JPH0558185B2 - - Google Patents
Info
- Publication number
- JPH0558185B2 JPH0558185B2 JP7721585A JP7721585A JPH0558185B2 JP H0558185 B2 JPH0558185 B2 JP H0558185B2 JP 7721585 A JP7721585 A JP 7721585A JP 7721585 A JP7721585 A JP 7721585A JP H0558185 B2 JPH0558185 B2 JP H0558185B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- atom
- formula
- hydrogen atom
- 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 69
- 238000005406 washing Methods 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 150000001768 cations Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 47
- 238000011282 treatment Methods 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000012545 processing Methods 0.000 description 27
- 230000000087 stabilizing effect Effects 0.000 description 23
- 239000002738 chelating agent Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- 230000006641 stabilisation Effects 0.000 description 15
- 238000011105 stabilization Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000003429 antifungal agent Substances 0.000 description 4
- 229940121375 antifungal agent Drugs 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- UOMQUZPKALKDCA-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UOMQUZPKALKDCA-UHFFFAOYSA-K 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 239000008237 rinsing water Substances 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- TXVWTOBHDDIASC-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diamine Chemical class C=1C=CC=CC=1C(N)=C(N)C1=CC=CC=C1 TXVWTOBHDDIASC-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 2
- GODCLGCOHHTLHX-UHFFFAOYSA-N 3,3-diphosphonopropanoic acid Chemical compound OC(=O)CC(P(O)(O)=O)P(O)(O)=O GODCLGCOHHTLHX-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
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 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 Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical group NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZZGUZQXLSHSYMH-UHFFFAOYSA-N ethane-1,2-diamine;propanoic acid Chemical compound NCCN.CCC(O)=O.CCC(O)=O ZZGUZQXLSHSYMH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- 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 2
- 125000001624 naphthyl group Chemical group 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229960004257 sulfaguanidine Drugs 0.000 description 2
- BRBKOPJOKNSWSG-UHFFFAOYSA-N sulfaguanidine Chemical compound NC(=N)NS(=O)(=O)C1=CC=C(N)C=C1 BRBKOPJOKNSWSG-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 2
- SIACJRVYIPXFKS-UHFFFAOYSA-N (4-sulfamoylphenyl)methylazanium;chloride Chemical compound Cl.NCC1=CC=C(S(N)(=O)=O)C=C1 SIACJRVYIPXFKS-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- KAMCBFNNGGVPPW-UHFFFAOYSA-N 1-(ethenylsulfonylmethoxymethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)COCS(=O)(=O)C=C KAMCBFNNGGVPPW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HILAYQUKKYWPJW-UHFFFAOYSA-N 1-dodecylguanidine Chemical compound CCCCCCCCCCCCN=C(N)N HILAYQUKKYWPJW-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- BOXPXLFVWVZCIU-UHFFFAOYSA-N 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)(C(O)=O)P(O)(O)=O BOXPXLFVWVZCIU-UHFFFAOYSA-N 0.000 description 1
- QZTKDVCDBIDYMD-UHFFFAOYSA-N 2,2'-[(2-amino-2-oxoethyl)imino]diacetic acid Chemical compound NC(=O)CN(CC(O)=O)CC(O)=O QZTKDVCDBIDYMD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RDMIJQCFPQDYQN-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC(O)=CC=C1O RDMIJQCFPQDYQN-UHFFFAOYSA-N 0.000 description 1
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- 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
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003152 propanolamines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 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
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- XNRNJIIJLOFJEK-UHFFFAOYSA-N sodium;1-oxidopyridine-2-thione Chemical compound [Na+].[O-]N1C=CC=CC1=S XNRNJIIJLOFJEK-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229960005379 succinylsulfathiazole Drugs 0.000 description 1
- 229960002673 sulfacetamide Drugs 0.000 description 1
- SKIVFJLNDNKQPD-UHFFFAOYSA-N sulfacetamide Chemical compound CC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 SKIVFJLNDNKQPD-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960002135 sulfadimidine Drugs 0.000 description 1
- 229960000654 sulfafurazole Drugs 0.000 description 1
- 229960002597 sulfamerazine Drugs 0.000 description 1
- QPPBRPIAZZHUNT-UHFFFAOYSA-N sulfamerazine Chemical compound CC1=CC=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 QPPBRPIAZZHUNT-UHFFFAOYSA-N 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- 229960005158 sulfamethizole Drugs 0.000 description 1
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229960002211 sulfapyridine Drugs 0.000 description 1
- GECHUMIMRBOMGK-UHFFFAOYSA-N sulfapyridine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CC=CC=N1 GECHUMIMRBOMGK-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001975 sulfisomidine Drugs 0.000 description 1
- YZMCKZRAOLZXAZ-UHFFFAOYSA-N sulfisomidine Chemical compound CC1=NC(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 YZMCKZRAOLZXAZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- AKUNSPZHHSNFFX-UHFFFAOYSA-M tributyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC AKUNSPZHHSNFFX-UHFFFAOYSA-M 0.000 description 1
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
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(以
下、感光材料と略す。)の処理方法に関し、特に
漂白定着処理後の多量の水を使用する水洗工程に
代えて少量の水溶液を使用する水洗代替処理液で
処理する方法に関するものである。
〔従来の技術〕
近年、感光材料の現像処理を自動的に且つ連続
的に行うフオトフイニツシヤーにおいて、環境保
全と水資源の問題が重要視されており、漂白定着
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。
このため多量に使用される水洗水を減少する方
法が提供されており、例えば水洗槽を少段構成し
て水を逆流させることにより水洗水を多量にする
技術として、***特許第2920222号明細書及び技
術文献としてのS.R.Goldwasser、“Water flow
rate in immersion−washing of motionpicture
film“Jour.SMPTE、64 248〜253、May(1955)
が知られている。更に水洗工程を省略し実質的に
水洗を行わずに安定化処理(水洗代替処理)する
方法が特開昭57−8543、同58−14834号、同58−
134636号公報等に記載されている。
このような安定化処理の前浴はチオ硫酸塩を含
有しており、かかるチオ硫酸塩を含有する漂白定
着液の後に、多量の水洗水による水洗処理ではな
く、前記したような少量の水洗水による予備水洗
や、多段向流少量水洗水を行つた場合や、少量の
補充量により補充しながら処理する水洗代替処理
を行つた場合では、これらの処理に用いられる処
理液の滞留時間が非常に長くなる。そのために保
存経時により処理液中に微細な黒色沈澱物が生じ
やすくなる欠点がある。
このような欠点を除くため水洗工程における硫
化物の沈澱を防止する方法として、例えば米国特
許第4059446号明細書によれば水洗浴にポリアル
キレンオキサイド系非イオン性活性剤を添加する
技術がある。更に、特開昭57−8542号等に記載の
如く、水洗水にイソチアゾリンやベンツインチア
ゾリン化合物を添加する技術がある。
しかしながら、防止効果は充分ではなく、更に
水洗水や安定化処理液に滞留に対して問題のない
技術が望まれている。
また、水洗代替処理の補充量を減少させると、
水洗代替安定液の最終槽の漂白定着成分濃度が増
大し、感光材料の未露光部分の長期保存によるイ
エローステインが増加する欠点がある。
〔発明の目的〕
従つて本発明の第1の目的は、水洗代替安定液
の経時保存によつて生じる黒色沈澱を防止するハ
ロゲン化銀カラー写真感光材料の処理方法を提供
することにある。
本発明の第2の目的は、水洗代替安定液の補充
量を減少しても、感光材料の未露光部分の長期保
存によるイエローステインの増加を防止できるハ
ロゲン化銀カラー写真感光材料の処理方法を提供
することにある。
〔発明の構成〕
本発明の目的は、ハロゲン化銀カラー写真感光
材料を発色現像後、漂白定着液で処理し、引き続
いて水洗代替安定液で処理する方法において、該
ハロゲン化銀カラー写真感光材料が下記一般式
〔〕、〔〕、〔〕又は〔〕で表される化合物
の少なくとも1つを含有し、かつ該水洗代替安定
液の補充量がハロゲン化銀カラー写真感光材料1
m2あたり60〜500mlであり、該漂白定着液が、遊
離酸の分子量が280未満である有機酸第2鉄錯塩、
チオ硫酸塩及び亜硫酸塩を主成分として含有する
ことを特徴とするハロゲン化銀カラー写真感光材
料の処理方法によつて達成される。
一般式〔〕
〔式中、R、R1、R2、R3、R4及びR5は各々水素
原子、ハロゲン原子、ヒドロキシ基、アルキル
基、アルコキシ基、スルホ基または−
NHR′SO3Mを表わす。ここでR′はアルキレン基
を、Mはカチオン基を表わす。〕
一般式〔〕
〔式中、R6及びR6′は各々水素原子、アルキル
基、アリール基、または複素環基を表わす。R7
及びR7′は各々ヒドロキシ基、アルコキシ基、シ
アノ基、トリフロロメチル基、−COOR8、−
CONHR8、−NHCOR8、ウレイド基、イミノ基、
アミノ基、炭素数1〜4のアルキル基で置換され
た置換アミノ基または
[Technical Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials), and in particular uses a small amount of an aqueous solution instead of a washing step that uses a large amount of water after bleach-fixing. The present invention relates to a method of processing with a water washing alternative treatment liquid. [Prior Art] In recent years, environmental conservation and water resource issues have become important in photofinishers, which automatically and continuously develop photosensitive materials. It is desired to reduce or eliminate the large amount of washing water used. For this reason, methods have been proposed to reduce the amount of washing water that is used in large quantities. For example, West German Patent No. 2920222 discloses a technique for increasing the amount of washing water by configuring the washing tank in small stages and causing the water to flow backwards. and technical literature SRGoldwasser, “Water flow
rate in immersion−washing of motionpicture
film “Jour.SMPTE, 64 248-253, May (1955)
It has been known. Furthermore, a method of omitting the water washing step and performing stabilization treatment (alternative treatment for water washing) without substantially performing water washing is disclosed in JP-A Nos. 57-8543, 58-14834, and 58-
It is described in Publication No. 134636, etc. The pre-bath for such stabilization treatment contains thiosulfate, and the bleach-fix solution containing such thiosulfate is followed by a small amount of rinsing water as described above, rather than a rinsing treatment with a large amount of rinsing water. When pre-rinsing with water, multi-stage counter-flow small amount rinsing water, or alternative rinsing treatment in which processing is performed while replenishing with a small amount of replenishment, the residence time of the processing liquid used in these treatments is very short. become longer. Therefore, there is a drawback that fine black precipitates are likely to form in the processing solution over time during storage. As a method of preventing sulfide precipitation in the water washing step in order to eliminate such drawbacks, there is a technique, for example, according to US Pat. No. 4,059,446, in which a polyalkylene oxide type nonionic activator is added to the water washing bath. Furthermore, as described in JP-A No. 57-8542, there is a technique of adding isothiazoline or benzinthiazoline compounds to the washing water. However, the prevention effect is not sufficient, and there is a need for a technology that does not cause problems with retention in washing water or stabilizing treatment liquid. In addition, if the amount of replenishment of the flushing alternative treatment is reduced,
There is a disadvantage that the concentration of bleach-fixing components in the final bath of the water-washing alternative stabilizer increases, and yellow stains due to long-term storage of unexposed areas of the photosensitive material increase. [Object of the Invention] Therefore, the first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which prevents black precipitate caused by storage of a water-washing substitute stabilizer over time. A second object of the present invention is to provide a method for processing silver halide color photographic light-sensitive materials that can prevent an increase in yellow stain due to long-term storage of unexposed areas of the light-sensitive material even if the amount of water-washing substitute stabilizer replenishment is reduced. It is about providing. [Structure of the Invention] An object of the present invention is to provide a method for processing a silver halide color photographic material after color development with a bleach-fixing solution and subsequently with a water-washing substitute stabilizing solution. contains at least one compound represented by the following general formula [], [], [] or [], and the replenishment amount of the water-washing alternative stabilizer is silver halide color photographic light-sensitive material 1.
60 to 500 ml per m2 , and the bleach-fix solution is an organic acid ferric complex salt whose free acid has a molecular weight of less than 280;
This is achieved by a method for processing a silver halide color photographic material, which is characterized by containing thiosulfate and sulfite as main components. General formula [] [In the formula, R, R 1 , R 2 , R 3 , R 4 and R 5 are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, a sulfo group or a -
Represents NHR′SO 3 M. Here, R' represents an alkylene group, and M represents a cation group. ] General formula [ ] [In the formula, R 6 and R 6 ' each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R 7
and R 7 ' are each a hydroxy group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR 8 , -
CONHR 8 , -NHCOR 8 , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or
【式】(ここ
でpおよびqは1または2を表わし、Xは酸素原
子、硫黄原子または−CH2−基を表わす。)で表
される環状アミノ基を表わす。R8は水素原子、
アルキル基またはアリール基を表わす。Lはメチ
ン基を表わす。nは0、1または2を表わす。m
およびm′は各々0または1を表わす。〕
一般式〔〕
〔式中、rは1〜3の整数を表わし、Wは酸素原
子または硫黄原子を表わし、Lはメチン基を表わ
し、R9〜R12は各々水素原子、アルキル基、アリ
ール基、アラルキル基または複素環基を表わし、
R9〜R12のうち少なくとも1つは水素原子以外の
置換基である。〕
一般式〔〕
〔式中、lは1または2の整数を表わし、Lはメ
チン基を表わし、R13はアルキル基、アリール基
または複素環基を表わす。R14およびR15は各々
ヒドロキシ基、アルキル基、アルコキシ基、シア
ノ基、トリフロロメチル基、−COOR8、−
CONHR8、−NHCOR8、ウレイド基、イミノ基、
アミノ基、炭素数1〜4のアルキル基で置換され
た置換アミノ基またはIt represents a cyclic amino group represented by the formula: (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom or a -CH 2 - group). R8 is a hydrogen atom,
Represents an alkyl group or an aryl group. L represents a methine group. n represents 0, 1 or 2. m
and m' each represent 0 or 1. ] General formula [ ] [In the formula, r represents an integer of 1 to 3, W represents an oxygen atom or a sulfur atom, L represents a methine group, and R 9 to R 12 are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or represents a heterocyclic group,
At least one of R 9 to R 12 is a substituent other than a hydrogen atom. ] General formula [ ] [In the formula, l represents an integer of 1 or 2, L represents a methine group, and R 13 represents an alkyl group, an aryl group, or a heterocyclic group. R 14 and R 15 are each a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR 8 , -
CONHR 8 , -NHCOR 8 , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or
【式】(ここ
でpおよびqは1または2を表わし、Xは酸素原
子、硫黄原子または−CH2−基を表わす。)で表
される環状アミノ基を表わす。R8は水素原子、
アルキル基またはアリール基を表わす。R16水素
原子、アルキル基、塩素原子またはアルコキシ基
を表わす。〕
以下、本発明について詳述する。
従来、漂白定着液に用いる漂白剤として有機酸
第2鉄塩が知られており、また、チオ硫酸塩を定
着剤として使用し、保恒剤として亜硫酸塩を使用
している通常の漂白定着液では有機酸第2鉄塩と
してエチレンジアミン四酢酸第2鉄が使用されて
いる。エチレンジアミン四酢酸第2鉄を用いる理
由は漂白定着液の脱銀性、復色性及び液保存性に
おいて好ましいからである。
従つて、漂白定着液による処理工程に続く多量
の水を使用する水洗工程を少量の水溶液で処理す
る水洗代替安定液による処理工程に置き替えた処
理はエチレンジアミン四酢酸第2鉄を漂白剤とし
て用いる漂白定着液による処理工程の次の浴とし
て用いられている。そしてこのような系におい
て、前記のような水洗代替安定液の経時保存性が
悪く、処理された感光材料の未露光部分に長期保
存でイエローステインが生ずるという問題が発生
している。
本発明者はこの問題について鋭意研究を重ねた
結果、驚くべきことに、漂白定着液の漂白剤とし
て遊離酸の分子量が280未満の有機酸第2鉄塩を
用いた場合に上記技術課題が解決されることを見
出だし本発明に至つたものである。
更に、該有機酸第2鉄塩が一般式〔〕で表さ
れる化合物であるとき本発明の効果が特に顕著で
あること、及びこのような系において感光材料に
一般式〔〕ないし〔〕で表される化合物を含
有させることが上記イエローステインの防止に対
して極めて好ましいことを見出したものである。
本発明に用いられる有機酸第2鉄錯塩の分子量
が280未満の遊離酸として、アミノポリカルボン
酸化合物及びポリホスホン酸化合物が好ましいも
のとして挙げられ、これらのうち前者がより好ま
しく、特に一般式〔〕で表される化合物が好ま
しい。
一般式〔〕
式中、Aは水素原子、炭素数1〜4のアルキル
基、炭素数1〜4のヒドロキシアルキル基、炭素
数1〜4のアルコキシ基又は炭素数1〜4のカル
ボシアル基を表す。特に好ましいAはメチル基、
ヒドロキシエチル基、カルボキシメチル基、ブチ
ル基及び水素原子である。
ポリホスホン酸化合物には
It represents a cyclic amino group represented by the formula: (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom or a -CH 2 - group). R8 is a hydrogen atom,
Represents an alkyl group or an aryl group. R 16 represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group. ] Hereinafter, the present invention will be explained in detail. Conventionally, organic acid ferric salts have been known as bleaching agents used in bleach-fix solutions, and ordinary bleach-fix solutions use thiosulfate as a fixing agent and sulfite as a preservative. In this method, ferric ethylenediaminetetraacetic acid is used as a ferric salt of an organic acid. The reason for using ferric ethylenediaminetetraacetate is that it is preferable in terms of desilvering properties, recoloring properties, and solution storage stability of the bleach-fix solution. Therefore, a process in which the washing process that uses a large amount of water following the bleach-fixing solution process is replaced with a process using a washing substitute stabilizing solution that uses a small amount of aqueous solution uses ferric ethylenediaminetetraacetic acid as a bleaching agent. It is used as a bath following the bleach-fix treatment step. In such a system, a problem arises in that the above-mentioned water-washing substitute stabilizer has poor storage stability over time, and yellow stains occur in unexposed areas of the processed light-sensitive material during long-term storage. As a result of intensive research into this problem, the present inventor surprisingly found that the above technical problem was solved when an organic acid ferric salt with a free acid molecular weight of less than 280 was used as a bleaching agent in a bleach-fix solution. This discovery led to the present invention. Furthermore, when the organic acid ferric salt is a compound represented by the general formula [], the effect of the present invention is particularly remarkable, and in such a system, the photosensitive material is a compound represented by the general formula [] to []. It has been found that the inclusion of the compound shown above is extremely preferable for preventing the above-mentioned yellow stain. As the free acid having a molecular weight of less than 280 in the organic acid ferric complex salt used in the present invention, aminopolycarboxylic acid compounds and polyphosphonic acid compounds are preferably mentioned, and among these, the former is more preferable, especially the general formula [] Compounds represented by are preferred. General formula [] In the formula, A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carbosial group having 1 to 4 carbon atoms. Particularly preferred A is a methyl group,
They are a hydroxyethyl group, a carboxymethyl group, a butyl group, and a hydrogen atom. For polyphosphonic acid compounds
【式】(ここで、B及びB1は
各々水素原子、ヒドロキシ基、アルキル基又はア
ミノ基を表す。)が包含される。
上記遊離酸の代表例を次にあげるがこれらに限
定されない。(括孤内は分子量)
(1) ニトリロトリ酢酸(191.14)
(2) ニトリロジ酢酸プロピオン酸(205.17)
(3) イミノジ酢酸(133.10)
(4) イミノジメチレンホスホン酸(204.98)
(5) N−メチルイミノジ酢酸(147.063)
(6) イミノジプロピオン酸(161.074)
(7) N−(3,3−ジメチルブチル)イミノジ酢
酸(217.12)
(8) ヒドロキシエチルイミノジプロピオン酢酸
(205.10)
(9) ヒドロキシプロピルイミノジ酢酸(191.09)
(10) メトキシエチルイミノジ酢酸(191.09)
(11) N−(カルバモイルメチル)イミノジ酢酸
(190.08)
(12) アミノエチルイミノジ酢酸(179.08)
(13) β−(N−トリメチルアンモニウム)エチ
ルイミノジ酢酸陽イオン(219.12)
(14) ホスホノメチルイミノジ酢酸(227.04)
(15) ホスホノエチルイミノジ酢酸(241.2)
(16) スルホエチルイミノジ酢酸(241.14)
(17) ヒドロキシエチルイミノジ酢酸(177.16)
(18) ジヒドロキシエチルグリシン(163.17)
(19) ニトリロトリプロピオン酸(233.22)
(20) エチレンジアミンジ酢酸(176.17)
(21) カルボキシエチルイミノジ酢酸(205.08)
(22) N,N′−エチレンジアミンジ酢酸
(172.08)
(23) N,N′−ジ(ヒドロキシエチル)エチレン
ジアミンジ酢酸(264.13)
(24) エチレンジアミンジプロピオン酸(277.15)
(25) ヒドロキシエチルエチレンジアミントリ酢
酸(278.26)
(26) 1−ヒドロキシエチリンデン−1,1−ジ
ホスホン酸(205.97)
(27) ヒドロキシメチリデンジホスホン酸
(191.96)
(28) 1−アミノエチリデン−1,1−ジホスホ
ン酸(203.98)
(29) 1−アミノプロピリデン−1,1−ジホス
ホン酸(217.99)
本発明に用いられる有機酸第2鉄錯塩は1種
で、また2種以上を組合わせて用いることができ
る。その濃度は処理する感光材料の銀量及びハロ
ゲン化銀組成等によつて選択する必要があるが、
通常使用液1当たり2×10-2〜2モルの範囲が
好ましく、より好ましくは0.1〜1.0モルの範囲で
ある。
本発明における漂白定着液は、漂白剤として上
記有機酸第2鉄錯塩以外の化合物例えば遊離酸の
分子量が280以上の有機酸第2鉄錯塩を含有する
ことができるが、その量は漂白剤前量の50モル%
以下であり、10モル%以下であることが好まし
い。
本発明の漂白定着液に含有させるチオ硫酸塩は
好ましくはアルカリ金属塩及びアンモニウム塩で
あり、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が挙げられる。その
濃度は5g/以上、溶解できる範囲でよいが好
ましくは40〜250g/の範囲である。
本発明において漂白定着液に含有させる亜硫酸
塩としては、亜硫酸ナトリウム、亜硫酸カリウ
ム、亜硫酸アンモニウム、重亜硫酸アンモニウ
ム、重亜硫酸カリウム、重亜硫酸ナトリウム、メ
タ重亜硫酸ナトリウム、メタ重酸カリウム、メタ
重亜硫酸アンモニウム、ハイドロサルフアイト、
グルタルアルデヒドビス重亜硫酸ナトリウム、コ
ハク酸アルデヒドビス重亜硫酸ナトリウム等の化
合物が上げられるが亜硫酸イオンを放出する化合
物であればいかなるものでもよい。
上記亜硫酸塩は漂白定着液中に1×10-3〜0.1
モル/含有させることが好ましい。
本発明における漂白定着液が上記有機酸第2鉄
錯塩、チオ硫酸塩及び亜硫酸塩を主成分として含
有するとは、該漂白定着液に含まれる漂白剤全量
の50%モル以上が上記有機酸第2鉄錯塩であるこ
と、及びこれらの3種の成分以外は漂白定着液に
通常用いられる添加剤を含有しても差支えないこ
とを意味する。すなわち、本発明の漂白定着液に
は硼酸、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PH緩衝剤を単独
あるいは2種以上組み上わせて含有せしめること
ができる。さらにまた、各種の蛍光増白剤や消泡
剤あるいは界面活性剤を含有せしめることもでき
る。
また、ヒドロキシルアミン、ヒドラジン、アル
デヒド化合物の重亜硫酸付加物等の保恒剤、アミ
ノポリカルボン酸等の有機キレート化剤あるいは
ニトロアルコール、硝酸塩等の安定剤、メタノー
ル、ジメチルスルアミド、ジメチルスルホキシド
等の有機溶媒等を適宜含有せしめることができ
る。また、特開昭46−280号、特公昭45−8506号、
同46−556号、ベルギー特許第770910号、特公昭
45−8836号、同53−9854号、特開昭54−71634及
び同49−42349号等に記載されている種々の漂白
促進剤を添加することができる。
本発明における漂白定着液のPHは4.0以上で用
いられるが、好ましくはPH5.0以上PH9.5以上であ
り、より好ましくはPH6.0以上PH8.5以下である。
処理の温度は80℃以下で発色現像槽の処理液温度
よりも3℃以上、好ましくは5℃以上低い温度で
使用されるが、望ましくは55℃以下で蒸発等を抑
えて使用する。
本発明において漂白定着で処理し、引き続いて
水洗代替安定液で処理するとは、安定化処理最前
槽に持ち込まれる定着液または漂白定着液の該槽
における濃度が1/200以下にならない程度であれ
ば、単槽または複数槽向流方式による極く短時間
のリンス処理、補助水洗および水洗促進浴などの
処理を行つてもよいということである。
本発明において水洗代替安定液による処理とは
漂白定着液による処理後直ちに安定化処理してし
まい実質的に水洗処理を行わない安定化処理のた
めの処理を指し、該安定化処理に用いる処理液を
水洗代替安定液といい、処理層を安定浴又は安定
層という。
本発明において安定化処理は一槽または多槽で
問題なく使用することができるが好ましくは1槽
〜4槽である。
本発明は安定浴への水洗代替安定液の補充量が
少ない場合に効果が大きく、該補充量が処理され
る感光材料の単位面積当たりの前浴からの持ち込
み量の2〜20倍の範囲において本発明の効果が特
に顕著である。
本発明の水洗水代替安定液には防黴剤を含有さ
せることが好ましい。好ましく用いられる防黴剤
は、ヒドロキシ安息香酸系化合物、アルキルフエ
ノール系化合物、チアゾール系化合物、ピリジン
系化合物、グアニジン系化合物、カーバメント系
化合物、モルホリン系化合物、四級ホスホニウム
系化合物、アンモニウム系化合物、尿素系化合
物、イソキサゾール系化合物、プロパノールアミ
ン系化合物、スルフアミド誘導体及びアミノ酸系
化合物である。
前記ヒドロキシ安息香酸系化合物は、ヒドロキ
シ安息香酸及びヒドロキシ安息香酸のエステル化
合物としてメチルエステル、エチルエステル、プ
ロピルエステル、ブチルエステル等があるが、好
ましくはヒドロキシ安息香酸のn−ブチルエステ
ル、イソブチルエステル、プロピルエステルであ
り、より好ましくは前記ヒドロキシ安息香酸エス
テル3種の混合物である。
アルキルフエノール系化合物は、アルキル基が
C1〜6のアルキル基が置換基として待つ化合物
であり、この他に好ましいフエノール系化合物は
オルトフエノール、オルトシクロヘキシフエノー
ルである。
チアゾール系化合物は、五員環に窒素原子及び
イオウ原子を持つ化合物であり、好ましくは1,
2−ベンツイチアゾリン3−オン、2−メチル−
4−イソチアゾリン3−オン、2−オクチル−4
−イソチアゾリン3−オン、5−クロロ−2−メ
チル−4−イソチアゾリン3−オン、2−(4−
チアゾリル)ベンツイミダゾールである。ピリジ
ン系化合物は具体的には2,6−ジメチルピリジ
ン、2,4,6−トリメチルピリジン、ソジウム
−2−ピリジンチオール−1−オキサイド等があ
るが、好ましくはソジウム−ピリジンチオール−
1−オキサイドである。
グアニジン系化合物は具体的にはシクロヘキシ
ジン、ポリヘキサメチレングアニジン塩酸塩、ド
デシルグアニジン塩酸塩があり、好ましくは、ド
デシルグアニジン及びその塩である。
カーバメイト系化合物は具体的にはメチル−1
−(ブチルカーバモイル)−2−ベンズイミダゾー
ルカーバメイト、メチルイミダゾールカーバメイ
ト等がある。
モルホリン系化合物は具体的には4−(2−ニト
ロブチル)モルホリン、4−(3−ニトロブチル)
モルホリン等がある。
四級ホスホニウム系化合物はテトラアルキルホ
スホニウム塩、テトラアルコキシホスホニウム塩
等があるが、好ましくはテトラアルキルホスホニ
ウム塩更に具体的な好ましい化合物はトリ−nブ
チル−テトラデシルホスホニウムクロライド、ト
リ−フエニル・ニトロフエニルホスホニウムクロ
ライドがある。
四級アンモニウム化合物は具体的にはベンザル
コニウム塩、ベンゼトニウム塩、テトラアルキル
アンモニウム塩、アルキルビリジニウム塩があ
り、具体的にはドデシルジメチルベンジルアンモ
ニウムクロライド、ジデシルジメチルアンモニウ
ムクロイド、ラウリルピリジニウムクロイド等が
ある。
尿素系化合物は具体的にはN−(3,4−ジク
ロロフエニル)−N′−(4−クロロフエニル)尿
素、N−(3−トリフルオロメチル−4−クロロ
フエニル)−N′−(4−クロロフエニル)尿素等
がある。
イソキサゾール系化合物は具体的には3−ヒド
ロキシ−5−メチル−イソキサゾール等がある。
プロパノールアミン系化合物は、n−プロパノ
ール類とイソプロパノール類があり、具体的には
DL−2−ベンジルアミノ−1−プロパノール、
3−ジエチルアミノ−1−プロパノール、2−ジ
メチルアミノ−2−メチル−1−プロパノール、
3−アミノ−1−プロパノール、イソプロパノー
ルアミノ、ジイソプロパノールアミン、NN−ジ
メチル−イソプロパノールアミン等がある。
スルフアミド誘導体は具体的にはフツ素化スル
フアミド、4−クロロ−3,5−ジニトロベンゼ
ンスルフアミド、スルフアニルアミド、アセトス
ルフアミン、スルフアピリジン、スルフアグアニ
ジン、スルフアチアゾール、スルフアジアジン、
スルフアメラジン、スルフアメタジン、スルフア
イソオキサゾール、ホモスルフアミン、スルフイ
ソミジン、スルフアグアニジン、スルフアメチゾ
ール、スルフアピラジン、フタルイソスルフアチ
アゾール、スクシニルスルフアチアゾール等があ
る。
アミノ酸系化合物は具体的にはN−ラウリル−
β−アラニンがある。
なお上記防黴剤のなかで本発明において好まし
く用いられる化合物はピリジン系化合物、グアニ
ジン系化合物及び四級アンモニウム系化合物であ
る。水洗代替処理液への防黴剤の添加量は、水洗
代替処理1リツトル当たり0.002g〜50gの範囲
が好ましく、より好ましくは0.005g〜10gの範
囲である。本発明における水洗代替安定液は鉄イ
オンに対するキレート安定度定数が8以上である
キレート剤を含有することが好ましい。
ここにキレート安定度定数とは、
L・G・Sill′en・A・E・Martell著、
“Stability Constants of Metel−ion
Complexes”、The Chemical Socity、London
(1964)、S.Chaberek・A.E.Martell著、
“Organic Sequestering Agents”、Wiley(1959)
等により一般に知られた定数を意味する。
本発明において鉄イオンに対するキレート安定
度定数が8以上であるキレート剤としては、有機
カルボン酸キレート剤、有機リン酸キレート剤、
無機リン酸キレート剤、ポリヒドロキシ化合物等
が挙げられる。尚上記鉄イオンとは第2鉄イオン
(Fe3+)を意味する。
本発明において第2鉄イオンとのキレート安定
度定数が8以上であるキレート剤の具体的化合物
例としては、下記化合物が挙げられるが、これら
に限定されるものではない。即ちエチレンジアミ
ンジオルトヒドロキシフエニル酢酸、ジアミノプ
ロパン四酢酸、ニトリロ三酢酸、ヒドロキシエチ
ルエチレンジアミン三酢酸、ジヒドロキシエチル
グリシン、エチレンジアミン二酢酸、エチレンジ
アミン二プロピオン酸、イミノ二酢酸、ジエチレ
ントリアミン五酢酸、ヒドロキシエチルイミノ二
酢酸、ジアミノプロパノール四酢酸、トランスシ
クロヘキサンジアミン四酢酸、エチレンジアミン
四酢酸、グリコールエーテルジアミン四酢酸、エ
チレンジアミンテトラキスメチレンホスホン酸、
ニトリロトリメチレンホスホン酸、1−ヒドロキ
シエチリデン−1,1−ジホスホン酸、1,1−
ジホスホノエタン−2−カルボン酸、2−ホスホ
ノブタン−1,2,4−トリカルボン酸、1−ヒ
ドロキシ−1−ホスホノプロパン−1,2,3−
トリカルボン酸、カテコール−3,5−ジスルホ
ン酸、ピロリン酸ナトリウム、テトラポリリン酸
ナトリウム、ヘキサメタリン酸ナトリウムが挙ら
れ、特に好ましくは、A−PO3M2(式中、Mは水
素原子、ナトリウム原子、カリウム原子、アンモ
ニウム等のカチオンを表す。Aは無機又は有機の
基を表す。)で表される化合物であり、例えば、
2−ホスホノブタン−1,2,4−トリカルボン
酸、1,1−ジホスホノエタン−2−カルボン
酸、ピロリン酸、テトラポリリン酸ナトリウム、
ヘキサメタリン酸ナトリウム、ポリリン酸ナトリ
ウム、ニトリロトリメチレンホスホン酸、エチレ
ンジアミンテトラホスホン酸、ジエチレントリア
ミンペンタホスホン酸、1−ヒドロキシプロピリ
デン−1,1−ジホスホン酸、1−アミノエチリ
デン−1,1−ジホスホン酸、1−ヒドロキシエ
チリデン−1,1−ジホスホン酸やこれらの塩が
挙げられる。上記キレート剤の使用量は水洗代替
1当たり、0.01〜50g、好ましくは0.05〜20g
の範囲である。
本発明における水洗代替安定液は前記キレート
剤と併用して金属塩を含有することが好ましい。
かかる金属塩としては、Ba、Ca、Ce、Co、In、
La、Mn、Ni、Pb、Sn、Zn、Ti、Zr、Mg、Al
又はSrの金属塩であり、ハロゲン化物、水酸化
物、硫酸塩、炭酸塩、リン酸塩、酢酸塩等の無機
塩又は水溶性キレート剤として供給できる。使用
量としては安定液1当たり1×10-4〜1×10-1
モルの範囲であり、好ましくは4×10-4〜2×
10-2モルの範囲である。
この他に通常知られている安定浴添加剤として
は、例えば蛍光増白剤、界面活性剤、有機硫黄化
合物、オニウム塩、ホルマリン、クロム等の硬膜
剤、各種金属塩などがあるが、これら化合物の添
加量は本発明による安定浴のPHを維持するに必要
でかつカラー写真画像の保存時の安定性と沈澱の
発生に対し悪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わせで使用してもさ
しつかえない。
安定化処理に際しての処理温度は、15℃〜60
℃、好ましくは20℃〜45℃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10分以下、好ましくは5分以下で
あり、複数槽安定化処理の場合は前段槽ほど短時
間で処理し、後段槽ほど処理時間が長いことが好
ましい。特に前槽の20%〜50%増しの処理時間で
順次処理する事が望ましい。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、表面洗浄
などは必要に応じて任意に行うことはできる。
本発明に係る安定化処理工程での水洗代替安定
液の供給方法は、多層カウンターカレント方式に
した場合、後浴に供給して前浴からオーバーフロ
ーさせることが好ましい。
本発明における水洗代替安定液による処理は前
記一般式〔〕、〔〕、〔〕または〔〕で表わ
される化合物の存在下に行う。
一般式〔〕
式中、R、R1、R2、R3、R4およびR5は各々水
素原子;ハロゲン原子(例えば、塩素原子、臭素
原子、フツ素原子);ヒドロキシ基;アルキル基
(炭素数1〜4が好ましい。例えば、メチル基、
エチル基、プロピル基);アルコキシ基(炭素数
1〜4が好ましい。例えば、メトキシ基、エトキ
シ基、プロポキシ基);−SO3M;または−
NHR′SO3M基を表わす。ここで、R′はアルキレ
ン基(例えばメチレン基、エチレン基)を表わ
し、Mはカチオンであり、水素原子;アルカリ金
属原子(例えば、ナトリウム原子、カリウム原
子);アンモニウム、有機アンモニウム塩(例え
ば、ピリジニウム、ピペリジニウム、トリエチル
アンモニウム、トリエタノールアミン等を表わ
す。
前記一般式〔〕で表わされる化合物の代表的
な具体例を次に示すが、該化合物がこれらによつ
て限定されるものではない。
(A−1)
(A−2)
(A−3)
(A−4)
(A−5)
(A−6)
一般式〔〕
式中、R6およびR6′は各々水素原子またはそれ
ぞれ置換されていてもよいアルキル基、アリール
基もしくは複素環基を表わし、このアルキル基は
直鎖、分岐、環状の何れでもよく、好ましくは炭
素数1〜4であり、例えばエチル基、β−スルホ
エチル基等が挙げられる。
上記アリール基は、例えばフエニル基、ナフチ
ル基等で、スルホ基(2価の有機基、例えばフエ
ニレンオキシ基、アルキレン基、アルキレンアミ
ノ基、アルキレンオキシ基等を介してアリール基
と結合していてもよい。)、カルボキシ基、炭素数
1〜5のアルキル基(例えばメチル基、エチル
基)、ハロゲン原子(例えば塩素原子、臭素原子
等)、炭素数1〜5のアルコキシ基(例えばメト
キシ基、エトキシ基等)、フエノキシ基等を有す
ることができ、例えば4−スルホフエニル基、4
−(δ−スルホブチル)フエニル基、3−スルホ
フエニル基、2,5−ジスルホフエニル基、3,
5−ジスルホフエニル基、6,8−ジスルホ−2
−ナフチル基、4,8−ジスルホ−2−ナフチル
基、3,5−ジカルボキシフエニル基、4−カル
ボキシフエニル基、4−(4−スルホフエノキシ)
フエニル基、4−(2−スルホエチル)フエニル
基、3−(スルホメチルアミノ)フエニル基、4
−(2−スルホエトキシ)フエニル基等を挙げる
ことができる。
上記複素環基としては、例えば、2−(6−ス
ルホ)ベンズチアゾリル基、2−(6−スルホ)
ベンズオキサゾリル基等を挙げることができ、ハ
ロゲン原子(例えば、フツ素原子、塩素原子、臭
素原子など)、アルキル基(例えば、メチル基、
エチル基など)、アリール基(例えばフエニル基
など)、カルボキシル基、スルホ基、ヒドロキシ
基、アルコキシ基(例えばメトキシ基など)、ア
リールオキシ基(例えばフエノキシ基など)等の
置換基を有していてもよい。
R7およびR7′は各々ヒドロキシ基;アルコキシ
基(炭素数1〜4が好ましい。例えばメトキシ
基、エトキシ基、イソプロポキシ基、n−ブトキ
シ基);置換アルコキシ基、たとえばハロゲン原
子又は炭素数2までのアルコキシ基で置換された
炭素数1〜4のアルコキシ基(たとえばβ−クロ
ロエトキシ基、β−メトキシエトキシ基);シア
ノ基;トリフロロメチル基;−COOR8;−
CONHR8;−NHCOR8(R8は水素原子;炭素数
1〜4のアルキル基(好ましくは炭素数1〜4で
ある。);またはアリール基、例えばフエニル基、
ナフチル基を表わし、該アルキル基およびアリー
ル基は置換基としてスルホ基またはカルボキシ基
を有してもよい。);ウレイド基;イミノ基;アミ
ノ基;炭素数1〜4のアルキル基で置換された置
換アミノ基(たとえば、エチルアミノ基、ジメチ
ルアミノ基、ジエチルアミノ基、ジ−n−ブチル
アミノ基);または[Formula] (where B and B 1 each represent a hydrogen atom, a hydroxy group, an alkyl group, or an amino group) are included. Representative examples of the above-mentioned free acids are listed below, but the invention is not limited thereto. (Molecular weight in parentheses) (1) Nitrilotriacetic acid (191.14) (2) Nitrilodiacetic acid propionic acid (205.17) (3) Iminodiacetic acid (133.10) (4) Iminodimethylenephosphonic acid (204.98) (5) N-methyliminodiacetic acid Acetic acid (147.063) (6) Iminodipropionic acid (161.074) (7) N-(3,3-dimethylbutyl)iminodiacetic acid (217.12) (8) Hydroxyethyliminodipropionic acid (205.10) (9) Hydroxypropylimino Diacetic acid (191.09) (10) Methoxyethyliminodiacetic acid (191.09) (11) N-(carbamoylmethyl)iminodiacetic acid (190.08) (12) Aminoethyliminodiacetic acid (179.08) (13) β-(N-trimethyl ammonium)ethyliminodiacetic acid cation (219.12) (14) Phosphonomethyliminodiacetic acid (227.04) (15) Phosphonoethyliminodiacetic acid (241.2) (16) Sulfoethyliminodiacetic acid (241.14) (17) Hydroxyethylimino Diacetic acid (177.16) (18) Dihydroxyethylglycine (163.17) (19) Nitrilotripropionic acid (233.22) (20) Ethylenediaminediacetic acid (176.17) (21) Carboxyethyliminodiacetic acid (205.08) (22) N, N' -Ethylenediaminediacetic acid (172.08) (23) N,N'-di(hydroxyethyl)ethylenediaminediacetic acid (264.13) (24) Ethylenediaminedipropionic acid (277.15) (25) Hydroxyethylethylenediaminetriacetic acid (278.26) (26) 1-Hydroxyethylidene-1,1-diphosphonic acid (205.97) (27) Hydroxymethylidene diphosphonic acid (191.96) (28) 1-Aminoethylidene-1,1-diphosphonic acid (203.98) (29) 1-Amino Propylidene-1,1-diphosphonic acid (217.99) The organic acid ferric complex salt used in the present invention can be used alone or in combination of two or more. The concentration needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed.
The amount is preferably in the range of 2×10 -2 to 2 mol, more preferably 0.1 to 1.0 mol per liquid used. The bleach-fix solution in the present invention may contain, as a bleaching agent, a compound other than the above organic acid ferric complex salt, such as an organic acid ferric complex salt whose free acid has a molecular weight of 280 or more. 50 mol% of the amount
It is preferably 10 mol% or less. The thiosulfate contained in the bleach-fix solution of the present invention is preferably an alkali metal salt or an ammonium salt, such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate. The concentration may be 5 g/or more, as long as it can be dissolved, but is preferably in the range of 40 to 250 g/. In the present invention, the sulfite to be contained in the bleach-fix solution includes sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, hydrosulfite,
Compounds such as sodium glutaraldehyde bisbisulfite and sodium succinic aldehyde bisbisulfite are mentioned, but any compound that releases sulfite ions may be used. The above sulfite is contained in the bleach-fix solution at a concentration of 1×10 -3 ~0.1
It is preferable to contain it in mol/mol. The bleach-fix solution in the present invention contains the organic acid ferric complex salt, thiosulfate, and sulfite as main components. This means that it is an iron complex salt, and that there is no problem in containing additives commonly used in bleach-fix solutions other than these three components. That is, the bleach-fix solution of the present invention contains various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. They can be contained singly or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, dimethylsulfamide, dimethylsulfoxide, etc. An organic solvent or the like can be appropriately contained. Also, JP-A-46-280, JP-A-45-8506,
No. 46-556, Belgian Patent No. 770910, Tokukosho
Various bleach accelerators described in JP-A-45-8836, JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The pH of the bleach-fix solution used in the present invention is 4.0 or higher, preferably PH5.0 or higher and PH9.5 or higher, and more preferably PH6.0 or higher and PH8.5 or lower.
The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation. In the present invention, processing with bleach-fixing and then processing with a water-washing substitute stabilizing solution means that the concentration of the fixing solution or bleach-fixing solution brought into the first stabilization tank does not become 1/200 or less. This means that treatments such as extremely short-time rinsing treatment using a single tank or multi-tank countercurrent system, auxiliary water washing, and washing promotion bath may be performed. In the present invention, the treatment with a water-washing substitute stabilizing solution refers to a stabilizing treatment that is performed immediately after the treatment with a bleach-fixing solution and does not substantially require a water-washing treatment, and the processing solution used for the stabilization treatment. is called a water washing alternative stabilizing solution, and the treated layer is called a stabilizing bath or stable layer. In the present invention, the stabilization treatment can be carried out in one tank or in multiple tanks without any problem, but preferably one to four tanks. The present invention is most effective when the amount of water-washing substitute stabilizing solution replenished into the stabilizing bath is small, and the amount of replenishment is in the range of 2 to 20 times the amount brought in from the previous bath per unit area of the photographic material to be processed. The effects of the present invention are particularly remarkable. It is preferable that the washing water substitute stabilizer of the present invention contains an antifungal agent. Preferably used antifungal agents include hydroxybenzoic acid compounds, alkylphenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbament compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, and urea. These are compound-based compounds, isoxazole-based compounds, propanolamine-based compounds, sulfamide derivatives, and amino acid-based compounds. The hydroxybenzoic acid compounds include hydroxybenzoic acid and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester, isobutyl ester, and propyl ester of hydroxybenzoic acid. It is an ester, and more preferably a mixture of the three hydroxybenzoic acid esters. Alkylphenol compounds have an alkyl group
It is a compound having a C1-6 alkyl group as a substituent, and other preferable phenolic compounds are orthophenol and orthocyclohexyphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,
2-Benzithiazolin 3-one, 2-methyl-
4-isothiazolin 3-one, 2-octyl-4
-Isothiazolin 3-one, 5-chloro-2-methyl-4-isothiazolin 3-one, 2-(4-
thiazolyl)benzimidazole. Specific examples of pyridine compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, and sodium-2-pyridinethiol-1-oxide, but preferably sodium-pyridinethiol-1-oxide.
1-oxide. Specific examples of the guanidine compound include cyclohexidine, polyhexamethylene guanidine hydrochloride, and dodecylguanidine hydrochloride, with dodecylguanidine and its salts being preferred. Carbamate compounds are specifically methyl-1
-(Butylcarbamoyl)-2-benzimidazole carbamate, methylimidazole carbamate, etc. Specifically, morpholine compounds include 4-(2-nitrobutyl)morpholine, 4-(3-nitrobutyl)
Morpholine etc. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetraalkylphosphonium salts are preferred.More specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride, tri-phenyl/nitrophenyl. There is phosphonium chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridinium salts, including dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, etc. There is. Specifically, the urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(3-trifluoromethyl-4-chlorophenyl)-N'-(4- chlorophenyl) urea, etc. Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Propanolamine compounds include n-propanols and isopropanols, and specifically,
DL-2-benzylamino-1-propanol,
3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol,
Examples include 3-amino-1-propanol, isopropanol-amino, diisopropanolamine, NN-dimethyl-isopropanolamine, and the like. Sulfamide derivatives specifically include fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, sulfanilamide, acetosulfamine, sulfapyridine, sulfaguanidine, sulfathiazole, sulfadiazine,
Examples include sulfamerazine, sulfamethazine, sulfisoxazole, homosulfamine, sulfisomidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole, and the like. Specifically, the amino acid compound is N-lauryl-
There is β-alanine. Among the above-mentioned antifungal agents, compounds preferably used in the present invention are pyridine compounds, guanidine compounds, and quaternary ammonium compounds. The amount of the antifungal agent added to the water-washing alternative treatment solution is preferably in the range of 0.002 g to 50 g, more preferably in the range of 0.005 g to 10 g per liter of the water-washing alternative treatment. It is preferable that the water washing substitute stabilizing solution in the present invention contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. What is the chelate stability constant here? Written by L.G. Sill'en and A.E. Martell,
“Stability Constants of Metel−ion
Complexes”, The Chemical Society, London
(1964), written by S.Chaberek・AE Martell,
“Organic Sequestering Agents”, Wiley (1959)
etc. means a commonly known constant. In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent,
Examples include inorganic phosphoric acid chelating agents and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe 3+ ). In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid. , diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid,
Nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-
Diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-
Tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate are mentioned, and particularly preferred are A-PO 3 M 2 (wherein M is a hydrogen atom, a sodium atom, Represents a cation such as a potassium atom or ammonium. A represents an inorganic or organic group.) For example,
2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, pyrophosphoric acid, sodium tetrapolyphosphate,
Sodium hexametaphosphate, sodium polyphosphate, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1- Examples include hydroxyethylidene-1,1-diphosphonic acid and salts thereof. The amount of the above chelating agent used is 0.01 to 50 g, preferably 0.05 to 20 g per 1 water washing alternative.
is within the range of The water washing substitute stabilizing solution in the present invention preferably contains a metal salt in combination with the chelating agent.
Such metal salts include Ba, Ca, Ce, Co, In,
La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg, Al
or a metal salt of Sr, which can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate, or a water-soluble chelating agent. The amount used is 1×10 -4 to 1×10 -1 per stabilizer.
molar range, preferably 4×10 −4 to 2×
It is in the range of 10 -2 mol. Other commonly known stabilizing bath additives include optical brighteners, surfactants, organic sulfur compounds, onium salts, formalin, hardeners such as chromium, and various metal salts. The amount of the compound to be added is determined by the amount necessary to maintain the pH of the stabilizing bath according to the present invention, and the amount of the compound to be added is within the range that does not adversely affect the stability of the color photographic image during storage and the occurrence of precipitation. It is okay to use it in The processing temperature during stabilization treatment is 15°C to 60°C.
℃, preferably in the range of 20℃ to 45℃. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 10 minutes or less, preferably 5 minutes or less. In the case of multiple tank stabilization treatment, the earlier tanks are treated in a shorter time, and the later tanks are treated in a shorter time. Preferably, the treatment time is long. In particular, it is desirable to perform sequential processing with 20% to 50% longer processing time than in the previous tank. After the stabilization treatment according to the present invention, there is no need for any water rinsing treatment, but rinsing by rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary. When the method for supplying the water-washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multilayer countercurrent method, it is preferable to supply it to the after bath and overflow from the front bath. The treatment with the water-washing substitute stabilizing solution in the present invention is carried out in the presence of the compound represented by the general formula [ ], [ ], [ ] or [ ]. General formula [] In the formula, R, R 1 , R 2 , R 3 , R 4 and R 5 are each a hydrogen atom; a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom); a hydroxy group; an alkyl group (having 1 to 1 carbon atoms); 4 is preferred. For example, methyl group,
ethyl group, propyl group); alkoxy group (preferably 1 to 4 carbon atoms; for example, methoxy group, ethoxy group, propoxy group); -SO 3 M; or -
Represents the NHR′SO 3 M group. Here, R' represents an alkylene group (e.g. methylene group, ethylene group), M is a cation, hydrogen atom; alkali metal atom (e.g. sodium atom, potassium atom); ammonium, organic ammonium salt (e.g. pyridinium , piperidinium, triethylammonium, triethanolamine, etc. Representative specific examples of the compound represented by the general formula [] are shown below, but the compound is not limited thereto. (A -1) (A-2) (A-3) (A-4) (A-5) (A-6) General formula [] In the formula, R 6 and R 6 ' each represent a hydrogen atom or an optionally substituted alkyl group, aryl group, or heterocyclic group, and this alkyl group may be linear, branched, or cyclic, and is preferably It has 1 to 4 carbon atoms, and examples thereof include ethyl group and β-sulfoethyl group. The above aryl group is, for example, a phenyl group, a naphthyl group, etc., and may be bonded to the aryl group via a sulfo group (a divalent organic group, such as a phenyleneoxy group, an alkylene group, an alkyleneamino group, an alkyleneoxy group, etc.). ), carboxy group, alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group), halogen atom (e.g. chlorine atom, bromine atom, etc.), alkoxy group having 1 to 5 carbon atoms (e.g. methoxy group, ethoxy group) etc.), phenoxy group, etc., for example, 4-sulfophenyl group, 4-sulfophenyl group,
-(δ-sulfobutyl)phenyl group, 3-sulfophenyl group, 2,5-disulfophenyl group, 3,
5-disulfophenyl group, 6,8-disulfo-2
-Naphthyl group, 4,8-disulfo-2-naphthyl group, 3,5-dicarboxyphenyl group, 4-carboxyphenyl group, 4-(4-sulfophenoxy)
Phenyl group, 4-(2-sulfoethyl)phenyl group, 3-(sulfomethylamino)phenyl group, 4
-(2-sulfoethoxy)phenyl group, etc. can be mentioned. Examples of the above heterocyclic group include 2-(6-sulfo)benzthiazolyl group, 2-(6-sulfo)
Examples include benzoxazolyl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (e.g., methyl groups,
ethyl group, etc.), aryl group (e.g., phenyl group, etc.), carboxyl group, sulfo group, hydroxy group, alkoxy group (e.g., methoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.). Good too. R 7 and R 7 ' are each a hydroxy group; an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, or a n-butoxy group); a substituted alkoxy group, such as a halogen atom or a carbon number 2 an alkoxy group having 1 to 4 carbon atoms substituted with an alkoxy group (e.g. β-chloroethoxy group, β-methoxyethoxy group); cyano group; trifluoromethyl group; -COOR 8 ;-
CONHR 8 ;-NHCOR 8 (R 8 is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms (preferably 1 to 4 carbon atoms); or an aryl group, such as a phenyl group,
It represents a naphthyl group, and the alkyl group and aryl group may have a sulfo group or a carboxy group as a substituent. ); ureido group; imino group; amino group; substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms (for example, ethylamino group, dimethylamino group, diethylamino group, di-n-butylamino group); or
以下実施例によつて本発明を具体的に説明する
が、これにより本発明の実施の態様が限定される
ものではない。
参考例 1
下記のカラーペーパーと処理液と処理工程とで
実験を行つた。
〔カラーペーパー〕
ポリエチレンコート紙支持体上に下記の各層を
支持体側から順次塗布し、感光材料を作製した。
なお、ポリエチレンコート紙としては、平均分
子量100000、密度0.95のポリエチレン200重量部
と平均分子量2000、密度0.80のポリエチレン20重
量部とを混合したものにアナターゼ型酸化チタン
を6.8重量%添加し、押し出しコーテイング法に
よつて重量170g/m2の上質紙表面に厚み0.035mm
の被覆層を形成させ、裏面にはポリエチレンのみ
によつて厚み0.040mmの被覆層を設けたものを用
いた。この支持体表面のポリエチレン被覆面上に
コロナ放電による前処理を施した後、各層を順次
塗布した。
第1層:
臭化銀80モル%を含む塩臭化銀乳剤かなる青感
性ハロゲン化銀乳剤層で該乳剤はハロゲン化銀1
モル当たりゼラチン350gを含み、ハロゲン化銀
1モル当たり下記構造の増感色素
2.5×10-3モルを用いて増感され(溶媒として
イソプロピルアルコールを使用)、ジブチルフタ
レートに溶解して分散させた2,5−ジ−t−ブ
チルハイドロキノン200mg/m2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−アミルフエノキシ)ブチルアミド]
アセトアニリドをハロゲン化銀1モル当たり2×
10-モル含み、銀量330mg/m2になるように塗布さ
れている。
第2層:
ジブチルフタレートに溶解し分散されたジ−t
−オクチルハイドロキノン300mg/m2、紫外線吸
収剤として2−(2′−ヒドロキシ−3′,5′−ジ−t
−ブチルフエニル)ベンゾトリアゾール2−
(2′−ヒドロキシ−5′−t−ブチルフエニル)ベ
ンゾトリアゾール、2−(2′−ヒドロキシ−3′−
t−ブチル−5′−メチルフエニル)−5−クロル
ベンゾトリアゾールおよび2−(2′−ヒドロキシ
−3′,5′−ジ−t−ブチルフエニル)−5−クロ
ル−ベンゾトリアゾールの混合物200mg/m2を含
有するゼラチン層でゼラチン2000mg/m2になるよ
うに塗布されている。
第3層:
臭化銀85モル%を含む塩臭化銀乳剤からなる緑
感性ハロゲン化銀乳剤層で、該乳剤はハロゲン化
銀1モル当たりゼラチン450gを含み、ハロゲン
化銀1モル当たり下記構造の増感色素
2.5×10-3モルを用いて増感され、ジブチルフ
タレートとトリクレンジルホスフエートを2:1
に混合した溶剤に溶解し分散した2,5−ジ−t
−ブチルハイドロキノン150mg/m2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−ピラゾロンをハ
ロゲン化銀1モル当たり1.5×10-1モル含有し、
銀量300mg/m2になるように塗布されている。な
お、前記一般式〔〕の例示化合物の(B−22)
を15mg/m2となるよう含有させた。
第4層:
ジオクチルフタレートに溶解し分散されたジ−
t−オクチルハイドロキノン30mg/m2及び紫外線
吸収剤として2−(2′−ヒドロキシ−3′,5′−ジ−
t−ブチルフエニル)ベンゾトリアゾール、2−
(2′−ヒドロキシ−5′−t−ブチルフエニル)ベ
ンゾトリアゾール、2−(2′−ヒドロキシ−3′−
t−ブチル−5′−メチルフエニル)−5−クロル
ベンゾトリアゾールおよび2−(2′−ヒドロキシ
−3′,5′−t−ブチルフエニル)−5−クロル−
ベンゾトリアゾールの混合物(2:1.5:1.5:
2)を500mg/m2含有するゼラチン層でゼラチン
量が2000mg/m2になるように塗布されている。
第5層:
臭化銀85モル%を含む塩臭化銀乳剤からなる赤
感性ハロゲン化銀乳剤層で、該乳剤はハロゲン化
銀1モル当たりゼラチン500gを含み、ハロゲン
化銀1モル当たり下記構造の増感色素
2.5×10-3モルを用いて増感され、ジブチルフ
タレートに溶解して分散された2,5−ジ−t−
ブチルハイドロキノンmg/m2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〕
フエノールをハロゲン化銀1モル当たり3.5×
10-1モル含有し、銀量300mg/m2になるように塗
布されている。
なお、前記一般式〔〕の例示化合物の(A−
1)を15mg/m2となるよう含有させた。
第6層:
ゼラチン層でゼラチン量が1000mg/m2となるよ
うに塗布されている。
各感光性乳剤層(第1、3、5層)に用いたハ
ロゲン化銀乳剤は特公昭46−7772号公報に記載さ
れている方法で調製し、それぞれチオ硫酸ナトリ
ウム5水和物を用いて化学増感し、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、硬膜剤としてビス(ビニル
スルホニルメチル)エーテルおよび塗布助剤とし
てサポニンを含有せしめた。
前記方法で作製したカラーペーパーを露光後、
次の処理工程と処理液により、連続処理を行つ
た。
基準処理工程
[1] 発色現像 38℃ 3分30秒
[2] 漂白定着 33℃ 1分30秒
[3] 安定化処理 25℃〜35℃ 3分
25℃〜35℃ 2分
[4] 乾燥 75℃〜100℃ 約2分
処理液組成
<発色現像タンク液>
ベンジンアルコール 15ml
エチレングリコール 〃
亜硫酸カリウム 2.0g
臭化カリウム 1.3g
塩化ナトリウム 0.2g
炭酸カリウム 30.0g
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 5.5g
蛍光増白剤(ジアミノスチルベン誘導体) 1.0
ヒドロキシルアミン硫酸塩 3.0g
1−ヒドロキシエチリデン−1,1−二ホスホン
酸 0.4g
ヒドロキシエチルイミノジ酢酸 5.0g
塩化マグネシウム、6水塩 0.7g
1,2−ジヒドロキシベンゼン−3,5−ジスル
ホ酸−二ナトリウム塩 0.2g
水を加えて1とし、KOHとH2SO4でPH10.20
とする。
<発色現像補充液>
ベンジルアルコール 20.0ml
エチレングリコール 20.0ml
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
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 7.5g
蛍光増白剤(ジアミノスチルベン誘導体) 2.5g
1−ヒドロキシエチリデン−1,1−二ホスホン
酸 0.5g
ヒドロキシエチルイミノジ酢酸 5.0g
塩化マグルシウム・6水塩 0.8g
1,2−ジヒドロキシベンゼン−3,5−ジスル
ホン酸−二ナトリウム塩 0.3g
水を加えて1とし、KOHでPH10.70とする。
<漂白定着タンク液>
表−1のキレート剤の第2鉄錯塩 80g
表−1のキレート剤 10g
チオ硫酸アンモニウム(70%溶解) 100g
亜硫酸アンモニウム(40%溶解) 27.5ml
アンモニウム水または氷酢酸で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>
表−1のキレート剤の第2鉄錯塩 300g
表−1のキレート剤 20g
炭酸カリウムまたは氷酢酸でPH6.7に調整する
と共に水を加えて全量を1とする。
<漂白鉄補充液B>
チオ硫酸アンモニウム(70%溶解) 500ml
亜硫酸アンモニウム(40%溶解) 250ml
表−1のキレート剤 15g
アンモニアまたは氷酢酸でPH5.3に調整すると
共に水を加えて全量を1とする。
<水洗代替安定タンク液および補充液>
5−クロロ−2−メチル−4−イソチアゾリン−
3−オン 0.02g
2−メチル−4−イソチアゾリン−3−オン
0.02g
エチレンジコール 1.0g
2−オクチル−4−イソチアゾリン−3−オン
0.01g
1−ヒドロキシエチリデン−1,1−二ホスホン
酸(60%水溶液) 3.0g
BiCl3(45%水溶液) 0.65g
アンモニア水(水酸化アンモニウム25%水溶液)
3.0g
ニトリロトリメチレンホスホン酸 1.5g
水で1とし、H2SO4とKOHでPH8.0とする。
自動現像機に上記の発色現像タンク液、漂白定
着タンク液および安定タンク液を満たし、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
液を通じて補充しながらランニングテストを行つ
た。補充液はカラーペーパー1m2当たりそれぞれ
発色現像タンクへの補充量として190ml、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50ml、安定化処理浴槽への補充量として水洗
代替安定補充液を190ml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
多槽向流方向とした。
水洗代替安定液の総補充量が安定タンク容量の
2倍となるまでの連続処理を表−1に示したキレ
ート剤を使用したNo.1〜No.10の各々の漂白定着液
について行い、連続処理の終了時に処理した前記
感光材料を試料として取り、また安定化処理第2
槽から安定液を採取した。また、比較として、連
続処理後、安定化処理を流水水洗として感光材料
を処理した。
得られた処理後の感光材料を80℃、70%RHの
恒温恒湿槽で3週間保存後のイエローステインを
光学濃度計PDA−65(小西六写真工業(株)製)のブ
ルー光で測定した。結果を表−1に示す。また、
採取した第1槽目の水洗代替安定処理液を1ビ
ーカーで室温放置し、黒色沈澱が発生するまでの
日数を観察し、結果を表−1示した。
The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. Reference Example 1 An experiment was conducted using the following color paper, processing liquid, and processing process. [Color Paper] The following layers were sequentially coated on a polyethylene coated paper support from the support side to prepare a photosensitive material. The polyethylene coated paper was made by adding 6.8% by weight of anatase titanium oxide to a mixture of 200 parts by weight of polyethylene with an average molecular weight of 100,000 and a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of 0.80, and extrusion coating. According to the law, the surface of high-quality paper with a weight of 170 g/m 2 and a thickness of 0.035 mm
A coating layer with a thickness of 0.040 mm was formed on the back surface of only polyethylene. The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied. 1st layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 80 mol% silver bromide, the emulsion containing 1 mol% silver halide.
Contains 350g of gelatin per mole and contains a sensitizing dye with the following structure per mole of silver halide. sensitized using 2.5×10 -3 mol (isopropyl alcohol as solvent) and 200 mg/m 2 of 2,5-di-t-butylhydroquinone dissolved and dispersed in dibutyl phthalate and α[ as yellow coupler. 4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidyl)]α-bivalyl-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)butyramide]
Acetanilide 2x per mole of silver halide
It contains 10 -mol and is coated to give a silver content of 330 mg/m 2 . 2nd layer: di-t dissolved and dispersed in dibutyl phthalate
-Octylhydroquinone 300mg/m 2 , 2-(2'-hydroxy-3',5'-di-t) as a UV absorber
-butylphenyl)benzotriazole 2-
(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-
200 mg/m 2 of a mixture of t-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole. The gelatin layer contains 2000mg/m 2 of gelatin. Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide, and having the following structure per mol of silver halide: sensitizing dye Sensitized using 2.5×10 -3 mol of dibutyl phthalate and tricrenyl phosphate at 2:1.
2,5-di-t dissolved and dispersed in a solvent mixed with
- Halogenated butylhydroquinone 150 mg/m 2 and 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone as magenta coupler Contains 1.5×10 -1 mol per mol of silver,
It is coated with a silver content of 300mg/ m2 . In addition, (B-22) of the exemplified compound of the general formula []
was contained at a concentration of 15 mg/m 2 . 4th layer: dioctyl phthalate dissolved and dispersed.
30mg/ m2 of t-octylhydroquinone and 2-(2'-hydroxy-3',5'-di-
t-butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-
t-Butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5'-t-butylphenyl)-5-chloro-
Mixture of benzotriazole (2:1.5:1.5:
A gelatin layer containing 2) at 500 mg/m 2 is applied so that the amount of gelatin is 2000 mg/m 2 . Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 500 g of gelatin per mol of silver halide, and having the following structure per mol of silver halide: sensitizing dye 2,5-di-t-sensitized using 2.5×10 -3 mol and dissolved and dispersed in dibutyl phthalate.
Butylhydroquinone mg/m 2 and 2,4-dichloro-3-methyl-6-[γ as cyan coupler
-(2,4-diamylphenoxy)butyramide]
3.5x phenol per mole of silver halide
It contains 10 -1 mol of silver and is coated with a silver content of 300 mg/m 2 . In addition, (A-
1) was contained at 15 mg/m 2 . 6th layer: Gelatin layer coated with a gelatin amount of 1000mg/m 2 . The silver halide emulsions used in each of the photosensitive emulsion layers (1st, 3rd, and 5th layers) were prepared by the method described in Japanese Patent Publication No. 46-7772, and each was prepared using sodium thiosulfate pentahydrate. Chemically sensitized and 4-hydroxy-6-methyl-1,3,3a,7 as a stabilizer
-tetrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid. After exposing the color paper produced by the above method,
Continuous treatment was performed using the following treatment steps and treatment liquids. Standard processing steps [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 33℃ 1 minute 30 seconds [3] Stabilization 25℃~35℃ 3 minutes 25℃~35℃ 2 minutes [4] Drying 75 ℃~100℃ Approximately 2 minutes Processing liquid composition <Color developing tank liquid> Benzine alcohol 15ml Ethylene glycol Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-N-ethyl -N-(β
-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (diaminostilbene derivative) 1.0 Hydroxylamine sulfate 3.0g 1-hydroxyethylidene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Chloride Magnesium, hexahydrate 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make 1, then add KOH and H 2 SO 4 to PH10.20
shall be. <Color developer replenisher> Benzyl alcohol 20.0ml Ethylene glycol 20.0ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g 3-Methyl-4-amino-N-ethyl-N-(β
-methanesulfonamidoethyl)-aniline sulfate 7.5g Fluorescent brightener (diaminostilbene derivative) 2.5g 1-hydroxyethylidene-1,1-diphosphonic acid 0.5g hydroxyethyliminodiacetic acid 5.0g Maglucium chloride hexahydrate 0.8g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Add water to make 1, and adjust the pH to 10.70 with KOH. <Bleach-fixing tank solution> 80 g of ferric complex salt of the chelating agent shown in Table 1 10 g of the chelating agent shown in Table 1 Ammonium thiosulfate (70% dissolved) 100 g Ammonium sulfite (40% dissolved) 27.5 ml Adjust pH to 7 with ammonium water or glacial acetic acid. Adjust to 1 and add water to bring the total volume to 1. <Bleach-fix replenisher> 300 g of ferric complex salt of the chelating agent shown in Table 1 20 g of the chelating agent shown in Table 1 Adjust the pH to 6.7 with potassium carbonate or glacial acetic acid, and add water to bring the total amount to 1. <Bleaching iron replenisher B> Ammonium thiosulfate (70% dissolved) 500ml Ammonium sulfite (40% dissolved) 250ml Chelating agent from Table 1 15g Adjust the pH to 5.3 with ammonia or glacial acetic acid, and add water to bring the total volume to 1. do. <Water wash alternative stable tank liquid and replenisher> 5-chloro-2-methyl-4-isothiazoline-
3-one 0.02g 2-methyl-4-isothiazolin-3-one
0.02g Ethylene dicol 1.0g 2-octyl-4-isothiazolin-3-one
0.01g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0g BiCl 3 (45% aqueous solution) 0.65g ammonia water (ammonium hydroxide 25% aqueous solution)
3.0g Nitrilotrimethylenephosphonic acid 1.5g Adjust to 1 with water and adjust to PH8.0 with H 2 SO 4 and KOH. Fill an automatic processor with the color developing tank solution, bleach-fixing tank solution, and stable tank solution mentioned above, and replenish the above-mentioned color developing replenisher, bleach-fixing replenisher A, and B at intervals of 3 minutes while processing the color paper. A running test was performed while replenishing with fluid. The amount of replenisher is 190 ml per 1 m 2 of color paper to be added to the color developing tank, and the amount of bleach-fixing replenisher A and B to be added to the bleach-fixing tank.
50 ml of each, and 190 ml of a water washing alternative stabilizing replenisher was replenished to the stabilization treatment bath. The stabilization processing baths of the automatic processor are the first to third stabilization 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, the multi-tank countercurrent direction was made such that this overflow liquid also flowed into the preceding tank. Continuous processing was performed on each bleach-fix solution No. 1 to No. 10 using the chelating agent shown in Table 1 until the total replenishment amount of the water washing substitute stabilizing solution became twice the capacity of the stabilizing tank. At the end of the processing, the processed photosensitive material was taken as a sample, and the second stabilization treatment was carried out.
A stabilizing solution was collected from the tank. For comparison, a photosensitive material was processed by washing with running water as stabilization treatment after continuous processing. After storing the resulting processed photosensitive material in a constant temperature and humidity chamber at 80°C and 70% RH for 3 weeks, the yellow stain was measured using the blue light of an optical densitometer PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.). did. The results are shown in Table-1. Also,
The collected stabilizing solution as an alternative to washing in the first tank was left in a beaker at room temperature, and the number of days until a black precipitate appeared was observed, and the results are shown in Table 1.
【表】
表−1の結果から明らかなように、分子量の大
きいキレート剤の第2鉄錯塩を漂白剤として使用
したもの(No.1〜No.4)に比較して、本発明のNo.
5〜No.10はイエローステイン、液保存性共に極め
て優れており、更に、No.5〜No.8とそれ以上との
比較から、一般式〔〕で表されるキレート剤を
使用することが極めて好ましいことがわかる。
実施例 1
参考例−1のNo.1、No.5及びNo.10の漂白定着液
を使用して、それぞれについて水洗代替補充液の
補充量を表−2に示したごとく30ml/m2、60ml/
m2、100ml/m2、250ml/m2、500ml/m2、800ml/
m2及び2/m2に変化させて連続処理を行い、参
考例1と同様の実験を行い、イエローステイン濃
度を求めた。結果を表−2に示す。
なお、感光材料によつて漂白定着タンクから水
洗代替安定タンク液に持ち込まれる液量は30ml/
m2であつた。[Table] As is clear from the results in Table 1, compared to bleaching agents using ferric complex salts of chelating agents with large molecular weights (No. 1 to No. 4), No. 1 of the present invention
5 to No. 10 are extremely excellent in both yellow stain and liquid preservability, and furthermore, from a comparison of No. 5 to No. 8 and above, it is possible to use a chelating agent represented by the general formula []. It turns out that this is extremely preferable. Example 1 Using the bleach-fixing solutions No. 1, No. 5 and No. 10 of Reference Example-1, the replenishment amount of the washing alternative replenishing solution for each was 30 ml/m 2 as shown in Table-2. 60ml/
m 2 , 100ml/m 2 , 250ml/m 2 , 500ml/m 2 , 800ml/
The same experiment as in Reference Example 1 was carried out by performing continuous treatment by changing the ratio of m 2 and 2/m 2 to determine the yellow stain concentration. The results are shown in Table-2. The amount of liquid carried from the bleach-fixing tank to the washing alternative stabilizing tank liquid due to the photosensitive material is 30 ml/
It was m2 .
【表】【table】
本発明の処理方法により、チオ硫酸塩を含む漂
白定着液による処理に引き続いて水洗代替安定液
の滞留時間が長くなるときに該液に発生する微細
な黒色沈澱の発生が防止され、また、水洗代替安
定液の補充量を減少させた処理がなされた写真画
像を長期に保存したときのイエローステインの発
生が改善される。
The treatment method of the present invention prevents the formation of fine black precipitates that occur in the water washing alternative stabilizing solution when the residence time of the solution increases following treatment with a bleach-fix solution containing thiosulfate; The occurrence of yellow stain when a photographic image processed by reducing the amount of substitute stabilizer replenishment is stored for a long period of time is improved.
Claims (1)
後、漂白定着液で処理し、引き続いて水洗代替安
定液で処理する方法において、該ハロゲン化銀カ
ラー写真感光材料が下記一般式〔〕、〔〕、
〔〕又は〔〕で表される化合物の少なくとも
1つを含有し、かつ該水洗代替安定液の補充量が
ハロゲン化銀カラー写真感光材料1m2あたり60〜
500mlであり、該漂白定着液が、遊離酸の分子量
が280未満である有機酸第2鉄錯塩、チオ硫酸塩
及び亜流酸塩を主成分として含有することを特徴
とするハロゲン化銀カラー写真感光材料の処理方
法。 一般式〔〕 〔式中、R、R1、R2、R3、R4及びR5は各々水素
原子、ハロゲン原子、ヒドロキシ基、アルキル
基、アルコキシ基、スルホ基または−
NHR′SO3Mを表わす。ここでR′はアルキレン基
を、Mはカチオン基を表わす。〕 一般式〔〕 〔式中、R6及びR6′は各々水素原子、アルキル
基、アリール基、または複素環基を表わす。R7
及びR7′は各々ヒドロキシ基、アルコキシ基、シ
アノ基、トリフロロメチル基、−COOR8、−
CONHR8、−NHCOR8、ウレイド基、イミノ基、
アミノ基、炭素数1〜4のアルキル基で置換され
た置換アミノ基または【式】(ここ でpおよびqは1または2を表わし、Xは酸素原
子、硫黄原子または−CH2−基を表わす。)で表
される環状アミノ基を表わす。R8は水素原子、
アルキル基またはアリール基を表わす。Lはメチ
ン基を表わす。nは0、1または2を表わす。m
およびm′は各々0または1を表わす。〕 一般式〔〕 〔式中、rは1〜3の整数を表わし、Wは酸素原
子または硫黄原子を表わし、Lはメチン基を表わ
し、R9〜R12は各々水素原子、アルキル基、アリ
ール基、アラルキル基または複素環基を表わし、
R9〜R12のうち少なくとも1つは水素原子以外の
置換基である。〕 一般式〔〕 〔式中、lは1または2の整数を表わし、Lはメ
チン基を表わし、R13はアルキル基、アリール基
または複素環基を表わす。R14およびR15は各々
ヒドロキシ基、アルキル基、アルコキシ基、シア
ノ基、トリフロロメチル基、−COOR8、−
CONHR8、−NHCOR8、ウレイド基、イミノ基、
アミノ基、炭素数1〜4のアルキル基で置換され
た置換アミノ基または【式】(ここ でpおよびqは1または2を表わし、Xは酸素原
子、硫黄原子または−CH2−基を表わす。)で表
される環状アミノ基を表わす。R8は水素原子、
アルキル基またはアリール基を表わす。R16は水
素原子、アルキル基、塩素原子またはアルコキシ
基を表わす。〕[Scope of Claims] 1. In a method in which a silver halide color photographic light-sensitive material is color-developed and then treated with a bleach-fixing solution, and subsequently treated with a water-washing substitute stabilizer, the silver halide color photographic light-sensitive material has the following general formula: [], [],
Contains at least one of the compounds represented by [ ] or [ ], and the replenishment amount of the water-washing alternative stabilizer is 60 to 60 per m 2 of the silver halide color photographic light-sensitive material.
500 ml, and the bleach-fix solution contains as main components an organic acid ferric complex salt, thiosulfate, and sulfite whose free acid has a molecular weight of less than 280. How materials are processed. General formula [] [In the formula, R, R 1 , R 2 , R 3 , R 4 and R 5 are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, a sulfo group or a -
Represents NHR′SO 3 M. Here, R' represents an alkylene group, and M represents a cation group. ] General formula [ ] [In the formula, R 6 and R 6 ' each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R 7
and R 7 ' are each a hydroxy group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR 8 , -
CONHR 8 , -NHCOR 8 , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or [Formula] (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom, or a -CH 2 - group) ) represents a cyclic amino group. R8 is a hydrogen atom,
Represents an alkyl group or an aryl group. L represents a methine group. n represents 0, 1 or 2. m
and m' each represent 0 or 1. ] General formula [ ] [In the formula, r represents an integer of 1 to 3, W represents an oxygen atom or a sulfur atom, L represents a methine group, and R 9 to R 12 are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or represents a heterocyclic group,
At least one of R 9 to R 12 is a substituent other than a hydrogen atom. ] General formula [ ] [In the formula, l represents an integer of 1 or 2, L represents a methine group, and R 13 represents an alkyl group, an aryl group, or a heterocyclic group. R 14 and R 15 are each a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR 8 , -
CONHR 8 , -NHCOR 8 , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or [Formula] (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom, or a -CH 2 - group) ) represents a cyclic amino group. R8 is a hydrogen atom,
Represents an alkyl group or an aryl group. R 16 represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group. ]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7721585A JPS61235837A (en) | 1985-04-10 | 1985-04-10 | Treatment of silver halide color photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7721585A JPS61235837A (en) | 1985-04-10 | 1985-04-10 | Treatment of silver halide color photographic sensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61235837A JPS61235837A (en) | 1986-10-21 |
JPH0558185B2 true JPH0558185B2 (en) | 1993-08-25 |
Family
ID=13627611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7721585A Granted JPS61235837A (en) | 1985-04-10 | 1985-04-10 | Treatment of silver halide color photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61235837A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07111569B2 (en) * | 1987-04-28 | 1995-11-29 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
JP3449435B2 (en) * | 1993-12-24 | 2003-09-22 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
-
1985
- 1985-04-10 JP JP7721585A patent/JPS61235837A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS61235837A (en) | 1986-10-21 |
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