing ability means that the processing solution having fixing ability contains a bleaching agent (oxidized There are two types of bleach-fix solutions: bleach-fix solutions that contain bleaching agents) and ordinary fix solutions that do not have bleaching ability. This refers to the process that includes both the fixing process and fixing process. Therefore, the photographic processing class having a fixing hall according to the present invention includes, as representative examples, simple fixing class, acidic fixing class, dura fixing class, bleach-fixing class, etc., and other types having a fixing hall. Includes all photographic processing. The processing of a photographic material by a photographic processing unit having such a fixing ability may be a single processing or may be divided into several stages and carried out in separate processing steps, such as silver halide color photography. This also includes cases where bleaching is performed after the first fixing process and then the fixing process is performed again, such as in the processing of materials. The thiocyanate ion as a fixing agent contained in the photographic processing solution having fixing ability of the present invention is used to cause the processing solution to contain the thiocyanate ion supplied to the solution by a soluble thiocyanate. Typical thiocyanate compounds include sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, and the like. In addition, any soluble thiocyanate compound can be used, regardless of whether it is an inorganic salt or an organic salt. Particularly preferred are ammonium salts and potassium salts which have a high diffusion rate into the gelatin layer of the photographic material to be processed. These thiocyanate compounds can be used alone or in an appropriate combination of two or more, but when two types of thiocyanate are used in combination, the total concentration of thiocyanate satisfies the above concentration. It requires that. The content of this thiocyanate is an amount that imparts fixing properties to the processing solution, and is at least 0.2 mol/an amount containing the thiocyanate ion, but in 65 mol Nocum Kukami, it is precipitated and the processing solution is becomes cloudy and cannot be used. The polymer having a pyrrolidone core unit in its molecular structure used in the present invention (hereinafter simply referred to as the polymer of the present invention or the polymer used in the present invention) is a polymer having a pyrrolidone core unit in the primary mirror or side chain of the polymer. It includes all polymerizable polymers in which an arbitrary number of positions are substituted, and may be a homopolymer thereof or a copolymer obtained by polymerizing two or more types of copolymer components. In the latter case, the polymer as a copolymer component that has a pyrrolidone core unit in its molecular structure is copolymerized with another polymer that does not have a pyrrolidone core unit in its molecular structure and is copolymerized with the polymer as a copolymerization component. In the copolymer obtained by polymerization, 2
It is desirable that the content is 0% or more, particularly 30% or more. In addition, other polymers that do not have a pyrrolidone core unit in their molecular structure to be copolymerized with the polymer as a copolymerization component that has a pyrrolidone core unit in their molecular structure are those that can obtain a hydrophilic polymer. Any can be used. Typical specific examples of polymers used in the present invention include the following. [1] Poly N-vinyl-2-pyrrolidone (*Note 1) [
2] Poly N-(2-acryloyloxy)ethyl-1
-pyrrolidone [3] Poly-N-glycidyl-2-pyrrolidone [4] Poly-N-aryl-2-pyrrolidone [5] Poly-N,N-dimethyl-N-[3(1-pyrrolidonyl)]
12-Hydroxy]propylamine-N'-acrylic. Iruimine [6] Copoly N-vinyl-2-pyrrolidone/N-acryloylmorpholine (molar ratio 42: spot) [7
] Copoly N-vinyl-2-pyrrolidone/N-acryloylpiveridine (molar ratio 35:65) [8] Poly N-
Vinyl-2-pyrrolidone/N-methacryloyl-2-methylimidazole (molar ratio 55:45)
〔９〕コポリ−
Ｎ一（２ーアクリロイルオキシ）−エチル−２−ピロリ
ドンノアクリル酸ジェチルアミド‐（モル比６０：４０
）〔１０〕 コポリ−Ｎ一（２ーメタクリロイルオキシ
）エチル−２一ピロリドンノアクリル酸ナトリウム（モ
ル比７５：２５）〔，１Ｕ コポリーＮ−（３ーアクリ
ロイルオキシ）プロピルー２ーピロリドン／メタクリル
酸メチル（モル比６５：３５）〔１２〕 コポリーＮ，
Ｎ−ジメチルーＮ一〔３一（１ーピロリドニル）一２−
ヒドロキシ〕ープロピルアミン−Ｎ′ーアクリロイルイ
ミンノアクリル酸エチル（モル比７０：３５）〔１３〕
コポリーＮ−ビニルー２ーピロリドン／酢酸ビニル（
モル比７０：３０）〔１０ コポリーＮービニルー２ー
ピロリドン／アクリル酸メチル（モル比７０：３０）〔
１５〕 コポリーＮービニル−２ーピロリドン／スチレ
ン（モル比８０：２０）〔１６〕 コポリ−Ｎービニル
ー２ーピロリドン／アクリル酸アミドノＮ−ビニルー２
−メチルイミダゾール（モル比５０：３０：２０）〔１
７〕 コポリ−Ｎービニル−２ーピロリドン／Ｎ−（１
，１ージメチル−３ーオキソ）ーブチルーアクリルアミ
ド（モル比７０：３０）〔１８〕 コボリ−Ｎーアリル
−２−ピロリドン／酢酸ピニル（モル比礎：３６）〔１
９〕 コポリーＮービニル−２−ピロリドン／４ービニ
ルピリジン（モル比６０：４０）〔２０〕 コポリーＮ
−ピニルー２ーピロリドン／アクリル酸エチルノアクリ
ル酸モノェタノールアミン酸（モル比５０：４５：５）
〔２１〕 コポリ−Ｎービニル−２−ピロリドン／ピベ
リジ／マレアミック酸ピベリジン酸（モル比斑：４７）
〔物〕 コポリーＮーピニルピロリドン／４ービニルピ
リジノーＮ−メチルアイオダイド（モル比４２：斑）〔
２３〕 コボリーＮ−ビニルピロリドン／マレイン酸チ
オ尿素ハーフアンモニウム塩（モル比６０：４０）＊注
１で示した例示重合体〔１〕は、ゼネラル・アニリン・
アンド・フイルム・コーポ（技能ｒａｌａｎｉｌｉｎｅ
ａｎｄ８１ｍＣｏｒｐ．）からＰＶＰＫ−３０．ＰＶＰ
Ｋ一６０，ＰＶＰＫ−９０という商品名で市販されてい
る。
本発明に用いる重合体は、前記した如くその一部が市販
されているので容易に入手できるし、ジヨン・ウイリー
・アンド・ソムズ・インコ（ＪｏｈｎＷｉｌｅひａＭＳ
ｏｍｓ，Ｉｎｃ．）発行（１９６１年）ダプリユ・アー
ル・ソレンソン，テイ・ダプリユ．キヤンプベル（Ｗ．
Ｒ．Ｓｏｒｅ船ｏｎ，Ｔ．Ｗ．Ｃａｍｐｂｅｌｌ）署の
プレパレィティブ・メソッド・オブ・ポリマー・ケミス
リトリー（ＰｒｅｐａｍｔｉｖｅＭｅｔｈｄ＄ｏｆＦｏ
ＩＭｍｅｒＣｈｅｍｉｓｔか）に記載された方法に従っ
て容易に合成することができる。
本発明の重合体は、前記定着館を有する写真用処理格お
よび／またはその後処理裕中に含有せしめることにより
使用されるが、定着館を有する写真用処理浴中に含有せ
しめた場合に、その後処理裕中にも含有せしめることも
できるが、定着能を有する写真用処理格のみに含有せし
めた場合に比べ、より好ましい効果が得られるわけでは
なく、本発明の必須条件ではない。そして、定着館を有
する写真用処理浴中に含有せしめられない場合には、そ
の後処理裕中に本発明の重合体が含有せしめられる。こ
の場合、定着館を有する写真用処理浴の後処理浴は、定
着館を有する写真用処理格、すなわち定着裕または漂白
定着格の直後に実施される処理俗であることが好ましい
が、定着浴または漂白定着格とその後処理格との間にリ
ンス処理等の処理工程が介在していてもよい。なお、前
述の如く定着館を有する写真用処理浴に本発明の重合体
が含有せしめられた場合には、その後に実施されるいず
れか任意の処理格に本発明の重合体を含有せしめること
ができる。なお、後処理液に本発明の重合体を含有せし
める場合には、この後処理液をスポンジ等を用いる塗布
法で被処理写真材料に塗布せしめてもよい。本発明に用
いられる重合体の添加量は、定着能を有する写真用処理
裕中に添加する場合とその後処理格に添加する場合とに
よって異なるが、前者の定着能を有する写真用処理浴中
に添加する場合には、一般に５〜２００タノそであり、
該処理裕中に銀イオンが被処理写真材料の乳剤層から溶
出し蓄積した場合、例えば銀イオンが４５夕／ぐという
大量に蓄積した場合には３０〜８０夕／そで充分である
。
その他、該俗による処理温度を勘考するほか、用いる重
合体の種類、共存する定着剤としてのチオシアン酸濃度
を参考にして上記範囲に限らず任意に決定することがで
きる。一般に、本発明の重合体の添加量が少なすぎると
きは、その後処理としての水洗工程中でチオシアン酸銀
鍵体の分解によるハロゲン化銀の析出が起り易くなるし
、必要以上に多量であると処理液の粘度が高くなり処理
速度に影響を及ぼすと共にキヤリーオーバーによる液成
分の減少がみられるので注意を要する。また、後者の定
着能を有する写真用処理浴の後処理裕中に添加する場合
には、前記した定着館を有する写真用処理格のように銀
イオンの溶出が多くみられることはないので、一般には
５〜４００夕／そ、望ましくは２０〜２０Ｍ／その範囲
で用いることができるが、この場合にも水洗工程でのチ
オシアン酸銀の枕析が生じないような量を、上記範囲に
限定されることなく実験により決定することが望ましい
。なお、本発明の重合体を添加する格には、その格の種
類に応じて各種の添加剤を含有せしめることができ、例
えば、保障剤、現像促進剤、抑制剤、アルカリ剤、ｐＨ
調節剤、緩衝剤、硬膜剤等を適量添加することもできる
。
なおまた、本発明の重合体を定着能を有する写真用処理
俗に添加するには、前述の如く直接に当該格に添加する
ことが好ましいが、その前処理裕中に添加せしめて被処
理写真材料によるキセリーィンによって定着能を有する
写真用処理格に含有せしめてもよいし、あるいは彼処理
写真材料中に添加せしめ、処理に際し定着館を有する写
真用処理裕中に漆出蓄積させる方法を採用してもよい。
しかしこの場合は、本発明の重合体が一定濃度以上にな
るだけの写真材料処理が必要であるので必ずしも好まし
い方法とはいえない。本発明の重合体を含有せしめる定
着能を有する写真用処理俗および／またはその後処理格
の処理温度は、高い方が処理速度は大になり、新液によ
る処理時間（クリアリングタイム）と多数の写真材料を
処理した後の疲労液によるクリアリングタイムとの差が
少ないし、かつ該処理裕中に被処理写真材料から漆出し
蓄積する定着阻害成分の影響を受け難く、再生反覆使用
の際にも有利であるので、できるだけ高温にて処理する
のが好ましいが、処理に使用する姿鷹や被処理写真材料
とくにその支持体の耐熱性、および写真材料の膜物性と
の関係上、６ぴＯＬ久上は一般に望ましくない場合があ
る。
従って、遠常２０〜５５℃の範囲で処理するのが−般的
である。本発明における定着館を有する写真用処理格お
よび本発明の重合体を含有せしめる格に用いる液の斑は
任意であるが、該処理液が定着液である場合には柵が低
すぎると定着剤としてのチオシアン酸イオンが酸化され
易くなるし、内が高すぎると写真材料のゼラチン膜等が
膨潤しすぎたりする場合があるので、一般にはＰＨ２〜
１２、望ましくは班３〜９で用いるのがよい。
そして、処理液が漂白定着液である場合にはｐＨカギ低
いほどそのクリアリングタイムが小になる頚向がみられ
るので餌を低くした方が望ましいが、反面柑が低すぎる
と写真材料に用いられたカプラ−の種類によっては形成
される色素画像がロィコ体になってその復色度が小さく
なるという問題が生じることがある。そこで、一般に柵
１．５〜１０．０筆まし〈は餌３．０〜９．０で用いた
方がよい。そしてまた本発明の重合体が定着能を有する
写真用処理格の後処理格で用いられる場合には、その格
のｐＨは望ましくは２〜１２の範囲であり、さらに好ま
しくはＰＨ３〜１０である。本発明に使用する定着能を
有する写真用処理格は、前述の如く定着格と漂白定着浴
とに大別されるが、前者の定着格に用いられる定着液と
しては上記濃度のチオシアン酸塩を定着剤として含有せ
しめる限り、いかなる組成のものも用いることができる
。最も単純な定着液としてはチオシアン酸イオンのみを
含有せしめた定着液、またはこれらの定着液に本発明の
重合体を含有せしめた定着液が挙げられる。また、これ
らの定着液には必要に応じて各種の写真用添加剤を１種
または２種以上絹合せて含有せしめてもよい。たとえば
棚酸、側砂、水酸化ナトリウム、水酸化カリウム、炭酸
ナトリウム、炭酸カリウム、重炭酸ナトリウム、ョウ化
アンモニウム、臭化アンモニウム、ョウ化カリ、臭化カ
リぐョウ化ナトリウム、臭化ナトリウム、重炭酸カリウ
ム、酢酸、酢酸ナトリウム、水酸化アンモニウム等のｐ
Ｈ緩衝剤を単独であるいは２種以上組合せて含有せしめ
ることができる。また、各種の姿光増白剤や沼泡剤ある
いは界面活性剤、定着促進剤、あるいは亜硫酸、ヒドロ
キシアミン、ヒドラジン、アルデヒド化合物の重亜硫酸
附加物等の保障剤、アミノポリカルボン酸等の有機キレ
ート化剤あるいはニトロアルコール硝酸塩等の一種の安
定剤、メタノール、ジメチルホルムアミド、ジメチルス
ルフオキシド等の有機溶媒等を適宜含有せしめることが
できる。これらの添加剤は０．１夕／夕から８００夕／
そまで添加する事ができる。そして、後者の漂白定着格
に用いられる漂白定着液としては、前述の定着成分のほ
かに漂白剤（酸化剤）が添加されるが、この漂白剤とし
ては任意のものを添加することができる。
たとえばフエリシアン化カリウム、フエリシアン化ナト
リウム、フヱリシアン化アンモニウム等のフヱリシアン
化物、過硫酸塩、重クロム酸塩、アミノポリカルボン酸
金属銭塩、ポリカルボン酸金属塩等がその代表的具体例
として挙げられるが、とくに本発明において望ましく用
いられる漂白剤は、公害防止の観点から有機酸の金属鍔
塩である。そしてこの有機酸としては、たとえば下記一
般式〔１〕または[9] Copoly
N-(2-acryloyloxy)-ethyl-2-pyrrolidonenoacrylic acid diethylamide (molar ratio 60:40
) [10] Copoly-N-(2-methacryloyloxy)ethyl-2-pyrrolidone sodium acrylate (molar ratio 75:25) [,1U Copoly-N-(3-acryloyloxy)propyl-2-pyrrolidone/methyl methacrylate ( Molar ratio 65:35) [12] Copoly N,
N-dimethyl-N-[3-(1-pyrrolidonyl)-2-
Ethyl hydroxy]-propylamine-N'-acryloyliminoacrylate (molar ratio 70:35) [13]
Copoly N-vinyl-2-pyrrolidone/vinyl acetate (
Molar ratio 70:30) [10 Copoly N-vinyl-2-pyrrolidone/methyl acrylate (molar ratio 70:30)
15] Copoly-N-vinyl-2-pyrrolidone/styrene (molar ratio 80:20) [16] Copoly-N-vinyl-2-pyrrolidone/acrylic acid amide N-vinyl-2
-Methylimidazole (molar ratio 50:30:20) [1
7] Copoly-N-vinyl-2-pyrrolidone/N-(1
,1-dimethyl-3-oxo)-butyl-acrylamide (molar ratio 70:30) [18] Coboly-N-allyl-2-pyrrolidone/pinyl acetate (molar ratio: 36) [1
9] Copoly N-vinyl-2-pyrrolidone/4-vinylpyridine (molar ratio 60:40) [20] Copoly N
-Pinyl-2-pyrrolidone/acrylic acid, ethylnoacrylic acid, monoethanolamine acid (molar ratio 50:45:5)
[21] Copoly-N-vinyl-2-pyrrolidone/piveridi/maleamic acid piberidic acid (molar ratio: 47)
[Material] Copoly N-pinylpyrrolidone/4-vinylpyridinone N-methyl iodide (molar ratio 42: spots) [
23] Coboly N-vinylpyrrolidone/thiourea maleate half ammonium salt (molar ratio 60:40) *Exemplary polymer [1] shown in Note 1 is General Aniline
and film corp (skill ralaniline
and81mCorp. ) from PVPK-30. PVP
It is commercially available under the trade names K-60 and PVPK-90. As mentioned above, some of the polymers used in the present invention are commercially available, so they can be easily obtained.
oms, Inc. ) Published (1961) Dapriyu Earl Sorenson, Tay Dapriyu. Camp Bell (W.
R. Sore ship on, T. W. Campbell) Department of Preparative Methods of Polymer Chemistry
It can be easily synthesized according to the method described in IMmerChemist. The polymer of the present invention is used by being incorporated into a photographic processing bath having a fixing chamber and/or a subsequent processing bath. Although it can also be included in the processing layer, a more favorable effect cannot be obtained than when it is contained only in the photographic processing layer having fixing ability, and this is not an essential condition of the present invention. If the polymer of the present invention is not contained in a photographic processing bath having a fixing chamber, the polymer of the present invention may be contained in a subsequent processing bath. In this case, the post-processing bath of a photographic processing bath having a fixing chamber is preferably a photographic processing bath having a fixing chamber, that is, a processing bath carried out immediately after a fixing bath or a bleach-fixing bath; Alternatively, a treatment step such as a rinsing treatment may be interposed between the bleach-fixing stage and the subsequent treatment stage. In addition, when the polymer of the present invention is contained in a photographic processing bath having a fixing chamber as described above, the polymer of the present invention may be contained in any arbitrary processing bath carried out thereafter. can. When the post-processing liquid contains the polymer of the present invention, the post-processing liquid may be applied to the photographic material to be processed by a coating method using a sponge or the like. The amount of the polymer used in the present invention differs depending on whether it is added to a photographic processing bath having fixing ability or to a subsequent processing bath. When added, it is generally 5 to 200 tanoso,
When silver ions are eluted from the emulsion layer of the photographic material to be processed and accumulated during the processing, for example, when silver ions are accumulated in a large amount of 45 days/day, 30 to 80 days/day is sufficient. In addition, the temperature can be arbitrarily determined without being limited to the above-mentioned range by taking into consideration the processing temperature according to the common practice, as well as the type of polymer used and the concentration of thiocyanic acid as a coexisting fixing agent. In general, if the amount of the polymer of the present invention added is too small, precipitation of silver halide due to decomposition of the silver thiocyanate key body is likely to occur during the water washing step as a subsequent treatment; Care must be taken, as the viscosity of the processing liquid increases, affecting the processing speed and reducing the liquid components due to carry over. Furthermore, when it is added to the post-processing bath of a photographic processing bath having the latter fixing ability, silver ions will not be eluted as much as in the photographic processing bath having the above-mentioned fixing chamber. Generally, it can be used in the range of 5 to 400 m/s, preferably 20 to 20 m/s, but in this case, the amount is limited to the above range so that no blockage of silver thiocyanate occurs in the water washing step. It is preferable to determine this experimentally without being subject to The container to which the polymer of the present invention is added may contain various additives depending on the type of the container. For example, a guarantee agent, a development accelerator, an inhibitor, an alkali agent, a pH
Appropriate amounts of regulators, buffers, hardeners, etc. can also be added. Furthermore, in order to add the polymer of the present invention to a photographic processing device having a fixing ability, it is preferable to add it directly to the photographic processing unit as described above, but it is preferable to add it directly to the photographic processing unit having a fixing ability. It may be contained in a photographic processing material having a fixing ability by xerin depending on the material, or it may be added to a photographic processing material and accumulated in a photographic processing material having a fixing chamber during processing. It's okay.
However, in this case, it is not necessarily a preferable method since it is necessary to process the photographic material such that the concentration of the polymer of the present invention exceeds a certain level. The higher the processing temperature for photographic processing and/or subsequent processing that contains the polymer of the present invention, the higher the processing speed, and the processing time with new solution (clearing time) There is little difference in clearing time due to fatigue solution after processing photographic materials, and it is less affected by fixation-inhibiting components that accumulate in the lacquer from photographic materials during processing, making it easier to use when recycled and used repeatedly. However, in relation to the heat resistance of the photographic material used for processing and the photographic material to be processed, especially its support, and the physical properties of the film of the photographic material, Kugami may generally be undesirable. Therefore, it is common to process at temperatures ranging from 20 to 55°C. The spots of the solution used in the photographic processing chamber having a fixing chamber in the present invention and in the case containing the polymer of the present invention are optional, but if the processing solution is a fixer, if the fence is too low, the fixer As thiocyanate ions become easily oxidized, and if the pH is too high, the gelatin film of the photographic material may swell too much, so generally the pH is between 2 and 2.
12, preferably used in groups 3-9. If the processing solution is a bleach-fix solution, the lower the pH, the shorter the clearing time, so it is better to lower the bait. Depending on the type of coupler used, a problem may arise in that the dye image formed becomes a leuco body and its degree of color recovery is reduced. Therefore, it is generally better to use a bait of 3.0 to 9.0 with a fence of 1.5 to 10.0. Furthermore, when the polymer of the present invention is used in a post-processing stage for photographic processing having fixing ability, the pH of the stage is preferably in the range of 2 to 12, more preferably PH3 to 10. . The photographic processing solution having fixing ability used in the present invention is roughly divided into fixing solution and bleach-fixing bath as described above. Any composition can be used as long as it is contained as a fixing agent. The simplest fixing solution includes a fixing solution containing only thiocyanate ions, or a fixing solution containing the polymer of the present invention in these fixing solutions. These fixing solutions may also contain one or more of various photographic additives, if necessary. For example, shelf acid, side sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonium iodide, ammonium bromide, potassium iodide, potassium bromide, sodium iodide, bromide. p of sodium, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
H buffering agents can be contained alone or in combination of two or more. In addition, various brightening agents, foaming agents, surfactants, fixing accelerators, guarantee agents such as sulfite, hydroxyamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelates such as aminopolycarboxylic acids, etc. A stabilizer such as a oxidizing agent or nitroalcohol nitrate, an organic solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained. These additives are used from 0.1 t/t to 800 t/t
You can add up to that amount. In addition to the above-mentioned fixing components, a bleaching agent (oxidizing agent) is added to the bleach-fixing solution used in the latter bleach-fixing process, and any bleaching agent can be added. For example, typical examples include ferricyanides such as potassium ferricyanide, sodium ferricyanide, and ammonium ferricyanide, persulfates, dichromates, metal salts of aminopolycarboxylic acids, and metal salts of polycarboxylic acids. In particular, the bleaching agent preferably used in the present invention is a metal salt of an organic acid from the viewpoint of preventing pollution. As this organic acid, for example, the following general formula [1] or
〔０〕で示されるアミノポリカルボン
酸がある。一般式〔１〕
ＨＯＣＯ−Ａ，一Ｚ−Ａ２ＣＯＯ日
一般式There is an aminopolycarboxylic acid represented by [0]. General formula [1] HOCO-A, 1Z-A2COO day general formula
〔０〕
〔前記各一般式中、Ａ，，Ａ２，Ａ３，Ａ４，Ａ５、お
よびＡ６はそれぞれ置換もしくは無置換炭化水素基、Ｚ
は炭化水素基、酸素原子、硫酸原子もしくは＞Ｎ−Ａ７
（Ａ７は炭化水素基）カルボキシル基を表わす。
〕これらの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ってもよい。
前記一般式〔１〕または〔ロ〕で示されるアミノポリカ
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。‘１ｌ エチレンジアミンテトラ酢酸
‘２１ ジェチレントリアミンベンタ酢酸‘８１ エチ
レンジアミンーＮ一（８ーオキシエチル）一Ｎ−Ｎ′，
Ｎ′−トリ酢酸‘４１ ブロピレンジアミンテトラ酢酸
‘５１ ニトリロトリ酢酸
■ シクロヘキサンジアミンテトラ酢酸
‘７１ィミノジ酢酸
‘８’ジヒドロキシエチルグリシン
側 エチルエーテルジアミンテトラ酢酸
ＯＱ グリコールェーテルジアミンテトラ酢酸（１１）
エチレンジアミンテトラプロピオン酸（１２）フェニレ
ンジアミンテトラ酢酸（１３ エチレンジアミンテトラ
酢酸ジナトリウム塩（１０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（１０ エチレン
ジアミンテトラ酢酸テトラナトリウム塩（１０ ジェチ
レントリアミンベンタ酢酸ペンタナトリウム塩（１７）
エチレンジアミン−Ｎ−（３ーオキシエチル）−Ｎ，Ｎ
′，Ｎ′−トリ酢酸ナトリウム塩（１８）プロピレンジ
アミンテトラ酢酸ナトリウム塩（１別 ニトリロトリ酢
酸ナトリウム塩
（２０）シクロヘキサンジアミンテトラ酢酸ナトリウム
塩上記各種の漂白剤に他に、特別な場合には過酸化水素
、臭素酸塩、ヨウ素酸塩、塩素酸塩、過ホウ素酸塩、亜
硝酸塩等の酸化性塩を含ませることもできる。
又前記定着液と全く同様な各種の添加剤を同様に添加す
る事もできる。本発明の重合体を含有せしめることがで
きる処理格は前述の如く定着能を有する写真用処理格お
よび／またはその後処理格であるが、その最も単純な後
処理格の液組成は、本発明の重合体（乃至共重合体）の
みを含有せしめた液である。
そしてこの液には酢酸、リン酸、棚酸等の醗類、水酸化
ナトリウム、炭酸ナトリウム等のアルカリ類を添加する
ことができ、さらに必要に応じて各種のキレート化合物
からなる沈澱防止剤、明ばん系やアルデヒド系を始めと
する各種の化合物からなる硬膜剤、ｐＨ緩衝剤、亜硫酸
塩、ヒドロキシルアミン、ヒドラジン等の酸化防止剤、
硫酸ナトリウム、硫酸マグネシウム等の膨油防止剤、消
泡剤、界面活性剤等を含有せしめることができる。また
、これら定着液、漂白定着液及び前俗、後格には通常は
不要であり添加しないことが望ましいが、所望により本
発明の効果に害のない程度の少量のチオ硫酸塩、チオグ
リコール類、ポリエチレングリコール類、チオ尿素類、
４級アミン塩、アリフアティックチオール類、（例えは
Ｑ−モノチオグリセロール）アロマテイックチオール類
（例えば５−アミノー２ーメルカプト、１，３，４，チ
アジアゾールなど）を処理裕中に含ませる事もできる。
本発明に係る写真材料の処理方法は、定着能を有する写
真用処理格で処理する工程を含むハロゲン化銀写真材料
の処理方法のすべてを包含するが、その好ましい処理方
法の代表的具体例を挙げると下記の諸工程が含まれる。
しかし本発明の処理方法がこれにより限定されるもので
はない。（□内は本発明の重合体を含有させた格であり
、定着能を有する写真処理浴の前処理工程に使用される
俗を前俗と指称し、後処理工程に使用される俗を後格と
指称する。）■ 黒白現像−庭費定着ｌ‐水洗‐安定
■ 黒白現像‐定着‐上歴町−安定
■ 黒白現像‐定着‐豚圏‐水洗‐安定
■ 黒白現像‐停止‐医副‐水洗
■ 黒白現像‐ｌ−建膜定割‐豚圏‐水洗■ 黒白現像
‐層圏‐垣圃‐水洗
■ 黒白第１現像−停止−水洗−発色現像−漂白−睦割
‐水洗‐安定■ 前硬膜−中和−黒白第１現像−停止−
水洗一発色現像‐停止‐水洗‐し瞳函痢‐水洗‐安定
■ 黒白第１現像−停止−水洗−発色現像−蝿墨趣灘‐
［剛‐燭‐安定■ 黒白第１現像−停止−カブリ浴−発
色現像−漂白‐ロ蚕町‐豚圏‐水洗‐安定■ 発色現像
‐［範囲覇‐晒鰯碇罰‐水洗‐安定■ 発色現像−Ｌ漂
白疋 ′−水洗−安定■ 発色現像−漂白定着−雁図〔
一水洗−安定■ 発色現像‐漂白定着‐’函園‐安定■
発色現像‐停止‐漂白‐Ｌ態副‐水洗−安定■発色現
像‐漂白‐水洗‐陸軍‐水洗‐安定
■ 特殊層除去浴‐発色現像‐ 藤官憲罰Ｊ−Ｌ園覇‐
水洗‐安定■ 前硬膜‐中和‐発色現像‐漂白‐圃圏鞄
週‐‘画腿肘水洗‐安定本発明に係る処理方法を施す前
に、被処理写真材料には現像処理を施すことができ、こ
の現像処理は写真材料の種類に応じて黒白現像、発色現
像、または黒白第１現像と発色現像との組合せ等のいず
れであってもよい。
上記黒白現像工程において使用される黒白現像液は、た
とえば、カラー写真感光材料の処理に用いられる黒白第
１現像液と呼ばれるもの、もしくは黒白写真材料の処理
に用いられるもの等のあらゆる現像液を用いることがで
きる。そして、この現像液には一般に黒白現像液に添加
される各種の添加剤を含有せしめる事もできる。代表的
な添加剤としては、１−フェニルー３−ビラゾリドンー
メトール、ハイドロキノン等の現像主楽、亜硫酸塩のよ
うな保恒剤、水酸化ナトリウム、炭酸ナトリウム、炭酸
カリウム等のアルカリから成る促進剤、臭化カリウムや
２−メチルベンツイミダゾール、メチルベンツチアゾー
ル等の無機性もしくは有機性の抑制剤、ポリリン酸塩の
ような硬水軟化剤、徴量の沃化物やメルカプト化合物か
ら成る表面過現像防止剤等をあげる事ができる。また、
上記発色現像の工程において使用される発色現像液は、
カラー写真感光材料の発色現像処理に用いられるあらゆ
る種類のものを使用することができ、たとえば芳香族第
１級ァミン発色現像主薬を含むアルカリ水溶液が本発明
において好ましく用いられ、これには水酸化ナトリウム
、炭酸ナトリウム、炭酸カリウム、メタ棚酸ナトリウム
、重炭酸ナトリウム、棚酸等の餌調整剤、解緩衝剤を含
ませる事ができるし、又特別の場合には塩化スズやポロ
／・ィドラィドの如きかぶらせ剤を添加することができ
るし、さらに又ペンジルアルコール等を含ませてもよい
。
発色現像主薬としては、たとえばＮ，Ｎージエチル−Ｐ
ーフエニレンジアミン硫酸塩、４−アミノ−Ｎーェチル
ーＮ−６−ヒドロキシェチルアニリン硫酸塩、３−メチ
ル−４ーアミノ−Ｎ−エチル一８−メタンスルホアミド
エチルアニリンセスキサルフエートモノヒドラート、３
ーメチル−４ーアミノーＮ−エチル−Ｎ−８−ヒドロキ
シェチルアニリン硫酸塩などがある。またこれらを用い
た現像液中には臭化物、沃化物、炭酸塩、重亜硫酸塩、
公知のカブリ防止剤や公知の現像促進剤、ジェチレング
リコールのような溶剤類等を含有せしめることもできる
。本発明に適用できる写真材料は、ハロゲン化銀写真感
光材料であればいずれでもよく、低感度のハロゲン化銀
写真感光材料はもとより、高感度のハロゲン化銀写真感
光材料の処理にも有効に適用できるものであり、感光材
料の型も、たとえば印画紙等の白黒またはカラープリン
ト用感光材料、ネガ白黒またはカラ−フィルム、リバー
サル白黒またはカラーフィルム等の撮影用感光材料等の
定着処理を必要とするあらゆる種類の型のハロゲン化銀
写真感光材料の処理に共通に適用することができる。
本発明に適用される写真材料がカラー用である場合、発
色剤が写真材料中に含まれている内式現像方式（米国特
許第２３７６６７計号、同第２８０１１７１号明細書）
のほか、発色剤が現像液中に含まれている外式現像方式
（米国特許第２２５２７１８号、同第２５９２２４３号
、同第２５９０９７び号明細書）のものであってもよい
。
また発色剤は、当業界で一般に知られている任意のもの
が使用できる。例えばシアン発色剤としてはナフトール
あるいはフェノール構造を基本とし、カップリングによ
りインドアニリン色素を形成するもの、マゼンタ発色剤
としては活性メチレン基を有する５−ピラゾロン環を骨
格構造として有するもの、イエロー発色剤としては活性
メチレン基を有するペンゾィルアセトアニラィド、ピバ
リルアセトアニライド、アシルアセトアニラィド構造の
ものなどでカップリング位置に置換基を有するものも、
有しないものも、いずれも使用できる。このように発色
剤としては、いわゆる２当量カプラ−および４当量カプ
ラーのいずれをも適用できるものである。本発明に適用
される写真材料に用いられるハロゲン化銀乳剤としては
塩化銀、臭化銀、沃化銀、塩臭化銀、塩沃化銀、沃臭化
銀、塩沃臭化線の如きいずれのハロゲン化銀を用いたも
のであってもよい。
また、これ等のハロゲン化繊の保護コロイドとしては、
ゼラチン等の天然物の他、合成によって得られる種々の
ものが使用できる。ハロゲン化銀乳剤には、安定剤、増
感剤、硬膜剤、増感色素、面活性剤等通常の写真用添加
剤が含まれてもよい。本発明の処理方法に用いられる定
着能を有する写真用処理浴の組成液は、その液中に溶解
した銀イオンを容易に回収することができると共に、液
の安定性が極めて良好なので、銀イオンを回収した後、
必要に応じて適宜再生剤あるいは補充剤を添加して定着
能力を向上した後、繰返し反覆使用に供することができ
る。その銀回収方法には、公知のあらゆる方法を採用で
きる。その代表的具体例を挙げれば、沈澱剤を用いる銀
沈澱法、電気分解を利用した電解法、イオン化額向を利
用した金属置換法、イオン交換樹脂によるイオン交換法
等が含まれ、特に本発明においては電解法が液の再生反
覆使用上好ましい。これらの銀の回収方法についてはヱ
ム・エル・シユレーべ（Ｍ．Ｌ．Ｓｅｈｒｅｉ広）、プ
レゼント・ステイタス・オブ・シルバー・リカバリー・
モーション・ピクチユア−・ラボラトリーズ（Ｐｒｅｓ
ｅｎｔＳねｔｕｓｏｆＳｉｌｖｅｒＲｅｃｏｖｅｒｙＭ
ｏｔｉｏｎ ＰｉｃｔｍｅＬａｂｏねｔｏｒｉｅｓ）７
４巻５０５乃至５１４頁（１９６３王）等に記載されて
いる。本発明に用いる定着能を有する写真用処理液から
の銀の回収は前記の如く公３句のあらゆる方法を採用で
きるが、より好ましくは次の操作を付随的に加えた方が
よい。すなわち、例えば金属置換法によるときは被処理
液のｐＨを低下させてやることが望ましい。また電解法
によるときは本発明のチオシァン酸イオンが酸化される
ことがあるので電解液のｐＨ、電流密度あるいは陰極の
回転速度等を変えることが望ましい。そして、本発明に
用いる定着館を有する写真用処理液が定着液の場合は銀
イオンを回収するのみで再使用できるが、漂白定着液の
場合は銀イオンの回収とあわせて漂白剤の還元体を酸化
し元の酸化剤にしてやることが好ましい。
すなわち、処理液が漂白定着液である場合には銀を漂白
酸化すると同時に自らは還元され、−漂白剤の還元体が
生成し蓄積することになり、これが処理液の漂白定着館
を低下させ所謂疲労現像を起こす原因になるからである
。ところが、本発明に用いられる漂白定着液はチオ硫酸
塩等の還元剤として活用する定着剤を含有せず、通常の
斑で酸化されるものは添加されていないので処理時に生
成する還元体は漂白剤の還元体のみである。そこで本発
明においては処理により生成する漂白剤の酸化は、通常
の酸化剤によって行うことができる。例えば空気、酸素
、オゾン等による酸化法、過酸化水素、過硫酸塩、塩素
酸塩、次亜塩素酸塩、臭素酸塩、函硝酸、趣棚素酸塩、
ハロゲンガスまたはその他の※機もしくは有機酸化剤に
よる酸化法、電解による陽極酸化法、金属キレート系や
キノン系等の酸化還元樹脂による酸化法等を用いる事が
できる。なお、本発明において定着剤として用いるチオ
シアン酸塩を用いた定着液は、本発明の目的である公害
防止の点から再生反覆使用する事が望ましい。又別の方
法として濃厚な処理液を少量ずつ補充する事により処理
鱗液の量の低下せしめる事もできる。又チオシアン酸塩
は種々の方法により無害化する事もできる。本発明のチ
オシアン酸塩を用いる事により処理により溶出するハロ
ゲンイオンの定着阻害を受けず本発明の目的を充分達成
できる。次に実施例を挙げて本発明を例証するが、本発
明の実施態様はこれにより限定されるものではない。
実施例 １
９．８モル％の沃化銀を含む高感度沃臭化銀ゼラチン乳
剤を第２熟成し、次の順に従って各写真用添加剤を添加
し赤感性乳剤を得た。
‘１｝ 下記組成物を高速回転ミキサーに通してカプラ
−分散液を調整し、１モルのハロゲン化線を含む乳剤に
添加したもの。
‘２’ ３％サポニン ９５肌／ハロゲン化銀１モル‘
３’０．５％ムコクロル酸 ８０舷ノハロゲン化銀１ュ
三ノレ次いで上記赤感性乳剤に１０％ゼラチン水溶液を
添加してからトリアセチルセルロースフィルム上に塗布
銀量２．４夕／れになるように塗布し乾燥して試料を作
成した。
得られた試料を常法により光渓を通して所定の露光を与
えた後、下記処理を行なった。〔処理法〕
（処理温度３軍０）‘１１ 発色現像 ３分１
９砂■ 漂 白 ． ６分３雌
‘３’水 洗 ３分１職
■ 定 着 ６分３胸
■水 洗 ３分１蛾
職 安 定 １分３蛾
なお、定着液を除き、用いた処理液の組成は次の通りで
ある。
像液
漂白液
水を加えて１夕にし、アンモニア水で柵６．０に調製し
た。
安定液
定着液及び後格は次に示す‘ａー乃至（１）を用いた。
定着液｛ａ｝・‘ｂ）
‐[0] [In each of the above general formulas, A,, A2, A3, A4, A5, and A6 are each substituted or unsubstituted hydrocarbon group, Z
is a hydrocarbon group, oxygen atom, sulfuric acid atom or >N-A7
(A7 is a hydrocarbon group) represents a carboxyl group. ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [1] or [b] include the following. '1l Ethylenediaminetetraacetic acid'21 Diethylenetriaminebentaacetic acid'81 Ethylenediamine-N-(8-oxyethyl)-N-N',
N'-Triacetic acid '41 Bropylene diamine tetraacetic acid '51 Nitrilotriacetic acid ■ Cyclohexane diamine tetraacetic acid '71 Iminodiacetic acid '8' Dihydroxyethylglycine side Ethyl ether diamine tetraacetic acid OQ Glycol ether diamine tetraacetic acid (11)
Ethylenediaminetetrapropionic acid (12) Phenylenediaminetetraacetic acid (13 Ethylenediaminetetraacetic acid disodium salt (10 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt) (10 Ethylenediaminetetraacetic acid tetrasodium salt (10) Dethylenediaminetetraacetic acid pentasodium salt (17) )
Ethylenediamine-N-(3-oxyethyl)-N,N
',N'-Sodium triacetate (18) Sodium propylene diamine tetraacetate (by 1) Sodium nitrilotriacetate (20) Sodium cyclohexane diamine tetraacetate In addition to the above various bleaches, in special cases peroxide Hydrogen, oxidizing salts such as bromates, iodates, chlorates, perborates, nitrites, etc. can also be included.Additionally, various additives that are exactly the same as those for the above-mentioned fixer can be added as well. Processing units that can contain the polymer of the present invention include photographic processing units and/or post-processing units having fixing ability as described above, and the simplest liquid composition of the post-processing units is as follows: , a liquid containing only the polymer (or copolymer) of the present invention. To this liquid, alcohols such as acetic acid, phosphoric acid, and shelf acid, and alkalis such as sodium hydroxide and sodium carbonate are added. In addition, if necessary, anti-settling agents made of various chelate compounds, hardening agents made of various compounds including alum-based and aldehyde-based, pH buffering agents, sulfites, hydroxylamine, and hydrazine can be added. antioxidants such as
Oil swelling inhibitors such as sodium sulfate and magnesium sulfate, antifoaming agents, surfactants, etc. can be contained. In addition, thiosulfates and thioglycols are normally unnecessary and desirably not added to these fixing solutions, bleach-fixing solutions, prefixes, and postfixes, but if desired, small amounts of thiosulfates and thioglycols may be added to the extent that they do not harm the effects of the present invention. , polyethylene glycols, thioureas,
Quaternary amine salts, aliphatic thiols, (e.g. Q-monothioglycerol) aromatic thiols (e.g. 5-amino-2-mercapto, 1,3,4,thiadiazole, etc.) may also be included in the treatment solution. can.
The method for processing a photographic material according to the present invention includes all methods for processing a silver halide photographic material including a step of processing with a photographic processing agent having a fixing ability. The following steps are included: However, the processing method of the present invention is not limited to this. (The box inside □ is a case containing the polymer of the present invention. The case used in the pre-processing step of a photographic processing bath having fixing ability is called the pre-processing step, and the case used in the post-processing step is called the post-processing step. ) ■ Black and white development - Fixation l - Washing - Stable ■ Black and white development - Fixing - Kamirekicho - Stable ■ Black and white development - Fixing - Pork area - Washing - Stable ■ Black and white development - Stop - Medical assistant - Water washing ■ Black and white development - l - Building film fixed division - Pig area - Water washing ■ Black and white development - Stratosphere - Fence field - Water washing ■ Black and white first development - Stop - Water washing - Color development - Bleaching - Mutsu division - Water washing - Stabilization ■ Before Dural mater - Neutralization - Black and white first development - Stop -
Washing with water - Color development - Stop - Washing with water - Pupil irritation - Washing with water - Stable■ Black and white first development - Stop - Washing with water - Color development - Fly ink painting -
[Strong - Candle - Stable ■ Black and white first development - Stop - Fog bath - Color development - Bleaching - Ro-Sericho - Butakun - Washing - Stable ■ Color development - [Range control - Bleaching - Sardine anchorage - Washing - Stable ■ Color development Development - L bleaching - Washing - Stable■ Color development - Bleach fixing - Wild goose diagram
One water wash - Stable ■ Color development - Bleach fixing - 'Hakoen - Stable ■
Color development - Stop - Bleaching - L-state secondary - Washing - Stable Color development - Bleach - Washing - Army - Washing - Stable ■ Special layer removal bath - Color development - Fujikan Penalty J-L Sonoha -
Washing with water - Stable ■ Pre-hardening - Neutralization - Color development - Bleaching - Field bag week - Washing with water - Stability Before applying the processing method according to the present invention, the photographic material to be processed must be subjected to a development process. Depending on the type of photographic material, this development treatment may be black and white development, color development, or a combination of black and white first development and color development. The black-and-white developer used in the black-and-white developing step is, for example, a so-called black-and-white first developer used in the processing of color photographic materials, or any developer used in the processing of black-and-white photographic materials. be able to. This developer may also contain various additives that are generally added to black and white developers. Typical additives include developing agents such as 1-phenyl-3-virazolidone-methol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and surface overdevelopment prevention agents consisting of iodides and mercapto compounds. I can give you medicine, etc. Also,
The color developer used in the above color development process is
All kinds of materials used in color development processing of color photographic light-sensitive materials can be used. For example, an alkaline aqueous solution containing an aromatic primary amine color developing agent is preferably used in the present invention. Bait conditioners such as sodium carbonate, potassium carbonate, sodium metashelate, sodium bicarbonate, shelate acid, debuffering agents, and in special cases, such as tin chloride and polohydride, can be included. A fogging agent may be added, and pendyl alcohol or the like may also be included. As a color developing agent, for example, N,N-diethyl-P
-phenylenediamine sulfate, 4-amino-N-ethyl-N-6-hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-8-methanesulfamide ethylaniline sesquisulfate monohydrate, 3
-Methyl-4-amino-N-ethyl-N-8-hydroxyethylaniline sulfate. In addition, developers using these compounds contain bromides, iodides, carbonates, bisulfites,
It is also possible to contain known antifoggants, known development accelerators, solvents such as diethylene glycol, and the like. The photographic material applicable to the present invention may be any silver halide photographic light-sensitive material, and can be effectively applied to processing not only low-sensitivity silver halide photographic materials but also high-sensitivity silver halide photographic materials. The type of photosensitive material also requires a fixing process, such as photosensitive materials for black and white or color printing such as photographic paper, photosensitive materials for photography such as negative black and white or color film, and reversal black and white or color film. It can be commonly applied to the processing of all types of silver halide photographic materials. When the photographic material applied to the present invention is for color, an internal development method in which a coloring agent is included in the photographic material (U.S. Pat. No. 237,667, U.S. Pat. No. 2,801,171)
In addition, external development methods (US Pat. No. 2,252,718, US Pat. No. 2,592,243, US Pat. No. 2,590,97) in which a coloring agent is contained in the developer may be used. Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta color formers have a 5-pyrazolone ring with an active methylene group as a backbone structure, and yellow color formers is penzoylacetanilide, pivalylacetanilide, or acylacetanilide structure having an active methylene group, and also those having a substituent at the coupling position,
You can use any of them even if you don't have one. As described above, both so-called 2-equivalent couplers and 4-equivalent couplers can be used as color formers. Silver halide emulsions used in the photographic material applied to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Any silver halide may be used. In addition, protective colloids for these halogenated synthetic fibers include:
In addition to natural products such as gelatin, various synthetically obtained products can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants. The composition liquid of the photographic processing bath having fixing ability used in the processing method of the present invention allows silver ions dissolved in the liquid to be easily recovered and has extremely good stability. After collecting the
After improving the fixing ability by adding a regenerating agent or a replenisher as necessary, it can be used repeatedly. Any known method can be used to recover the silver. Typical specific examples thereof include a silver precipitation method using a precipitant, an electrolysis method using electrolysis, a metal replacement method using ionization, and an ion exchange method using an ion exchange resin. In this case, the electrolytic method is preferred for recycling and repeated use of the liquid. For information on how to recover these silvers, see M.L. Sehrei, Present Status of Silver Recovery.
Motion Picture Your Laboratories (Pres.
entSnetusofSilverRecoveryM
tion PictmeLabonetories)7
4, pp. 505-514 (King, 1963). As mentioned above, any of the three methods mentioned above can be used to recover silver from the photographic processing solution having fixing ability used in the present invention, but it is more preferable to add the following operation incidentally. That is, when using the metal substitution method, for example, it is desirable to lower the pH of the liquid to be treated. Furthermore, when using an electrolytic method, the thiocyanate ion of the present invention may be oxidized, so it is desirable to change the pH of the electrolytic solution, the current density, the rotation speed of the cathode, etc. If the photographic processing solution having a fixing chamber used in the present invention is a fixing solution, it can be reused by simply recovering the silver ions, but in the case of a bleach-fixing solution, in addition to recovering the silver ions, the reduced form of the bleaching agent must be recovered. It is preferable to oxidize it to the original oxidizing agent. That is, when the processing solution is a bleach-fix solution, silver is bleached and oxidized and at the same time itself is reduced, resulting in the production and accumulation of a reduced form of the bleach, which lowers the bleach-fix capacity of the processing solution and causes the so-called This is because it causes fatigue development. However, the bleach-fix solution used in the present invention does not contain a fixing agent such as thiosulfate that is used as a reducing agent, and does not contain substances that are oxidized by normal spots, so the reduced product produced during processing does not bleach. It is only the reduced form of the agent. Therefore, in the present invention, the bleaching agent produced by the treatment can be oxidized using a conventional oxidizing agent. For example, oxidation method using air, oxygen, ozone, etc., hydrogen peroxide, persulfate, chlorate, hypochlorite, bromate, nitric acid, chlorate,
Oxidation methods using halogen gas or other organic or organic oxidizing agents, anodization methods using electrolysis, oxidation methods using redox resins such as metal chelate systems or quinone systems, etc. can be used. Note that the fixing solution using thiocyanate used as a fixing agent in the present invention is desirably recycled and used repeatedly from the viewpoint of preventing pollution, which is an object of the present invention. Alternatively, the amount of treated scale liquid can be reduced by replenishing the concentrated treatment liquid little by little. Thiocyanate can also be made harmless by various methods. By using the thiocyanate of the present invention, the objects of the present invention can be fully achieved without being inhibited by the fixation of halogen ions eluted during treatment. The present invention will now be illustrated by examples, but the embodiments of the present invention are not limited thereto. Example 1 A highly sensitive silver iodobromide gelatin emulsion containing 9.8 mol % of silver iodide was subjected to second ripening, and each photographic additive was added in the following order to obtain a red-sensitive emulsion. '1} The following composition was passed through a high-speed rotating mixer to prepare a coupler dispersion, which was added to an emulsion containing 1 mol of halogenated radiation. '2' 3% saponin 95 skin/silver halide 1 mole'
3' 0.5% mucochloric acid 80 1/3 g of silver halide Next, add a 10% aqueous gelatin solution to the above red-sensitive emulsion and apply it on a triacetyl cellulose film so that the amount of silver coated is 2.4 kg/layer. A sample was prepared by coating and drying. The obtained sample was passed through a light beam and exposed to a predetermined amount of light in a conventional manner, and then subjected to the following treatments. [Processing method]
(Processing temperature 3 groups 0) '11 Color development 3 minutes 1
9 Sand■ Bleaching. 6 minutes 3 females '3' Water wash 3 minutes 1 job ■ Set 6 minutes 3 breasts ■ Water wash 1 minute 1 moth job Stable 1 minute 3 moths The composition of the processing solution used, excluding the fixer, is as follows. That's right. An image solution bleaching solution water was added and the solution was left overnight, and then adjusted to 6.0 with ammonia water. As the stabilizer fixer and the postfix, the following 'a' to (1) were used. Fixer {a}・'b) -
【Ｃ１
定着液‘ｄ｝
．‘ｅ｝
定着液の
定着液（ｇ）
定着液（ｈ）
比較用後格（ｉ）
後格（ｉ）
後格（ｋ）
後浴（１）
注 １ 前記した市販品ＰＶＰＫ−１５を用いた。
なお、各定着液および後浴は、いずれもアンモニア水ま
たは氷酢酸で柵７．０に調製した。
なお上記処理は全処理を斑℃で行い、後裕‘肌ま定着処
理後の後に１分間行った。
前記定着液‘ａ｝〜（ｈ）は前記作製試料１．０枕をそ
れぞれ達続浸潰しあらかじめ疲労させたものを用いた。
表一１に示す如き定着処理及び後浴処理の組み合せによ
り前記処理工程に従って処理を行った。そして処理した
フィルムの定着完了時間（クＩＪアリングタイム）及び
仕上りフィルムの透明度を測定した。更に仕上がったフ
ィルムを高温高温テスト（８０℃湿度８０％）と耐光性
テスト（Ｆａｄｅ−０一ｍｅｔｅｒ）により色素退色度
を測定して色素保存性を試験し色濃度の測定は光学濃度
計ＰＤ−９（小西六製）を用いて行った。それぞれのテ
ストの結果を表−１に示した。表 一 １
表−１の結果から明らかなようにチオ硫酸塩を定着剤と
する定着液【ａ｝を用いた処理（Ｍ．１）の場合は、仕
上りフィルムの透明性が良好であるが、疲労液によるク
リアリングタイムがズが富な長時間となる欠点がある。
また、本発明に係る処理法によらない定着液‘ｂ｝乃至
｛ｄ｝を用いた処理（Ｍ．２乃至４）の場合は、定着剤
としてチオシアン酸塩、臭化物、沃化物を単独で用いる
と仕上りフィルムが不透明となり、とくにこの場合の如
く銀イオンを多量に含む疲労液によるときに著しく不透
明となる欠点がある。又色素保存による色素退色率が著
しく高い。さらに定着剤として沃素イオンを多量に用い
、本発明の重合体を含有せしめた定着液■を用いた本発
明の処理法によらない処理（Ｍ．５）の場合は、フィル
ムの透明性やクリアリングタイムは良好であるが、定着
液‘ａぬいし｛ｄーと同様に色素保存テストによる色素
退色率が著しく高い欠点がある。これに対し、定着剤と
してチオシアン酸塩を用いると共に、本発明の重合体（
乃至英重合体）を含有せしめた定着液‘ｆ）乃至（ｈ）
を用いた本発明に係る処理（Ｍ．６乃至８）の場合は、
疲労液によるクリアリングも良好でありかつ透明性もよ
く又画像色素保存テストによる色素退色率が低く従来処
方にくらべ著しく良好である事がわかる。
本発明の処理法は、後浴中に本発明の重合体（乃至共重
合体）を含有せしめた場合（Ｍ．１０乃至１２）も、透
明性が良くクリアリングタイムについても良好でありか
つ色素画像の保存テストによる退色率も少なく優れた処
理法である事がわかる。ところが、本発明の重合体（乃
至共重合体）に代えて比較化合物を添加した後浴（ｉ）
による処理（Ｍ．９）の場合は、透明性が不良でフィル
ムが著しく不透明になる匁点が生じかつ色素画像の安定
性も劣る事が判る。なお、上記処理法（地．１０）にお
いて、後俗（ｉ）液をスポンジを用いて塗布したところ
、上記地．１０の処理結果と同様の効果が得られた。
また、上記本発明に係る処理法（Ｍ．６乃至８、１０乃
至１２）において処理温度を２ぴ０および５０℃で行っ
たところ、透明性及び色素安定性については同様の好結
果が得られたほか、５ぴ○の場合は前述の３籍０の処理
温度による結果よりもクリアリングタイムが短縮され良
好な結果が得られた。なお又、定着液および後格の風を
４．０と８．６に調整し本実施例と同様の処理を行った
が本発明に係る処理法についてはクリアリングタイムお
よび仕上りフィルムの透明性並びに色素画像安定性とも
良好な結果が得られた。本実施例に変えて試料を市販の
白黒ネガフイルム（コニバンＳＳ、小西六写真工業製）
を用いて同様な試験を行い本実施例と同様にクリアリン
グタイム及び仕上りフィルムの透明性、銀画像の保存安
定性を調べたが、本発明に基ずく定着液及び後格を用い
たものは全く良好な結果が得られた。
特に銀画像の保存試験では本発明以外の定着液を用いた
場合褐色に変色するが本発明による定着液もしくは後浴
を用いたものはこのような事は全くみられず線画像の安
定性が優れている事がわかつた。実施例 ２
下引き処理を施したセルローズトリアセテートフィルム
支持体上に次の各層を順次塗布してハロゲン化銀カラー
ネガ写真感光材料の試料を作製した。
‘１｝ ハレーション防止層
黒色コロイド銀をゼラチン水溶液中に分散させてゼラチ
ン３夕／め、銀０．斑夕／〆の割合で塗布した。
‘２） シアン形成赤感性ハロゲン化銀乳剤層カラード
シアンカプラ−（１）５夕とシアンカプラー（０）２０
夕の混合物をトリクレジルホスフェ−トに溶解したゼラ
チン水溶液に分散せしめた沃臭化銀ゼラチン乳剤（６モ
ル％の沃化銀含有）を、ゼラチン４．５夕／め、銀３．
８タノで、シアンカプラー１．４タノでの割合で塗布し
た。
【３１中間層
ゼラチン水溶液をゼラチン１．３夕／〆の割合で塗布し
た。
■ マゼンタ形成線感性ハロゲン化銀乳剤層カラードマ
ゼンタカプラー（町）５夕とマゼンタカプラ−（Ｗ）２
５夕の混合物をトリクレジルホスフェートに溶解しゼラ
チン水溶液中に分散せしめた沃臭化銀ゼラチン乳剤（６
モル％の沃化線含有）をゼラチン５．０タノで、銀３７
夕／〆、マゼンタカプラー１．２夕／枕の割合で塗布し
た。
‘５１中間層
ゼラチン水溶液をゼラチン１．３夕／〆の割合で塗布し
た。
【６’黄色フィルター層
黄色コロイド銀をゼラチン水溶液中に分散せしめて、銀
０．１夕／で、ゼラチン１．３夕／あの割合で塗布した
。
【７’イエロー形成青感性ハロゲン化銀乳剤層イエロー
カプラ−（Ｖ）３０夕をジブチルフタレートに溶解し、
ゼラチン水溶液中に分散せしめたものを含む沃臭化銀ゼ
ラチン乳剤（７モル％の沃化銀含有）を、ゼラチン４．
０夕／で、銀１．４夕／〆およびイエローカプラー１．
６夕／〆の割合で塗布した。
‘８１ 保護層
ゼラチン水溶液をゼラチン１．３夕／〆の割合で塗布し
た。
なお、各層には硬膿剤として１，２−ビス（ビニルスル
ホニル）ヱタンを２咳夕／タゼラチンの割合で含有せし
めた。
また、各カプラーは次のものを用いた。
（１）カラードシアンカプラー
１ーヒドロキシ−４−〔４一（２ーヒドロキシ−３，６
−ジスルホ−１ーナフチルアゾ）アニリノカルボニルオ
キシ〕−Ｎ一〔Ｑ一２，４ージ−ｔ−アミルフエノキシ
）ブチル〕一２ーナフトアミドージアンモニウム塩（０
）シアンカプラ−
２−｛４−（２，４ージ−ｔ−アミルフエノキシ）ブチ
ル｝力ルバモイルー１ーナフトール（虹）カラードマゼ
ンタカブラー３−（２−クロロー５ーオクタデシルサク
シンイミドーアニＩＪ／）−１一（２，４，６ートリク
ロロフエニル）−４一（１−ナフチルアゾ）−５ーピラ
ゾロン（Ｎ）マゼンタカプラー
１一（２，４，６ートリク。
ロフエニル）一３−（３−オクタデシルサクシンイミド
ベンズアミド）一５−ピラゾロン（Ｖ）イエローカプラ
ー
Ｑ−サクシンイミドーＱーピバリル−６−ク。
〇−５−〔ｒ一（２，４ージーｔ−アミルフヱノキシ）
ブチルアシド〕アセトアニリド得られた試料に常法によ
り光蝶を通して所定の露光を与えた後、下記の処理を行
った。
〔処理法〕 〔処理温度３８００）
‘１｝ 発色現像 ３分１９砂‘２｝ 漂白
定着 ６分
‘３’水 洗 ３分１職
次に、用いた処理液の組成を示す。
〔発色現像液〕 実施例１と同じ
〔漂白定着液〕
下記漂白剤等に実施例１の定着液１夕を加えたものを用
いた。
漂白剤
漂白定着液（ｍ）
漂白定着液（ｎ）
漂白定着液（ｏ）
漂白定着液（ｐ）
漂白定着液（Ｑ）
漂白定着液（Ｒ）
漂白定着液（Ｓ）
漂白定着液（ｔ）
なお、上記漂白定着液（ｍ）乃至（Ｓ）についてはＰＨ
６２にアンモニア水または氷酢酸を用いて調整し、漂白
定着液（ｔ）については水酸化ナトリウムでｐＨｉｌ．
０に調整した。
上記の試料を１．０〆を用いてそれぞれについて上記処
理を行って、実施例１と同様の方法で漂白定着液のクリ
アリングタイムをフィルムの裏面から目視測定し、さら
に仕上がりフィルムの透明性を宮視測定した。
更に仕上がったフィルムに残存するＡｇ量を測定した。
又仕上がりフィルムの色素画像の保存試験を高温高湿テ
ストにより試験した。これらのテスト結果を下記表−２
に示した。泰 一 ２表−２の結果から明らかな如く本
発明によらない処理法実験番号（Ｍ．１３乃至１６）で
はクリアリングタイムが長い（Ｍ．１３）濁度が高く仕
上がりフィルムが不透明（Ｍ．１４，１５）又、色素保
存試験による赤濃度測定での色素退色率が高い（Ｍ．】
３乃至１６）などの欠点がいずれもみられ、全ての性能
を満足するものではない。
又表−２から明らかな如く色素退色率は仕上がりフィル
ム中の残存銀量に起因するものと推定できる。本発明に
よらない処理法（Ｍ．１６）は透明性が良好でありなが
ら仕上がりフィルム中に残存銀量が高いという結果が得
られたが恐らくピロリドン核を有する重合体と銀の透明
性銀錯塩が残存するものと考えられる。これに対し本発
明の処理法（船．１６乃至２０）は彼処理写真材料が高
銀量のハロゲン化銀カラーネガ写真材料であっても疲労
液によるクリアリングタイムが短時間でありかつ仕上が
りフィルムが透明で残存銀量もほとんど皆無という結果
が得られた。又残存銀量が無いために色素保存安定性（
および赤濃度退色率）も非常に優れている事がわかる。
また、本実施例の処理法において、‘２）の漂白定着と
（３’の水洗の間に後浴３現砂を介在させた処理を行っ
た。すなわち、上記漂白定着液（ｏ）による処理の後、
実施例１の後格（Ｊ），（Ｒ）および（１）による処理
を行ったところ、上記本発明に係る処理法と同様の良い
結果が得られた。そして、この後裕処理をスポンジ塗布
法で実施した場合も同様の結果が得られた。さらに、本
実施例において処理温度を５ぴ０で行ったところ、クリ
アリングタイムが更に短縮され極めて良い結果が得られ
た。
さらにまた、本実施例の本発明に係る処理法において漂
白定着液のｐＨを５．５と７．６に調整して同様の処理
を行ったところ、斑７．６の場合については本実施例の
クリアリングタイムより若干遅いクリアリングタイムで
あるほかフィルムの透明性については同様の好結果が得
られたし、ｐＨ５．５の場合には本実施例のクリアリン
グタイムが更に短縮され極めて良好な結果が得られた。[C1 Fixer'd}. 'e} Fixer of fixer (g) Fixer (h) Comparative post case (i) Post case (i) Post case (k) Post bath (1) Note 1 The above-mentioned commercial product PVPK-15 was used. . Each of the fixing solutions and the post-bath was prepared with aqueous ammonia or glacial acetic acid to a pH of 7.0. All of the above treatments were carried out at 0.degree. C., and were carried out for 1 minute after the fixing treatment on the skin. For the fixing solutions 'a} to (h), the prepared sample 1.0 pillows were successively immersed and fatigued in advance, respectively. Processing was carried out according to the above processing steps using combinations of fixing processing and post-bath processing as shown in Table 1. Then, the fixing completion time (IJ fixing time) of the processed film and the transparency of the finished film were measured. Furthermore, the finished film was subjected to a high-temperature test (80°C, 80% humidity) and a light fastness test (Fade-01 meter) to measure the degree of dye fading and test the dye preservability.The color density was measured using an optical densitometer PD- 9 (manufactured by Roku Konishi). The results of each test are shown in Table-1. Table 1 1 As is clear from the results in Table 1, in the case of treatment (M.1) using fixer [a} containing thiosulfate as a fixer, the transparency of the finished film was good; The disadvantage is that the clearing time due to the fatigue fluid is extremely long. In addition, in the case of processing using fixing solutions 'b} to {d} (M.2 to 4) which is not based on the processing method according to the present invention, thiocyanate, bromide, or iodide is used alone as the fixing agent. The disadvantage is that the finished film becomes opaque, especially when a fatigue solution containing a large amount of silver ions is used as in this case. Furthermore, the rate of dye fading due to dye storage is extremely high. Furthermore, in the case of processing not based on the processing method of the present invention (M.5), which uses a large amount of iodide ions as a fixing agent and a fixing solution containing the polymer of the present invention, film transparency and clear Although the ring time is good, it has the disadvantage of a significantly high rate of dye fading in the dye preservation test, similar to the fixer 'a-d'. On the other hand, in addition to using thiocyanate as a fixing agent, the polymer of the present invention (
Fixing liquids containing a mixture of polymers 'f) to (h)
In the case of the treatment according to the present invention (M.6 to 8) using
It can be seen that the clearing with fatigue solution is good and the transparency is also good, and the dye fading rate in the image dye preservation test is low and is significantly better than the conventional formulation. The treatment method of the present invention provides good transparency and clearing time even when the polymer (or copolymer) of the present invention is contained in the post bath (M.10 to 12). It can be seen that this is an excellent processing method with a low rate of color fading in image preservation tests. However, after bath (i) in which a comparative compound was added instead of the polymer (or copolymer) of the present invention,
It can be seen that in the case of the treatment (M.9), the transparency is poor, a momme point occurs where the film becomes extremely opaque, and the stability of the dye image is also poor. In addition, in the above-mentioned treatment method (ground.10), when the liquid (i) was applied using a sponge, the above-mentioned surface. Effects similar to the results of treatment No. 10 were obtained. In addition, when the treatment method according to the present invention (M.6 to 8, 10 to 12) was carried out at a treatment temperature of 20°C and 50°C, similar good results were obtained regarding transparency and dye stability. In addition, in the case of 5 pi○, the clearing time was shorter than the results obtained with the above-mentioned treatment temperature of 3 0, and better results were obtained. In addition, the fixing solution and the after-grade wind were adjusted to 4.0 and 8.6, and the same processing as in this example was carried out, but the processing method according to the present invention was improved in terms of clearing time, transparency of the finished film, and Good results were obtained in terms of dye image stability. Instead of using this example, the sample was a commercially available black and white negative film (Koniban SS, manufactured by Konishiroku Photo Industry).
A similar test was conducted using the same method as in this example to examine the clearing time, the transparency of the finished film, and the storage stability of the silver image. All good results were obtained. In particular, in storage tests for silver images, when a fixer other than the one according to the present invention was used, the color changed to brown, but when the fixer according to the present invention or post-bath was used, this problem was not observed at all, and the stability of the line image was improved. I found it to be excellent. Example 2 A sample of a silver halide color negative photographic material was prepared by sequentially coating the following layers on a cellulose triacetate film support which had been subjected to subbing treatment. '1} Anti-halation layer Black colloidal silver was dispersed in an aqueous gelatin solution, and gelatin was added 3 times a day and silver was added 0.5 times a day. It was applied at a ratio of Madarayu/Finish. '2) Cyan forming red-sensitive silver halide emulsion layer colored cyan coupler (1) 5 and cyan coupler (0) 20
A silver iodobromide gelatin emulsion (containing 6 mol % silver iodide), which was prepared by dispersing the mixture in an aqueous gelatin solution in tricresyl phosphate, was prepared using 4.5 molar ratios of gelatin and 3.5 molar ratios of silver.
It was applied at a ratio of 1.8 mm and 1.4 mm of cyan coupler. [31 Intermediate layer gelatin aqueous solution was coated at a ratio of 1.3 gelatin/gelatin. ■ Magenta forming line-sensitive silver halide emulsion layer Colored magenta coupler (machi) 5 and magenta coupler (W) 2
A silver iodobromide gelatin emulsion (6.5%
(containing mol% of iodide) with gelatin of 5.0% and silver of 37%
The magenta coupler was applied at a ratio of 1.2 mm/pillow. '51 intermediate layer gelatin aqueous solution was coated at a ratio of 1.3 gelatin/gelatin. [6' Yellow filter layer Yellow colloidal silver was dispersed in an aqueous gelatin solution and coated at a ratio of 0.1 silver/gelatin and 1.3 gelatin/gelatin. [7' Yellow-forming blue-sensitive silver halide emulsion layer Yellow coupler (V) 30% was dissolved in dibutyl phthalate,
A silver iodobromide gelatin emulsion (containing 7 mol% silver iodide) containing silver iodobromide gelatin dispersed in an aqueous gelatin solution was added to gelatin 4.
0/, silver 1.4/, and yellow coupler 1.
It was applied at a ratio of 6 coats/1 coat. '81 Protective layer A gelatin aqueous solution was applied at a ratio of 1.3 gelatin/gelatin. In addition, each layer contained 1,2-bis(vinylsulfonyl)ethane as a purulent agent at a ratio of 2 parts per tagelatin. In addition, the following couplers were used. (1) Colored cyan coupler 1-hydroxy-4-[4-(2-hydroxy-3,6
-disulfo-1naphthylazo)anilinocarbonyloxy]-N-[Q-2,4-di-t-amylphenoxy)butyl]-2-naphthamide diammonium salt (0
) Cyan coupler 2-{4-(2,4-di-t-amylphenoxy)butyl}ruvamoyl 1 naphthol (rainbow) colored magenta coupler 3-(2-chloro 5-octadecylsuccinimidoani IJ/)-1 (2,4,6-trichlorophenyl)-4-(1-naphthylazo)-5-pyrazolone (N) magenta coupler 1-(2,4,6-trichlorophenyl)-3-(3-octadecylsuccinimidebenzamide) -5-pyrazolone (V) yellow coupler Q-succinimide Q-pivalyl-6-k. 〇-5-[r-(2,4-G-t-amylphenoxy)
Butylacetanilide] The obtained sample was exposed to a predetermined amount of light through a light beam in a conventional manner, and then subjected to the following treatments. [Processing method] [Processing temperature 3800] '1' Color development 3 minutes 19 sand '2} Bleach fixing 6 minutes '3' Water Washing 3 minutes 1 The following shows the composition of the processing solution used. [Color developing solution] Same as Example 1 [Bleach-fixing solution] One portion of the fixing solution of Example 1 was added to the following bleaching agent and the like. Bleach bleach-fix solution (m) bleach-fix solution (n) bleach-fix solution (o) bleach-fix solution (p) bleach-fix solution (Q) bleach-fix solution (R) bleach-fix solution (S) bleach-fix solution (t) In addition, for the above bleach-fix solutions (m) to (S), the PH
62 with aqueous ammonia or glacial acetic acid, and bleach-fix solution (t) with sodium hydroxide.
Adjusted to 0. Each of the above samples was subjected to the above treatment using 1.0㎜, and the clearing time of the bleach-fix solution was visually measured from the back side of the film in the same manner as in Example 1, and the transparency of the finished film was further evaluated. Miyaji was measured. Furthermore, the amount of Ag remaining in the finished film was measured.
The preservation test of the dye image of the finished film was also carried out by a high temperature and high humidity test. These test results are shown in Table 2 below.
It was shown to. As is clear from the results in Table 2, the treatment method experiment numbers (M.13 to 16) not based on the present invention had long clearing times (M.13), high turbidity, and opaque finished films (M.13). 14,15) Also, the dye fading rate is high when measuring red density by dye storage test (M.)
All of the disadvantages such as 3 to 16) are observed, and all performances are not satisfied. Furthermore, as is clear from Table 2, it can be assumed that the dye fading rate is caused by the amount of silver remaining in the finished film. Although the processing method (M.16) not according to the present invention had good transparency, the amount of residual silver in the finished film was high. It is thought that some remains. On the other hand, the processing method of the present invention (Ships 16 to 20) requires only a short clearing time due to the fatigue solution and the finished film is transparent even if the processed photographic material is a silver halide color negative photographic material with a high silver content. The result was that there was almost no residual silver. In addition, since there is no residual silver, dye storage stability (
It can be seen that the red density and fading rate) are also very good.
In addition, in the processing method of this example, post-bath 3 present sand was interposed between the bleach-fixing in '2) and the water washing in (3'). That is, the treatment with the bleach-fixing solution (o) was carried out. After,
When the treatments according to the postfixes (J), (R), and (1) of Example 1 were performed, good results similar to those of the treatment method according to the present invention described above were obtained. Similar results were obtained when the post-wet treatment was carried out using a sponge coating method. Furthermore, in this example, when the treatment temperature was set to 50 mm, the clearing time was further shortened and very good results were obtained. Furthermore, when the pH of the bleach-fixing solution was adjusted to 5.5 and 7.6 in the processing method according to the present invention in this example, and the same treatment was performed, the result was 7.6 spots. In addition to the clearing time being slightly slower than the clearing time of the above example, similar good results were obtained regarding the transparency of the film.In the case of pH 5.5, the clearing time of this example was further shortened and extremely good results were obtained. The results were obtained.
Claims (1)
含有する定着能を有する写真用処理浴で処理する工程を
含むハロゲン化銀写真材料の処理方法において、前記写
真用処理浴および／またはその後処理浴中に、分子構造
中にピロリドン核単位を有する重合体を含有せしめるこ
とを特徴とするハロゲン化銀写真材料の処理方法。 ２ 定着能を有する写真用処理浴がアミノポリカルボン
酸金属錯塩の如き有機酸の金属錯塩、赤血塩、第２鉄塩
等の漂白剤（酸化剤）を含有し漂白能を併せ有する漂白
定着液、または漂白能を有しない通常の定着液であるこ
とを特徴とする特許請求の範囲第１項記載の写真材料の
処理方法。 ３ 写真処理浴に対するチオシアン酸イオンの含有量が
０．３〜６．５モル／ｌであることを特徴とする特許請
求の範囲第１項または第２項記載の写真材料の処理方法
。[Scope of Claims] 1. A method for processing a silver halide photographic material, comprising the step of processing with a photographic processing bath having a fixing ability and containing at least 0.2 mol/l of thiocyanate ion, the photographic processing bath having a fixing ability. and/or a method for processing a silver halide photographic material, characterized in that a polymer having a pyrrolidone core unit in its molecular structure is contained in a subsequent processing bath. 2. A bleach-fixing method in which a photographic processing bath having a fixing ability contains a bleaching agent (oxidizing agent) such as a metal complex salt of an organic acid such as an aminopolycarboxylic acid metal complex salt, a red blood salt, or a ferric salt, and also has a bleaching ability. 2. The method for processing photographic materials according to claim 1, wherein the fixing solution is a fixing solution or an ordinary fixing solution having no bleaching ability. 3. A method for processing photographic materials according to claim 1 or 2, characterized in that the content of thiocyanate ions in the photographic processing bath is 0.3 to 6.5 mol/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5180377A JPS6024463B2 (en) | 1977-05-06 | 1977-05-06 | Processing methods for silver halide photographic materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5180377A JPS6024463B2 (en) | 1977-05-06 | 1977-05-06 | Processing methods for silver halide photographic materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53137143A JPS53137143A (en) | 1978-11-30 |
| JPS6024463B2 true JPS6024463B2 (en) | 1985-06-13 |
Family
ID=12897076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5180377A Expired JPS6024463B2 (en) | 1977-05-06 | 1977-05-06 | Processing methods for silver halide photographic materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6024463B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61248040A (en) * | 1985-04-25 | 1986-11-05 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide black and white photographic sensitive material |
| DE3786895D1 (en) * | 1986-10-08 | 1993-09-09 | Konishiroku Photo Ind | FIXING SOLUTION WITH A GOOD TREATMENT EFFECT AND METHOD FOR TREATING A LIGHT SENSITIVE MATERIAL USING THIS. |
| JP2805011B2 (en) * | 1988-12-23 | 1998-09-30 | コニカ株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JP2681173B2 (en) * | 1988-12-27 | 1997-11-26 | コニカ株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JP2893101B2 (en) * | 1991-02-19 | 1999-05-17 | 富士写真フイルム株式会社 | Processing method of silver halide photographic light-sensitive material and photographic fixing function composition |
| US10377928B2 (en) | 2015-12-10 | 2019-08-13 | Ppg Industries Ohio, Inc. | Structural adhesive compositions |
-
1977
- 1977-05-06 JP JP5180377A patent/JPS6024463B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53137143A (en) | 1978-11-30 |
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