JPH0434738B2 - - Google Patents
Info
- Publication number
- JPH0434738B2 JPH0434738B2 JP58058693A JP5869383A JPH0434738B2 JP H0434738 B2 JPH0434738 B2 JP H0434738B2 JP 58058693 A JP58058693 A JP 58058693A JP 5869383 A JP5869383 A JP 5869383A JP H0434738 B2 JPH0434738 B2 JP H0434738B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonium
- treatment
- processing
- group
- tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 40
- 238000012545 processing Methods 0.000 claims description 38
- 229910052709 silver Inorganic materials 0.000 claims description 30
- 239000004332 silver Substances 0.000 claims description 30
- 230000000087 stabilizing effect Effects 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 21
- 230000006641 stabilisation Effects 0.000 claims description 21
- 238000011105 stabilization Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 150000003868 ammonium compounds Chemical class 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 12
- 238000011161 development Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000004061 bleaching Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 description 54
- 238000005562 fading Methods 0.000 description 23
- 239000000975 dye Substances 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 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 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 238000010186 staining Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 150000007524 organic acids Chemical class 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 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 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 229940093915 gynecological organic acid Drugs 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 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 3
- 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 3
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- FZERHIULMFGESH-UHFFFAOYSA-N methylenecarboxanilide Natural products CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 3
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 3
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 3
- 235000019252 potassium sulphite Nutrition 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 2
- JKRNNIGZNCVVHA-UHFFFAOYSA-N 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;trimethylazanium Chemical compound C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JKRNNIGZNCVVHA-UHFFFAOYSA-N 0.000 description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- AUJUKHGWOKKPAN-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Na+].CC(CN(CC([O-])=O)CC([O-])=O)N(CC([O-])=O)CC([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].CC(CN(CC([O-])=O)CC([O-])=O)N(CC([O-])=O)CC([O-])=O AUJUKHGWOKKPAN-UHFFFAOYSA-J 0.000 description 2
- 229960001413 acetanilide Drugs 0.000 description 2
- LRSAWRZHGQQHBJ-UHFFFAOYSA-N acetic acid;benzene-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NC1=CC=CC=C1N LRSAWRZHGQQHBJ-UHFFFAOYSA-N 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- PBHVCRIXMXQXPD-UHFFFAOYSA-N chembl2369102 Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(=N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)S(O)(=O)=O)=C2N=C1C=C2 PBHVCRIXMXQXPD-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 2
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- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 1
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- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
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- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
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- KGECWXXIGSTYSQ-UHFFFAOYSA-N ammonium malate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)CC([O-])=O KGECWXXIGSTYSQ-UHFFFAOYSA-N 0.000 description 1
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- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- DKFFVMCMYIVCMK-UHFFFAOYSA-N azane 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid dihydrate Chemical compound O.[OH-].[NH4+].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O DKFFVMCMYIVCMK-UHFFFAOYSA-N 0.000 description 1
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- AWZACWPILWGEQL-UHFFFAOYSA-M azanium;copper(1+);sulfate Chemical compound [NH4+].[Cu+].[O-]S([O-])(=O)=O AWZACWPILWGEQL-UHFFFAOYSA-M 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- OSKNUZYLXFBIHL-UHFFFAOYSA-N azanium;hydron;phthalate Chemical compound N.OC(=O)C1=CC=CC=C1C(O)=O OSKNUZYLXFBIHL-UHFFFAOYSA-N 0.000 description 1
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- UZMZVDOOVXLRID-UHFFFAOYSA-N azanylidyne-(nitrosulfonylamino)methane Chemical group [O-][N+](=O)S(=O)(=O)NC#N UZMZVDOOVXLRID-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- OVIZSQRQYWEGON-UHFFFAOYSA-N butane-1-sulfonamide Chemical compound CCCCS(N)(=O)=O OVIZSQRQYWEGON-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- DIOLOCSXUMYFJN-UHFFFAOYSA-N calcium;azane Chemical compound N.[Ca+2] DIOLOCSXUMYFJN-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 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
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 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
- CKKXWJDFFQPBQL-UAIGNFCESA-N diazanium;(z)-but-2-enedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)\C=C/C([O-])=O CKKXWJDFFQPBQL-UAIGNFCESA-N 0.000 description 1
- OEDPMSDASHAOCT-UHFFFAOYSA-N diazanium;2-(carboxylatomethylamino)acetate Chemical compound [NH4+].[NH4+].[O-]C(=O)CNCC([O-])=O OEDPMSDASHAOCT-UHFFFAOYSA-N 0.000 description 1
- QDHHNSIGXVMRCX-UHFFFAOYSA-N diazanium;2-[carboxylatomethyl(2-hydroxyethyl)amino]acetate Chemical compound [NH4+].[NH4+].OCCN(CC([O-])=O)CC([O-])=O QDHHNSIGXVMRCX-UHFFFAOYSA-N 0.000 description 1
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 1
- VODGJKZAAVKBAL-UHFFFAOYSA-L diazanium;manganese(2+);disulfate Chemical compound [NH4+].[NH4+].[Mn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VODGJKZAAVKBAL-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical compound [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 description 1
- PADMMUFPGNGRGI-UHFFFAOYSA-N dunnite Chemical compound [NH4+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O PADMMUFPGNGRGI-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical group 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins 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
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 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
- 239000000126 substance Substances 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
〔技術分野〕
本発明はハロゲン化銀カラー写真感光材料の安
定化処理方法に関し、特に明退色暗退色を防止
し、かつブルーイングやステインの発生を防止出
来る色素画像の安定化処理方法に関する。
〔従来技術〕
ハロゲン化銀カラー写真感光材料では、周知の
如く、発色現像法により、アゾメチン色素、イン
ドアニリン色素を形成することによつて発色画像
が得られる。
これらの色素は紫外線や可視光線の照射によつ
て退色がおこることは周知のことであり、また、
これらの色素は暗所において保存しても退色す
る。特に高温、高湿の下ではこの退色が促進され
る。これらの発色画像の退色はカラー写真にとつ
て大きな欠陥であり、この欠陥の改善が強く要望
されていた。
従来、ハロゲン化銀カラー写真感光材料による
発色画像の明所又は暗所における退色防止法につ
いては、種々のものが知られている。例えば、米
国特許第2788274号の亜鉛溶液による処理、同第
2913338号明細書に記載のカルシウム、マグネシ
ウム、カドミウム塩による処理、英国特許第
909824号、同第1001446明細書に記載のモノサツ
カライド、ジサツカライド、ヘキシトールを含む
溶液で処理する方法、フオルムアルデヒドとポカ
ルボン酸を含む溶液による処理等が知られてい
る。
しかし、これらの方法では得られる効果が僅か
であつたり、暗所での退色性は改良できても光に
よる退色即ち明退色を逆に大きくさせたり、ある
場合にはステインの上昇は抑えられても色素の退
色を劣化させてしまう等の欠点があつた。
また、近年カラー写真感光材料の現像処理を自
動的に且つ連続的に行なうフオトフイニツシヤー
においては環境保全と水質源の問題が重要視され
ており、定着液及び漂白定着液処理に続く水洗工
程において使用される多量の水洗水を低減又はゼ
ロにすることが望まれている。
このため定着又は漂白定着の処理の後、水洗を
行なわないで直接安定化処理する技術が提出され
ている。例えば特開昭57−8542号公報記載のイソ
チアゾリン−3−オン化合物の誘導体を用いる技
術、特開昭58−14834号公報記載の可溶性鉄塩を
含有させる技術、特開昭57−132146号公報、同58
−18631号公報記載のポリカルボン酸、有機ホス
ホン酸等のキレート剤を用いる技術等がある。し
かしながら、これらの技術は画像保存の劣化、特
に長期保存による未発色部分のイエローステイン
の上昇を抑える効果が弱いという欠点がある。
この欠点を解決する技術としては、特開昭58−
8543号公報に記載された安定液を酸性にする技術
が知られている。しかし、安定液を酸性にすると
新しい問題として螢光増白剤が原因と思われる、
いわゆるブルーイングという最大濃度部分の黒色
が太陽光下で青くなつてしまう問題と、連続処理
によつて感光材料から溶出する色素が吸着し易く
なることが原因と思われる、いわゆるステインと
いう未露光部が黄色く汚染される問題が発生する
ことがわかつた。更に、安定液中に定着成分及び
可溶性銀錯塩が増大し、シアン色素の光に対する
安定性(明退色性)が低下することがわかつた。
〔発明の目的〕
本発明の目的は上記欠点を解決し、明退色、暗
退色を防止し、かつブルーイングやステインの発
生を防止出来、特に水洗水の低減や水洗処理を行
なわない安定化処理によつても色素画像の仕上り
に何ら影響を与えない、色素画像の安定化処理方
法を提供することである。
〔発明の要旨〕
本発明に係るハロゲン化銀カラー写真感光材料
の処理方法は、ハロゲン化銀カラー写真感光材料
を発色現像処理し、漂白定着処理又は漂白処理及
び定着処理した後、3槽以上の槽で構成される処
理槽で安定化処理をするに際して、アンモニウム
化合物を含有する安定液補充液を該3槽以上の処
理槽の最終処理槽に補充し、該最終処理槽のオー
バープロー液を処理される写真材料の移動方向と
は逆方向に順次オーバーフローさせ、安定化処理
工程の上記最終処理槽での安定液のPHを5.0以上
にし、該最終処理槽での安定液のアンモニウム化
合物の濃度を0.002〜1.0mol/にすると共に上
記安定化処理工程の最終処理槽の直前の処理槽の
アンモニウム化合物濃度が該最終処理槽のアンモ
ニウム化合物濃度よりも低く、かつ上記直前の処
理槽の前の処理槽のアンモニウム化合物濃度が該
直前の処理槽のアンモニウム化合物濃度よりも低
いことを特徴とする。
本発明の好ましい一実施態様に従えば、前記漂
白定着処理又は前記定着処理した後、水洗処理を
行わないで安定化処理することである。
〔発明の構成〕
以下、本発明について詳説する。
本発明者等は写真材料から溶出する増感色素の
逆染着が酸性安定液で処理する事により起る事を
つきとめ、安定液をPH5以上にする事で螢光染料
や増感色素の逆染着が防止出来る事もつきとめ
た。しかしながら、中性以上のPHを持つ安定液に
よる処理では前記従来技術の欠点は解消されるも
のの、処理後の試料が保存によつてイエローステ
インの発生を起し易くかつシアン色素の退色が大
きくなるという欠点が生じてくる。この両者を同
時に解決出来る技術を鋭意研究した結果、安定液
のPHが5.0以上の安定液にアンモニウム化合物を
添加し最終の処理工程で用いる事により、螢光染
料や増感色素の染着を防止しかつ保存による画像
の劣化を完全に防止出来る事を見い出した。又、
アンモニウム化合物の添加による安定液ではPHが
5.0未満では染料や色素の染着が起り易いのみな
らずシアン色素の退色が著しく大きくなる欠点が
あり好ましくない事もわかつた。
本発明の安定液に添加するアンモニウム化合物
とは、水溶液中でアンモニウムイオンを放出する
可能性のある化合物であり、具体的には例えばア
ンモニア水、臭化アンモニウム、炭酸アンモニウ
ム、塩化アンモニウム、クロム酸アンモニウム、
重クロム酸アンモニウム、次亜リン酸アンモニウ
ム、リン酸アンモニウム、亜リン酸アンモニウ
ム、フツ化アンモニウム、酸性フツ化アンモニウ
ム、フルオロホウ酸アンモニウム、ヒ酸アンモニ
ウム、炭酸水素アンモニウム、フツ化水素アンモ
ニウム、硫酸水素アンモニウム、亜硫酸水素アン
モニウム、ヨウ化アンモニウム、硝酸アンモニウ
ム、五ホウ酸アンモニウム、過塩素酸アンモニウ
ム、ペルオキソ二硫酸アンモニウム、過硫酸アン
モニウム、リンモリブテン酸アンモニウム、リン
タングステン酸アンモニウム、ケイフツ化アンモ
ニウム、フルフアミン酸アンモニウム、硫酸アン
モニウム、亜硫酸アンモニウム、四ほう酸アンモ
ニウム、テトラフルオロホウ酸アンモニウム、チ
オシアン酸アンモニウム、タングステン酸アンモ
ニウム、バナジン酸アンモニウム、ポリリン酸ア
ンモニウム、ピロリン酸アンモニウム等の無機酸
のアンモニウム塩、酢酸アンモニウム、アジピン
酸アンモニウム、アウリントリカルボン酸アンモ
ニウム、安息香酸アンモニウム、カルバミン酸ア
ンモニウム、クエン酸アンモニウム、ジエチルジ
チオカルバミン酸アンモニウム、ギ酸アンモニウ
ム、リンゴ酸水素アンモニウム、シユウ酸水素ア
ンモニウム、フタル酸水素アンモニウム、酒石酸
水素アンモニウム、乳酸アンモニウム、リンゴ酸
アンモニウム、マレイン酸アンモニウム、シユウ
酸アンモニウム、フタル酸アンモニウム、ピクリ
ン酸アンモニウム、ピロリジンジチオカルバミン
酸アンモニウム、サリチル酸アンモニウム、コハ
ク酸アンモニウム、スルフアニル酸アンモニウ
ム、酒石酸アンモニウム、チオグリコール酸アン
モニウム、2,4,6−トリニトロフエノールア
ンモニウム、イミノジ酢酸アンモニウム、ヒドロ
キシエチルイミノジ酢酸アンモニウム、ニトリロ
トリ酢酸アンモニウム、エチレンジアミンテトラ
酢酸アンモニウム、ジエチレントリアミンペンタ
酢酸アンモニウム、ヒドロキシエチルエチレンジ
アミントリ酢酸アンモニウム、トランス−シクロ
ヘキサンジアミンテトラ酢酸アンモニウム、ジア
ミノプロパノールテトラ酢酸アンモニウム、ニト
リロトリプロピオン酸アンモニウム、ニトリロト
リスメチレンホスホン酸アンモニウム、エチレン
ジアミンテトラメチレンホスホン酸アンモニウ
ム、1−ヒドロキシエチリデン−1,1′−ジホス
ホン酸アンモニウム、2−ホスホフブタン−1,
2,4−トリカルボン酸アンモニウム、ジ(2−
ヒドロキシエチル)アミノメタンスルホン酸アン
モニウム等の有機酸のアンモニウム塩、アンモニ
ウムみようばん、硫酸第二セリウムアンモニウ
ム、硫酸アンモニウムマンガン、硫酸鉄()ア
ンモニウム(12水)、ライネツケ塩(水和物)、ア
ンモニウム硫酸銅、アンモニウムカルシウム錯
塩、アンモニウムマグネシウム錯塩等のアンモニ
ア−金属錯体等が挙げられる。即ち安定液にアン
モニウム化合物を添加した状態においてアンモニ
ア又はアンモニウムイオン(水和物と結合したも
のも含む)又は水酸化アンモニウムを放出する化
合物であり、前記具体的化合物例に限定されるも
のではない。
本発明に用いられるアンモニウム化合物は安定
浴1当り0.001〜1.0モルの範囲で添加する事が
でき、好ましくは0.002〜0.2モルの範囲で添加す
る事ができる。
本発明による安定液(安定浴)はPH5.0以上で
あり、好ましくはPH5.0〜10.0である。特に望ま
しいPHとしては6.0〜9.0の範囲があげられる。な
お処理工程が多数槽の安定浴から成り、かつ向流
法で処理され、最終槽から補充される連続処理方
法での上記安定浴の望ましいPHは、安定浴の最終
槽におけるPHである。安定浴のPHが5.0未満の場
合には本発明に用いられるアンモニウム化合物の
退色防止効果が得られず、場合によつては逆に色
素退色を促進することもある。また、PHが10以上
の場合にはゼラチン膜が弱くなり、好ましくな
い。
本発明の安定液には種々の化合物が添加されて
もよく、例えばPH緩衝剤、螢光増白剤、界面活性
剤、防ばい剤、防腐剤、キレート剤、硬膜剤、各
種金属塩等であり、写真性能に影響を及ぼさない
範囲で、どのような化合物をどのような組み合せ
で使用してもさしつかえない。
本発明の好ましい安定化処理が漂白定着浴もし
くは定着浴に続く工程で実質的に水洗処理を行な
わないとは、漂白定着もしくは定着後直接安定化
処理をする工程であり、水洗処理は基本的には行
なわないが、漂白定着浴もしくは定着浴と安定化
処理の間に銀回収のための短時間の銀回収浴、リ
ンス等を設けてもよいということを意味する。し
かし、好ましくは漂白定着浴もしくは定着浴と安
定浴の間には何も設けない方が望ましい。
本発明による安定化処理の後には水洗処理を全
く必要としないが、極く短時間内での少量水洗に
よるリンス、表面清浄などは必要に応じて任意に
行なうことができるが、好ましくは安定化処理
後、直接乾燥工程になるのが望ましい。安定化処
理に際しての処理温度は10℃〜60℃、好ましくは
15℃〜40℃の範囲がよい。また処理時間も迅速処
理の観点から短時間であるほど好ましいが、通常
20秒〜10分、最も好ましくは30秒〜5分程度であ
る。また乾燥工程の温度と時間は任意に選べる
が、50℃以上にすることが望ましい。
本発明の定着浴もしくは漂白定着浴は別に限定
されるものではなく、定着剤としては例えば、チ
オ硫酸塩、チオシアン酸塩、沃化物、臭化物、、
チオエーテル、チオ尿素等が用いられ、漂白剤と
しては例えば、赤血塩、塩化鉄、過硫酸塩、過酸
化水素、有機酸第2鉄錯塩等が用いられる。
本発明の安定液を感光材料と接触させる方法
は、一般の処理液と同様に液中に感光材料を浸漬
するのがよいが、スポンジ、合成繊維布等により
感光材料の乳剤面及び搬送リーダーの両面、搬送
ベルトに塗り付けてもよく、又スプレー等により
吹き付けてもよい。
本発明の処理方法は、カラーペーパー、反転カ
ラーペーパー、カラーポジフイルム、カラーネガ
フイルム、カラー反転フイルム、カラーXレイフ
イルム等の処理に使用する事ができる。
なお、本発明の安定液に可溶性銀塩を含有する
場合には、該液から銀回収をすることもできる。
銀回収方法としては、イオン交換樹脂法、金属置
換法、電気分解法、硫化銀沈澱法等を用いる事が
できる。
本発明において、ハロゲン化銀カラー写真感光
材料に用いられるシアンカプラーが下記一般色
()または()で示されるカプラーであると
き、発色現像で生成されたシアン色素の光に対す
る安定性が改善されるという効果が付加される。
一般式()
一般式()
Xは−COR2、
[Technical Field] The present invention relates to a method for stabilizing a silver halide color photographic light-sensitive material, and more particularly to a method for stabilizing a dye image that can prevent bright and dark fading and also prevent the occurrence of bluing and staining. [Prior Art] As is well known, in silver halide color photographic materials, color images can be obtained by forming azomethine dyes and indoaniline dyes by a color development method. It is well known that these pigments fade when exposed to ultraviolet or visible light, and
These dyes fade even when stored in the dark. This fading is particularly accelerated under high temperature and high humidity. Fading of these colored images is a major defect in color photography, and there has been a strong demand for improvement of this defect. Conventionally, various methods have been known for preventing fading of colored images in bright or dark places using silver halide color photographic materials. For example, treatment with zinc solution in U.S. Pat. No. 2,788,274;
Treatment with calcium, magnesium and cadmium salts as described in patent no. 2913338, UK patent no.
A method of treatment with a solution containing monosaccharide, disaccharide, and hexitol described in No. 909824 and No. 1001446, a treatment with a solution containing formaldehyde and polycarboxylic acid, and the like are known. However, with these methods, the effect obtained is slight, or even if the fading property in the dark can be improved, the fading caused by light (bright fading) may be increased, or in some cases, the increase in staining cannot be suppressed. However, it also had drawbacks such as deteriorating the color fading of the dye. In addition, in recent years, environmental conservation and water quality issues have become important in photofinishers, which automatically and continuously develop color photographic materials. It is desired to reduce or eliminate the large amount of washing water used in the process. For this reason, a technique has been proposed that directly performs stabilization treatment without washing with water after fixing or bleach-fixing. For example, the technique using derivatives of isothiazolin-3-one compounds described in JP-A-57-8542, the technique of incorporating soluble iron salts as described in JP-A-58-14834, JP-A-57-132146, 58
There are techniques using chelating agents such as polycarboxylic acids and organic phosphonic acids described in Japanese Patent No. 18631. However, these techniques have a drawback in that they are weakly effective in suppressing deterioration in image storage, particularly an increase in yellow stain in uncolored areas due to long-term storage. As a technique to solve this drawback, JP-A-58-
A technique for making a stabilizing liquid acidic is known, as described in Japanese Patent No. 8543. However, when the stabilizer is made acidic, a new problem appears to be caused by the fluorescent brightener.
The problem is so-called bluing, where the black color in the highest density part turns blue in sunlight, and so-called stain, which is the unexposed part, which is thought to be caused by the fact that the dye eluted from the light-sensitive material becomes easier to adsorb during continuous processing. It was found that the problem of yellow contamination occurred. Furthermore, it was found that the fixing component and soluble silver complex salt increased in the stabilizing solution, and the stability of the cyan dye against light (bright fading) decreased. [Object of the Invention] The object of the present invention is to solve the above-mentioned drawbacks, to prevent light fading and dark fading, and to prevent the occurrence of bluing and staining, and in particular to reduce washing water and stabilize treatment without washing. It is an object of the present invention to provide a method for stabilizing a dye image, which does not affect the finish of the dye image even if [Summary of the Invention] The method for processing a silver halide color photographic light-sensitive material according to the present invention is to subject the silver halide color photographic light-sensitive material to color development processing, bleach-fixing processing, or bleaching and fixing processing, and then processing the material in three or more tanks. When performing stabilization treatment in a treatment tank composed of tanks, a stabilizing solution replenisher containing an ammonium compound is replenished into the final treatment tank of the three or more treatment tanks, and the overflow liquid in the final treatment tank is treated. The pH of the stabilizing solution in the final processing tank of the stabilization processing step is set to 5.0 or higher by sequentially overflowing in the direction opposite to the moving direction of the photographic material being processed, and the concentration of ammonium compounds in the stabilizing solution in the final processing tank is reduced. 0.002 to 1.0 mol/, and the ammonium compound concentration in the treatment tank immediately before the final treatment tank in the stabilization treatment step is lower than the ammonium compound concentration in the final treatment tank, and the treatment tank in front of the treatment tank immediately before the above. The ammonium compound concentration in the treatment tank is lower than the ammonium compound concentration in the immediately preceding treatment tank. According to a preferred embodiment of the present invention, after the bleach-fixing treatment or the fixing treatment, a stabilization treatment is performed without performing a water washing treatment. [Structure of the Invention] The present invention will be explained in detail below. The present inventors have found that the reverse dyeing of sensitizing dyes eluted from photographic materials occurs when treated with an acidic stabilizing solution. It was also found that staining can be prevented. However, although the above-mentioned drawbacks of the conventional technology are overcome by treatment with a stabilizer solution having a pH higher than neutrality, the sample after treatment tends to generate yellow stain when stored, and the color fading of the cyan dye increases. A drawback arises. As a result of intensive research into a technology that can solve both of these issues at the same time, we added an ammonium compound to the stabilizer solution with a pH of 5.0 or higher and used it in the final processing step to prevent staining of fluorescent dyes and sensitizing dyes. Moreover, it has been found that deterioration of images due to storage can be completely prevented. or,
In stabilized solutions with the addition of ammonium compounds, the pH is
It was found that a value of less than 5.0 is not preferable because it not only tends to cause staining of dyes and pigments, but also causes significant fading of cyan pigments. The ammonium compound added to the stabilizing solution of the present invention is a compound that may release ammonium ions in an aqueous solution, and specifically, for example, aqueous ammonia, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium chromate. ,
Ammonium dichromate, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, Ammonium bisulfite, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium perchlorate, ammonium peroxodisulfate, ammonium persulfate, ammonium phosphomolybutate, ammonium phosphotungstate, ammonium silicate, ammonium sulfamate, ammonium sulfate, ammonium sulfite, Ammonium salts of inorganic acids such as ammonium tetraborate, ammonium tetrafluoroborate, ammonium thiocyanate, ammonium tungstate, ammonium vanadate, ammonium polyphosphate, ammonium pyrophosphate, ammonium acetate, ammonium adipate, ammonium aurintricarboxylate, benzoic acid. Ammonium acid, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium lactate, ammonium malate, ammonium maleate, sulfur ammonium acid, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenolammonium, ammonium iminodiacetate, Ammonium hydroxyethyliminodiacetate, ammonium nitrilotriacetate, ammonium ethylenediaminetetraacetate, ammonium diethylenetriaminepentaacetate, ammonium hydroxyethylethylenediaminetriacetate, ammonium trans-cyclohexanediaminetetraacetate, ammonium diaminopropanoltetraacetate, ammonium nitrilotripropionate, nitrilotrismethylene Ammonium phosphonate, ammonium ethylenediaminetetramethylenephosphonate, ammonium 1-hydroxyethylidene-1,1'-diphosphonate, 2-phosphofubutane-1,
Ammonium 2,4-tricarboxylate, di(2-
Ammonium salts of organic acids such as ammonium (hydroxyethyl) aminomethane sulfonate, ammonium alum, ceric ammonium sulfate, ammonium manganese sulfate, ammonium ferrous sulfate (12 hydrate), Reinetske's salt (hydrate), ammonium copper sulfate , ammonium-metal complexes such as ammonium calcium complex salts and ammonium magnesium complex salts. That is, it is a compound that releases ammonia, ammonium ions (including those bound to hydrates), or ammonium hydroxide when the ammonium compound is added to the stabilizing solution, and is not limited to the above-mentioned specific examples. The ammonium compound used in the present invention can be added in an amount of 0.001 to 1.0 mol, preferably 0.002 to 0.2 mol, per stabilizing bath. The stabilizer solution (stabilizing bath) according to the present invention has a pH of 5.0 or more, preferably 5.0 to 10.0. A particularly desirable pH range is 6.0 to 9.0. In addition, in a continuous treatment method in which the treatment process consists of multiple stabilizing baths, the treatment is carried out in a countercurrent manner, and the final bath is replenished, the desired pH of the stabilizing bath is the pH in the final bath of the stabilizing bath. If the pH of the stabilizing bath is less than 5.0, the effect of preventing the ammonium compound used in the present invention from fading cannot be obtained, and in some cases, it may even accelerate the fading of the dye. Further, if the pH is 10 or more, the gelatin film becomes weak, which is not preferable. Various compounds may be added to the stabilizer of the present invention, such as PH buffers, fluorescent brighteners, surfactants, fungicides, preservatives, chelating agents, hardeners, various metal salts, etc. Therefore, any combination of compounds may be used as long as the photographic performance is not affected. The preferred stabilization treatment of the present invention is a step in which water washing is not substantially performed in the step following the bleach-fixing bath or fixing bath, which means that the stabilization treatment is performed directly after bleach-fixing or fixing, and the washing treatment is basically However, it does mean that a short silver recovery bath, rinse, etc. for silver recovery may be provided between the bleach-fix bath or fix bath and the stabilization process. However, it is preferable that nothing be provided between the bleach-fix bath or the fix bath and the stabilizing bath. After the stabilization treatment according to the present invention, there is no need for water washing at all, but rinsing with a small amount of water within a very short period of time, surface cleaning, etc. can be optionally performed as necessary, but stabilization is preferable. Preferably, the treatment is followed by a direct drying step. The treatment temperature during stabilization treatment is 10℃ to 60℃, preferably
A range of 15°C to 40°C is preferable. In addition, from the viewpoint of speedy processing, it is preferable that the processing time is short, but usually
It is about 20 seconds to 10 minutes, most preferably about 30 seconds to 5 minutes. The temperature and time of the drying process can be selected arbitrarily, but it is preferable to set the temperature to 50°C or higher. The fixing bath or bleach-fixing bath of the present invention is not particularly limited, and examples of fixing agents include thiosulfates, thiocyanates, iodides, bromides,
Thioether, thiourea, etc. are used, and as the bleaching agent, for example, red blood salt, iron chloride, persulfate, hydrogen peroxide, organic acid ferric complex salt, etc. are used. The method of bringing the stabilizing solution of the present invention into contact with a photosensitive material is to immerse the photosensitive material in the solution in the same way as a general processing solution. It may be applied to both sides and the conveyor belt, or it may be sprayed onto the conveyor belt. The processing method of the present invention can be used to process color paper, color reversal paper, color positive film, color negative film, color reversal film, color X-ray film, and the like. In addition, when the stabilizing solution of the present invention contains a soluble silver salt, silver can also be recovered from the solution.
As a silver recovery method, an ion exchange resin method, a metal substitution method, an electrolysis method, a silver sulfide precipitation method, etc. can be used. In the present invention, when the cyan coupler used in the silver halide color photographic light-sensitive material is a coupler represented by the general color () or () below, the stability of the cyan dye produced by color development against light is improved. This effect is added. General formula () General formula () X is −COR 2 ,
【式】−SO2R2、[Formula] −SO 2 R 2 ,
【式】【formula】
【式】
−CONHCOR2または−CONHSO2R2で表わされ
る基である。
ここで、R2はアルキル基(好ましくは炭素数
1〜20のアルキル基、例えばメチル、エチル、ブ
チル、ドデシルなど)、アルケニル基、(好ましく
は炭素数2〜20のアルケニル基、例えばアシル、
オレイルなど)、シクロアルキル基(好ましくは
5〜7員環で、例えばシクロヘキシルなど)、ア
リール基(フエニル基、トリル基、ナフチル基な
ど)、ヘテロ環基(好ましくは窒素原子、酸素原
子もしくはイオウ原子を1〜4個含む5員〜6員
のヘテロ環で、例えばフリル基、チエニル基、ベ
ンゾチアゾリル基など)を表わす。R3は水素原
子もしくはR2で表わされる基を表わす。R2とR3
とは互いに結合して、窒素原子を含む5員〜6員
のヘテロ環を形成してもよい。なお、R2、R3に
は任意の置換基を導入することができ、例えば炭
素数1〜10のアルキル基(例えばエチル、i−プ
ロピル、i−ブチル、t−ブチル、t−オクチル
など)、アリール基(例えばフエニル、ナフチ
ル)、ハロゲン原子(例えばフツ素、塩素、臭素
などの各原子)、シアノ、ニトロ、スルホンアミ
ド基(例えばメタンスルホンアミド、ブタンスル
ホンアミド、p−トルエンスルホンアミドなど)、
スルフアモイル基(例えばメチルスルフアモイ
ル、フエニルスルフアモイルなど)、スルホニル
基(例えばメタンスルホニル、p−トルエンスル
ホニルなど)、フルオロスルホニル、カルバモイ
ル基(例えばジメチルカルバモイル、フエニルカ
ルバモイルなど)、オキシカルボニル基(例えば
エトキシカルボニル、フエノキシカルボニルな
ど)、アシル基、(例えばアセチル、ベンゾイルな
ど)、ヘテロ環基(例えばピリジル基、ピラゾリ
ル基など)、アルコキシ基、アリールオキシ基、
アシルオキシ基などを挙げることができる。
一般式()および()において、R1は一
般式()および()で表わされるシアンカプ
ラーおよび該シアンカプラーから形成されるシア
ン色素に耐拡散性を付与するのに必要なバラスト
基を表わす。好ましくは炭素数4〜30個のアルキ
ル基、アリール基またはヘテロ環基である。例え
ば直鎖または分岐のアルキル基(例えばt−ブチ
ル、n−オクチル、t−オクチル、n−ドデシル
など)、アルケニル基、シクロアルキル基、5員
〜6員環ヘテロ環基などが挙げられる。
一般式()および()において、Zは水素
原子または発色現像主薬の酸化生成物とのカツプ
リング反応時に離脱可能な基を表わす。例えば、
ハロゲン原子(例えば塩素、臭素、フツ素などの
各原子)、酸素原子または窒素原子が直接カツプ
リング位に結合しているアリールオキシ基、カル
バモイルオキシ基、カルバモイルメトキシ基、ア
シルオキシ基、スルホンアミド基、コハク酸イミ
ド基などが挙げられ、更には具体的な例としては
米国特許第3741563号、特開昭47−37425号、特公
昭48−36894号、特開昭50−10135号、同50−
117422号、同50−130441号、同51−108841号、同
50−120334号、同52−18315号、同53−105226号、
同54−14736号、同54−48237号、同55−32071号、
同55−65957号、同56−1938号、同56−12643号、
同56−27147号各公報に記載されているものが挙
げられる。
本発明においては、下記一般式()、一般式
()または一般式()で表わされるシアンカ
プラーが更に好ましい。
一般式()
一般式()
一般式()
一般式()において、R4は置換、未置換の
アリール基(特に好ましくはフエニル基)であ
る。該アリール基が置換基を有する場合の置換基
としては、−SO2R6、ハロゲン原子(例えばフツ
素、臭素、塩素等の各原子)、−CF3、−NO2、−
CN、−COR6、−COOR6、−SO2OR6、
[Formula] A group represented by -CONHCOR 2 or -CONHSO 2 R 2 . Here, R 2 is an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, butyl, dodecyl, etc.), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, such as acyl,
oleyl, etc.), cycloalkyl groups (preferably 5- to 7-membered rings, such as cyclohexyl), aryl groups (phenyl, tolyl, naphthyl, etc.), heterocyclic groups (preferably nitrogen, oxygen, or sulfur atoms) A 5- to 6-membered heterocycle containing 1 to 4 such as a furyl group, a thienyl group, a benzothiazolyl group, etc.). R 3 represents a hydrogen atom or a group represented by R 2 . R2 and R3
may be bonded to each other to form a 5- to 6-membered heterocycle containing a nitrogen atom. Note that any substituent can be introduced into R 2 and R 3 , such as an alkyl group having 1 to 10 carbon atoms (for example, ethyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.) , aryl groups (e.g. phenyl, naphthyl), halogen atoms (e.g. fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.) ,
Sulfamoyl group (e.g. methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (e.g. methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl, carbamoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (e.g. acetyl, benzoyl, etc.), heterocyclic group (e.g. pyridyl group, pyrazolyl group, etc.), alkoxy group, aryloxy group,
Examples include acyloxy groups. In the general formulas () and (), R 1 represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formulas () and () and the cyan dye formed from the cyan coupler. Preferred are alkyl groups, aryl groups, or heterocyclic groups having 4 to 30 carbon atoms. Examples include linear or branched alkyl groups (eg, t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- to 6-membered heterocyclic groups, and the like. In the general formulas () and (), Z represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidation product of a color developing agent. for example,
Halogen atoms (e.g. chlorine, bromine, fluorine, etc.), aryloxy groups, carbamoyloxy groups, carbamoylmethoxy groups, acyloxy groups, sulfonamide groups, succinic groups in which an oxygen or nitrogen atom is directly bonded to the coupling position. Examples include acid imide groups, and further specific examples include U.S. Pat.
No. 117422, No. 50-130441, No. 51-108841, No. 117422, No. 50-130441, No. 51-108841, No.
No. 50-120334, No. 52-18315, No. 53-105226,
No. 54-14736, No. 54-48237, No. 55-32071,
No. 55-65957, No. 56-1938, No. 56-12643,
Examples include those described in each publication of No. 56-27147. In the present invention, cyan couplers represented by the following general formula (), general formula () or general formula () are more preferred. General formula () General formula () General formula () In the general formula (), R 4 is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, examples of the substituent include -SO 2 R 6 , halogen atom (e.g., fluorine, bromine, chlorine, etc.), -CF 3 , -NO 2 , -
CN, −COR 6 , −COOR 6 , −SO 2 OR 6 ,
【式】−OR6、− OCOR6、[Formula] −OR 6 , − OCOR 6 ,
【式】およ び[Formula] and Beauty
【式】から選ばれる少なくとも1つの置
換基が包含される。
ここで、R6はアルキル基(好ましくは炭素数
1〜20のアルキル基、例えばメチル、エチル、t
−ブチル、ドデシル等の各基)、アルケニル基
(好ましくは炭素数2〜20のアルケニル基、例え
ばアシル基、オレイル基等)、シクロアルキル基
(好ましくは5員〜7員環で、例えばシクロヘキ
シル基等)、アリール基(フエニル基、トリル基、
ナフチル基等)を表わし、R7は水素原子もしく
は前記R6で表わされる基である。
一般式()で表わされるフエノール系シアン
カプラーの好適な化合物としては、R4が置換な
いし未置換のフエニル基であり、フエニル基への
置換基としてシアノ、ニトロ、−SO2R6(R6はア
ルキル基)、ハロゲン原子、トリフルオロメチル
であるような化合物である。
一般式()および()において、R5はア
ルキル基(好ましくは炭素数1〜20のアルキル
基、例えばメチル、エチル、t−ブチル、ドデシ
ル等)、アルケニル基(好ましくは炭素数2〜20
のアルケニル基、例えばアシル、オレイル等)、
シクロアルキル基(好ましくは5員〜7員環で、
例えばシクロヘキシル等)、アリール基(フエニ
ル基、トリル基、ナフチル基等)、ヘテロ環基
(窒素原子、酸素原子もしくはイオウ原子を1〜
4個含む5員〜6員環のヘテロ環が好ましい。例
えばフリル基、チエニル基、ベンゾチアゾリル基
等)を表わす。
一般式()のR6、R7および一般式()お
よび()のR5には、さらに任意の置換基を導
入することができ、具体的には、一般式()お
よび()においてR2またはR3に導入すること
のできるが如き置換基である。そして、置換基と
しては特にハロゲン原子(例えば塩素原子、フツ
素原子等の各原子)が好ましい。
一般式()、()および()においてZお
よびR1は各々、一般式()および()と同
様の意味を有している。R1で表わされるバラス
ト基の好ましい例は、下記一般式()で表わさ
れる基である。
一般式()
式中、Jは酸素原子もしくは硫黄原子又はスル
ホニル基を、kは0〜4の整数、lは0または1
を示し、kが2以上の場合2つ以上存在するR8
は同一でも異なつていてもよく、R7は炭素数1
〜20の直鎖または分岐、及びアリール基等の置換
したアルキレン基、R8は一価の基を示し、例え
ば水素原子、ハロゲン原子(好ましくは塩素、臭
素)、アルキル基〔好ましくは直鎖または分岐の
炭素数1〜20のアルキル基(例えばメチル、t−
ブチル、t−ペンチル、t−オクチル、ドデシ
ル、ペンタデシル、ベンジル、フエネチル)〕、ア
リール基(例えばフエニル)、複素環基(好まし
くは含チツ素複素環基)、アルコキシ基(好まし
くは直鎖または分岐の炭素数1〜20のアルコキシ
基(例えばメトキシ、エトキシ、t−ブチルオキ
シ、オクチルオキシ、デシルオキシ、ドデシルオ
キシ)、アリールオキシ基(例えばフエノキシ)、
ヒドロキシ、アシルオキシ基(好ましくはアルキ
ルカルボニルオキシ基、アリールカルボニルオキ
シ基(例えばアセトキシ、ベンゾイルオキシ))、
カルボキシ、アルキルオキシカルボニル基(好ま
しくは炭素数1〜20の直鎖または分岐のアルキル
オキシカルボニル基)、アリールオキシカルボニ
ル基(好ましくはフエノキシカルボニル)、アル
キルチオ基(好ましくは炭素数1〜20)、アシル
基(好ましくは炭素数1〜20の直鎖または分岐の
アルキルカルボニル基)、アシルアミノ基(好ま
しくは炭素数1〜20の直鎖または分岐のアルキル
カルボアミド、ベンゼンカルボアミド)、スルホ
ンアミド基(好ましくは炭素数1〜20の直鎖また
は分岐のアルキルスルホンアミド基、ベンゼンス
ルホンアミド基)、カルバモイル基(好ましくは
炭素数1〜20の直鎖または分岐のアルキルアミノ
カルボニル基、フエニルアミノカルボニル基)、
スルフアモイル基(好ましくは炭素数1〜20の直
鎖または分岐のアルキルアミノスルホニル基、フ
エニルアミノスルホニル基)等。
以下、本発明に用いられるシアンカプラーの具
体的な化合物例を示す。
本発明に適用できるハロゲン化銀カラー写真感
光材料は、発色剤が感光材料中に含まれている内
式現像方式(米国特許第2376679号、同第2801171
号明細書参照)のほか、発色剤が現像液中に含ま
れている外式現像方式(米国特許第2252718号、
同第2592243号、同第2590970号明細書参照)のも
のであつてもよい。また発色剤は前記シアンカプ
ラーの他に当業界で一般に知られている任意のも
のが使用できる。
マゼンタ発色剤としては活性メチレン基を有す
る5−ピラゾロン環を骨格構造として有するも
の、イエロー発色剤としては活性メチレン鎖を有
するベンゾイルアセトアニライド、ピバリルアセ
トアニライド、アシルアセトアニライド構造のも
のなどでカツプリング位置に置換基を有するも
の、有しないもののいずれも使用できる。このよ
うに発色剤としては、所謂2当量型カプラーおよ
び4当量型カプラーのいずれをも適用できるもの
である。使用し得るハロゲン化銀乳剤としては塩
化銀、臭素銀、沃化銀、塩臭化銀、塩沃化銀、沃
臭化銀、塩沃臭化銀の如きいずれのハロゲン化銀
を用いたものであつてもよい。また、これらのハ
ロゲン化銀の保護コロイドとしては、ゼラチン等
の天然物の他、合成によつて得られる種々のもの
が使用できる。ハロゲン化銀乳剤には、安定剤、
増感剤、硬膜剤、増感色素、界面活性剤等通常の
写真用添加剤が含まれてもよい。
支持体としては、ポリエチレンコート紙、トリ
アセテートフイルム、ポリエチレンテレフタレー
トフイルム、白色ポリエチレンテレフタレートフ
イルムなど何であつても良い。
本発明の処理に使用される黒白現像液は通常知
られているカラー写真感光材料の処理に用いられ
る黒白第1現像液と呼ばれるもの、もしくは黒白
写真感光材料の処理に用いられるものであり、一
般に黒白現像液に添加される各種の添加剤を含有
せしめることができる。
代表的な添加剤としては1−フエニル−3−ピ
ラゾリドン、メトールおよびハイドロキノンのよ
うな現像主薬、亜硫酸塩のような保恒剤、水酸化
ナトリウム、炭酸ナトリウム、炭酸カリウム等の
アルカリから成る促進剤、臭化カリウムや、2−
メチルベンツイミダゾール、メチルベンツチアゾ
ール等の無機性、もしくは有機性の抑制剤、ポリ
リン酸塩のような硬水軟化剤、微量のヨウ化物や
メルカプト化合物から成る表面過現像防止等をあ
げることができる。
本発明の処理に使用されるカラー現像液に使用
される芳香族第1級アミン発色現像主薬は種々の
カラー写真プロセスにおいて広範囲に使用されて
いる公知のものが包含される。これらの現像剤は
アミノフエノール系およびp−フエニレンジアミ
ン系誘導体が含まれる。これらの化合物は遊離状
態より安定のため一般に塩の形、例えば塩酸塩ま
たは硫酸塩の形で使用される。また、これらの化
合物は、一般に発色現像液1について約0.1g
〜約30gの濃度、更に好ましくは、発色現像液1
について約1g〜約15gの濃度で使用する。
アミノフエノール系現像剤としては例えば、o
−アミノフエノール、p−アミノフエノール、5
−アミノ−2−オキシ−トルエン、2−アミノ−
3−オキシ−トルエン、2−オキシ−3−アミノ
−1,4−ジメチル−ベンゼンなどが含まれる。
特に有用な第1級芳香族アミノ系発色現像剤は
N,N−ジアルキル−p−フエニレジアミン系化
合物であり、アルキル基およびフエニル基は置換
されていても、あるいは置換されていなくてもよ
い。その中でも特に有用な化合物例としてはN,
N−ジエチル−p−フエニレンジアミン塩酸塩、
N−メチル−p−フエニレンジアミン塩酸塩、
N,N−ジメチル−p−フエニレンジアミン塩酸
塩、2−アミノ−5−(N−エチル−N−ドデシ
ルアミノ)−トルエン、N−エチル−N−β−メ
タンスルホンアミドエチル−3−メチル−4−ア
ミノアニリン硫酸塩、N−エチル−N−β−ヒド
ロキシエチルアミノアニリン、4−アミノ−3−
メチル−N,N−ジエチルアニリン、4−アミノ
−N−(2−メトキシエチル)−N−エチル−3−
メチルアニリン−p−トルエンスルホネートなど
を挙げることができる。
本発明の処理において使用されるアルカリ性発
色現像液は、前記第1級芳香族アミン系発色現像
剤に加えて、更に、発色現像液に通常添加されて
いる種々の成分、例えば水酸化ナトリウム、炭酸
ナトリウム、炭酸カリウムなどのアルカリ剤、ア
ルカリ金属亜硫酸塩、アルカリ金属重亜硫酸塩、
アルカリ金属チオシアン酸塩、アルカリ金属ハロ
ゲン化物、ベンジルアルコール、水軟化剤および
濃厚化剤などを任意に含有することもできる。こ
の発色現像液のPH値は、通常7以上であり、最も
一般的には約10〜約13である。
漂白工程に用いる漂白液もしくは漂白定着液に
おいて使用される漂白剤としての有機酸の金属錯
塩は、現像によつて生成した金属銀を酸化してハ
ロゲン化銀にかえると同時に発色剤の未発色部を
発色させる作用を有するもので、その構造はアミ
ノポリカルボン酸または蓚酸、クエン酸等の有機
酸で鉄、コバルト、銅等の金属イオンを配位した
ものである。このような有機酸の金属錯塩を形成
するために用いられる最も好ましい有機酸として
は、ポリカルボン酸またはアミノポリカルボン酸
があげられる。これらのポリカルボン酸またはア
ミノポリカルボン酸はアルカリ金属塩、アンモニ
ウム塩もしくは水溶性アミン塩であつてもよい。
これらの具体的代表例としては次の如きものを挙
げることができる。
〔1〕 エチレンジアミンテトラ酢酸
〔2〕 ジエチレントリアミンペンタ酢酸
〔3〕 エチレンジアミン−N−(β−オキシエチ
ル)−N,N′,N′−トリ酢酸
〔4〕 プロピレンジアミンテトラ酢酸
〔5〕 ニトリロトリ酢酸
〔6〕 シクロヘキサンジアミンテトラ酢酸
〔7〕 イミノジ酢酸
〔8〕 ジヒドロキシエチルグリシンクエン酸(ま
たは酒石酸)
〔9〕 エチルエーテルジアミンテトラ酢酸
〔10〕 グリコールエーテルジアミンテトラ酢酸
〔11〕 エチレンジアミンテトラプロピオン酸
〔12〕 フエニレンジアミンテトラ酢酸
〔13〕 エチレンジアミンテトラ酢酸ジナトリウム
塩
〔14〕 エチレンジアミンテトラ酢酸テトラ(トリ
メチルアンモニウム)塩
〔15〕 エチレンジアミンテトラ酢酸テトラナトリ
ウム塩
〔16〕 ジエチレントリアミンペンタ酢酸ペンタナ
トリウム塩
〔17〕 エチレンジアミン−N−(β−オキシエチ
ル)−N,N′,N′−トリ酢酸ナトリウム塩
〔18〕 プロピレンジアミンテトラ酢酸ナトリウム
塩
〔19〕 ニトロトリ酢酸ナトリウム塩
〔20〕 シクロヘキサンジアミンテトラ酢酸ナトリ
ウム塩
使用される漂白液は、前記の如き有機酸の金属
錯塩を漂白剤として含有すると共に、種々の添加
剤を含むことができる。添加剤としては、とくに
アルカリハライドまたはアンモニウムハライド、
例えば臭化カリウム、臭化ナトリウム、塩化ナト
リウム、臭化アンモニウム等の再ハロゲン化剤を
含有させることが望ましい。また硼酸塩、蓚酸
塩、酢酸塩、炭酸塩、燐酸塩等のPH緩衝剤、アル
キルアミン類、ポリエチレンオキサイド類等の通
常漂白液に添加することが知られているものを適
宜添加することができる。
漂白工程を漂白定着液を用いて行なう場合には
漂白定着液は漂白能の他に定着能を有することに
なり、漂白剤の他に、定着液に用いられるのと同
じ定着剤を含有する組成の液が適用される。使用
される定着液及び漂白定着液は、前記漂白剤の他
にハロゲン化銀と反応して水溶性の錯塩を形成す
る化合物、例えばチオ硫酸カリウム、チオ硫酸ナ
トリウム、チオ硫酸アンモニウムの如きチオ硫酸
塩、チオシアン酸カリウム、チオシアン酸ナトリ
ウム、チオシアン酸アンモニウムの如きチオシア
ン酸塩、あるいはチオ尿素、チオエーテル等が挙
げられる。
更に、定着液及び漂白定着液は、亜硫酸アンモ
ニウム、亜硫酸カリウム、重亜硫酸アンモニウ
ム、重亜硫硫酸カリウム、重亜酸ナトリウム、メ
タ重亜硫酸アンモニウム、メタ重亜硫酸カリウ
ム、メタ重亜硫酸ナトリウム等の亜硫酸塩や硼
酸、硼砂、水酸化ナトリウム、水酸化カリウム、
炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウ
ム、重炭酸カリウム、酢酸、酢酸ナトリウム、水
酸化アンモニウム等の各種の塩から成るPH緩衝剤
を単独あるいは2種以上含むことが出来る。
漂白定着液(浴)に漂白定着補充液剤を分離補
充する場合の本発明の構成液剤は、チオ硫酸塩、
チオシアン酸塩又は亜硫酸塩等を含有しても良い
が、分離して補充されるのが好ましい。
本発明においては漂白定着液の活性度を高める
為に漂白定着浴中及び漂白定着補充貯蔵タンク内
で所望により空気の吹き込み、又は酸素の吹き込
みを行つて良く、あるいは適当な酸化剤、例えば
過酸化水素、臭素酸塩、過硫酸塩等を適宜添加し
ても良い。
本発明の処理においては、安定液はもちろん定
着液及び漂白定着液等の可溶性錯塩を含有する処
理液から公知の方法で銀回収しても良い。例えば
電気分解法(仏国特許2299667号明細書記載)、沈
澱法(特開昭52−73037号公報記載、独国特許
2331220号明細書記載)、イオン交換法(特開昭51
−17114号公報記載、独国特許2548237号明細書記
載)及び金属置換法(英国特許1353805号明細書
記載)などが有効に利用できる。
〔実施例〕
次に実施例によつて本発明を詳しく説明する
が、本発明がこれら実施例によつて限定されるも
のではない。
実施例 1
白色顔料としてアナターゼ型の酸化チタンを含
むポリエチレン層によつて、表面を被覆した紙支
持体上にコロナ放電による前処理を施こした後、
次の各層を順次塗設してカラー印画紙を作つた。
第1層:5モル%の塩化銀を含む塩臭化銀写真乳
剤を、アンヒドロ−5−メチル−5′−メトキシ
−3,3−ジ(3−スルホプロピル)セレナシ
アニンヒドロオキシドにより光学増感し、これ
に2,5−ジ−t−ブチルハイドロキノン及び
イエローカプラーとしてα−〔4−(1−ベンジ
ル−2−フエニル−3,5−ジオキソ−1,
2,4−トリアゾリジル)〕−α−ビバリル−2
−クロロ−5−〔γ−(2,4−ジ−t−アミル
フエキシ)ブチルアミド〕アセトアニリドのプ
ロテクト分散液を加えたものを銀0.35g/m2と
なるように塗設した。
第2層:ジ−t−オクチルハイドロキノン及び紫
外線吸収剤としての2−(2′−ヒドロキシ−3′,
5′−ジ−t−ブチルフエニル)ベンツトリアゾ
ール、2−(2′−ヒドロキシ−5′−t−ブチル
フエニル)ベンツトリアゾール、2−(2′−ヒ
ドロキシ−3′−t−ブチル−5′−メチルフエニ
ル)−5−クロルベンツトリアゾール及び2−
(2−ヒドロキシ−3′,5′−ジ−t−ブチルフ
エニル)−5−クロルベンツトリアゾールの混
合物を含むプロテクト分散液を加えたゼラチン
溶液を中間層として塗設した。
第3層:15モル%の塩化銀を含む塩臭化銀写真乳
剤を、アンヒドロ−9−エチル−5,5′−ジフ
エニル−3,3′−ジ−(3−スルホプロピル)
オキサカルボシアニンヒドロオキシドにより光
学増感し、これに2,5−ジ−t−ブチルハイ
ドロキノン、2,2,4−トリメチル−6−ラ
ウリルオキシ−7−t−オクチルクロマン及び
マゼンタカプラーとして1−(2,4,6−ト
リクロロフエニル)−3−(2−クロロ−5−オ
クタデセニルサクシンイミドアニリノ)−5−
ピラゾロンのプロテクト分散液を加えたもの
を、銀0.4g/m2となるように塗設した。
第4層:第2層と同じ液を中間層として塗設し
た。
第5層:15モル%の塩化銀を含む塩臭化銀写真乳
剤を、アンヒドロ−2−〔3−エチル−5−(1
−エチル−4(1H)−キノリリデン)エチリデ
ン−4−オキソ−チアゾリジン−2−イリデ
ン〕メチル−3−(3−スルホプロピル)ベン
ゾオキサゾリウムヒドロオキシドを用いて光学
増感し、これに2,5−ジ−t−ブチルハイド
ロキノン及びシアンカプラーとして2,4−ジ
クロロ−3−メチル−6−〔γ−(2,4−ジア
ミルフエノキシ)ブチルアミド〕フエノールの
プロテクト分散液を加えたものを、銀0.27g/
m2となるように塗設した。
第6層:ゼラチン溶液を保護層として塗設した。
上記の各感光性層に用いたハロゲン化銀写真乳
剤は、特公昭46−7772号公報記載の方法で調製
し、それぞれチオ硫酸ナトリウムにより化学増感
を施こし、安定剤として4−ヒドロキシ−6−メ
チル−1,3,3a,7−テトラザインデンを添
加した。またすべての層の塗布液には、塗布助剤
としてサポニンと、硬膜剤としてビス(ビニルス
ルホニルメチル)エーテルをそれぞれ添加した。
以上のようにして作つたカラー印画紙にKS−7
型感光計(小西六写真工業社製)を用いて段階露
光を与え発色現像、漂白定着、水洗を行なつた
後、7枚の試料を各々下記表−1に示すNo.(1)〜(7)
の処方の溶液に30℃、1分間浸漬した後、乾燥し
て試験試料とした。この試料を光学濃度計
(PDA−65、小西六写真工業社製)を用いて青
色、緑色、赤色の反射濃度を測定し、70℃、75%
RHの恒温恒湿槽に40日間保存した後、再び濃度
測定を行ない、初期濃度約1.5の部分の濃度低下
率と未露光部のイエローステイン濃度(青色で測
定)を求めた。結果を表−2に示す。At least one substituent selected from the formula is included. Here, R 6 is an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, t
-butyl, dodecyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, such as acyl groups, oleyl groups, etc.), cycloalkyl groups (preferably 5- to 7-membered rings, such as cyclohexyl groups), etc.), aryl groups (phenyl group, tolyl group,
naphthyl group, etc.), and R 7 is a hydrogen atom or a group represented by R 6 above. A suitable compound of the phenolic cyan coupler represented by the general formula () is one in which R 4 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -SO 2 R 6 (R 6 is an alkyl group), a halogen atom, or trifluoromethyl. In the general formulas () and (), R 5 is an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group (preferably a carbon number 2 to 20
alkenyl groups, such as acyl, oleyl, etc.),
Cycloalkyl group (preferably a 5- to 7-membered ring,
For example, cyclohexyl, etc.), aryl groups (phenyl, tolyl, naphthyl, etc.), heterocyclic groups (1 to 1 nitrogen, oxygen, or sulfur atom)
A 5- to 6-membered heterocycle containing 4 rings is preferred. For example, it represents a furyl group, a thienyl group, a benzothiazolyl group, etc.). Any substituent can be further introduced into R 6 and R 7 in general formula () and R 5 in general formula () and (). Specifically, in general formula () and (), R Such a substituent can be introduced into 2 or R 3 . As the substituent, a halogen atom (for example, a chlorine atom, a fluorine atom, etc.) is particularly preferable. In the general formulas (), () and (), Z and R 1 have the same meanings as in the general formulas () and (), respectively. A preferred example of the ballast group represented by R 1 is a group represented by the following general formula (). General formula () In the formula, J is an oxygen atom, a sulfur atom, or a sulfonyl group, k is an integer of 0 to 4, and l is 0 or 1.
, and if k is 2 or more, there are two or more R 8
may be the same or different, R 7 has 1 carbon number
~20 linear or branched, and substituted alkylene groups such as aryl groups, R 8 represents a monovalent group, such as a hydrogen atom, a halogen atom (preferably chlorine, bromine), an alkyl group [preferably a linear or Branched alkyl groups having 1 to 20 carbon atoms (e.g. methyl, t-
butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl)], aryl groups (e.g. phenyl), heterocyclic groups (preferably nitrogen-containing heterocyclic groups), alkoxy groups (preferably linear or branched an alkoxy group having 1 to 20 carbon atoms (e.g. methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy), an aryloxy group (e.g. phenoxy),
hydroxy, acyloxy group (preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)),
Carboxy, alkyloxycarbonyl group (preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms), aryloxycarbonyl group (preferably phenoxycarbonyl), alkylthio group (preferably having 1 to 20 carbon atoms) , an acyl group (preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms), an acylamino group (preferably a linear or branched alkylcarboxamide having 1 to 20 carbon atoms, benzenecarboxamide), a sulfonamide group (preferably a straight-chain or branched alkylsulfonamide group having 1 to 20 carbon atoms, benzenesulfonamide group), carbamoyl group (preferably a straight-chain or branched alkylaminocarbonyl group having 1 to 20 carbon atoms, phenylaminocarbonyl group) basis),
A sulfamoyl group (preferably a linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms), etc. Specific compound examples of the cyan coupler used in the present invention are shown below. The silver halide color photographic light-sensitive material that can be applied to the present invention uses an internal development method (U.S. Pat. No. 2,376,679, U.S. Pat.
In addition to external development methods (see US Pat. No. 2,252,718) in which a color former is contained in the developer,
2592243 and 2590970). In addition to the cyan coupler mentioned above, any coloring agent generally known in the art can be used. Magenta color formers include those having a 5-pyrazolone ring having an active methylene group as a skeleton structure, yellow color formers include those having a benzoylacetanilide, pivalyl acetanilide, and acylacetanilide structure having an active methylene chain. Both those with and without substituents at the coupling position can be used. Thus, as the coloring agent, both so-called 2-equivalent type couplers and 4-equivalent type couplers can be applied. Silver halide emulsions that can be used include those using any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. It may be. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. Silver halide emulsions include stabilizers,
Common photographic additives such as sensitizers, hardeners, sensitizing dyes, and surfactants may also be included. The support may be anything such as polyethylene coated paper, triacetate film, polyethylene terephthalate film, white polyethylene terephthalate film, etc. The black-and-white developer used in the processing of the present invention is a so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or a developer used in the processing of black-and-white photographic materials. Various additives added to the black and white developer can be contained. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. Potassium bromide, 2-
Examples include inorganic or organic inhibitors such as methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and surface overdevelopment prevention consisting of trace amounts of iodides and mercapto compounds. The aromatic primary amine color developing agents used in the color developer used in the process of the present invention include those known and widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used in an amount of about 0.1g per color developer.
~30g concentration, more preferably color developer 1
It is used at a concentration of about 1 g to about 15 g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxy-toluene, 2-amino-
Included are 3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. Particularly useful primary aromatic amino color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,
N-diethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride,
N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl- 4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-
Methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-
Examples include methylaniline-p-toluenesulfonate. In addition to the above-mentioned primary aromatic amine color developer, the alkaline color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and carbonate. Alkaline agents such as sodium and potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. A metal complex salt of an organic acid as a bleaching agent used in a bleaching solution or a bleach-fixing solution used in the bleaching process oxidizes the metallic silver produced during development and converts it into silver halide, and at the same time removes the uncolored areas of the coloring agent. Its structure is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.
Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylene diamine Tetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β -oxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used is In addition to containing a metal complex salt of an organic acid such as a bleaching agent, various additives may be included. As additives, in particular alkali halides or ammonium halides,
For example, it is desirable to contain a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, or the like. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . When the bleaching process is carried out using a bleach-fix solution, the bleach-fix solution has a fixing ability in addition to the bleaching ability, and in addition to the bleaching agent, a composition containing the same fixing agent as used in the fixing solution is used. liquid is applied. The fixing solution and bleach-fixing solution used include, in addition to the bleaching agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate; Examples include thiocyanate salts such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. Furthermore, the fixer and bleach-fixer may contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. Boric acid, borax, sodium hydroxide, potassium hydroxide,
It can contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When a bleach-fix replenisher is separated and replenished in a bleach-fix solution (bath), the constituent solution of the present invention includes thiosulfate,
It may contain thiocyanate or sulfite, but is preferably separated and replenished. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenishment storage tank, if desired, or a suitable oxidizing agent, such as peroxidation Hydrogen, bromate, persulfate, etc. may be added as appropriate. In the processing of the present invention, silver may be recovered by known methods from processing solutions containing soluble complex salts, such as fixing solutions and bleach-fixing solutions, as well as stabilizing solutions. For example, electrolysis method (described in French patent No. 2299667), precipitation method (described in JP-A-52-73037, German patent)
2331220), ion exchange method (Japanese Unexamined Patent Publication No. 1983)
-17114, German Patent No. 2548237), metal substitution method (British Patent No. 1353805), etc. can be effectively used. [Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 After pretreatment by corona discharge on a paper support coated on the surface with a polyethylene layer containing anatase titanium oxide as white pigment,
Color photographic paper was made by applying each of the following layers in sequence. First layer: Optically sensitized silver chlorobromide photographic emulsion containing 5 mol% silver chloride with anhydro-5-methyl-5'-methoxy-3,3-di(3-sulfopropyl) selenacyanine hydroxide. and 2,5-di-t-butylhydroquinone and α-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,
2,4-triazolidyl)]-α-bivalyl-2
A protective dispersion of -chloro-5-[γ-(2,4-di-t-amylphexy)butyramide]acetanilide was added to the coating at a silver density of 0.35 g/m 2 . 2nd layer: di-t-octylhydroquinone and 2-(2'-hydroxy-3',
5'-di-t-butylphenyl)benztriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benztriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenztriazole and 2-
A gelatin solution to which a protect dispersion containing a mixture of (2-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenztriazole was added was applied as an intermediate layer. Third layer: A silver chlorobromide photographic emulsion containing 15 mol% of silver chloride was mixed with anhydro-9-ethyl-5,5'-diphenyl-3,3'-di-(3-sulfopropyl).
Optically sensitized with oxacarbocyanine hydroxide, 2,5-di-t-butylhydroquinone, 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman and magenta coupler 1-( 2,4,6-Trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-
A protective dispersion of pyrazolone was added to the coating so that the silver concentration was 0.4 g/m 2 . Fourth layer: The same liquid as the second layer was applied as an intermediate layer. Fifth layer: Anhydro-2-[3-ethyl-5-(1
-Ethyl-4(1H)-quinolilidene)ethylidene-4-oxo-thiazolidin-2-ylidene]methyl-3-(3-sulfopropyl)benzoxazolium hydroxide, and optically sensitized with 2, 5-di-t-butylhydroquinone and a protected dispersion of 2,4-dichloro-3-methyl-6-[γ-(2,4-diamylphenoxy)butyramide]phenol as a cyan coupler were added. Silver 0.27g/
It was painted so that it was 2 m2. Sixth layer: A gelatin solution was applied as a protective layer. The silver halide photographic emulsions used in each of the above-mentioned photosensitive layers were prepared by the method described in Japanese Patent Publication No. 46-7772, chemically sensitized using sodium thiosulfate, and 4-hydroxy-6 as a stabilizer. -Methyl-1,3,3a,7-tetrazaindene was added. In addition, saponin as a coating aid and bis(vinylsulfonylmethyl) ether as a hardening agent were added to the coating solution for all layers.
KS-7 on the color photographic paper made as described above.
After applying stepwise exposure using a type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), performing color development, bleaching and fixing, and washing with water, seven samples were prepared with Nos. (1) to (1) shown in Table 1 below. 7)
The sample was immersed in a solution of the following formulation at 30°C for 1 minute, and then dried to obtain a test sample. The blue, green, and red reflection densities of this sample were measured using an optical densitometer (PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.) at 70℃ and 75%.
After storing it in a constant temperature and humidity chamber at RH for 40 days, the concentration was measured again to determine the rate of decrease in concentration in the area where the initial concentration was approximately 1.5 and the yellow stain concentration (measured in blue) in the unexposed area. The results are shown in Table-2.
【表】【table】
【表】
表−2から、処方No.(1)、(2)のように単に有機酸
を一種又は二種添加するのみでアンモニアが未添
加の場合に比較して、本発明のようにアンモニア
を本発明の範囲で加え安定化処理を行なう処方No.
(4)、(7)はイエローステインが上昇せず、赤色反射
濃度の退色も少なく、極めて有効であることがわ
かる。
又、アンモニアの添加量が本発明の範囲外の処
方No.(3)では、イエローステインは極めて良好であ
るにもかかわらず赤色の退色率が非常に大きく好
ましくないことがわかる。
実施例 2
実施例1と同様の実験方法で下記表−3に示す
No.(8)〜(12)の処方について実験を行なつた。結
果を表−4に示す。[Table] From Table 2, compared to the case where one or two types of organic acids are simply added and no ammonia is added, as in Prescription No. (1) and (2), the ammonia Formula No. in which stabilization treatment is carried out by adding within the scope of the present invention.
It can be seen that (4) and (7) are extremely effective, with no increase in yellow stain and little fading of red reflection density. In addition, it can be seen that in prescription No. (3), in which the amount of ammonia added is outside the range of the present invention, although the yellow stain is extremely good, the rate of red color fading is extremely large, which is not preferable. Example 2 Using the same experimental method as Example 1, the results are shown in Table 3 below.
Experiments were conducted on formulations No. (8) to (12). The results are shown in Table 4.
【表】【table】
【表】
表−4から明らかなように、アンモニウム塩を
全く含まない処方No.(8)と、アンモニウムは含むが
安定液のPHが本発明の範囲より低い場合の処方No.
(9)では、いずれも赤色反射濃度の保存による退色
が大きくなり好ましくない。これに対しアンモニ
ウム塩が存在しかつ本発明範囲の望ましい値にあ
るNo.(10)〜(13)の場合は、ステインや赤色反射濃
度が望ましい値となり、保存による退色を防止し
ている事がわかる。但し、PHが11.5の安定液で処
理したNo.(14)は乳剤膜の膨潤が大きく軟化して
おり、スリキズ、故障の原因となり好ましくな
い。
実施例 3
実施例1で自作したカラーペーパーを絵焼プリ
ント後、自動現像機で連続補充処理(ランニング
処理と称する)した。この時の処理工程と処理液
の組成は以下の通りである。
基準処理工程
〔1〕 発色現像 33℃ 3分30秒
〔2〕 漂白定着 33℃ 1分30秒
〔3〕 安定化処理 25〜30℃ 3分
〔4〕 乾燥 75〜80℃ 約2分
処理液組成
<発色現像タンク液>
ベンジルアルコール 15ml
エチレングリコール 15ml
亜硫酸カリウム 2.0g
臭化カリウム 0.7g
塩化ナトリウム 0.2g
炭酸カリウム 30.0g
ヒドロキシルアミン硫酸塩 3.0g
ポリリン酸(TPPS) 2.5g
3−メチル−4−アミノ−N−エチル−N−
(β−メタンスルホンアミドエチル)−アニリン
硫酸塩 5.5g
螢光増白剤(4,4′−ジアミノスチルベンズ
スルホン酸誘導体) 1.0g
水酸化カリウム
2.0g水を加えて全量を1とする。
<発色現像補充液>
ベンジルアルコール 20ml
エチレングリコール 20ml
亜硫酸カリウム 3.0g
炭酸カリウム 30.0g
ヒドロキシルアミン硫酸塩 4.0g
ポリリン酸(TPPS) 3.0g
3−メチル−4−アミノ−N−エチル−N−
(β−メタンスルホンアミドエチル)−アニリン
硫酸塩 7.0g
螢光増白剤(4,4′−ジアミノスチルベンズ
スルホン酸誘導体) 1.5g
水酸化カリウム 3.0g
水を加えて全量を1とする。
<漂白定着タンク液>
エチレンジアミンテトラ酢酸第2鉄アンモニ
ウム2水塩 60g
エチレンジアミンテトラ酢酸 3g
チオ硫酸アンモニウム(70%溶液) 100ml
亜硫酸アンモニウム(40%溶液) 27.5ml
炭酸カリウムまたは氷酢酸でPH7.1に調整す
ると共に、水を加えて全量を1とする。
<漂白定着補充液A>
エチレンジアミンテトラ酢酸第2鉄アンモニ
ウム2水塩 260g
炭酸カリウム 42g
水を加えて全量を1にする。
この溶液のPHは6.7±0.1である。
<漂白定着補充液B>
チオ硫酸アンモニウム(70%溶液) 500ml
亜硫酸アンモニウム(40%溶液) 250ml
エチレンジアミンテトラ酢酸 17g
氷酢酸 85ml
水を加えて全量を1とする。
この溶液のPHは4.6±0.1である。
自動現像機に上記の発色現像タンク液、漂白定
着タンク液および下記安定液を満し、カラーペー
パーを処理しながら3分間隔毎に上記した発色現
像補充液と漂白定着補充液A、Bと安定補充液を
定量カツプを通じて補充しながらランニングテス
トを行なつた。補充量はカラーペーパー1m2当り
それぞれ発色現像タンクへの補充量として324ml、
漂白定着タンクへの補充量として漂白定着補充液
A、B各々25ml、安定化処理タンクへの補充量と
して下記安定液を150ml補充した。
なお、自動現像機の安定化処理浴槽は感光材料
の流れの方向に第1槽〜第3槽となる安定槽と
し、最終槽から補充を行ない、最終槽からオーバ
ーフローをその前段の槽へ流入させ、さらにこの
オーバーフロー液をまたその前段の槽に流入させ
る多槽向流方式とした。
漂白定着補充液A、Bの合計使用量が漂白定着
液のタンク容量の3倍となるまで連続処理を行な
つた。
安定液
1−ヒドロキシエチリデン1,1−ジホスホン
酸 2.0g
塩化ビスマス(塩酸を含む50%水溶液) 0.6g
塩化カルシウム 0.4g
5−クロロ−2−メチル−4−イソチアゾリン
−3−オン 0.05g
2−オクチル−4−イソチアゾリン−3−オン
0.05g
オルトフエニルフエノール 0.04g
アンモニウム水(25%) 5.0g
水を加えて1とし、硫酸と水酸化カリウムで
PHを7.5に調整した。
連続処理した後、実施例1の自作ペーパーに段
階露光を与え試料とした。安定浴の1〜3槽をそ
れぞれ全て表−5の如くPHを変化させた。PHの調
整は水酸化カリウムと硫酸で行なつた。
次に各々の安定液で試料を処理した。処理後安
定液を捨て水道水に入れ換え別の試料を処理し、
各々の試料について実施例1と同様に画像保存の
強性劣化試験を行なつた。その結果を表−5に示
す。また試料の処理直後の未露光部のステインに
ついて445nmで反射率を測定し、目視により黒
色部分(Dmax)のブルーイングを太陽光下で観
察した。その結果を表−5に示す。[Table] As is clear from Table 4, Formulation No. (8) does not contain any ammonium salt, and Formulation No. (8) contains ammonium but the pH of the stabilizer is lower than the range of the present invention.
In both cases (9), discoloration due to preservation of red reflection density increases, which is undesirable. On the other hand, in the case of Nos. (10) to (13) where ammonium salt is present and the desired value is within the range of the present invention, the stain and red reflection density are at desirable values, and it is confirmed that fading due to storage is prevented. Recognize. However, No. (14), which was treated with a stabilizer with a pH of 11.5, had a large swelling and softening of the emulsion film, which was undesirable as it could cause scratches and malfunctions. Example 3 After the color paper produced in Example 1 was printed, it was subjected to continuous replenishment processing (referred to as running processing) using an automatic developing machine. The treatment steps and composition of the treatment liquid at this time are as follows. Standard processing steps [1] Color development 33°C 3 minutes 30 seconds [2] Bleach-fixing 33°C 1 minute 30 seconds [3] Stabilization 25-30°C 3 minutes [4] Drying 75-80°C approximately 2 minutes Processing solution Composition <Color development tank liquid> Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4-amino -N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide
Add 2.0g water to bring the total amount to 1. <Color developer replenisher> Benzyl alcohol 20ml Ethylene glycol 20ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g Polyphosphoric acid (TPPS) 3.0g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 7.0g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.5g Potassium hydroxide 3.0g Add water to bring the total amount to 1. <Bleach-fix tank solution> Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid At the same time, add water to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260g Potassium carbonate 42g Add water to bring the total amount to 1. The pH of this solution is 6.7±0.1. <Bleach-fix replenisher B> Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Add water to bring the total volume to 1. The pH of this solution is 4.6±0.1. Fill an automatic processor with the above color developer tank liquid, bleach-fix tank liquid and the following stabilizer, and add the above color developer replenisher and bleach-fix replenisher A and B to the stabilizer every 3 minutes while processing the color paper. A running test was conducted while replenishing the replenisher through a metered cup. The amount of replenishment is 324ml per 1m2 of color paper to the color development tank.
The bleach-fix tank was replenished with 25 ml each of bleach-fix replenishers A and B, and the stabilization tank was replenished with 150 ml of the following stabilizing solution. The stabilization processing baths of the automatic processor are the first to third tanks in the direction of the flow of the photosensitive material, and the final tank is replenished, and the overflow from the final tank is allowed to flow into the preceding tank. Furthermore, a multi-tank countercurrent system was adopted in which this overflow liquid also flows into the preceding tank. Continuous processing was carried out until the total amount of bleach-fix replenishers A and B used was three times the tank capacity of the bleach-fix solution. Stabilizer 1-Hydroxyethylidene 1,1-diphosphonic acid 2.0g Bismuth chloride (50% aqueous solution containing hydrochloric acid) 0.6g Calcium chloride 0.4g 5-chloro-2-methyl-4-isothiazolin-3-one 0.05g 2-octyl -4-isothiazolin-3-one
0.05g Ortho-phenylphenol 0.04g Ammonium water (25%) 5.0g Add water to make 1, and add sulfuric acid and potassium hydroxide.
The pH was adjusted to 7.5. After continuous processing, the self-made paper of Example 1 was subjected to stepwise exposure and used as a sample. The pH of each of the stabilizing baths 1 to 3 was changed as shown in Table 5. The pH was adjusted with potassium hydroxide and sulfuric acid. Samples were then treated with each stabilizing solution. After processing, discard the stabilizing solution and replace it with tap water, process another sample,
A strength deterioration test for image storage was conducted on each sample in the same manner as in Example 1. The results are shown in Table-5. In addition, the reflectance of the stain in the unexposed area of the sample immediately after processing was measured at 445 nm, and bluing in the black area (Dmax) was visually observed under sunlight. The results are shown in Table-5.
【表】
表−5からも明らかなように、比較例の水洗処
理による処方No.(14)では、即日でのステインや
ブルーイングは問題ないのに対し、保存でのイエ
ローステインの発生と赤色退色率が大きく、又安
定化処理でアンモニウム塩を含むが安定液のPHが
低い処理による処方No.(15)では、即日でのステ
インが大きくかつ目視によるブルーイングも著し
く大い、又保存によるイエローステインは問題な
いものの赤色濃度退色率が大きく好ましくない。
一方、本発明による安定液で処理した処方No.
(16)〜(18)の場合では、即日での増感色素の
附着に起因するイエローステインや螢光増白剤の
附着によるブルーイングはもちろん、保存でのイ
エローステインの発生もなく、又、赤色濃度の退
色も極めて小さく好ましい値となつている事がわ
かる。
実施例 4
化合物例に示した本発明の例示シアンカプラー
(7)、(11)、(22)、(45)、(53)及び下記比較例
シ
アンカプラー6gを高沸点有機溶媒ジブチルフタ
レート3g、ならびに酢酸エチル18g、また必要
に応じてジメチルホルムアミドを必要量加えた混
合溶液を60℃に加熱して溶解した後、これをアル
カノールB(アルキルナフタレンスルホネート、
デユポン社製)の5%水溶液10mlを含む5%ゼラ
チン水溶液100mlに混合し、超音波分散機で乳化
分散して分散液を得た。
次に表−1に示すシアンカプラーが銀に対して
10モル%になる様に分散液を塩臭化銀乳剤(塩化
銀10モル%含有)に添加し、更に硬膜剤として
1,2−ビス(ビニルスルホニル)エタンをゼラ
チン1g当り12mgの割合で加え、ポリエチレンコ
ーテツドペーパー支持体上に塗布銀量が5mg/
100cm2になるように塗布した。かくして得られた
カラーペーパー試料を常法により700nmの干渉
フイルターを設置し、ウエツジ露光した後、実施
例3のランニング処理した安定液の1〜3槽をPH
3.5とPH7.5に水酸化カリウム及び硫酸を用いて調
整し、実施例3に示される処理公定と処理液で処
理した。試料の赤色反射濃度約1.0の部分を測定
した後、太陽光に250時間放置し、前回測定部分
を再度測定し、シアン色素の退色率を求め、表−
6に示した。
比較用カプラーとしては次のものを使用した。
[Table] As is clear from Table 5, with formulation No. (14) that was washed with water as a comparative example, there was no problem with staining or bluing on the same day, but yellow staining and red coloring occurred during storage. Formula No. (15), which has a high fading rate and contains ammonium salt in the stabilization treatment but has a low pH stabilizer, has large stains on the same day and significant visual bluing, and also due to storage. Although yellow stain is not a problem, it has a large fading rate of red color density and is not preferable. On the other hand, formulation No. treated with the stabilizer according to the present invention.
In the cases of (16) to (18), there is no yellow stain caused by the attachment of the sensitizing dye on the same day or blueing due to the attachment of the fluorescent whitening agent, and no yellow stain occurs during storage. It can be seen that the fading of the red color density is also extremely small and a desirable value. Example 4 Illustrative cyan couplers of the invention shown in compound examples
(7), (11), (22), (45), (53) and the following comparative example: 6 g of cyan coupler, 3 g of high-boiling organic solvent dibutyl phthalate, 18 g of ethyl acetate, and the required amount of dimethylformamide as necessary. After heating the added mixed solution to 60°C and dissolving it, this was mixed with alkanol B (alkylnaphthalene sulfonate,
The mixture was mixed with 100 ml of a 5% aqueous gelatin solution containing 10 ml of a 5% aqueous solution (manufactured by Dupont) and emulsified and dispersed using an ultrasonic disperser to obtain a dispersion. Next, the cyan coupler shown in Table 1 is applied to silver.
The dispersion was added to a silver chlorobromide emulsion (containing 10 mol% silver chloride) so that the concentration was 10 mol%, and 1,2-bis(vinylsulfonyl)ethane was added as a hardening agent at a rate of 12 mg per 1 g of gelatin. In addition, the amount of silver coated on the polyethylene coated paper support was 5 mg/
It was applied to a thickness of 100cm2 . The thus obtained color paper sample was exposed to light using a 700 nm interference filter using a conventional method, and then 1 to 3 baths of the running-treated stabilizing solution of Example 3 were added to the PH.
3.5 and pH 7.5 using potassium hydroxide and sulfuric acid, and treated with the official treatment formula and treatment solution shown in Example 3. After measuring the part of the sample with a red reflection density of approximately 1.0, it was left exposed to sunlight for 250 hours, the previously measured part was measured again, and the fading rate of the cyan dye was determined.
6. The following couplers were used for comparison.
【表】【table】
以上の実施例から明らかなように、本発明によ
れば、明退色を防止し、かつブルーイングやステ
インの発生を防止出来、特に水洗水の低減や水洗
処理を行なわない安定化処理によつても色素画像
と仕上りに何ら影響を与えないという効果を発揮
する。
As is clear from the above examples, according to the present invention, it is possible to prevent bright color fading and the occurrence of bluing and staining, and in particular, by reducing the amount of washing water and performing stabilization treatment without washing. It also exhibits the effect of not affecting the dye image and finish in any way.
Claims (1)
処理し、漂白定着処理又は漂白処理及び定着処理
した後、3槽以上の槽で構成される処理槽で安定
化処理をするに際して、アンモニウム化合物を含
有する安定液補充液を該3槽以上の処理槽の最終
処理槽に補充し、該最終処理槽のオーバーフロー
液を処理される写真材料の移動方向とは逆方向に
順次オーバーフローさせ、安定化処理工程の上記
最終処理槽での安定液のPHを5.0以上にし、該最
終処理槽での安定液のアンモニウム化合物の濃度
を0.002〜1.0mol/にすると共に上記安定化処
理工程の最終処理槽の直前の処理槽のアンモニウ
ム化合物濃度が該最終処理槽のアンモニウム化合
物よりも低く、かつ上記直前の処理槽の前の処理
槽のアンモニウム化合物濃度が該直前の処理槽の
アンモニウム化合物濃度よりも低いことを特徴と
するハロゲン化銀カラー写真感光材料の処理方
法。 2 前記漂白定着処理又は前記定着処理した後、
水洗処理を行わないで安定化処理することを特徴
とする特許請求の範囲第1項記載のハロゲン化銀
カラー写真感光材料の処理方法。[Scope of Claims] 1. When a silver halide color photographic light-sensitive material is subjected to color development processing, bleach-fixing processing, or bleaching and fixing processing, and then stabilization processing is performed in a processing tank consisting of three or more tanks. , replenishing the final processing tank of the three or more processing tanks with a stabilizing solution replenisher containing an ammonium compound, and causing the overflow liquid of the final processing tank to sequentially overflow in a direction opposite to the moving direction of the photographic material to be processed. , the pH of the stabilizing solution in the final treatment tank of the stabilization treatment step is set to 5.0 or higher, the concentration of ammonium compound in the stabilizing solution in the final treatment tank is set to 0.002 to 1.0 mol/, and the final treatment of the stabilization treatment step is The ammonium compound concentration in the treatment tank immediately before the treatment tank is lower than the ammonium compound concentration in the final treatment tank, and the ammonium compound concentration in the treatment tank immediately before the treatment tank is lower than the ammonium compound concentration in the treatment tank immediately before the treatment tank. A method for processing a silver halide color photographic light-sensitive material characterized by low levels of silver halide. 2 After the bleach-fixing treatment or the fixing treatment,
A method for processing a silver halide color photographic material according to claim 1, characterized in that a stabilization treatment is performed without performing a water washing treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5869383A JPS59184345A (en) | 1983-04-05 | 1983-04-05 | Method for processing color photographic sensitive silver halide material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5869383A JPS59184345A (en) | 1983-04-05 | 1983-04-05 | Method for processing color photographic sensitive silver halide material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59184345A JPS59184345A (en) | 1984-10-19 |
JPH0434738B2 true JPH0434738B2 (en) | 1992-06-08 |
Family
ID=13091619
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5869383A Granted JPS59184345A (en) | 1983-04-05 | 1983-04-05 | Method for processing color photographic sensitive silver halide material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59184345A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61148448A (en) * | 1984-12-21 | 1986-07-07 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
JPS61149949A (en) * | 1984-12-25 | 1986-07-08 | Konishiroku Photo Ind Co Ltd | Method for controlling processing solution for silver halide photographic sensitive material |
JPS61151649A (en) * | 1984-12-26 | 1986-07-10 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
JPS61151650A (en) * | 1984-12-26 | 1986-07-10 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
JPS61170742A (en) * | 1985-01-24 | 1986-08-01 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photographic sensitive material |
JPH07120026B2 (en) * | 1985-05-15 | 1995-12-20 | コニカ株式会社 | Processing method of silver halide color photographic light-sensitive material |
JPH0627936B2 (en) * | 1985-06-11 | 1994-04-13 | コニカ株式会社 | Dye image stabilization method |
JPS62249156A (en) * | 1986-04-22 | 1987-10-30 | Konika Corp | Rinse-replacing stable solution and method for processing silver halide color photographic sensitive material using this solution |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5814834A (en) * | 1981-07-21 | 1983-01-27 | Konishiroku Photo Ind Co Ltd | Method for stabilizing silver halide color photosensitive material |
-
1983
- 1983-04-05 JP JP5869383A patent/JPS59184345A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5814834A (en) * | 1981-07-21 | 1983-01-27 | Konishiroku Photo Ind Co Ltd | Method for stabilizing silver halide color photosensitive material |
Also Published As
Publication number | Publication date |
---|---|
JPS59184345A (en) | 1984-10-19 |
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