JPS63129343A - Development of silver halide photographic sensitive material - Google Patents
Development of silver halide photographic sensitive materialInfo
- Publication number
- JPS63129343A JPS63129343A JP27539086A JP27539086A JPS63129343A JP S63129343 A JPS63129343 A JP S63129343A JP 27539086 A JP27539086 A JP 27539086A JP 27539086 A JP27539086 A JP 27539086A JP S63129343 A JPS63129343 A JP S63129343A
- Authority
- JP
- Japan
- Prior art keywords
- water
- tank
- washing
- stock
- liquid
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 44
- -1 silver halide Chemical class 0.000 title claims abstract description 43
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 37
- 239000004332 silver Substances 0.000 title claims abstract description 37
- 238000011161 development Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 137
- 238000000034 method Methods 0.000 claims abstract description 62
- 238000005406 washing Methods 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 16
- 238000003672 processing method Methods 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 18
- 238000007865 diluting Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 54
- 150000001875 compounds Chemical class 0.000 description 32
- 239000003795 chemical substances by application Substances 0.000 description 27
- 239000012895 dilution Substances 0.000 description 22
- 238000010790 dilution Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 238000012545 processing Methods 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000005291 magnetic effect Effects 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229940079593 drug Drugs 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 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 3
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 206010070834 Sensitisation Diseases 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- QWZOJDWOQYTACD-UHFFFAOYSA-N 2-ethenylsulfonyl-n-[2-[(2-ethenylsulfonylacetyl)amino]ethyl]acetamide Chemical compound C=CS(=O)(=O)CC(=O)NCCNC(=O)CS(=O)(=O)C=C QWZOJDWOQYTACD-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 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
- 239000003381 stabilizer Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- OXZRQDIWHYFSGL-UHFFFAOYSA-N 1,2-dimethylpyrazolidin-3-one Chemical compound CN1CCC(=O)N1C OXZRQDIWHYFSGL-UHFFFAOYSA-N 0.000 description 1
- IFKVSABTHWCIGO-UHFFFAOYSA-N 1,5-dihydropyrazol-5-ide Chemical compound C=1C=NN[C-]=1 IFKVSABTHWCIGO-UHFFFAOYSA-N 0.000 description 1
- IWPGKPWCKGMJMG-UHFFFAOYSA-N 1-(4-aminophenyl)-4,4-dimethylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=C(N)C=C1 IWPGKPWCKGMJMG-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- XIWRQEFBSZWJTH-UHFFFAOYSA-N 2,3-dibromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1Br XIWRQEFBSZWJTH-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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 1
- REFDOIWRJDGBHY-UHFFFAOYSA-N 2-bromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1 REFDOIWRJDGBHY-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- IJSPKRNXRSYASK-UHFFFAOYSA-N 3,3,5,5-tetramethyl-2-[2-(2-phenoxyethoxy)ethoxy]hexane-2-sulfonic acid Chemical compound CC(C)(C)CC(C)(C)C(C)(OCCOCCOC1=CC=CC=C1)S(=O)(=O)O IJSPKRNXRSYASK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 1
- SRYYOKKLTBRLHT-UHFFFAOYSA-N 4-(benzylamino)phenol Chemical compound C1=CC(O)=CC=C1NCC1=CC=CC=C1 SRYYOKKLTBRLHT-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 1
- XPAZGLFMMUODDK-UHFFFAOYSA-N 6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=CNC2=C1 XPAZGLFMMUODDK-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000006519 CCH3 Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- 229910018828 PO3H2 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-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
- 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 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
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 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 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 150000002473 indoazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910052759 nickel 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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ATGAWOHQWWULNK-UHFFFAOYSA-I pentapotassium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ATGAWOHQWWULNK-UHFFFAOYSA-I 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 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 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000012224 working solution 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
- G03C7/407—Development processes or agents therefor
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はハロゲン化銀写真感光材料の自動現像機を用い
ての現像処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for developing silver halide photographic materials using an automatic processor.
(従来技術とその問題点)
ハロゲン化銀写真感光材料の自動現像機による現像や定
着(又は漂白・定着)処理は従来それらの処理液成分を
互いに悪影!#を及ぼし合わない複数の原液薬剤、e−
ツに分IIf″′C製造保管し、使用に際して手動又は
自動的にかかる複数の薬剤パーツを混合し更に水で希釈
して現像液や定着液として各々自動現像機に併設するス
トック槽に保存し、感光材料が処理されるに応じて該希
釈した処理液をそのまま供給する方法がとられてきてい
た。しかしながら、複数の薬剤ノξ−ツを混合宿駅して
、ストック槽に入れることは煩雑で手間がかかる。(Prior art and its problems) Conventionally, when developing and fixing (or bleaching and fixing) silver halide photographic materials using an automatic processor, the components of the processing solution have negative effects on each other! # Multiple stock drugs that do not interact with each other, e-
When used, multiple chemical parts are mixed manually or automatically, diluted with water, and stored as developer and fixer in stock tanks attached to automatic processors. A method has been adopted in which the diluted processing solution is directly supplied as the photosensitive material is processed.However, it is cumbersome to mix multiple chemicals and put them into a stock tank. It takes time and effort.
更に、処理液は既に希釈した状態であるため、そのスト
ック槽の容量は必然的に大きくせざるを得す、かなりの
スペースが必要であるとともに、希釈した処理液は酸化
劣化が起こりやすくストック槽中への長期保存に限界が
あり、写真性能を保持するためには一定期間内に処理液
を交替しなければならないという問題を有する。Furthermore, since the processing solution is already diluted, the capacity of the stock tank must necessarily be large, which requires a considerable amount of space, and the diluted processing solution is susceptible to oxidative deterioration. There is a problem that there is a limit to long-term storage, and the processing solution must be replaced within a certain period of time in order to maintain photographic performance.
上記の如き複数薬剤の有する1つの欠点を解消するため
にそり剤数を減少させて、例えば処理液の原液を一剤の
みとして混合する手間を軽減する方法も公知である。し
かしながら複数薬剤の場合と同様水で希釈しなければな
らないため原液が一剤のみであってもそれを希釈した状
態で自動現像機のストック槽中に保存する限り、上記の
如きスに一部や酸化劣化の問題は何ら解決することはで
きなかった。In order to solve one of the drawbacks of multiple chemicals as described above, a method is also known in which the number of shaving agents is reduced to reduce the effort of mixing the stock solution of the treatment liquid as only one agent. However, as in the case of multiple drugs, it must be diluted with water, so even if the stock solution is only one drug, as long as it is stored in a diluted state in the stock tank of an automatic processor, some of it may be The problem of oxidative deterioration could not be solved at all.
一方、処理液の原液を予め希釈してストック槽に保管し
てお(のではなく、使用の直前に水と混合希釈して処理
槽に補充する方法も知られている。On the other hand, a method is also known in which the stock solution of the processing solution is diluted in advance and stored in a stock tank, but the solution is mixed and diluted with water immediately before use and then replenished into the processing tank.
しかしながら、写真特性や仕上り等に悪影響を及ぼさな
いためには、調液希釈水として新鮮な水を処理液に供給
する必要があった。従って、自動現像機に直接水道水を
導くための配管の必要性により自動現像機の設置条件が
制約されたり、あるいは希釈水を自動現像機に併設する
ストック槽中に保管するにしても新鮮さを保つために非
常に頻繁に希釈水を交替したり、あるいは常に洗浄を心
掛ける等の煩雑な作業が必要であった。However, in order to avoid adverse effects on photographic properties, finish, etc., it has been necessary to supply fresh water to the processing solution as solution dilution water. Therefore, the installation conditions for automatic processors are restricted due to the need for piping to lead tap water directly to the automatic processor, and even if dilution water is stored in a stock tank attached to the automatic processor, freshness cannot be maintained. In order to maintain this level, it was necessary to perform complicated operations such as changing the dilution water very frequently and constantly cleaning the water.
他方、ハロゲン化銀写真感光材料の現像処理において、
現像、定着(又は漂白・定着)後に施される水洗又は安
定化処理では、水垢の発生等を防止するために水洗水又
は安定化液中に種々の防菌剤を添加する技術が知られて
いる。特に近年環境保全や省エネルギー及び処理の迅速
化等の観点から要求の高いタメ水水洗や極少量補充水洗
の如き節水処理を行なうにあたってはかかる防菌剤の使
用は非常に重要である。しかしながら、従来は水洗水(
又は安定化液)用と調液希釈水用の少なくとも2種類の
水を各々別個のものとして使用していた。これは非常に
煩雑であるとともに大きなスペースが必要であり、自動
現像機に水道水を導(配管が必要となり、自動現像機を
稼動させるのに”いつでもどこでも”というわけにはい
かず大きな制約となる。On the other hand, in the development process of silver halide photographic materials,
In the washing or stabilization treatment performed after development and fixing (or bleaching/fixing), there are known techniques for adding various antibacterial agents to the washing water or stabilizing solution in order to prevent the formation of limescale, etc. There is. In particular, the use of such antibacterial agents is very important when performing water-saving treatments such as additional flushing and extremely low-volume replenishment flushing, which have recently been in high demand from the viewpoint of environmental protection, energy saving, and speeding up of processing. However, conventionally, washing water (
At least two types of water, one for (or stabilizing liquid) and one for liquid preparation dilution water, were each used separately. This is very complicated and requires a large space, and it also requires piping to lead tap water to the automatic processor, which is a big constraint as the automatic processor cannot be operated anytime and anywhere. .
また、現像、定着液が自動的に調液できるシステムが組
み込まれた自動現像処理方法が望まれて〜る。Furthermore, there is a need for an automatic processing method incorporating a system that can automatically prepare developing and fixing solutions.
一方、環境保全の問題と銀資源の節減の問題が重視され
、廃液による公害の減少および水洗水からの銀の回収が
強く望まれている。On the other hand, issues of environmental conservation and conservation of silver resources are emphasized, and reduction of pollution caused by waste liquid and recovery of silver from washing water are strongly desired.
このための処理液の廃液から銀回収だけでなく、水洗水
廃液からの回収方法もいろいろと提案されている。たと
えば***特許分開第2,532,018号その他に電解
法、特開昭50−183l8号公報その他に金属置換法
、同53−76029号その他に薬品による沈殿法、同
53−59254号に微生物による沈殿法が開示されて
いる。しかしながら、これらの方法を用いても水洗水廃
液中では可溶性銀塩の濃度が希釈されて希薄になってい
るため回収効率が低い欠点があった。For this purpose, various methods have been proposed not only for recovering silver from the waste liquid of the processing solution, but also for recovering silver from the waste liquid of washing water. For example, the electrolytic method is described in West German Patent Application No. 2,532,018 and others, the metal substitution method is described in Japanese Patent Application Laid-Open No. 50-18318 and others, the chemical precipitation method is described in Japanese Patent Application Publication No. 53-76029 and others, and the microbial method is described in Japanese Patent Application Publication No. 53-59254. A precipitation method is disclosed. However, even when these methods are used, the concentration of soluble silver salts in the washing water waste liquid is diluted and the recovery efficiency is low.
従って本発明の第1の目的は、現像液や定着液の調液、
希釈水の交替、ストック槽の洗浄等の煩雑な手間がいら
ず、現像液や定着液の安定性に優れ、さらに自動現像機
においては水道水の配管や大きなスペースの必要がなく
設置条件が制約されないハロゲン化銀写真感光材料の現
像処理方法を提供することKある。Therefore, the first object of the present invention is to prepare a developer and a fixer,
There is no need for complicated work such as changing dilution water or cleaning stock tanks, and the stability of the developer and fixer is excellent.Furthermore, in automatic processors, there is no need for tap water piping or large space, so installation conditions are limited. It is an object of the present invention to provide a method for developing a silver halide photographic light-sensitive material.
本発明の第2の目的は、水洗水又は安定化液と現像液用
及び/又は定着液用の調液希釈水とを共用させて、−タ
ンクとして極少量水洗の如き節水処理が可能でしかも現
像液や定着液の安定性や得られる写真性能が良好なハロ
ゲン化銀写真感光材料の現像処理方法を提供することに
ある。A second object of the present invention is to share the washing water or stabilizing solution with the developer and/or fixer diluent water, thereby making it possible to save water such as washing with a very small amount of water as a tank. It is an object of the present invention to provide a method for developing a silver halide photographic light-sensitive material, which provides good stability of a developer and a fixer and good photographic performance.
本発明の第3の目的は、使用する水量を少なくし、即ち
、廃液量を少なくし、銀回収がほぼ完全に可能な現像処
理方法を提供することにある。A third object of the present invention is to provide a development processing method that reduces the amount of water used, that is, reduces the amount of waste liquid, and allows almost complete recovery of silver.
(問題点を解決するための手段)
本発明の目的は、ハロゲン化銀写真感光材料を防黴手段
を施した水を含有するストック槽が設けられた自動現像
機を用いて現像、定着および水洗または安定化する方法
において、濃縮現像液および該防黴手段を施した水を現
像液槽に、濃縮定着液を定着液槽に各々移送し、かつ感
光材料1−轟り3l以下の該防黴手段を施した水を水洗
または安定化槽に補充し、水洗または安定化槽のオーバ
ーフロー液の一部または全部を定着槽へ移送して濃縮定
着液の希釈液に利用することを特徴とする現像処理方法
により達成される。(Means for Solving the Problems) An object of the present invention is to develop, fix and wash silver halide photographic materials using an automatic developing machine equipped with a stock tank containing water treated with anti-mildew means. Alternatively, in a stabilizing method, a concentrated developer and water treated with the anti-mildew means are transferred to a developer tank, a concentrated fixer is transferred to a fixer tank, and the anti-mildew solution is transferred to the photosensitive material 1 - 3 liters or less of the anti-mildew material. A developing method characterized by replenishing a washing or stabilizing tank with the water treated with the method, and transferring part or all of the overflow liquid from the washing or stabilizing tank to a fixing tank and using it as a diluent for the concentrated fixer. This is achieved through a processing method.
本発明においては、ストック槽中の防黴手段を施し丸木
(以下ストック水という)t−濃縮現像液の希釈水とし
て用いると同時に感光材料1−当り3l以下、好ましく
は50−〜11、という節水水洗処理における水洗水又
は安定化液(以下特にことわりのない限り単に水洗水と
いう)の補充液として用いる。好ましくは上記現像液用
希釈水と水洗水用補充液は同一のストック漕から供給さ
れる。従って、核、ストック水は防黴手段が施されてお
り写真性能への悪影響や水垢の発生なくしてストック槽
への保管が可能となると同時に上記の好適態様の如く現
像液用希釈水と水洗水用補充液との共用が可能となるた
め、自動現像機の簡易化、さらには一層のコンパクト化
が可能となる。In the present invention, the stock tank is treated with anti-mold means and the log water (hereinafter referred to as stock water) is used as dilution water for the T-concentrated developer, and at the same time, water is saved at 3 liters or less, preferably 50 to 11 liters, per one photosensitive material. It is used as a replenisher for washing water or stabilizing liquid (hereinafter simply referred to as washing water unless otherwise specified) in washing treatment. Preferably, the developer dilution water and the washing water replenisher are supplied from the same stock tank. Therefore, the core and stock water are treated with anti-mold measures, and can be stored in the stock tank without adversely affecting photographic performance or causing water stains. Since it can be used in common with a replenisher, the automatic developing machine can be simplified and further made more compact.
また、本発明においては、該ストック水の補充された水
洗水のオーバーフロー液の一部又は全部を、定着液槽に
移送して更に濃縮定着液の希釈水として用いる。ここで
いう定着液とは定着能を有する液のことを意味し、具体
的には定着液のはかに漂白定着液なども含む。本発明の
濃縮定着液は2モル/1以上のチオ硫酸塩を含有するこ
とが好ましい。Further, in the present invention, part or all of the overflow liquid of the washing water supplemented with the stock water is transferred to the fixing liquid tank and further used as dilution water for the concentrated fixing liquid. The term "fixer" as used herein means a solution having a fixing ability, and specifically includes not only a fixer but also a bleach-fixer and the like. The concentrated fixer of the present invention preferably contains thiosulfate in an amount of 2 mol/1 or more.
本発明に従い、水洗水のオーバーフロー液の一部又は全
部を濃縮定着液の希釈水として、しかも自動現像機内に
ての直前希釈水として流用することにより、水洗水廃液
の有効利用を図ることができると同時に定着液用希釈水
の節減乃至削除が可能となる。また、定着液からの廃液
中の銀回収率も向上する。According to the present invention, by diverting part or all of the overflow of the washing water as dilution water for the concentrated fixer, and moreover, as dilution water immediately before use in the automatic developing machine, it is possible to effectively utilize the washing water waste. At the same time, it is possible to save or eliminate dilution water for the fixer. Furthermore, the recovery rate of silver in the waste liquid from the fixer is also improved.
自動現像機において本発明の方法を採用することにより
、自動現像機の簡易化及びコンパクト化並びに更なる節
水及び廃液中の銀回収率の向上が図れるとともに、更に
、自動現像機による完全自動調液化の達成された、即ち
人為的調液作業の不要なハロゲン化銀写真感光材料の現
像処理システムが可能となる。By adopting the method of the present invention in an automatic processor, it is possible to simplify and downsize the automatic processor, further save water, and improve the recovery rate of silver in waste liquid. In other words, it becomes possible to develop a silver halide photographic material development processing system that achieves the following, which eliminates the need for artificial liquid preparation work.
従って、本発明においてはストック水や濃縮処理液の補
充や移送は、感光材料が処理されるに応じて自動的に行
なわれることが好ましく、更に自動調液化を更に容易に
するためには、現像液及び濃縮定着液は各々2つ以上の
パーツから成るものではない1剤であることが好ましく
、そのためには、現像処理過程中に硬膜する必要があま
りないように感光材料は処理以前に充分に硬膜されてい
ることが望ましい。Therefore, in the present invention, it is preferable that stock water and concentrated processing liquid be replenished and transferred automatically as the photosensitive material is processed. It is preferable that the solution and the concentrated fixer are each not made up of two or more parts, but are one part.For this purpose, the photosensitive material should be sufficiently coated before processing so that there is little need for hardening during the development process. It is desirable that the membrane is hardened.
本発明におけるストック水の防黴手段は、ストック水が
現像、定着性能に悪影’J’?与えず、得られた処理済
感光材料の品質が良好に維持可能であれは、特に限定さ
れるものではないが、好ましくは、紫外線照射、磁場照
射、イオン交換及び防黴剤添加等のうちの1種又はこれ
らの併用である。The anti-mold means for stock water in the present invention is that stock water has an adverse effect on developing and fixing performance 'J'? Although there are no particular limitations as long as the quality of the processed photosensitive material obtained can be maintained well without applying any additives, it is preferable to use ultraviolet irradiation, magnetic field irradiation, ion exchange, addition of antifungal agents, etc. One type or a combination thereof.
より好ましくは、後述する防黴剤の添加である。More preferred is the addition of an antifungal agent, which will be described later.
磁場照射とは磁場の正極と負極の間に発生する磁場に水
洗水及び希釈水を通過させることである。Magnetic field irradiation refers to passing washing water and dilution water through a magnetic field generated between a positive pole and a negative pole of a magnetic field.
磁場は、強磁性体の鉄、コバルト、ニッケルからなる永
久磁石等を使用することにより得られ、又はコイル等に
直流を流すことによっても得ることができるが、特に限
定されず、磁場を形成しうる全ての手段を用いることが
できる。なお、磁場は1個の磁石を用いて磁力線を形成
するよ5Ktてもよいし、2個(正極と負極)の磁石を
対向させて対向磁石間に磁力線を形成す2ようにしても
よい。The magnetic field can be obtained by using a permanent magnet made of ferromagnetic materials such as iron, cobalt, and nickel, or by passing a direct current through a coil, but is not particularly limited. All possible means can be used. In addition, the magnetic field may be 5 Kt so that lines of magnetic force are formed using one magnet, or it may be 5Kt where lines of magnetic force are formed between the opposing magnets by arranging two magnets (positive and negative poles) facing each other.
水洗水及び希釈水を磁場に通す方法としては、磁場を形
成する永久磁石等を使用して水ストック槽中及び/又は
液外に設けた永久磁石を移動(回転を含む)させるか、
又は水を攪拌又は循環により水を移動する等の方法があ
る。特に望ましい方法としては、循環系パイプの内部又
は外部の一部又は全部に永久磁石を固定し水を循環させ
る方法である。The method of passing the rinsing water and dilution water through a magnetic field is to use a permanent magnet that forms a magnetic field and move (including rotation) a permanent magnet installed in the water stock tank and/or outside the liquid.
Alternatively, there are methods such as moving the water by stirring or circulating the water. A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of a circulation system pipe and circulate water.
水洗水及び希釈水に紫外線を照射する方法は、一般に市
販されている紫外線ランプ又は紫外線照射装置等によっ
て行なわれ、好ましくは紫外線ランプの出力は5W〜s
oow(管出力)のものが好ましいが、これに限定され
るものではない。また1本発明の好ましい実施態様によ
れば紫外線の波長が220nm〜35Qnmの範囲のも
のである。The method of irradiating the washing water and dilution water with ultraviolet rays is carried out using a generally commercially available ultraviolet lamp or ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is 5 W to s.
oow (tube output) is preferable, but is not limited to this. According to a preferred embodiment of the present invention, the wavelength of the ultraviolet rays is in the range of 220 nm to 35 Q nm.
イオン交換樹脂処理する方法は、一般に市販されている
H型強酸性カチオン交換樹脂とOH型強塩基***換樹脂
を充填した混床式カラムで通水処理して水中のカルシウ
ムやマグネシウムイオンを著しく除去する方法である。The ion exchange resin treatment method involves passing water through a mixed bed column filled with a commercially available H-type strongly acidic cation exchange resin and an OH-type strongly basic exchange resin to significantly remove calcium and magnesium ions in the water. This is the way to do it.
これと同意義の方法として、本発明の水洗水及び希釈水
として蒸留水を用いることも含まれる。A similar method includes using distilled water as the washing water and dilution water of the present invention.
紫外線を用いる方法につ(戸ては例えば特開昭60−2
63939号公報などに、磁場を用いる方法については
例えば特開昭60−263940号公報などに、イオン
交換樹脂を用いる方法については例えば特願昭61−1
3l632号明細書など詳しく記載されている。Regarding the method using ultraviolet rays (for example, JP-A-60-2
63939, for example, Japanese Patent Application Laid-Open No. 60-263940 for a method using a magnetic field, and Japanese Patent Application No. 61-1 for a method using an ion exchange resin.
It is described in detail in the specification of No. 3l632.
防黴剤として、写真用として公知のものはいずれも用い
ることができるが好ましくは、現像処理に対して悪影響
を与えないような化合物であり、具体的にはアミノポリ
カルボン酸類、ホスホン酸類等が挙げられ、アミノポリ
カルボン酸類としての具体的な化合物を挙げるとエチレ
ンジアミン四酢g(EDTA)、ジエチレントリアミン
五酢酸、エチレンジアミン−N−(β−オキシエチル)
−N。Any antifungal agent known for photography can be used, but preferably it is a compound that does not have an adverse effect on the development process, specifically aminopolycarboxylic acids, phosphonic acids, etc. Specific examples of aminopolycarboxylic acids include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxyethyl).
-N.
N/、 N/ −三酢酸、プロピレンジアミン四酢酸、
ニトリロ三酢酸、シクロヘキサンジアミン四酢酸、イミ
ノニ酢醒、アルキルアミノニ酢酸、ジヒト90キシエチ
ルグリシン、エチルエーテルジアミン四1[、グリコー
ルエーテルジアミン四酢酸、エチレンジアミン四プロピ
オン酸、フェニレンジアミン四酢酸、1,3−ジアミノ
−2−プロパツール四酢酸、トリエチレンテトラミン木
酢酸、ヒドロキシエチルイミノ酢f!!、オキシビス(
エチレンオキシニトリロ)四酢酸、リンぜ酸、およびこ
れらのポリカルボン酸のナトリウム塩、カリウム塩等で
ある。N/, N/-triacetic acid, propylenediaminetetraacetic acid,
Nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, alkylaminoniacetic acid, dihythyl 90xethylglycine, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylene diamine tetraacetic acid, 1,3 -Diamino-2-propatoltetraacetic acid, triethylenetetraminewood acetic acid, hydroxyethylimino vinegar f! ! , oxybis (
These include ethyleneoxynitrilo)tetraacetic acid, rinsic acid, and the sodium salts and potassium salts of these polycarboxylic acids.
ホスホン酸類として具体的な化合物例としては下記の一
般式(IJ〜(IV)で示される化合物等が好ましい。As specific examples of the phosphonic acids, compounds represented by the following general formulas (IJ to (IV)) are preferred.
一般式CI)
一般式(n)
一般式(III)
R,、N(CH2PO3M2) 2
一般式(IV)
1−0.1.2
式中、R1−R6は、水素原子、ヒドロキシル基、アル
キル基(炭素数1〜3、例えばメチル基、エチル基、プ
ロピル基など)、アミノ基、アルコキシ基(炭素数1〜
3)、例えばメトキシ基、エトキシ基など)、アルキル
アミノ基(好ましくは、炭素数1〜3)、アリールアミ
ノ基(好ましくは、炭素数6〜8)、アリールオキシ基
(好ましくは、炭素数6〜8)を表わす。General formula CI) General formula (n) General formula (III) R,, N(CH2PO3M2) 2 General formula (IV) 1-0.1.2 In the formula, R1-R6 are a hydrogen atom, a hydroxyl group, an alkyl group (1 to 3 carbon atoms, e.g. methyl group, ethyl group, propyl group, etc.), amino group, alkoxy group (1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group, etc.)
3), for example, methoxy group, ethoxy group, etc.), alkylamino group (preferably having 1 to 3 carbon atoms), arylamino group (preferably having 6 to 8 carbon atoms), aryloxy group (preferably having 6 carbon atoms), ~8).
R7−R13は、水素原子、ヒト90キシル基、−CO
OM 、−PO3M2、アルキル基(炭素数1〜3、例
えばメチル基、エチル基、プロピル基など)を表わす。R7-R13 are hydrogen atoms, human 90xyl groups, -CO
OM, -PO3M2, represents an alkyl group (having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc.).
R14は、水素原子、アルキル基(炭素数1〜3、例え
ばメチル基、エチル基、プロピル基など)を表わす、ま
た、Mはナトリウム原子、カリウム原子などのアルカリ
金属を表わす。R14 represents a hydrogen atom or an alkyl group (having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc.), and M represents an alkali metal such as a sodium atom or a potassium atom.
前記一般式(1)〜−一般式IV)によって表わされる
具体的な化合物としては次のものがあげられる。Specific compounds represented by the above general formulas (1) to -general formula IV) include the following.
化合物(1)
化合物(2)
化合物(3)
化合物(4)
CH2COONa
C−CH3
■
CH3−C−C00N a
03Na2
化合物(5)
CH2COOH
CH2
HOOCCH−C−Co○H
03H2
化合物(6)
CF2COOH
■
化合物(7)
CH2−Co○H
■
HOOC−C−PO3H2
CH2
CH2COOH
化合物(8)
化合物(9)
化合物C1l
化合物aυ
化合物(12
化合物03
これらの化合物はナトリウム塩及び/又はカリウム塩の
形で添加された方がよい。Compound (1) Compound (2) Compound (3) Compound (4) CH2COONa C-CH3 ■ CH3-C-C00N a 03Na2 Compound (5) CH2COOH CH2 HOOCCH-C-Co○H 03H2 Compound (6) CF2COOH ■ Compound ( 7) CH2-Co○H ■ HOOC-C-PO3H2 CH2 CH2COOH Compound (8) Compound (9) Compound C1l Compound aυ Compound (12 Compound 03 These compounds are added in the form of sodium salt and/or potassium salt Good.
これらの化合物の中で特に好ましいものとして、エチレ
ンジアミン四酢酸(EDTA)、ジエチレントリアミン
五酢酸、エチレンジアミン−N−ヒドロキシエチル−N
、N/、N/−三酢酸、プロピレンジアミン四酢酸、ト
リエチレンテトラミン六酢酸、などのアミノポリカルボ
ン酸、エチレンジアミンテトラメチレンホスホン酸、1
−ヒドロキシエチリデン−1,1−ジホスホン酸及びこ
れらのナトリウム塩、カリウム塩、アンモニウム塩など
を挙げることができる。Particularly preferred among these compounds are ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, and ethylenediamine-N-hydroxyethyl-N
, N/, N/-triacetic acid, propylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, etc., aminopolycarboxylic acids, ethylenediaminetetramethylenephosphonic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid and their sodium salts, potassium salts, ammonium salts, etc. can be mentioned.
特定化合物群のうちの1種類を用いれば充分であるが、
2種類以上併用してもよい。Although it is sufficient to use one type of a specific group of compounds,
Two or more types may be used in combination.
特定化合物は好ましくは希釈水1ノに対して0.029
〜209の範囲で含有されるがより好ましくは0.05
g〜5gである。The specific compound is preferably 0.029 to 1 part of dilution water.
-209, more preferably 0.05
g to 5 g.
一般的に上記のアミノポリカルボン酸類、ホスホン酸類
等はいわゆる金属に対するキレート化剤として知られて
いるものである。従ってこれらの化合物は写真用現像液
には水に含まれるCa、Mgイオンを封鎖するために用
いられることはり、F。Generally, the above-mentioned aminopolycarboxylic acids, phosphonic acids, etc. are known as so-called chelating agents for metals. Therefore, these compounds are used in photographic developers to sequester Ca and Mg ions contained in water.
Mason : Photographic Proc
eesing Chemistry(F’ocal L
ibrary 1975 )でもよく仰られていること
であり、またこれらの化合物を定着液中にキレート剤と
して用いることも公知である。しかしながら、これらの
化合物を含有する水を現像液や定着液の希釈水として用
いることについては何ら教示するものではない。Mason: Photographic Proc
easing Chemistry (F'ocal L
Ibrary 1975), and it is also known to use these compounds as chelating agents in fixers. However, there is no teaching about using water containing these compounds as dilution water for a developer or a fixer.
本発明で用いることのできる濃縮現像液及び濃縮定着液
は本分野で公知のあらゆる処理g、ヲ用いることができ
る。また、複数の薬剤パーツを各々自動現像機内の原液
ストック槽に保管して本発明に従うストック水と同時に
又は前後して自動的に混合調液して用いることができる
が、濃縮現像液などは複数であるよりは少ない方がよく
、−剤の場合が装置的にも簡易化される点で好ましい。The concentrated developing solution and concentrated fixing solution that can be used in the present invention can be subjected to any processing method known in the art. In addition, it is possible to store a plurality of chemical parts in stock solution stock tanks in an automatic developing machine and use the stock water according to the present invention by automatically mixing and preparing them at the same time or before or after, but when using a concentrated developer, etc. It is better to have a smaller amount than a - agent, and the - agent is preferable because it simplifies the equipment.
かかる観点からは、カラー現像液、漂白定着液などより
も黒白現像液、定着液の方がより本発明の方式に適して
いる。From this point of view, black and white developers and fixers are more suitable for the method of the present invention than color developers, bleach-fixers, and the like.
各濃縮液の濃縮率は特に限定的ではないが1.5〜8倍
の範囲が好ましい。The concentration ratio of each concentrate is not particularly limited, but is preferably in the range of 1.5 to 8 times.
本発明に使用する黒白現像液に用いる現像主薬には特別
な制限はなく、ジヒドロキシはンゼン類(例えばハイド
ロキノン)、3−ピラゾリ上9ン類アミンフェノール類
(例えばN−メチル−p−アミノフェノール)等の公知
の現像主薬を単独或いは組み合わせて用いることができ
る。良好な性能を得やすい点で、ジヒドロキシベンゼン
類を含むことが好1しく、ジヒドロキシベンゼン類と1
−フェニル−3−ピラゾリドン類の組合せまたはジヒド
ロキシベンゼン類とp−アミンフェノール類の組合せを
用いる場合もある。There are no particular restrictions on the developing agent used in the black and white developer used in the present invention, including dihydroxy compounds (e.g. hydroquinone), 3-pyrazolyne amine phenols (e.g. N-methyl-p-aminophenol), etc. Known developing agents such as these can be used alone or in combination. It is preferable to contain dihydroxybenzenes because it is easy to obtain good performance, and dihydroxybenzenes and 1
A combination of -phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminephenols may also be used.
本発明に用いるジヒドロキシベンゼン現像主薬としては
ハイド90キノン、クロロハイピロキノン、ブロムハイ
ドロキノン、イソプロピルハイド90キノン、メチルハ
イドロキノン、2#3−uクロロハイドロキノン、2,
5−ジクロロハイドロキノン、2.3−ジブロムハイド
ロキノン、2.5−ジメチルハイド90キノンなどがあ
るが特にハイドロキノンが好ましい。The dihydroxybenzene developing agents used in the present invention include hydro-90 quinone, chlorohypyroquinone, bromohydroquinone, isopropyl hydro-90 quinone, methylhydroquinone, 2#3-u chlorohydroquinone, 2,
Examples include 5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.
本発明に用いる3−ピラゾリド系現像主薬としては1−
フェニル−4,4−ジメチル−3−ピラゾリドン、1−
フェニル−4−メチル−4−ヒドロキシメチル−3−ピ
ラゾリビン、1−フェニル−4,4−ジヒドロキシメチ
ル−3−2ラゾリドン、1−フェニル−5−メチル−3
−ピラゾリビン、1−p−アミノフェニル−4,4−ジ
メチル−3−ピラゾリドン、1−p−トリル−4,4−
ジメチル−3−ピラゾリドン、1−p−)ジル−4−メ
チル−4−ヒドロキシメチル−3−ピラゾリドン、など
がある。The 3-pyrazolide developing agent used in the present invention is 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolibine, 1-phenyl-4,4-dihydroxymethyl-3-2 lazolidone, 1-phenyl-5-methyl-3
-pyrazolibine, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-p-)dyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and the like.
本発明に用いるp−アミノフェノール系現像主薬として
はN−メチル−p−アミノフェノール、p−アミンフェ
ノール、N−(β−ヒドロキシエチル)−p−アミンフ
ェノール、N−(4−ヒドロキシフェニル)グリシン、
2−メチk −p −7ミノフエノール、p−ベンジル
アミノフェノール等があるが、なかでもN−メチル−p
−アミノフェノールが好ましい。Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminephenol, N-(β-hydroxyethyl)-p-aminephenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyk-p-7 minophenol, p-benzylaminophenol, etc., among which N-methyl-p
-Aminophenol is preferred.
現像主薬は通常0.01モル/l〜0.8モル/lの量
で用いられるのが好ましい。またジヒドロキシベンゼン
類と1−フェニル−3−ピラゾリドン類又はp−アミン
フェノール類との組合せを用いる場合には前者t−0.
01モル/l〜0.5モル/!、後者’to、06モル
/l以下の量で用いるのが好ましい。The developing agent is preferably used in an amount of usually 0.01 mol/l to 0.8 mol/l. Further, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminephenols, the former t-0.
01 mol/l to 0.5 mol/! , the latter is preferably used in an amount of 0.6 mol/l or less.
本発明に用いる亜硫酸塩の保恒剤としては亜硫酸ナトリ
ウム、亜硫酸カリウム、亜硫酸リチウム、亜硫酸アンモ
ニウム、重亜硫酸ナトリウム、メタ重亜硫酸カリウム、
などがある。亜硫酸塩は0.2モル/1以上特に0.4
モル/1以上が好ましい。Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
and so on. Sulfite is 0.2 mol/1 or more, especially 0.4
It is preferably mol/1 or more.
また、上限は2.5モル/lまでとするのが好まし−)
。In addition, it is preferable that the upper limit is 2.5 mol/l.
.
本発明に用いる現像液のpHは9から13までの範囲の
ものが好ましい。The pH of the developer used in the present invention is preferably in the range of 9 to 13.
pHの設定のために用いるアルカリ剤には水酸化ナトリ
ウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム
、第三リン酸ナトリウム、第三リン酸カリウムの如きp
H調節剤を含む0
特願昭61−28708号(ホウ酸塩)、特開昭60−
93433号(例えば、サッカロース、アセトオキシム
、5−スルホサルチル酸)、リン酸塩、炭酸塩などの緩
衝剤を用いてもよい。Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator 0 Japanese Patent Application No. 1987-28708 (Borate), Japanese Patent Application No. 1987-28708 (Borate)
Buffers such as No. 93433 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may be used.
上記成分以外に用いられる添加剤としては、臭化ナトリ
ウム、美化カリウム、沃化カリウムの如き現像抑制剤:
エチレングリコール、ジエチレングリー−ル、トリエチ
レングリコール、ジメチルホルムアミド、メチルセロソ
ルブ、ヘキシレングリコール、エタノール、メタノール
の如き有機溶剤:1−フェニル−5−メルカプトテトラ
ゾール、2−メルカプトインライミダゾール−5−スル
ホン酸ナトリウム塩等のメルカプト系化合物、5−二ト
ロインダゾール等のインダゾール系化合物、5−メチル
ベンツトリアゾール等のペンツトリアゾール系化合物な
どのカプリ防止剤を含んでもよく、更に必要に応じて色
調剤、界面活性剤、消泡剤、硬水軟化剤、特開昭56−
106244号記載のアミン化合物などを含んでもよい
。Additives used in addition to the above components include development inhibitors such as sodium bromide, beautifying potassium, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, sodium 2-mercaptoinlimidazole-5-sulfonate It may contain capri-preventing agents such as mercapto compounds such as salts, indazole compounds such as 5-nitroindazole, and penztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents and surfactants as necessary. , antifoaming agent, water softener, JP-A-1983-
The amine compound described in No. 106244 may also be included.
本発明においては現像液に銀汚れ防止剤、例えは特開昭
56−24347号に記載の化合物、を用いることがで
きる。In the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.
本発明の現像液には、特開昭56−106244号(E
K)に記載のアルカノールアミンなどのアミノ化合物を
用いることができる。The developer of the present invention includes Japanese Patent Application Laid-Open No. 56-106244 (E
Amino compounds such as the alkanolamines described in K) can be used.
さらに、あらかじめ現像主薬が感光材料中に加えられて
いる場合には、本発明の現像処理をアルカリ活性化処理
で置き代えても何ら支障はない。Furthermore, if a developing agent has been added to the light-sensitive material in advance, there is no problem in replacing the development treatment of the present invention with an alkali activation treatment.
アルカリ活性化処理に用いられる処理液(アルカリ活性
化液)は、通常の白黒現像液に使用する現像主薬以外の
いかなる成分をも含むことができる。該アルカリ活性化
液のpHは、通常的10〜14であり、好ましくは約1
1〜14である。The processing solution (alkali activation solution) used in the alkali activation treatment can contain any components other than the developing agent used in ordinary black and white developers. The pH of the alkaline activation solution is usually 10 to 14, preferably about 1.
1 to 14.
この他り、F’、A、メソン著「フォトグラフィック・
プロセシン・ケミストリー」、フォーカル・プレス刊(
1966年)の226〜229頁、米国特許第2,19
3,015号、同2,592,364号、特開昭48−
64933号などに記載のものと用いてもよい。In addition, F', A. Meson's "Photographic
"Processin Chemistry", published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2,19
No. 3,015, No. 2,592,364, Japanese Unexamined Patent Publication No. 1973-
It may also be used with those described in No. 64933.
濃縮現像液が本発明の方法で自動現像機に感光材料から
処理されるに従って、それを希釈する水と共に補充され
る場合、該濃縮液は1剤で構成されることが機械の簡略
性、補充精度上から最も好ましいが、現像液の組成上2
剤構成にしてそれ2水で希釈する方法もとりうる。2剤
の場合はポンプ台数をその分、増して補充するとか、包
装材料の工夫で使用直前まで2剤に分離させて、使用す
るときには完全混合でき実質的に1剤構成と同じように
補充するということによっても本発明の方法は可能であ
る。When a concentrated developer is refilled with water to dilute it as it is processed from a light-sensitive material in an automatic processing machine in the method of the present invention, it is advantageous for machine simplicity and replenishment that the concentrated developer is composed of one agent. It is most preferable from the viewpoint of accuracy, but 2 is preferable because of the composition of the developer.
It is also possible to prepare a drug and dilute it with water. In the case of two drugs, the number of pumps can be increased accordingly, or the packaging material can be devised to separate the two drugs until just before use, and when they are ready to use, they can be completely mixed and refilled in the same way as a single drug configuration. This also makes the method of the present invention possible.
濃縮現像液が1剤になるためには現像硬膜剤が含まれて
いてはその不安定性のために事実上不可能である。従っ
て感光材料自身が既に処理硬膜を要しない程、充分に硬
膜されていることが必要である。例えば特開昭58−1
11933号に記載されている方法。It is virtually impossible for a concentrated developer to become a single agent if it contains a developer hardener due to its instability. Therefore, it is necessary that the photosensitive material itself has already been sufficiently hardened so that no hardening process is required. For example, JP-A-58-1
11933.
また濃縮現像液が1剤であるためのもう一つの必要条件
は3−ピラゾリドン系現像主薬を使用するとき、この主
薬がアルカリ液中で加水分解を受けに(い充分に安定な
生薬であることである。すなわち前記3−ピラゾリドン
類の内、より好ましくは4−位がメチル及び/又はヒビ
ロキシメチルでジ置換された3−ピラゾリドン類が特に
好まし〜)。Another necessary condition for the concentrated developer to be one agent is that when using a 3-pyrazolidone developing agent, this agent must be a crude drug that is sufficiently stable to undergo hydrolysis in an alkaline solution. That is, among the above-mentioned 3-pyrazolidones, 3-pyrazolidones in which the 4-position is di-substituted with methyl and/or hibiloxymethyl are particularly preferred.
濃縮定着液の水希釈調液(以下、単に定着液という)は
、例えば定着のみでも、定着漂白等に用いてもよい。A water-diluted solution of a concentrated fixer (hereinafter simply referred to as fixer) may be used, for example, only for fixing or for fixing and bleaching.
濃縮定着液はチオ硫酸塩、必要に応じて水溶性アルミニ
ウム化合物、酢酸、グルコン酸及び二塩基酸(例えば―
5酸、クエン酸又はこれらの塩)を含む水溶液であり、
pf(3,8以上、好ましくは4.0〜5,5をMする
。更に好ましくはpH4,65〜5.5である。The concentrated fixer contains thiosulfates, optionally water-soluble aluminum compounds, acetic acid, gluconic acid and dibasic acids (e.g.
5 acids, citric acid or their salts),
pf (3.8 or higher, preferably 4.0 to 5.5). More preferably, the pH is 4.65 to 5.5.
定着剤としてはチオ硫醒ナトリウム、チオ硫酸アンモニ
ウムがあるが、チオ硫酸イオンとアンモニウムイオンと
を必須成分とするものであり、定着速度の点からチオ硫
酸アンモニウムが特に好ましい。Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.
定着液中で主として硬膜剤として作用する水溶性アルミ
ニウム塩は一般に酸性硬膜定着液の硬膜剤としてしられ
ている化合物であり、例えば塩化アルミニウム、硫酸ア
ルミニウム、カリ明ばんなどがある。The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, such as aluminum chloride, aluminum sulfate, and potassium alum.
前述の二塩基酸として、酒石酸あるいはその誘導体を単
独で、あるいは2種以上、併用することができる。これ
らの化合物は定着液11につき0.005モル以上含む
ものが有効で、特に0.01モル/13−0.03モル
/!!が脣に有効である。As the above-mentioned dibasic acid, tartaric acid or its derivatives can be used alone or in combination of two or more kinds. It is effective to contain these compounds in an amount of 0.005 mol or more per fixer 11, especially 0.01 mol/13-0.03 mol/! ! is reasonably valid.
具体的には、酒石酸、酒石酸カリウム、w5酸ナトリウ
ム、酒石酸カリウムナトリウム、などがある。Specifically, there are tartaric acid, potassium tartrate, sodium w5ate, potassium sodium tartrate, and the like.
本発明において有効なりエン酸あるいはその誘導体の例
としてクエン酸、クエン酸ナトリウム、クエン酸カリウ
ム、クエン酸リチウム、クエン酸アンモニウムなどがあ
る。Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.
定着液には所望により保恒剤(例えば、亜硫酸塩、重亜
硫酸塩)、pH緩衝剤(例えば、酢酸。The fixer may optionally contain a preservative (eg, sulfite, bisulfite) and a pH buffer (eg, acetic acid).
硼酸)、pHp!整剤(例えば、硫#2)、硬水軟化能
のあるキレート剤や特願昭60−218562号記載の
化合物を含むことができる。ここでpH緩衝剤は、現像
液のpHが高いので10〜40g/l。boric acid), pHp! It can contain a conditioner (for example, sulfur #2), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-218562. Here, the pH buffering agent is 10 to 40 g/l because the pH of the developer is high.
より好ましくは18〜25g/l程度用いる。More preferably, about 18 to 25 g/l is used.
定着温度及び時間は現像の場合と同様であり、約り0℃
〜約50℃で10秒〜2分が好ましい。The fixing temperature and time are the same as for development, approximately 0°C.
10 seconds to 2 minutes at ~50°C is preferred.
a#J定着液が本発明の方法で自動現像機に、感光材料
が処理されるに従って、それケ希釈する本発明のオーバ
ーフロー液やストック水と共に補充される場合、この濃
縮液は1剤で構成されることが最も好ましいことは現像
液の場合と同じである。When the a#J fixer is replenished into the automatic processing machine according to the method of the present invention together with the overflow solution and stock water of the present invention which are diluted as the photosensitive material is processed, this concentrated solution consists of one part. What is most preferable is the same as in the case of the developer.
1剤として濃縮定着液が安定に存在しうるのはpH4,
5以上でありより好ましくはpH4,65以上である。The concentration fixer can exist stably as a single agent at pH 4,
The pH is 5 or higher, more preferably 4.65 or higher.
pH4,5未満では、それが実際に使われるまでの期間
長年放置された場合にチオ硫酸塩が分解して最終的には
硫化してしまうためであろう。従ってpH4,5以上の
く囲では亜硫改ガスの発生も少なく、作業環境上も、良
くなな。pHの上限はそれ程厳しくないが余り高pHで
定着されると、以後水洗されても膜pHが高くなって膜
膨潤が大きくなり従って乾燥負荷が犬さくなるのでp)
I 7まで位か限度である。アルミニウム塩を使つて硬
膜する定着液ではアルミニウム塩の析出沈澱防止上pH
は5.5までが限界である。This is probably because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided if it is left for a long time before it is actually used. Therefore, in an environment with a pH of 4.5 or higher, less sulfur reformed gas is generated, which is good for the working environment. The upper limit of the pH is not so strict, but if the pH is too high, the pH of the membrane will be high even after washing with water, the swelling of the membrane will be large, and the drying load will be low (p)
I is up to 7 or so. In fixing solutions that use aluminum salts to harden films, the pH level is high to prevent precipitation of aluminum salts.
The limit is up to 5.5.
勿論、本発明は濃縮定着液でも1剤に限らず、2剤で構
成されても構わない、1その時は機械的すなわちポンプ
台数を増すとかで実現は可能である。Of course, the present invention is not limited to one concentrated fixing solution, and may be composed of two components. In that case, it can be realized mechanically, ie, by increasing the number of pumps.
本発明は濃縮現像液が上記のような希釈水を必要としな
い(すなわち原液のままで補充する)いわゆる使用液で
あっても構わない。In the present invention, the concentrated developer may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).
濃縮現像液の現像液槽への供給量と希釈水であるストッ
ク水との混合割合、濃縮定着液の定着液槽への供給量と
ストック水および/または水洗液槽のオーバーフロー液
である希釈水との混合割合は、それぞれ濃縮液の組成に
依存して種々変化させることができるが、一般に濃縮液
対希釈水は1対0.5〜8の割合で、これらの全量は感
光材料1−に対して100mJから1500mlである
ことが好ましい。The amount of concentrated developer supplied to the developer tank and the mixing ratio with stock water which is dilution water, the amount of concentrated fixer supplied to the fixer tank and the dilution water which is the overflow liquid of the stock water and/or washing tank. The mixing ratio can be varied depending on the composition of the concentrated solution, but generally the ratio of concentrated solution to dilution water is 1:0.5 to 8, and the total amount of these is 1:1 to 0.5 to 8. On the other hand, it is preferable that the amount is from 100 mJ to 1500 ml.
本発明においては感光材料は現像、定着した後、水洗又
は安定化処理に施される。In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.
水洗又は安定化処理は本分野で分類のあらゆる方法を適
用することができる。For water washing or stabilization treatment, any method of classification in this field can be applied.
本発明においては、ストック水を水洗水又は安定化液に
使用し、更に、そのオーバーフロー液を濃縮定着液の希
釈水に用いることにより、感光材料12当り3l以下の
補充量という節水処理が可能となるのみならず、更に別
の水洗水のストック槽の削減が可能となった。即ち濃縮
現像液の希釈調液及び濃縮定着液の希釈調液のための希
釈水及び水洗水又は安定化液を共通の一層のストック槽
のストック水から供給でき、自動現像機の一層のコンノ
クト化が可能となった。In the present invention, by using stock water as washing water or stabilizing liquid and further using the overflow liquid as diluting water for concentrated fixer, it is possible to save water by requiring less than 3 liters of replenishment per 12 photosensitive materials. Not only this, but also the need for a separate stock tank for washing water can be reduced. In other words, the dilution water and washing water or stabilizing solution for diluting the concentrated developing solution and the concentrated fixing solution can be supplied from the stock water in a common single-layer stock tank, making the automatic processor more compact. became possible.
本発明は、水垢の発生等が有効に防止し得るため、感光
材料1−当りO〜3l.好ましくはθ〜11、の節水処
理を行なうことができる。また、自動!1gシステムを
有する自動現像機をどこにでも設置でさることになる。The present invention can effectively prevent the formation of limescale, and therefore the present invention can effectively prevent the formation of limescale, and therefore can be used in a range of 0 to 3 liters per photosensitive material. Preferably, water saving treatment of θ to 11 can be performed. Also automatic! Automatic processors with 1g system can be installed anywhere.
水洗または安定化槽へのストック水の補充量を少なくす
る方法として、古(より多段向流方式(例えば2段、3
段など)が知られている。この多段向流方式を本発明に
適用すれば定着後の感光材料はだんだんと清浄な方向、
つまり定着液で汚れていない処理液の万に順次接触して
処理されて行(ので、更に効率の良い水洗がなされる。As a method to reduce the amount of stock water added to the washing or stabilization tank, the old
etc.) are known. If this multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will gradually move in a cleaner direction.
In other words, the fixer is sequentially brought into contact with all parts of the processing solution that are not contaminated with the fixing solution (therefore, even more efficient water washing can be achieved).
本発明の方法においては、少量のストック水を水洗水と
して用いているため、特願昭60−172968号に記
載のスクイズローラー洗浄槽等を設けることが自現機の
コスト、ス啄−ス上より好ましい。In the method of the present invention, since a small amount of stock water is used as washing water, it is recommended to provide a squeeze roller washing tank as described in Japanese Patent Application No. 60-172968, which reduces the cost of the automatic processor and increases the scrubbing speed. More preferred.
また、水洗槽に特願昭60−178049に記載の如き
前水洗浴を設けることが好ましい。Further, it is preferable that the washing tank is provided with a pre-washing bath as described in Japanese Patent Application No. 178049/1983.
本発明は、ローラー搬送自動現像機に特に有利である。The invention is particularly advantageous for roller conveyance automatic processors.
本発明において、ストック水は必要に応じて各種添加剤
を含有することができ、あるいは、水洗または安定化槽
、定着g槽、現像液槽に各々個別に各種添加剤を添加す
ることもできる。In the present invention, the stock water can contain various additives as required, or various additives can be added to the washing or stabilizing tank, the fixing tank, and the developer tank individually.
例えば、特開昭58−43452号、同58−1140
35号及び同61−83534号公報に記載の如き銀画
像安定化剤、水滴むらを防止する目的で、各棟の界面活
性剤を添加することができる。界面活性剤としては、陽
イオン型、陰イオン型、非イオン型および両イオン型の
いずれを用いてもよい。界面活性剤の具体例としてはた
とえば工学図書■発行の「界面活性剤ハンドブック」に
記載されている化合物などがある。For example, JP-A-58-43452, JP-A-58-1140
Silver image stabilizers such as those described in No. 35 and No. 61-83534, and surfactants of various types can be added for the purpose of preventing unevenness of water droplets. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho ■.
又、これら添加剤は%開昭57−8543号記載のよう
な多段向流安定化処理工程(いわゆる安定化処理)を実
施する場合に、特に有効である。Further, these additives are particularly effective when carrying out a multistage countercurrent stabilization treatment process (so-called stabilization treatment) as described in % Japanese Patent Publication No. 57-8543.
水洗または安定化槽には、例えば膜pHを調整する(例
えばpH3〜8)のためのも櫨の緩衝剤(例えばホウI
k塩、メタホウ酸塩、ホウ砂、リン酸塩、炭酸塩、水酸
化カリ、水酸化ナトリウム、アンモニア水、モノカルボ
ン酸、ジカルボン散、ポリカルボン酸などを組み合わせ
て使用)などを添カロすることができる。その他、キレ
ート削、殺菌剤(チアゾール系、イソチアゾール系、ハ
ロゲン化フェノール、スルフォニルアミビ、インシトリ
アゾールなど)、界面活性剤、螢光増白i11などの各
棹面加剤?使用してもよく、同一もしくは異様の目的の
化合物を二種以上併用しても良い。The water washing or stabilization tank may contain, for example, an oak buffer (e.g. Hou I) to adjust the membrane pH (e.g. pH 3-8).
Addition of potassium salt, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic powder, polycarboxylic acid, etc.) I can do it. In addition, various surface additives such as chelate cutting, fungicides (thiazole type, isothiazole type, halogenated phenol, sulfonylamibi, incitriazole, etc.), surfactants, and fluorescent whitening i11? It may be used, or two or more compounds for the same or different purposes may be used in combination.
また、処理後の膜pH調整剤として塩化アンモニウム、
硝酸アンモニウム、硫酸アンモニウム、リン酸アンモニ
ウム、亜硫酸アンモニウム、チオ硫酸アンモニウム等の
各種アンモニウム塩を添加することもできる。In addition, ammonium chloride,
Various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can also be added.
本発明の方法に適用できるハロゲン化銀写真感光材料と
しては、種々のカラー及び黒白感光材料を挙げることが
できる。例えば撮影用カラーネガフィルム(一般用、映
画用等)、カラー反転フィルム(スライド°用、映画用
等、またカラー印画紙しない場合もする場合もある)、
カラー印画紙、カラーポジフィルム(映画用等)、カラ
ー反転印画紙、医療用又は工業用X線写真材料、X−レ
イ用デユープ写真材料、医療CRT画像用写真材料、印
刷用感光材料(例えばスキャナー感光材料、撮網感光材
料、撮ツメ感光材料、返し感光材料など)一般黒白ネガ
感光材料。黒白印画紙などを挙げることができる。本発
明は特に黒白写Jc感光材料に適用するのに有効である
。Silver halide photographic materials applicable to the method of the present invention include various color and black and white photographic materials. For example, color negative film for photography (general use, movies, etc.), color reversal film (for slides, movies, etc., and sometimes without color photographic paper),
Color photographic paper, color positive film (for movies, etc.), color reversal photographic paper, medical or industrial X-ray photographic material, duplex photographic material for X-ray, photographic material for medical CRT images, photosensitive material for printing (e.g. scanner photosensitive material) General black-and-white negative photosensitive materials. Examples include black and white photographic paper. The present invention is particularly effective when applied to black-and-white photosensitive materials.
本発明の方法によれば、現像、定着及び水洗された写真
材料は乾燥される。乾燥は約り0℃〜約100℃で行な
われ、乾燥時間は周囲の状態によって適宜変えられるが
、通常は約5秒〜3分30秒でよい。According to the method of the invention, the developed, fixed and washed photographic material is dried. Drying is carried out at a temperature of about 0° C. to about 100° C., and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 3 minutes and 30 seconds.
ローラー搬送型の自動現像機については米国時1lfF
第3025779号明細書、同第3545971号明細
書などに記載されている。1lfF in the US for roller conveyance type automatic processors.
It is described in Specification No. 3025779, Specification No. 3545971, etc.
本発明の方法K jM用できるハロゲン化銀写真感光材
料は支持体とその上に塗布された少なくとも一つの・・
ロゲン化銀乳剤層からなる。もちろん、必要によりバッ
ク層、アンチハレーション層、中間層、最上層(例えば
、保護層)などを有することができる。A silver halide photographic light-sensitive material that can be used in the method KjM of the present invention comprises a support and at least one coated material on the support.
Consists of a silver halide emulsion layer. Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary.
ハロゲン化銀乳剤は、塩化銀、沃化銀、美化銀、塩臭化
銀、沃臭化銀、塩沃臭化銀、の如きハロゲン化銀を親水
性コロイド°(例えばゼラチン)に分散したものである
。ハロゲン化銀乳剤は、通常当業界でよ(知られた方法
(例えばシングルジェット法、ダブルジェット法、コン
トロールジェット法など)によって水溶性銀塩(例えば
、硫酸銀)と水溶性ハロゲン塩とを水及び親水性コロイ
ドの存在下で混合し、物理熟成及び金増感及び/又は硫
黄増感などの化学熟成をへて製造される。Silver halide emulsions are silver halides such as silver chloride, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., dispersed in a hydrophilic colloid (e.g. gelatin). It is. Silver halide emulsions are usually prepared by mixing a water-soluble silver salt (e.g., silver sulfate) and a water-soluble halide salt in water using methods known in the art (e.g., single jet method, double jet method, control jet method, etc.). and a hydrophilic colloid, and undergoes physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization.
ハロゲン化銀乳剤には、その製造工程中又は塗布直前で
、分光増感剤(例えば、シアニン色素、メロシアニン色
素又はその混合物)、安定剤(例えば、4−ヒドロキシ
−6−メチル−LL3a+7−チトラザインデン)、増
感剤(例えば、米国特許第3619198号明細書に記
載の化合物)、カプリ防止剤(例えば、ベンゾトリアゾ
ール、5−ニトロベンツイミダゾール、ポリエチレンオ
キサイド)、硬膜剤(例えば、ホルマリン、グリオキサ
ル、ムコクロル酸、2−ヒドロキシ−46−ジクロロ−
d−トリアシ/、N、N’−エチレンビス(ビニルスル
フォニルアセトアミド)など、塗布助剤(例えば、サポ
ニン、ソジウムラウリルサル7エート、ドデシルフェノ
ールボリエテレ/オキサイドエーテル、ヘキサデシルト
リメチルアンモニウムブロマイド)などを添加すること
ができる。この様にして製造されたハロゲン化銀乳剤は
ノζライタ紙、レジンコーテツド紙、セルロースアセテ
ートフィルムポリエチレンテレフタレートフィルムなど
の支持体にグイツブ法、エアーナイフ法、ビード法、エ
クストルージョンドクター法、両面塗布法などによって
塗布乾燥される。Silver halide emulsions may contain spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-6-methyl-LL3a+7-titrazaindene) during the manufacturing process or immediately before coating. , sensitizers (e.g., the compounds described in U.S. Pat. No. 3,619,198), anti-capri agents (e.g., benzotriazole, 5-nitrobenzimidazole, polyethylene oxide), hardeners (e.g., formalin, glyoxal, mucochlor). acid, 2-hydroxy-46-dichloro-
d-triacyl/, N,N'-ethylenebis(vinylsulfonylacetamide), coating aids (e.g., saponin, sodium lauryl sulfate, dodecylphenol borietele/oxide ether, hexadecyltrimethylammonium bromide), etc. Can be added. The silver halide emulsion produced in this manner can be coated on a support such as zeta lighter paper, resin coated paper, cellulose acetate film, polyethylene terephthalate film, etc. using the guitubing method, air knife method, bead method, extrusion doctor method, double-sided coating method, etc. It is applied and dried by
(実施例)
以下に実施例を挙げて本発明を例証するが本発明はこれ
に限定されるものではない。(Example) The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.
実施例1
(1)ハロゲン化銀乳剤の調製
ゼラチンと臭化カリウムと水が入った55℃に加温され
た容器に適当量のアンモニアを入れた後、反応容器中の
pAg値’に7.60に保ちつつ硝rfl銀水溶液と臭
化カリウム水溶液とをダブルジェット法により添加して
平均粒子サイズが0.55μの単分散臭化銀乳剤粒子を
調製した。この乳剤を脱塩処理後・pHを6.2、pA
gを86に合わせてから、チオ硫酸ナトリウムと塩化金
酸とにより金・硫黄増感とを行ない所望の写真性を得た
。この乳剤の(100)面/(111)面比率をタベル
カムンク法で測定したところ98/2であった。Example 1 (1) Preparation of silver halide emulsion After adding an appropriate amount of ammonia to a container heated to 55°C containing gelatin, potassium bromide, and water, the pAg value in the reaction container was adjusted to 7. Monodisperse silver bromide emulsion grains having an average grain size of 0.55 μm were prepared by adding an aqueous solution of silver nitrate and a potassium bromide solution by a double-jet method while maintaining the temperature at 60 μm. After desalting this emulsion, the pH was adjusted to 6.2, pA
After adjusting g to 86, gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain desired photographic properties. The (100) plane/(111) plane ratio of this emulsion was measured by the Taberka-Munk method and was found to be 98/2.
(2)乳剤塗布液の調製
この乳剤’1llp秤取し、40℃に加温溶解後、近赤
外域増感色素=構造式Aのメタノール溶液(9X10
’μ/1)f70cc、4−?l−’oキシー6−メ
チルー113l3a、7−チトラザインデン水溶液、塗
布助剤ドデシルベンゼンスルフォンrR[の水溶液、増
粘剤ボリボタシウムーp−ビニルRノゼンスルフオネー
ト化合物の水溶液を添加して乳剤塗布液とした。(2) Preparation of emulsion coating solution Weigh out 1llp of this emulsion, heat and dissolve at 40°C, and add a methanol solution of near-infrared sensitizing dye = structural formula A (9 x 10
'μ/1) f70cc, 4-? An emulsion coating solution was prepared by adding l-'o xy-6-methyl-113l3a, an aqueous solution of 7-titrazaindene, an aqueous solution of a coating aid dodecylbenzenesulfone rR, and an aqueous solution of a thickener p-vinylR nozenesulfonate compound. did.
構造式A
(3)感材層の表面保護層用塗布液の調製40℃に加温
されたlQwt%ゼラチン水溶液に増粘剤ポリエチレン
スルフォン峻ソーダ水溶液、マット剤ポリメチルメタク
リレート微粒子(平均粒子サイズ3.0μm)、硬膜剤
N、N’−エチレンビス−(ビニルスル7オニルアセト
アミド)、塗布助剤t−オクチルフェノキシエトキシエ
トキシエタンスルフオン酸ナトリウム水溶液及び含フツ
素界面活性剤とノニオン性界面活性剤を添加して塗布液
とした。Structural formula A (3) Preparation of coating solution for surface protective layer of photosensitive material layer A 1Qwt% gelatin aqueous solution heated to 40°C, a thickener polyethylene sulfone soda aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3) .0 μm), hardening agent N, N'-ethylenebis-(vinylsulfonylacetamide), coating aid t-octylphenoxyethoxyethoxyethoxyethanesulfonate aqueous solution, fluorine-containing surfactant, and nonionic surfactant. A coating solution was prepared by adding a coating agent.
(41バック塗布液の調製
40℃に加温された10wt% のゼラチン水溶液I
Kpに増粘剤ポリエチレンスルフオン酸ソーダ水溶液、
構造式Bの染料水溶液、硬膜剤N、N/−エチレンビス
−(ビニルスルフォニルアセトアミド)水溶液、塗布助
剤t−オクチルフェノキシエトキシエトキシエタンスル
フオン酸ナトリウム水溶液とを加えて塗布液とした。(41 Preparation of back coating solution 10 wt% aqueous gelatin solution I heated to 40°C
Kp is thickener polyethylene sodium sulfonate aqueous solution,
A coating solution was prepared by adding an aqueous solution of the dye of structural formula B, a hardener N, an aqueous N/-ethylenebis-(vinylsulfonylacetamide) solution, and an aqueous solution of sodium t-octylphenoxyethoxyethoxyethanesulfonate as a coating aid.
(5)バック層の表面保護層用塗布液の調製40℃に加
温された1 0 wt%ゼラチン水溶液に増粘剤ポリエ
チレンス1Lf7オン酸ソーダ水溶液、マット剤ポリメ
チルメタクリレート微粒子(平均粒子サイズ3.0μm
)、塗布助剤t−オクチルフェノキシエトキシエトキシ
エタンスル7オン酸ナトリウム水溶液及び含フツ素界面
活性剤とノニオン性界面活性剤とを添加して塗布液とし
た。(5) Preparation of coating solution for the surface protective layer of the back layer A 10 wt% gelatin aqueous solution heated to 40°C, a thickener polyethylene 1Lf7 sodium ionate aqueous solution, and a matting agent polymethyl methacrylate fine particles (average particle size 3 .0μm
), a coating aid t-octylphenoxyethoxyethoxyethoxyethanesulfonate aqueous solution, a fluorine-containing surfactant, and a nonionic surfactant were added to prepare a coating liquid.
(6)塗布試料の作成
前述のバック塗布液をバックの表面保護層塗布液ととも
にポリエチレンテレフタレート支持体の一方の側にゼラ
チン塗布量が41//−となるように塗布した。これに
続いて支持体の反対の側に先ず近赤外増感色素入りの乳
剤塗布液とこれ用の表面保護層塗布液とを塗布銀量が4
.097−となるように塗布したら
こうして得られた試料フィルムを第1図及び以下に示す
現像処理システムで現像処理をした。(6) Preparation of coating sample The above-mentioned back coating solution and the back surface protective layer coating solution were coated on one side of a polyethylene terephthalate support so that the gelatin coating amount was 41//-. Subsequently, on the opposite side of the support, an emulsion coating solution containing a near-infrared sensitizing dye and a surface protective layer coating solution for this were first coated with a silver amount of 4.
.. 097-, the sample film thus obtained was developed using the development system shown in FIG. 1 and below.
現像液及び定着液の濃縮液の組成は次の通りである。The compositions of the developer and fixer concentrates are as follows.
〈濃縮現像液〉
水酸化カリウム 56.6g亜
硫酸オトリウム 200 、pジ
エチレントリアミン五酢rt16.79炭酸カリ
16.7gホウ酸
10 fiヒト90キノ
ン 83.39ジエチレング
リコール 40 .95−メチルベンゾ
トリアゾール 2g水で11とする(p
H10,30に調整する)。<Concentrated developer> Potassium hydroxide 56.6g Otrium sulfite 200, p diethylene triamine penta vinegar rt 16.79 Potassium carbonate
16.7g boric acid
10 fi human 90 quinone 83.39 diethylene glycol 40. 95-Methylbenzotriazole Adjust to 11 with 2g water (p
Adjust to H10,30).
く濃縮定着液〉
チオ硫酸アンモニウム 560g亜硫酸
ナトリウム 60,9水改化ナ
トリウム 24g水で11 とf
る(酢[でpH5,10Kv4整する)。Concentrated fixing solution> Ammonium thiosulfate 560g Sodium sulfite 60,9 water modified sodium 24g 11 with water
(Adjust the pH to 5,10Kv4 with vinegar).
くストック水〉
エチレンジアミン四酢酸二ナトリウム垣・二水塩
0.5 fi/1自動現像機
(第1図参照) Dry to Dryで60秒処理
現像タンク(1) 6.5135℃X 12.
5秒定着タンク(2) 6.51 35℃
X 12.5秒水洗タンク(3) 6.51
20℃×7.5秒前水洗浴 (8) 200−
スクイズローラー洗浄槽(73200wt1ストツク水
タンク(4) 251乾燥 60℃
Dry to Dryで60秒
現像処理をスタートするときには各タンクに以下の如き
処理液を満たした。Stock water〉 Ethylenediaminetetraacetic acid disodium salt dihydrate
0.5 fi/1 automatic developing machine (see Figure 1) Dry to Dry for 60 seconds Development tank (1) 6.5135℃X 12.
5 seconds fixing tank (2) 6.51 35℃
X 12.5 seconds flush tank (3) 6.51
20℃ x 7.5 seconds pre-washing bath (8) 200- Squeeze roller cleaning tank (73200wt 1 stock water tank (4) 251 Drying 60℃ Dry to Dry for 60 seconds When starting the development process, perform the following treatment on each tank. filled with liquid.
現像タンク:上記濃縮現像液333R1,ストック水6
671及び臭化カリウム2yと酢酸
1.8Iとを含む水溶液10m1を力口えてpHを10
.15とした
定着タンク二上記濃縮定着液250IR1及びストック
水750耐
前水洗浴水洗タンク及び洗浄槽:
上記ストック水と同組成のもの
上記感光材料B4サイズ(25,7cInX36.4c
Wt) 1枚処理される毎に
現像タンクに濃縮現像液20rttlとストック水40
md定着タンクに濃縮定着液10IILl
洗浄佑から水洗タンクを通って前水洗浴にストック水3
〇−
を補充し、前水洗浴のオーバーフロー液約30−を定着
タンクに移し、−日15枚のランニング処理は継続した
。この間現像液、定着液、ストック水兵なくなれば同様
に新たなる補充液を追加し良。Developing tank: above concentrated developer 333R1, stock water 6
671, 2y of potassium bromide, and 1.8I of acetic acid, the pH was adjusted to 10.
.. 15 fixing tank 2 The above concentrated fixer 250IR1 and the stock water 750 resistant pre-washing bath Washing tank and washing tank: Same composition as the above stock water The above photosensitive material B4 size (25.7 cIn x 36.4 c
Wt) 20rttl of concentrated developer and 40ml of stock water are added to the developing tank every time one sheet is processed.
10IIL of concentrated fixer in the md fixing tank.3 stock water from Washing Yu through the washing tank to the pre-washing bath.
- was replenished, and about 30 - of the overflow liquid from the pre-washing bath was transferred to the fixing tank, and the running process of 15 sheets was continued on - day. During this time, if you run out of developer, fixer, or stock sailor, you can add new replenisher in the same way.
こうしてう/二ング′!i−2ケ月間継続したが初期の
写真特性は維持され、更に水洗タンクの水洗液は全く交
換しないでも水垢が発生せずにランニングを継続するこ
とができた。In this way/two'! Although the use continued for i-2 months, the initial photographic characteristics were maintained, and even without replacing the washing liquid in the washing tank, running could be continued without limescale formation.
この間の廃液は現像液が38.51、定着液が21.5
Jでこの定着液には銀が7.89/l含まれていた。勿
論、水洗水の廃液は0であった。使用したストック水は
52.5A’である。During this time, the waste liquid was 38.51 for developer and 21.5 for fixer.
J, this fixer contained 7.89/l silver. Of course, the amount of waste liquid from the washing water was zero. The stock water used was 52.5 A'.
上記とは違って前水洗浴からのオーバーフロー液は廃却
し、定着タンクにはストック水を直接30dt−補充す
る方法をとり、他は全く同様な方法でランニング実験し
た。Unlike the above, the overflow liquid from the pre-washing bath was discarded and the fixing tank was directly replenished with 30 dt of stock water, but otherwise a running experiment was conducted in exactly the same manner.
この間の廃液は次の通りであり、現像液は上記と変らず
3B、51.定着液は25/、銀濃度6.41//l、
水洗水は191、銀濃度0.4j9/1.使ったストッ
ク水は全部で751であった。The waste liquids during this period were as follows, and the developing solutions were the same as above: 3B, 51. Fixer: 25/, silver concentration: 6.41//l,
Washing water is 191, silver concentration 0.4j9/1. The total amount of stock water used was 751.
この結果、本方法は、比較法より節水、銀回収効率の双
方で優れていることが分かる。The results show that the present method is superior to the comparative method in both water saving and silver recovery efficiency.
本発明の方式は次の利点を有する。The method of the invention has the following advantages.
■ 少ない水の供給で処理できるので、水道水の配管が
全く不要となりどこでも自現機の設置が可能になった。■ Since it can be processed with a small supply of water, there is no need for any tap water piping, making it possible to install the machine anywhere.
■ 廃液が少ないので廃液の公害処理負荷が少なX、
S 。■ Since there is less waste liquid, the burden of waste liquid pollution treatment is low.
S.
■ 銀濃度が高い定着液廃液として回収できるので、銀
回収効率も回収率も高い。■ Silver recovery efficiency and recovery rate are high because it can be recovered as fixer waste liquid with high silver concentration.
■ 水洗液を非常に少なくしても水垢が発生せずローラ
ーラックの洗浄などのメンテナンスが不要になった。■ Even with a very small amount of washing liquid, limescale does not form, making maintenance such as cleaning the roller rack unnecessary.
■ 現像液、定着液の調液が不要となり作業が楽である
。■ No need to prepare developer and fixer, making work easier.
(リ 現像定M液のストックタンクが不要となり自現機
の設置スペースが小さくてすむ。(Li) A stock tank for development constant M solution is not required, and the installation space for the automatic processor is small.
第1図は、本発明の方法の実施例説明図である。
1:現像タンク 2:定懲タンク3:水洗タンク
4ニスドック水タンク5:濃縮現像准ストッ
クタンク
6:濃縮定着液ストックタンク
7:スクイズローラー洗浄槽
8:前水洗浴 9:ローラー
P:ボンプ
(ほか3名)
手続補正書
昭和62年 1月 90
I?i’is’f’JT長官 殿
6、 補正により増加する発明の数: 0(1) 明細
J1第4頁第15行目の1現像、」を「現像液、」と補
正する。
(2) 同書第4頁第19〜20行目の「水洗水からの
」を「水洗水からも」と補正する。
(3) 同書第5頁第1行目の「このための処理液の廃
液から銀回収だけでなく、」を「このため、処理液の廃
液からの銀回収だけでなく、」と補正する。
(4) 同書第7頁第7行目の「該、ストック水」を「
該ストック水」と補正する。
(5) 同書第18頁第3行目の[Proceesin
(IJをl’PrOceQssing jと補正する。
(6) 同書第23頁第15行目の「プロセシン」を「
プロヒシング」と補正する。
(7) 同書第24頁第1行目の「材料から」を「材料
が」と補正する。
(8) 同店第24頁第14〜16行目の「必要である
。例えば特開昭58−111933号に記載されている
方法。」を「必要である(例えば特開昭58−1119
33号に記載されている方法)。」と補正する。
(9) 明l1ll書第25頁第1〜2行目の「より好
ましくは」を削除する。
(10) 同店第25頁第15〜16行目の「チオ硫
酸イオンとアンモニウムイオンとを必須成分とするもの
であり、」を削除する。
(11) 同書第26頁第1行目の「しられている」
を「知られている」と補正する。
(12) 同店第26頁第8行目の「特に」を削除す
る。
(13) 同書第27頁第7行目の「発明のオーバー
フ【コー液」を「発明の水洗水オーバーフ「コー液」と
補正する。
(14) 同書第27頁第14〜15行目の「ためで
あろう。」を「ためである。」と補正する。
(15) 同書第28頁第18行目〜第29頁第 1
行目の「本発明においては・・・・適用することができ
る」を削除する。
(16) l1il″iT′i第39頁第3行目の「
曲硫酸オトリウム」を「亜硫酸ナトリウム」と補正する
。
(17) 同書第40頁第4行目のrDry to
Dryで60秒処理」を削除する。
(18) 同よ第40頁下から8行目と下から9行目
との間に「現像タンク(1)及び定着タンク(2)では
湿度調節のための冷却水は用いない。」を特徴するFIG. 1 is an explanatory diagram of an embodiment of the method of the present invention. 1: Developing tank 2: Punishing tank 3: Washing tank 4 Varnish dock water tank 5: Concentrated developing stock tank 6: Concentrated fixer stock tank 7: Squeeze roller cleaning tank 8: Pre-washing bath 9: Roller P: Bump (etc.) 3 persons) Procedural Amendment January 1988 90 I? i'is'f' JT Director 6, Number of inventions increased by the amendment: 0 (1) 1.Development,” on page 4, line 15 of Specification J1, is amended to read ``developer,''. (2) "From the washing water" on page 4, lines 19-20 of the same book is amended to "also from the washing water." (3) In the first line of page 5 of the same book, ``In addition to the recovery of silver from the waste liquid of the processing liquid for this purpose'' is amended to ``For this reason, not only the recovery of silver from the waste liquid of the processing liquid.'' (4) "Stock water" on page 7, line 7 of the same book is replaced with "
"Stock water". (5) [Proceesin, page 18, line 3 of the same book]
(Correct IJ to l'PrOceQssing j. (6) Change "processin" in page 23, line 15 of the same book to "
"Prohising" is corrected. (7) "From materials" in the first line of page 24 of the same book is amended to "materials". (8) On page 24, lines 14 to 16 of the same store, "It is necessary. For example, the method described in Japanese Patent Application Laid-Open No. 58-111933."
(method described in No. 33). ” he corrected. (9) Delete "more preferably" from the 1st and 2nd lines of page 25 of Book 11. (10) Delete "It contains thiosulfate ions and ammonium ions as essential components" in lines 15 and 16 of page 25 of the same store. (11) “Known” in the first line of page 26 of the same book
be corrected to "known". (12) Delete "especially" in line 8 of page 26 of the store. (13) In the same document, page 27, line 7, ``Overflow of the invention [coe liquid''] is amended to ``Water wash overflow of the invention ``coe liquid''. (14) In the same book, page 27, lines 14-15, ``Tame derou.'' is amended to ``Tame deru.'' (15) Same book, page 28, line 18 to page 29, line 1
Delete the line ``The present invention can be applied.'' (16) l1il''iT'i, page 39, line 3, ``
Correct "odorium sulfate" to "sodium sulfite". (17) rDry to, page 40, line 4 of the same book
60 seconds processing with Dry” is deleted. (18) Similarly, on page 40, between the 8th line and 9th line from the bottom, there is a feature that says ``Cooling water is not used for humidity control in the developing tank (1) and fixing tank (2).'' do
Claims (1)
するストック槽が設けられた自動現像機を用いて現像、
定着および水洗または安定化する方法において、濃縮現
像液および該防黴手段を施した水を現像液槽に、濃縮定
着液を定着液槽に各々移送し、かつ感光材料1m^2当
り3l以下の該防黴手段を施した水を水洗または安定化
槽に補充し水洗または安定化槽のオーバーフロー液の一
部または全部を定着槽へ移送して濃縮定着液の希釈液に
利用することを特徴とする現像処理方法。The silver halide photographic light-sensitive material is developed using an automatic developing machine equipped with a stock tank containing anti-mildew water.
In the method of fixing and washing or stabilizing, a concentrated developer and water treated with the anti-mildew means are transferred to a developer tank, and a concentrated fixer is transferred to a fixer tank, and an amount of 3 liters or less per 1 m^2 of the photosensitive material is transferred. A washing or stabilizing tank is replenished with the water subjected to the anti-mold treatment, and part or all of the overflow liquid from the washing or stabilizing tank is transferred to the fixing tank and used as a diluent for the concentrated fixing solution. Development processing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27539086A JPS63129343A (en) | 1986-11-20 | 1986-11-20 | Development of silver halide photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27539086A JPS63129343A (en) | 1986-11-20 | 1986-11-20 | Development of silver halide photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63129343A true JPS63129343A (en) | 1988-06-01 |
Family
ID=17554826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27539086A Pending JPS63129343A (en) | 1986-11-20 | 1986-11-20 | Development of silver halide photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63129343A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01281446A (en) * | 1988-05-07 | 1989-11-13 | Konica Corp | Replenishing method for automatic processor |
JPH03287260A (en) * | 1990-04-03 | 1991-12-17 | Fuji Photo Film Co Ltd | Processing method for silver halide photographic sensitive material |
JPH0453948A (en) * | 1990-06-22 | 1992-02-21 | Fuji Photo Film Co Ltd | Processing method for silver halide photographic sensitive material |
EP0514675A1 (en) | 1991-04-22 | 1992-11-25 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials and method for processing the same |
JPH05119445A (en) * | 1991-10-24 | 1993-05-18 | Fuji Photo Film Co Ltd | Fixing liquid and treating method using that |
US5272499A (en) * | 1990-07-09 | 1993-12-21 | Fuji Photo Film Co., Ltd. | Photographic silver halide photosensitive material processing apparatus |
-
1986
- 1986-11-20 JP JP27539086A patent/JPS63129343A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01281446A (en) * | 1988-05-07 | 1989-11-13 | Konica Corp | Replenishing method for automatic processor |
JPH03287260A (en) * | 1990-04-03 | 1991-12-17 | Fuji Photo Film Co Ltd | Processing method for silver halide photographic sensitive material |
JPH0453948A (en) * | 1990-06-22 | 1992-02-21 | Fuji Photo Film Co Ltd | Processing method for silver halide photographic sensitive material |
US5272499A (en) * | 1990-07-09 | 1993-12-21 | Fuji Photo Film Co., Ltd. | Photographic silver halide photosensitive material processing apparatus |
EP0514675A1 (en) | 1991-04-22 | 1992-11-25 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials and method for processing the same |
JPH05119445A (en) * | 1991-10-24 | 1993-05-18 | Fuji Photo Film Co Ltd | Fixing liquid and treating method using that |
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