JPH0115861B2 - - Google Patents
Info
- Publication number
- JPH0115861B2 JPH0115861B2 JP7104778A JP7104778A JPH0115861B2 JP H0115861 B2 JPH0115861 B2 JP H0115861B2 JP 7104778 A JP7104778 A JP 7104778A JP 7104778 A JP7104778 A JP 7104778A JP H0115861 B2 JPH0115861 B2 JP H0115861B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrogen atom
- bleach
- carbon atoms
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 76
- 238000012545 processing Methods 0.000 claims description 63
- -1 silver halide Chemical class 0.000 claims description 63
- 229910052709 silver Inorganic materials 0.000 claims description 61
- 239000004332 silver Substances 0.000 claims description 61
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 21
- 238000011161 development Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001340 alkali metals Chemical group 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 5
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 5
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000005336 allyloxy group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003009 phosphonic acids Chemical class 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 111
- 238000004061 bleaching Methods 0.000 description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 29
- 238000011282 treatment Methods 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000007844 bleaching agent Substances 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 229960005102 foscarnet Drugs 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 239000006260 foam Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 238000003672 processing method Methods 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- DURRSEGFTCZKMK-UHFFFAOYSA-N 1-prop-2-enylpyrrolidin-2-one Chemical compound C=CCN1CCCC1=O DURRSEGFTCZKMK-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 230000001603 reducing effect Effects 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- AWXUBHMURFEJMY-UHFFFAOYSA-N 1-n,4-n,4-n-trimethylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N(C)C)C=C1 AWXUBHMURFEJMY-UHFFFAOYSA-N 0.000 description 2
- PGNYNCTUBKSHHL-UHFFFAOYSA-N 2,3-diaminobutanedioic acid Chemical compound OC(=O)C(N)C(N)C(O)=O PGNYNCTUBKSHHL-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- JINBYESILADKFW-UHFFFAOYSA-N aminomalonic acid Chemical compound OC(=O)C(N)C(O)=O JINBYESILADKFW-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 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 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-UHFFFAOYSA-N 0.000 description 1
- KAJALVWKFPQZOO-UHFFFAOYSA-N (4-azaniumylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C=C1 KAJALVWKFPQZOO-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- JYHRLWMNMMXIHF-UHFFFAOYSA-N (tert-butylamino)boron Chemical compound [B]NC(C)(C)C JYHRLWMNMMXIHF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IBNCJAHITPFKNI-UHFFFAOYSA-N 2-(4-amino-3-methylanilino)ethanol;sulfuric acid Chemical compound OS(O)(=O)=O.CC1=CC(NCCO)=CC=C1N IBNCJAHITPFKNI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 description 1
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- GKIFPROMYBQIHS-UHFFFAOYSA-N 4-n-ethyl-2-methoxy-4-n-(2-methoxyethyl)benzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(OC)=C1 GKIFPROMYBQIHS-UHFFFAOYSA-N 0.000 description 1
- VVYWUQOTMZEJRJ-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N)C=C1 VVYWUQOTMZEJRJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- FEZVSECFBZGYQO-UHFFFAOYSA-N S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1.S(=O)(=O)(O)O.S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1 Chemical compound S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1.S(=O)(=O)(O)O.S(=O)(=O)(O)O.C(C)NC1=CC=CC=C1 FEZVSECFBZGYQO-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- MPLZNPZPPXERDA-UHFFFAOYSA-N [4-(diethylamino)-2-methylphenyl]azanium;chloride Chemical compound [Cl-].CC[NH+](CC)C1=CC=C(N)C(C)=C1 MPLZNPZPPXERDA-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- RMHJJUOPOWPRBP-UHFFFAOYSA-N naphthalene-1-carboxamide Chemical compound C1=CC=C2C(C(=O)N)=CC=CC2=C1 RMHJJUOPOWPRBP-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
- G03C7/421—Additives other than bleaching or fixing agents
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
本発明はハロゲン化銀カラー写真感光材料の処
理方法に関し、特に像様露光されたハロゲン化銀
カラー写真感光材料を発色現像後、画像銀を除去
するために過酸化水素を含有する浴で処理する工
程を有するハロゲン化銀カラー写真感光材料の処
理方法に関する。
一般に露光されたハロゲン化銀カラー写真感光
材料を現像処理してカラー画像を得るには、発色
現像工程後に、現像された銀像を酸化剤（漂白
剤）によつて漂白し、次いど定着剤によつて脱銀
し定着する工程が施される。このような漂白と定
着とを別個の処理工程で行なう方式に対し、迅速
処理化、省力化を目的として処理工程をより簡略
化し、漂白と定着とを同時に一工程で完了させる
漂白定着と称される処理方式が提案されている。
本発明者らは過酸化水素を画像補強の起らない
領域で用いる事によつて画像銀の漂白が可能であ
る事を見い出し、既に特開昭53−23633号明細書
の中で提案した。
本発明者は上記提案に係るハロゲン化銀カラー
写真材料の処理方法について更に研究を続けた結
果、該過酸化水素含有の漂白液または漂白定着液
で処理するとブリスター泡故障とよばれる、フイ
ルム膜面が泡状を呈する故障が非常に起り易い事
がわかつた。例えばブリスター故障の起らない様
な処方の過酸化水素含有漂白液または漂白定着液
を使用しても処理条件（例えばPH、湿度）が多少
でも変化すると泡故障が発生し易くなるという欠
点を生ずる。更に過酸化水素含有漂白液は、ハロ
ゲンイオン等が少量混入しても反応が著しく抑制
され、実際のランニング処理でハロゲンイオンの
混入が増加するような場合には処理数の増加とと
もに処理性が徐々に低下するという欠点も見い出
された。本発明者は鋭意研究を続けた結果、この
ような欠点のない優れたハロゲン化銀カラー写真
感光材料の処理方法を完成するに至つた。
本発明の第１の目的は、過酸化水素又は過酸化
水素を放出する化合物を用いた漂白又は漂白定着
処理をする際に漂白定着液の安定性を改良する事
にある。
本発明の第２の目的は、特に漂白定着工程を施
すハロゲン化銀カラー写真感光材料の処理におい
て、漂白定着速度を高め、処理時間を短縮化し、
しかも泡故障をおこさず画質の良好なカラー写真
画像を得ることの出来る漂白液または漂白定着液
を用いるハロゲン化銀カラー写真感光材料の処理
方法を提供する事である。
本発明の第３の目的は、単純な組成で安価な素
材を使用し、資源保護の要請に適合し、多量に処
理した場合にも漂白速度が優れ、かつ泡故障等の
欠点のないハロゲン化銀カラー写真感光材料の処
理方法を提供する事である。
本発明の第４の目的は、環境汚染の危険性が低
く公害防止の要請に適合したハロゲン化銀カラー
写真感光材料の処理方法を提供する事にある。
前記目的および以下に述べられる本発明のその
他の目的は、像様露光されたハロゲン化銀カラー
写真感光材料を発色現像後、１当り0.05〜3.0
モルの過酸化水素または過酸化水素を放出する化
合物から選ばれる少なくとも１種（以下、過酸化
水素化合物という。）、１当り0.05〜3.0モルの
下記一般式〔〕または〔〕で示される低級脂
肪族カルボン酸またはそのアルカリ金属塩（ただ
し、該カルボン酸またはそのアルカリ金属塩の金
属錯塩を除く。）から選ばれる少なくとも１種
（以下、本発明のカルボン酸という。）および１
当り0.005から1.5モルの下記一般式〔〕ないし
〔〕で示される有機ホスホン酸もしくはホスホ
ノカルボン酸またはその塩から選ばれる少なくと
も１種を含有し、かつ浴のPHが2.0〜5.5の処理浴
で処理して画像銀を除去する工程を含ませる事に
より達成される。
一般式〔〕
R1−COOH
〔式中、R1は水素原子または炭素原子数１〜３
のアルキル基であり、該アルキル基は１つ以上の
水酸基および／またはアミノ基で置換されていて
もよい。
一般式〔〕
HOOC−（R2）o1−COOH
〔式中、R2は炭素原子数１〜５のアルキレン基
またはアルケニレン基であり、該アルキレン基ま
たはアルケニレン基は１つ以上の水酸基、低級ア
ルキル基、カルボキシル基および／またはアミノ
基で置換されていてもよい。n1は０または１を示
す。〕
前記した本発明のカルボン酸はモノおよびポリ
カルボン酸であり、アルキル基の水素原子を水酸
基、低級アルキル基および／またはアミノ基で置
換したオキシカルボン酸およびアミノ酸も包含す
る。また、これらのカルボン酸はそのアルカリ金
属塩でも良い。ただし、これらのカルボン酸のう
ちアルキル基の水素原子をハロゲンで置換したハ
ロゲン酸（例えばクロル酢酸）の存在は本発明の
目的を充分に達成出来ず、そのため本発明の範囲
から除かれる。
一般式〔〕
〔式中、R1は−COOMまたは−PO（OM）2；R2
は水素原子、炭素原子数１ないし４のアルキル基
または−（CH2）oCOOM；R3は水素原子または−
（CH2）o−COOMで表わされる原子または原子群
であり、Ｍは水素原子、アルカリ金属原子または
アンモニウム基、ｍは０または１、ｎは０または
１〜４の整数を表わす。〕
一般式〔〕
R4N（CH2PO（OM）2）2
〔式中、R4は炭素原子数１〜４のアルキル基、
アリール基（これらは−OH、−OR5、−PO
（OM）2、−CH2PO（OM）2、−Ｎ（CH2PO
（OM）2）2、−COOMまたは−Ｎ（CH2COOM）2で
表わされる原子群で置換されていてもよい。）；Ｍ
は水素原子、アルカリ金属原子またはアンモニウ
ム基；R5は炭素原子数１ないし４のアルキル基
を表わす。〕
一般式〔〕
〔式中、R6およびR7はそれぞれ水素原子、−
COOMで置換されてもよい炭素原子数１ないし
３のアルキル基、ヒドロキシ基または−Ｎ(A)2で
表わされる基（ここでＡは水素原子、またはヒド
ロキシ基で置換されてもよいメチル基もしくはエ
チル基を表わす）；R8は水素原子、炭素原子数１
ないし３のアルキル基、ヒドロキシ基−PO
（OM）2または−Ｎ(D)2で表わされる基（ここでＤ
は水素原子またはヒドロキシ基で置換されてもよ
いメチル基もしくはエチル基を表わす）；Ｘは−
COOM、PO（OM）2またはヒドロキシ基；Ｙは水
素原子、−COOM、−PO（OM）2またはヒドロキシ
基（ただしR8がヒドロキシ基の時はヒドロキシ
基ではない）；Ｚは水素原子、ヒドロキシ基、−
COOMまたは−PO（OM）2；Ｍは水素原子、アル
カリ金属原子またはアンモニウム基；ｌは０ない
し２の整数を表わす。〕
一般式〔〕
〔式中、R9およびR10はそれぞれ水素原子、アル
カリ金属原子、アンモニウム基、炭素原子数１な
いし12の置換基を有してもよいアルキル基、アル
ケニル基；Ｍは水素原子、アルカリ金属原子また
はアンモニウム基を表わす。〕
一般式〔〕
〔式中、R11は炭素原子数１ないし12のアルコキ
シ基、炭素原子数２ないし12のアルキルカルボニ
ル基、炭素原子数２ないし12のジアルキルアミノ
基、アミノ基、炭素原子数１ないし21のアリロキ
シ基、炭素原子数６ないし24のアシルオキシ基；
Q1、Q2およびQ3はそれぞれヒドロキシ基、炭素
原子数１ないし24のアルコキシ基、アラルキルオ
キシ基、アリロキシ基、アミノ基、モルホリノ
基、環状アミノ基、アルキルアミノ基、ジアルキ
ルアミノ基、アリールアミノ基、アシルオキシ基
または−OMで表わされる基；Ｍは水素原子、ア
ルカリ金属原子またはアンモニウム基を表わす。〕
上記一般式〔〕ないし〔〕で示される本発
明の有機ホスホン酸、又はホスホノカルボン酸は
そのアルカリ金属塩であつても良い。
過酸化水素化合物と脂肪族カルボン酸またはそ
のアルカリ金属塩とから成る漂白液、また過酸化
水素化合物と有機ホスホン酸化合物とから成る漂
白液等では泡故障等が非常に発生し易い欠点があ
り、かつ処理液調製時にはこれらの泡故障を起さ
ない場合でも処理を長い間続けたり、あるいはわ
ずかの処理条件（例えばPH、温度）の変化が起つ
ても、前記の泡故障を起す。しかしながら、本発
明の過酸化水素化合物、本発明のカルボン酸およ
び有機ホスホン酸、ホスホノカルボン酸を組み合
せて用いることにより処理液の安定性が著るしく
向上し、泡故障が起らず、しかも漂白反応も抑制
しないことがわかつた。通常、この泡故障は過酸
化水素による銀の漂白反応の進行が急激すぎるた
めに発生するものと考えられている。従つて、こ
の泡故障を抑制しようとすると銀漂白反応をも抑
制してしまうという二律背反の関係がある。この
ため、泡故障の抑制と漂白反応を両立させる事は
非常に難しいと考えられた。しかしながら、驚く
べき事に本発明の脂肪族カルボン酸、本発明の有
機ホスホン酸、ホスホノカルボン酸および本発明
の過酸化水素を前記の本発明の濃度で用いる事に
より多少の処理条件の変化が起つても泡故障がほ
とんど起らず、かつ漂白反応も促進し、過酸化水
素とカルボン酸または過酸化水素と有機ホスホン
酸もしくはホスホノカルボン酸の２成分から成る
場合に比べて著しく漂白液の安定性が向上し、か
つブリスター抑制効果も永続的であるという全く
予想し得ない事がわかつた。
本発明の過酸化水素化合物、低級脂肪族カルボ
ン酸および有機ホスホン酸、ホスホノカルボン酸
を組み合せて用いる漂白液または漂白定着液は処
理によるハロゲンイオン等の混入によつて起る処
理性の低下現象が著しく改善できるという非常に
優れた漂白液または漂白定着液である事がわかつ
た。
特に本発明による処理液は金属で出来た処理タ
ンクを用いて処理したときも保存安定性が著しく
優れている事がわかつた。特に通常の現像機はス
テンレススケールタンクを用いているが、本発明
の処理液はこのタンク中でも高い安定性を有す
る。
本発明に用いられる漂白液または漂白定着液に
含有させる本発明の過酸化水素化合物は、例えば
市販されている過酸化水素溶液またはガス状の過
酸化水素でも良く、さらには水溶液中で過酸化水
素を放出するような化合物、例えばNaBO2・
H2O2・3H2O Na2SiO3・H2O2・H2O、過硫酸
塩、Na2CO3・2/3H2O2、Na2O2、MgO、ペルオ
キソ燐酸塩等を用いる事が出来る。
本発明において、画像銀の漂白定着を可能と
し、過酸化水素と組み合せる化合物の１つである
本発明のカルボン酸としては、例えば次のような
ものが代表的具体例としてあけられる。
(1) 蟻酸
(2) 酢酸
(3) プロピオン酸
(4) 酪酸
(5) 蓚酸
(6) マロン酸
(7) コハク酸
(8) 乳酸
(9) イソコハク酸
(10) グルタル酸
(11) アジピン酸
(12) グリコール酸
(13) クエン酸
(14) オキシクエン酸
(15) 酒石酸
(16) α−オキシ−Ｄ−酪酸
(17) オキシマロン酸
(18) リンゴ酸
(19) α−メチルリンゴ酸
(20) α−オキシグルタル酸
(21) ２，３−ジオキシプロピオン酸
(22) アスパラギン酸
(23) グルタミン酸
(24) アミノ酢酸
(25) β−アラニン
(26) セリン
(27) ジアミノコハク酸
(28) アミノマロン酸
(29) マレイン酸
これら本発明のカルボン酸は、そのアルカリ金
属塩を用いても良い。また、これらのカルボン酸
のうち、漂白性や入手し易さ、コスト等の面では
蟻酸、酢酸、プロピオン酸、クエン酸およびこれ
らのアルカリ金属塩等が最も好ましく用いられ
る。
ポリカルボン酸の場合、問題となるアルキル基
の炭素原子数はカルボキシル基とカルボキシル基
の間の炭素原子数である。即ち−COOH基と−
COOH基の間の炭素原子数が５個以下であれば、
アルキル基の側鎖として多少の炭素鎖が結合して
いても問題とならない。
次に本発明で、特に有効に用いられる有機ホス
ホン酸もしくはホスホノカルボン酸の具体例を以
下に示す。
The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material that has been imagewise exposed to light, after color development, it is treated with a bath containing hydrogen peroxide in order to remove image silver. The present invention relates to a method for processing a silver halide color photographic light-sensitive material. Generally, in order to obtain a color image by developing a silver halide color photographic material that has been exposed to light, after the color development process, the developed silver image is bleached with an oxidizing agent (bleaching agent), and then fixed. A process of desilvering and fixing is carried out using an agent. In contrast to this type of method in which bleaching and fixing are performed in separate processing steps, a method called bleach-fixing is a method that simplifies the processing steps and completes bleaching and fixing simultaneously in one step for the purpose of speeding up processing and saving labor. A processing method has been proposed. The present inventors have discovered that it is possible to bleach image silver by using hydrogen peroxide in areas where image reinforcement does not occur, and have already proposed this in JP-A-53-23633. As a result of further research into the processing method for silver halide color photographic materials according to the above proposal, the present inventor found that processing with the hydrogen peroxide-containing bleach solution or bleach-fix solution causes a problem called blister bubble failure on the film surface. It was found that failures in which bubbles appear are very likely to occur. For example, even if a hydrogen peroxide-containing bleach or bleach-fix solution is used with a formulation that does not cause blister failure, even slight changes in processing conditions (e.g., pH, humidity) may cause bubble failure. . Furthermore, with hydrogen peroxide-containing bleaching solutions, even if a small amount of halogen ions etc. are mixed in, the reaction is significantly inhibited, and if the amount of halogen ions mixed in during actual running processing increases, the processability will gradually decrease as the number of processing increases. A drawback was also found in that it decreased. As a result of intensive research, the present inventors have completed an excellent method for processing silver halide color photographic materials that does not have these drawbacks. A first object of the present invention is to improve the stability of bleach-fix solutions during bleaching or bleach-fixing processes using hydrogen peroxide or compounds that release hydrogen peroxide. A second object of the present invention is to increase the bleach-fixing speed and shorten the processing time, particularly in the processing of silver halide color photographic materials that undergo a bleach-fixing step.
Moreover, it is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material using a bleaching solution or a bleach-fixing solution, which can produce color photographic images of good quality without causing bubble failure. The third object of the present invention is to use halogenated materials with a simple composition and low cost, meet the requirements for resource conservation, have an excellent bleaching speed even when processed in large quantities, and have no drawbacks such as foam failure. The object of the present invention is to provide a method for processing silver color photographic materials. A fourth object of the present invention is to provide a method for processing silver halide color photographic materials that has a low risk of environmental pollution and meets the requirements for pollution prevention. The above object and other objects of the present invention described below are such that, after color development, a silver halide color photographic light-sensitive material subjected to imagewise exposure has a density of 0.05 to 3.0 per silver halide.
At least one type selected from moles of hydrogen peroxide or compounds that release hydrogen peroxide (hereinafter referred to as hydrogen peroxide compounds), 0.05 to 3.0 moles per 1 lower fat represented by the following general formula [] or [] At least one selected from group carboxylic acids or alkali metal salts thereof (excluding metal complex salts of the carboxylic acids or alkali metal salts thereof) (hereinafter referred to as the carboxylic acid of the present invention);
A treatment bath containing 0.005 to 1.5 mol per mol of at least one selected from organic phosphonic acids or phosphonocarboxylic acids or salts thereof represented by the following general formulas [] to [], and whose pH is 2.0 to 5.5. This is accomplished by including a step of processing to remove the image silver. General formula [] R 1 -COOH [In the formula, R 1 is a hydrogen atom or has 1 to 3 carbon atoms]
is an alkyl group, and the alkyl group may be substituted with one or more hydroxyl groups and/or amino groups. General formula [] HOOC-(R 2 ) o1 -COOH [In the formula, R 2 is an alkylene group or alkenylene group having 1 to 5 carbon atoms, and the alkylene group or alkenylene group has one or more hydroxyl group, lower alkyl may be substituted with groups, carboxyl groups and/or amino groups. n 1 indicates 0 or 1. ] The carboxylic acids of the present invention described above are mono- and polycarboxylic acids, and also include oxycarboxylic acids and amino acids in which the hydrogen atom of an alkyl group is substituted with a hydroxyl group, a lower alkyl group, and/or an amino group. Further, these carboxylic acids may be their alkali metal salts. However, among these carboxylic acids, the presence of halogen acids (for example, chloroacetic acid) in which the hydrogen atom of an alkyl group is substituted with a halogen cannot sufficiently achieve the object of the present invention, and is therefore excluded from the scope of the present invention. General formula [] [In the formula, R 1 is −COOM or −PO(OM) 2 ; R 2
is a hydrogen atom, a C1-C4 alkyl group or -(CH 2 ) o COOM; R 3 is a hydrogen atom or -
(CH 2 ) o -COOM, M is a hydrogen atom, an alkali metal atom or an ammonium group, m is 0 or 1, and n is 0 or an integer from 1 to 4. ] General formula [] R 4 N(CH 2 PO(OM) 2 ) 2 [In the formula, R 4 is an alkyl group having 1 to 4 carbon atoms,
Aryl groups (these are -OH, -OR5 , -PO
(OM) 2 , -CH 2 PO (OM) 2 , -N (CH 2 PO
(OM) 2 ) 2 , -COOM or -N(CH 2 COOM) 2 may be substituted. );M
represents a hydrogen atom, an alkali metal atom or an ammonium group; R 5 represents an alkyl group having 1 to 4 carbon atoms. ] General formula [ ] [In the formula, R 6 and R 7 are hydrogen atoms, −
An alkyl group having 1 to 3 carbon atoms which may be substituted with COOM, a hydroxy group or a group represented by -N(A) 2 (where A is a hydrogen atom, or a methyl group which may be substituted with a hydroxy group or (represents an ethyl group); R 8 is a hydrogen atom, number of carbon atoms is 1
-3 alkyl group, hydroxy group -PO
(OM) 2 or -N(D) 2 (where D
represents a hydrogen atom or a methyl group or an ethyl group which may be substituted with a hydroxy group);
COOM, PO(OM) 2 or a hydroxy group; Y is a hydrogen atom, -COOM, -PO(OM) 2 or a hydroxy group (however, when R 8 is a hydroxy group, it is not a hydroxy group); Z is a hydrogen atom, a hydroxy group base, -
COOM or -PO(OM) 2 ; M represents a hydrogen atom, an alkali metal atom or an ammonium group; l represents an integer of 0 to 2; ] General formula [ ] [In the formula, R 9 and R 10 are each a hydrogen atom, an alkali metal atom, an ammonium group, an alkyl group or an alkenyl group which may have a substituent having 1 to 12 carbon atoms; M is a hydrogen atom or an alkali metal atom Or represents an ammonium group. ] General formula [ ] [In the formula, R 11 is an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an amino group, or an allyloxy group having 1 to 21 carbon atoms. group, C6-C24 acyloxy group;
Q 1 , Q 2 and Q 3 are each a hydroxy group, a C1-C24 alkoxy group, an aralkyloxy group, an allyloxy group, an amino group, a morpholino group, a cyclic amino group, an alkylamino group, a dialkylamino group, or an arylamino group. group, acyloxy group or -OM; M represents a hydrogen atom, an alkali metal atom or an ammonium group. ] The organic phosphonic acid or phosphonocarboxylic acid of the present invention represented by the above general formulas [] to [] may be an alkali metal salt thereof. Bleaching solutions made of a hydrogen peroxide compound and an aliphatic carboxylic acid or an alkali metal salt thereof, or bleaching solutions made of a hydrogen peroxide compound and an organic phosphonic acid compound have the disadvantage that foam failure is very likely to occur. In addition, even if these bubble failures do not occur during the preparation of the processing solution, the above-mentioned bubble failures will occur if the treatment continues for a long time or even if there is a slight change in the processing conditions (for example, PH, temperature). However, by using a combination of the hydrogen peroxide compound of the present invention, the carboxylic acid and organic phosphonic acid of the present invention, and the phosphonocarboxylic acid, the stability of the treatment liquid is significantly improved, foam failure does not occur, and It was also found that the bleaching reaction was not inhibited. It is generally believed that this bubble failure occurs because the bleaching reaction of silver with hydrogen peroxide progresses too rapidly. Therefore, there is a trade-off between attempts to suppress this foam failure, in which case the silver bleaching reaction will also be suppressed. For this reason, it was thought to be extremely difficult to achieve both suppression of foam failure and bleaching reaction. However, surprisingly, by using the aliphatic carboxylic acid of the present invention, the organic phosphonic acid of the present invention, the phosphonocarboxylic acid of the present invention, and the hydrogen peroxide of the present invention at the concentrations of the present invention, some changes in processing conditions can be achieved. Even if foaming occurs, there is almost no foam failure, and the bleaching reaction is accelerated, making the bleaching solution significantly more effective than when the bleaching solution is composed of two components: hydrogen peroxide and carboxylic acid, or hydrogen peroxide and organic phosphonic acid or phosphonocarboxylic acid. It was found that the stability was improved and the blister suppression effect was permanent, which was completely unexpected. The bleaching solution or bleach-fixing solution using a combination of the hydrogen peroxide compound, lower aliphatic carboxylic acid, organic phosphonic acid, and phosphonocarboxylic acid of the present invention has a phenomenon in which processability is reduced due to the contamination of halogen ions, etc. during processing. It was found that this is an extremely excellent bleaching solution or bleach-fixing solution that can significantly improve the In particular, it was found that the treatment solution according to the present invention has extremely excellent storage stability even when treated using a treatment tank made of metal. In particular, although ordinary developing machines use a stainless steel scale tank, the processing solution of the present invention has high stability even in this tank. The hydrogen peroxide compound of the present invention to be contained in the bleach solution or bleach-fix solution used in the present invention may be, for example, a commercially available hydrogen peroxide solution or gaseous hydrogen peroxide, and further, hydrogen peroxide may be added in an aqueous solution. Compounds that release NaBO2 , e.g.
H 2 O 2・3H 2 O Na 2 SiO 3・H 2 O 2・H 2 O, persulfate, Na 2 CO 3・2/3H 2 O 2 , Na 2 O 2 , MgO, peroxophosphate, etc. It can be used. In the present invention, the following are typical examples of the carboxylic acid of the present invention, which is one of the compounds to be combined with hydrogen peroxide and which enables the bleach-fixing of silver images. (1) Formic acid (2) Acetic acid (3) Propionic acid (4) Butyric acid (5) Oxalic acid (6) Malonic acid (7) Succinic acid (8) Lactic acid (9) Isosuccinic acid (10) Glutaric acid (11) Adipic acid (12) Glycolic acid (13) Citric acid (14) Oxycitric acid (15) Tartaric acid (16) α-oxy-D-butyric acid (17) Oxymalonic acid (18) Malic acid (19) α-Methylmalic acid ( 20) α-oxyglutaric acid (21) 2,3-dioxypropionic acid (22) Aspartic acid (23) Glutamic acid (24) Aminoacetic acid (25) β-Alanine (26) Serine (27) Diaminosuccinic acid (28) ) Aminomalonic acid (29) Maleic acid These carboxylic acids of the present invention may be used in their alkali metal salts. Furthermore, among these carboxylic acids, formic acid, acetic acid, propionic acid, citric acid, and their alkali metal salts are most preferably used in terms of bleaching properties, easy availability, cost, and the like. In the case of polycarboxylic acids, the number of carbon atoms in the alkyl group that matters is the number of carbon atoms between carboxyl groups. That is, −COOH group and −
If the number of carbon atoms between COOH groups is 5 or less,
There is no problem even if some carbon chains are bonded as side chains of the alkyl group. Next, specific examples of organic phosphonic acids or phosphonocarboxylic acids that are particularly effectively used in the present invention are shown below.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】 (17) Ｎ（CH2PO3H2）3 [Formula] (17) N(CH 2 PO 3 H 2 ) 3
【式】【formula】
【式】【formula】
【式】【formula】
【式】 (22) C3H7N（CH2PO3H2）2 (23) CH3C（PO3H2）3 [Formula] (22) C 3 H 7 N (CH 2 PO 3 H 2 ) 2 (23) CH 3 C (PO 3 H 2 ) 3
【式】【formula】
【式】【formula】
【式】 (29) HOCH2CH（OH）CH2OPO3Na2 (30) HO（CH2）2OPO3H2 (31) （HOCH2）2CHOPO3Na2 [Formula] (29) HOCH 2 CH(OH)CH 2 OPO 3 Na 2 (30) HO(CH 2 ) 2 OPO 3 H 2 (31) (HOCH 2 ) 2 CHOPO 3 Na 2
【式】
(33) HOCH2CH（OH）CH2OPO3H2
(34) （HOCH2）2CH−PO3Na2
(35) HOOCCH（NH2）CH2OPO3H2
(36) H2C＝Ｃ（COOK）OPO3K
(37) H3CCH（COOH）OPO3H2
(38) H2NCH2CH2OPO3H2
[Formula] (33) HOCH 2 CH(OH)CH 2 OPO 3 H 2 (34) (HOCH 2 ) 2 CH−PO 3 Na 2 (35) HOOCCH(NH 2 )CH 2 OPO 3 H 2 (36) H 2 C=C(COOK)OPO 3 K (37) H 3 CCH(COOH)OPO 3 H 2 (38) H 2 NCH 2 CH 2 OPO 3 H 2
【式】【formula】
【式】【formula】
これらの化合物は西ドイツ特許2015068号公開
公報等によつて合成出来るし、又一般に金属イオ
ンのキレート剤として市販されており容易に入手
出来る。
本発明に用いる漂白液または漂白定着液に含有
させる本発明の過酸化水素化合物、カルボン酸お
よびホスホノカルボン酸、有機ホスホン酸の添加
量は、前記の本発明の濃度範囲に於いて最も好ま
しい結果が得られるが、一般に過酸化水素に対し
てカルボン酸およひ有機ホスホン酸またはホスホ
ノカルボン酸の量は比例して変える事が望まし
い。例えば処理の迅速化のため多量の過酸化水素
を用いるようなときは、本発明のカルボン酸およ
び有機ホスホン酸またはホスホノカルボン酸の量
も増加した方が本発明の目的をより効果的に達成
する事が出来る。有機ホスホン酸またはホスホノ
カルボン酸は単独もしくは両者を併用してもよ
い。
本発明の過酸化水素化合物を、処理液（漂白液
または漂白定着液）１当り3.0モルよりも多量
に用いると泡故障等が出るおそれが生じるばかり
でなく、火傷等の人体に対する危険性が生じる
し、また１当り0.05モルよりも少量に用いると
所望の漂白定着効果が得られなくなる場合があ
る。そして、本発明のカルボン酸を１当り3.0
モルよりも多く用いると漂白定着反応性が著しく
抑制されるし、１当り0.05モルよりも少なく用
いると泡故障が発生し易くなり、銀の定着ができ
なくなるおそれがある。そしてまた、本発明の有
機ホスホン酸もしくはホスホノカルボン酸の添加
量を本発明以上に増加すると反応促進作用がみら
れなくなり、むしろ抑制作用が現われ始めるし、
同時に膜軟化等の現象がみられることがあるので
好ましくない。また、１当り0.005モルよりも
少量に用いると漂白定着反応促進効果がみられな
くなるばかりでなく、泡故障が生じるおそれがあ
るため好ましくない。
いずれにしろ、本発明の過酸化水素化合物、カ
ルボン酸および有機ホスホン酸もしくはホスホノ
カルボン酸の３成分の添加量は処理するハロゲン
化銀カラー写真感光材料の種類、必要とする処理
時間、処理液のPH等によつて異なるから、適宜最
適添加量の組合せを実験により決定すればよい。
本発明に係る漂白液または漂白定着液のPHは
2.0〜5.5の範囲に調整する必要がある。浴のPHが
2.0より下の場合には漂白反応が著しく抑制され
る。またPHが5.5より上では本発明による泡故障
の防止効果が充分発揮されなくなる点で好ましく
ない。そして浴のPHを5.5以下に抑える事は浴の
保存安定性に対しても望ましいことである。しか
しながら、本発明のホスホノカルボン酸もしくは
有機ホスホン酸を加えるとPH5.5以下でも著しい
過酸化水素の安定化作用を示し、過酸化水素の分
解は実質的に起らない程の効果がある事がわかつ
た。
本発明に用いる漂白液または漂白定着液はハロ
ゲン化銀カラー写真感光材料を処理したときに溶
出する銀イオンやその他該感光材料からの溶出物
質の影響で漂白性が著しく促進される事がある。
また、あらかじめ本発明の漂白液または漂白定着
液に金属銀等を添加し溶解すると漂白性が著しく
高められる場合があるので、本発明においてはあ
らかじめ金属銀や銀塩等を添加しておくこともで
きる。
本発明による漂白液または漂白定着液は画像銀
の酸化剤として過酸化水素を用いているため特に
他の酸化剤は不要である。しかしながら過硫酸塩
などの無機酸化剤１当り0.1ｇ〜250ｇ程を添加
して使用することも出来る。又極く少量の有機金
属錯塩、特に鉄、銅、コバルト等の有機金層錯塩
は過酸化水素による漂白反応を促進するため添加
することが出来る。
更に本発明の漂白定着液にはビニルピロリドン
核を有する重合体もしくは共重合体を添加し処理
液の保存安定性を高めることが出来る。
〔1〕 ポリ−Ｎ−ビニル−２−ピロリドン
〔2〕 ポリ−Ｎ−（2′−アクリロイルオキシ）エチ
ル−１−ピロリドン
〔3〕 ポリ−Ｎ−グリシジル−２−ピロリドン
〔4〕 ポリ−Ｎ−アリル−２−ピロリドン
〔5〕 ポリ−Ｎ，Ｎ−ジメチル−Ｎ−〔３（１−ピ
ロリドニル）−２−ヒドロキシ〕プロピル−ア
ミン−Ｎ−アクリロイルイミン
〔6〕 コポリ−Ｎ−ビニル−２−ピロリドン／Ｎ
−アクリロイルモルホリン（モル比42：58）
〔7〕 コポリ−Ｎ−ビニル−２−ピロリドン／Ｎ
−アクリロイルピペリジン（モル比35：65）
〔8〕 ポリ−Ｎ−ビニル−２−ピロリドン／Ｎ−
メタクリロイル−２−メチルイミダゾール（モ
ル比55：45）
〔9〕 コポリ−Ｎ−（２−アクリロイルオキシ）−
エチル−２−ピロリドン／アクリル酸ジエチル
アミド（モル比60：40）
〔10〕 コポリ−Ｎ−（２−メタクリロイルオキシ）
エチル−２−ピロリドン／アクリル酸ナトリウ
ム（モル比75：25）
〔11〕 コポリ−Ｎ−（３−アクリロイルオキシ）
プロピル−２−ピロリドン／メタクリル酸メチ
ル（モル比65：35）
〔12〕 コポリ−Ｎ，Ｎ−ジメチル−Ｎ−〔３−（１
−ピロリドニル）−２−ヒドロキシ〕−プロピル
アミン−Ｎ−アクリロイルイミン／アクリル酸
エチル（モル比70：35）
〔13〕 コポリ−Ｎ−ビニル−２−ピロリドン／酢
酸ビニル（モル比70：30）
〔14〕 コポリ−Ｎ−ビニル−２−ピロリドン／ア
クリル酸メチル（モル比70：30）
〔15〕 コポリ−Ｎ−ビニル−２−ピロリドン／ス
チレン（モル比80：20）
〔16〕 コポリ−Ｎ−ビニル−２−ピロリドン／ア
クリル酸アミド／Ｎ−ビニル−２−メチルイミ
ダゾール（モル比50：30：20）
〔17〕 コポリ−Ｎ−ビニル−２−ピロリドン／Ｎ
−（１，１−ジメチル−３−オキソ）−ブチル−
アクリルアミド（モル比70：30）
〔18〕 コポリ−Ｎ−アリル−２−ピロリドン／酢
酸ビニル（モル比64：36）
〔19〕 コポリ−Ｎ−ビニル−２−ピロリドン／４
−ビニルピリジン（モル比60：40）
〔20〕 コポリ−Ｎ−ビニル−２−ピロリドン／ア
クリル酸エチル／アクリル酸モノエタノールア
ミン酸（モル比50：45：５）
〔21〕 コポリ−Ｎ−ビニル−２−ピロリドン／ピ
ペリジノマレアミン酸−Ｎ−３−アミノプロピ
ルピペラジン塩（モル比53：47）
〔22〕 コポリ−Ｎ−ビニルピロリドン／４−ビニ
ルピリジノ−Ｎ−メチルアイオタイド（モル比
42：58）
〔23〕 コポリ−Ｎ−ビニルピロリドン／マレイン
酸チオ尿素ハーフアンモニウム塩（モル比60：
40）
等を含有する事が出来る。これらの重合体もしく
は共重合体の添加量は任意の量で添加する事が出
来るが好ましくは１当り１ｇから100ｇの範囲
である。
更に下記一般式で表わされる芳香族アミンを
0.01ｇ／から100ｇ／まで添加し漂白反応を
著しく促進する事が出来る。
〔式中、X1及びY1は水素又は低級アルキル、
R21、R22、R23、R24及びR25はそれぞれ水素原
子、アミノ基、水酸基、低級アルキル基、低級ア
ルキルアミノ基または低級ジアルキルアミノ基を
表わす。〕
これらの芳香族アミンの具体的化合物はｐ−フ
エニレンジアミン、ｐ−アミノフエノール、ｐ−
トルイジン、ｐ−メチルアミノフエノール、ｐ−
ジメチルアミノフエノール、Ｎ−メチル−ｐ−フ
エニレンジアミン、Ｎ，Ｎ−ジメチル−ｐ−フエ
ニレンジアミン、Ｎ，Ｎ，N′−トリメチル−ｐ
−フエニレンジアミン、Ｎ，Ｎ，N′，N′−テト
ラメチル−ｐ−フエニレンジアミン、α−メチル
−４−ジエチルアミノアニリン、α−メチル−４
−ジエチルアミノアニリン、α−メチル−４−メ
チルアミノ−アニリン、４−ジメチルアミノ−Ｎ
−メチルアニリン、ｍ−フエニレンジアミン、Ｏ
−フエニレンジアミン、２，３，５，６−テトラ
メチル−ｐ−フエニレンジアミン、２，４−ジア
ミノフエノール等である。
過酸化水素は分解すれば容易に水と酸素になり
容易に、かつ完全に無害化出来る。また本発明に
よる処理液（漂白液または漂白定着液）に用いる
素材は安価であり、かつ低濃度で使用しても優れ
た漂白性または漂白定着性が得られるという利点
を有している。この利点は資源の点でも直接に反
映する利点であつて、公害負荷の少ない安価な漂
白液または漂白定着液を容易に供給する事を可能
にするものである。本発明による漂白液または漂
白定着液は、溶解性が高く調製が容易であり、液
自身極めて安定性が高い。
ハロゲン化銀カラー写真感光材料を処理する事
によつて、本発明による処理浴（漂白浴または漂
白定着浴）に溶出する銀は、一部は恐らく有機酸
銀（カルボン酸銀）として溶解していると考えら
れた事実、本発明のカルボン酸として酢酸を用い
たとき銀イオンは１〜６ｇ／程度処理液中に溶
解出来る。更に多量に感光材料を処理したときは
可溶量以上の銀塩が非常に細かい沈澱として沈降
する。この沈降しやすさは有機ホスホン酸もしく
はホスホノカルボン酸の存在で著しく高められ
る。従つて、本発明の処理浴からの銀回収は連続
式遠心分離、フイルター濾過、沈澱分離、金属置
換法等で連続的にかつ容易に行い又、液を再生反
復使用する事も出来る。また別には処理液を単に
アルカリ性にする事で酸化銀として沈澱銀と溶解
銀の全ての銀を回収出来かつ過酸化水素も同時に
水と酸素に分解し無害化する事が出来る。処理液
をアルカリ性にする場合には現像液等のアルカリ
性処理液の廃液が利用出来る。
本発明による処理液（漂白液または漂白定着
液）は処理液単位面積当り処理可能な写真感光材
料面積が著しく大のため連続処理したときの補充
量を大幅に低下する事が出来る。また場合によつ
ては実質上オーバーフローしない程度に補充量を
低下させる事も可能であるという利点も有してい
る。
本発明に用いる漂白液または漂白定着液は酸化
電位が充分高いため形成された発色色素がロイコ
色素に止ることがない。従来の漂白液、特に鉄
（）アミノポリカルボン酸を酸化剤とする漂白
液や漂白定着液では多くのカプラーがロイコ色素
に止まる率が多かつた。特に４当量のイエローカ
プラーや、２当量および４当量のシアンカプラー
はロイコ色素に止まる事が多く実用上大きな障害
となつていた。さらに従来の漂白液および漂白定
着液、特に鉄（）アミノポリカルボン酸を酸化
剤とする場合には銀を酸化した後、鉄（）アミ
ノポリカルボン酸が生成する。このものは還元性
が強く処理液の処理性を低下したり色素を還元し
たりする作用が見られる。本発明の過酸化水素
は、銀の酸化反応によつてこのような還元体の生
成はみられないため、使用途中での処理性の低下
等が全くみられない。
本発明による処理液（漂白液または漂白定着
液）は前記のようにその漂白または漂白定着力が
優れているため、本発明に係る処理法は低感度の
ハロゲン化銀のカラー写真感光材料はもとより高
感度のハロゲン化銀カラー写真感光材料の処理に
も有効に適用出来る。特に本発明の処理法に用い
る処理液（漂白液または漂白定着液）での反応の
性質上、高銀量タイプの感光材料、特にカラーリ
バーサル感光材料等に有効に使用出来る。
本発明に係る処理法は一般のハロゲン化銀カラ
ー写真材料のいずれの処理にも適用できる。また
銀色素漂白法カラー処理にも適用できる。
本発明に係る処理方法に適用されるハロゲン化
銀カラー写真感光材料は支持体上に塗布された少
なくとも１層のハロゲン化銀乳剤層からなる。ハ
ロゲン化銀乳剤は塩化銀、沃化銀、塩臭化銀、臭
化銀、沃臭化銀、塩沃臭化銀等の感光性ハロゲン
化銀を親水性コロイドバインダーに分散して製造
される。
本発明の方法は現像、漂白または漂白定着それ
ぞれ独立した工程を含むが、ここに現像とは黒白
現像と発色現像を意味し発色現像のみの場合ある
いは黒白現像と発色現像両方を含むものも用いら
れる。
上記の工程は必ずしも連続して行われる必要は
なく、前記各工程の前後に種々の処理工程を含む
ことが出来る。このような工程を付加工程と呼ぶ
が該付加工程としては停止浴、停止定着浴、硬膜
浴、中和浴、水洗、リンス画像安定浴等がある。
本発明による漂白液または漂白定着液は、処理
工程の簡略化という観点からすれば、発色現像後
直ちに漂白または漂白定着する処理プロセスに適
用するのが望ましい。しかしながら本発明漂白定
着液では漂白定着液に現像主薬やハロゲンイオン
が混入しない事がより好ましく、かつ処理する写
真感光材料の種類およびその他必要に応じ発色現
像後に水洗処理、リンス処理、停止処理、停止定
着処理および漂白定着前浴（漂白定着を効率よく
行わせるための所謂コンデシヨナー）あるいは硬
膜処理等の１種以上の処理を適宜介した後、漂白
定着することがより望ましい。
また特殊の目的で漂白定着処理後、別途に本発
明によらない漂白定着液や定着液で処理を行なう
ことは任意である。即ち、画像銀を除去するため
に本発明による漂白液または漂白定着液をいかな
る処理プロセス位置に配するのも任意である。
本発明の漂白定着処理液による処理は未現像の
ハロゲン化銀が残らない処理工程が好ましい。本
発明の方法による現像工程のうち黒白現像とは、
通常知られているカラー写真感光材料処理用の黒
白第１現像液とよばれるものおよび黒白写真感光
材料処理に用いられるもので、黒白現像液に添加
される既知の各種添加剤を含有せしめる事が出来
る。
本発明の方法において用いられる発色現像液に
既知の芳香族１級アミン発色現像主薬を含むアル
カリ水溶液で、発色現像主薬としてはフエニレン
ジアミン誘導体で例えばＮ，Ｎ−ジエチル−ｐ−
フエニレンジアミン硫酸塩、４−アミノ−Ｎ−エ
チル−Ｎ−β−ヒドロキシエチルアニリン硫酸
塩、３−メチル−４−アミノ−Ｎ−エチル−β−
メタンスルホアミドエチルアニリンセスキサルフ
エートモノヒドラード、３−メチル−４−アミノ
−Ｎ−β−ヒドロキシエチルアニリン硫酸塩、３
−メチル−４−アミノ−Ｎ，Ｎ−ジエチルアニリ
ン塩酸塩、４−アミノ−Ｎ−エチル−３−メトキ
シ−Ｎ−（β−メトキシエチル）アニリン、ジ−
ｐ−トルエンスルフオン酸塩等があげられる。
本発明による漂白液または漂白定着液の処理後
にステイン除去等の特殊の目的で漂白定着液が用
いられる事があるがこれらは本発明によらない従
来処方の漂白定着液や定着液であり、既知のタイ
プのいかなる漂白定着液および定着液をも用いる
事が出来る。例えば酸化剤としてエチレンジアミ
ン四酢酸鉄（）錯塩、定着剤としてチオ硫酸、
チオエーテルグリコール、チオシアン酸塩、臭化
物、チオ尿素、ヨウ化物の一種またはそれ以上を
組み合せた漂白定着液や定着液を任意に用いる事
が出来る。これらを本発明に係る処理法に用いる
漂白液または漂白定着液の処理後に用いる場合に
は画像銀の酸化による漂白（定着）が目的ではな
いため、通常の濃度の1/20〜1/3程度で充分目的
を達成することができる。
本発明による処理液（漂白液または漂白定着
液）は本発明の過酸化水素、低級脂肪族カルボン
酸および有機ホスホン酸もしくはホスホノカルボ
ン酸を組み合せる事によつて目的を達成する事が
出来るが、必要に応じ更に添加剤を含有させる事
が出来る。例えば硫酸、ホウ酸、ホウ砂、水酸化
ナトリウム、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なるPH
緩衝剤を含有させることができる。さらにまた、
各種の螢光増白剤や消泡剤あるいはアニオン、カ
チオン、ノニオン系サポニンなどの各種の界面活
性剤、また、さらに必要に応じハロゲン化銀定着
剤；メタノール、ジメチルホルムアミド等の有機
溶媒、を含ませてもよい。さらに、処理する感光
材料の種類によつては明はん系やアルデヒド系を
始めとする各種の化合物から成る硬膜剤、硫酸マ
グネシウムや硫酸ナトリウム等のような膨潤防止
剤および亜硫酸塩、ヒドラジン等の還元剤をも含
有してもよい。
本発明法に用いられる処理液（漂白定着液）に
チオ硫酸塩、チオシアン酸塩等の従来の定着剤を
添加すると、未現像のハロゲン化銀は定着される
が、画像銀の表面活性を失なわせて過酸化水素に
よる銀の漂白がされなくなり、従つて画像銀の除
去ができなくなることがあるので、本発明におい
ては、これら従来の定着剤を本発明の漂白定着液
に添加しないことが望ましい。
本発明による漂白液または漂白定着液の処理温
度は、一般に迅速処理のために35℃〜60℃の範囲
で処理する事が望ましい。
実施例 １
９モル％の沃化銀を含む赤感性沃臭化銀ゼラチ
ン乳剤にシアンカプラーとして１−ヒドロキシ−
２−ｎ−δ−（２，４−ジ−ｔ−アミルフエノキ
シブチル）ナフトアミドを添加し乳化混合したシ
アン形成赤感性ハロゲン化銀乳剤を塗布銀量2.0
ｇ／m2となるように、また８モル％の沃化銀を含
む緑感性沃臭化銀乳剤にマゼンタカプラーとして
１−（2′，4′，6′−トリクロロフエノール）−3″−
〔2″−クロロ−3″−（2″，4″−ジ−ｔ−アミルフエ
ノキシアセタミド）アニリノ〕−５−ピラゾロン
を添加し乳化混合したマゼンタ形成緑感性ハロゲ
ン化銀乳剤を塗布銀量2.0ｇ／m2となるように、
さらに７モル％の沃化銀を含む青感性沃臭化銀乳
剤にイエローカプラーとしてα−ベンゾイル−
〔２−クロル−５−α−（ドデシルオキシカルボニ
ル）プロピルオキシカルボニル〕アセトアニリド
を添加し乳化混合したイエロー形成青感性ハロゲ
ン化銀乳剤を塗布銀量2.0ｇ／m2となるように、
下引加工したポリエチレンテレフタレートフイル
ム上にそれぞれ塗布してカラー反転用ハロゲン化
銀カラー写真感光材料の試料を作製した。
得られた試料に常法により光楔を通して所定の
露光を与えた後、下記の処理を行つた。なお、処
理温度は38℃で行つた。
処理工程
〔第１現像（３分30秒）〕→〔第１停止（30
秒）〕→〔第１水洗（１分）〕→〔発色現像（３分
40秒）〕→〔第２停止（１分）〕→〔第２水洗（１
分）〕→〔漂白定着（６分）〕→〔ステイン除去浴
（30秒）〕→〔第３水洗（１分）〕→〔安定（１
分）〕
次に使用した各処理液の組成を示す。なお、下
記の漂白定着液(a)は本発明に基づかない比較用漂
白定着液であり、漂白定着液(b)〜（ｐ）は本発明
に係る漂白定着液である。
〔第１現像〕
カードラホス 2.0ｇ
フエニドン 0.25ｇ
亜硫酸ナトリウム（無水） 50.0ｇ
ハイドロキノン 6.0ｇ
炭酸ナトリウム（１水塩） 30.0ｇ
臭化カリウム 2.0ｇ
チオシアン酸ナトリウム 1.3ｇ
氷酸化ナトリウム 6.0ml
ヨウ化カリウム（0.1％水溶液） 6.0ml
水 で １
〔第１、第２停止〕
酢酸ナトリウム 10ｇ
氷酢酸 36ml
水 で １
〔発色現像〕
カードラホス 5.0ｇ
第３燐酸ソーダ 40.0ｇ
水酸化ナトリウム 3.0ｇ
エチレンジアミン 2.0ｇ
ベンジルアルコール 5.8ml
ｔ−ブチルアミンボラン 0.1ｇ
シドラジン酸 1.3ｇ
コダツクCD−３ 11.3ｇ
亜硫酸ナトリウム 5.0ｇ
水 で １
〔ステイン除去浴〕
エチレンジアミン四酢酸鉄（）アンモニウム錯
塩 30ｇ
亜硫酸ナトリウム ７ｇ
チオ硫酸アンモニウム 60ｇ
水で１にし、水酸化アンモニウムでPH7.5に調
整した。
〔安定浴〕 These compounds can be synthesized according to West German Patent Publication No. 2015068, etc., and are generally commercially available as metal ion chelating agents and can be easily obtained. The amount of the hydrogen peroxide compound, carboxylic acid, phosphonocarboxylic acid, and organic phosphonic acid of the present invention to be contained in the bleach solution or bleach-fix solution used in the present invention is determined to achieve the most preferable result within the concentration range of the present invention described above. However, it is generally desirable to vary the amount of carboxylic acid and organic phosphonic acid or phosphonocarboxylic acid in proportion to hydrogen peroxide. For example, when using a large amount of hydrogen peroxide to speed up the process, the purpose of the present invention can be more effectively achieved by increasing the amount of the carboxylic acid and organic phosphonic acid or phosphonocarboxylic acid of the present invention. I can do it. The organic phosphonic acid or the phosphonocarboxylic acid may be used alone or in combination. If the hydrogen peroxide compound of the present invention is used in an amount greater than 3.0 mol per processing solution (bleach solution or bleach-fix solution), there is a risk of foam failure, etc., as well as danger to the human body such as burns. However, if the amount used is less than 0.05 mol per mol, the desired bleach-fixing effect may not be obtained. Then, the carboxylic acid of the present invention was added at a rate of 3.0 per 1
If it is used in an amount larger than 1 mole, the bleach-fixing reactivity will be significantly suppressed, and if it is used in an amount less than 0.05 mol per mole, bubble failure is likely to occur, and silver fixing may not be possible. Furthermore, if the amount of the organic phosphonic acid or phosphonocarboxylic acid of the present invention is increased beyond that of the present invention, the reaction promoting effect will no longer be observed, but rather a suppressing effect will begin to appear.
At the same time, phenomena such as film softening may occur, which is not preferable. Furthermore, if it is used in a smaller amount than 0.005 mol per mol, not only the effect of promoting the bleach-fixing reaction will not be observed, but also bubble failure may occur, which is not preferable. In any case, the amount of the three components of the present invention, hydrogen peroxide compound, carboxylic acid, and organic phosphonic acid or phosphonocarboxylic acid, should be determined based on the type of silver halide color photographic light-sensitive material to be processed, the required processing time, and the processing solution. Since it differs depending on the pH, etc., the optimum combination of addition amounts may be determined through experiments. The pH of the bleach solution or bleach-fix solution according to the present invention is
It needs to be adjusted to a range of 2.0 to 5.5. The pH of the bath
When the value is less than 2.0, the bleaching reaction is significantly inhibited. Moreover, if the pH is higher than 5.5, the effect of preventing foam failure by the present invention will not be sufficiently exerted, which is not preferable. It is also desirable for the storage stability of the bath to keep the pH of the bath below 5.5. However, when the phosphonocarboxylic acid or organic phosphonic acid of the present invention is added, it exhibits a remarkable stabilizing effect on hydrogen peroxide even at pH 5.5 or lower, and is so effective that hydrogen peroxide decomposition does not substantially occur. I understood. The bleaching properties of the bleaching solution or bleach-fixing solution used in the present invention may be significantly accelerated by the influence of silver ions and other substances eluted from the silver halide color photographic material when it is processed.
Furthermore, if metallic silver or the like is added and dissolved in the bleaching solution or bleach-fixing solution of the present invention in advance, the bleaching properties may be significantly enhanced, so in the present invention, it is also possible to add metallic silver, silver salt, etc. in advance. can. Since the bleaching solution or bleach-fixing solution according to the present invention uses hydrogen peroxide as an oxidizing agent for image silver, no other oxidizing agent is particularly required. However, it is also possible to add about 0.1 g to 250 g per inorganic oxidizing agent such as persulfate. Also, a very small amount of an organic metal complex salt, especially an organic gold layer complex salt of iron, copper, cobalt, etc., can be added to accelerate the bleaching reaction with hydrogen peroxide. Furthermore, a polymer or copolymer having a vinylpyrrolidone nucleus can be added to the bleach-fixing solution of the present invention to improve the storage stability of the processing solution. [1] Poly-N-vinyl-2-pyrrolidone [2] Poly-N-(2'-acryloyloxy)ethyl-1-pyrrolidone [3] Poly-N-glycidyl-2-pyrrolidone [4] Poly-N- Allyl-2-pyrrolidone [5] Poly-N,N-dimethyl-N-[3(1-pyrrolidonyl)-2-hydroxy]propyl-amine-N-acrylolimine [6] Copoly-N-vinyl-2-pyrrolidone /N
-Acryloylmorpholine (molar ratio 42:58) [7] Copoly-N-vinyl-2-pyrrolidone/N
-Acryloylpiperidine (molar ratio 35:65) [8] Poly-N-vinyl-2-pyrrolidone/N-
Methacryloyl-2-methylimidazole (molar ratio 55:45) [9] Copoly-N-(2-acryloyloxy)-
Ethyl-2-pyrrolidone/acrylic acid diethylamide (molar ratio 60:40) [10] Copoly-N-(2-methacryloyloxy)
Ethyl-2-pyrrolidone/sodium acrylate (molar ratio 75:25) [11] Copoly-N-(3-acryloyloxy)
Propyl-2-pyrrolidone/methyl methacrylate (molar ratio 65:35) [12] Copoly-N,N-dimethyl-N-[3-(1
-pyrrolidonyl)-2-hydroxy]-propylamine-N-acrylolimine/ethyl acrylate (molar ratio 70:35) [13] Copoly-N-vinyl-2-pyrrolidone/vinyl acetate (molar ratio 70:30) [13] 14] Copoly-N-vinyl-2-pyrrolidone/methyl acrylate (molar ratio 70:30) [15] Copoly-N-vinyl-2-pyrrolidone/styrene (molar ratio 80:20) [16] Copoly-N- Vinyl-2-pyrrolidone/acrylic acid amide/N-vinyl-2-methylimidazole (molar ratio 50:30:20) [17] Copoly-N-vinyl-2-pyrrolidone/N
-(1,1-dimethyl-3-oxo)-butyl-
Acrylamide (molar ratio 70:30) [18] Copoly-N-allyl-2-pyrrolidone/vinyl acetate (molar ratio 64:36) [19] Copoly-N-vinyl-2-pyrrolidone/4
-Vinylpyridine (molar ratio 60:40) [20] Copoly-N-vinyl-2-pyrrolidone/ethyl acrylate/acrylic acid monoethanolamine acid (molar ratio 50:45:5) [21] Copoly-N-vinyl -2-pyrrolidone/piperidinomaleamic acid-N-3-aminopropylpiperazine salt (molar ratio 53:47) [22] Copoly-N-vinylpyrrolidone/4-vinylpyridino-N-methyliotide (molar ratio
42:58) [23] Copoly-N-vinylpyrrolidone/thiourea maleate half ammonium salt (molar ratio 60:
40) etc. These polymers or copolymers can be added in any amount, but preferably range from 1 g to 100 g per polymer or copolymer. Furthermore, an aromatic amine represented by the following general formula
The bleaching reaction can be significantly accelerated by adding from 0.01g/ to 100g/. [In the formula, X 1 and Y 1 are hydrogen or lower alkyl,
R 21 , R 22 , R 23 , R 24 and R 25 each represent a hydrogen atom, an amino group, a hydroxyl group, a lower alkyl group, a lower alkylamino group or a lower dialkylamino group. ] Specific compounds of these aromatic amines include p-phenylenediamine, p-aminophenol, p-
Toluidine, p-methylaminophenol, p-
Dimethylaminophenol, N-methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N,N'-trimethyl-p
-phenylenediamine, N,N,N',N'-tetramethyl-p-phenylenediamine, α-methyl-4-diethylaminoaniline, α-methyl-4
-diethylaminoaniline, α-methyl-4-methylamino-aniline, 4-dimethylamino-N
-Methylaniline, m-phenylenediamine, O
-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4-diaminophenol, and the like. Hydrogen peroxide easily decomposes into water and oxygen, making it easily and completely harmless. Further, the material used in the processing solution (bleach solution or bleach-fix solution) according to the present invention is inexpensive and has the advantage that excellent bleaching or bleach-fixing properties can be obtained even when used at low concentrations. This advantage is also directly reflected in terms of resources, and makes it possible to easily supply inexpensive bleaching solutions or bleach-fixing solutions with low pollution loads. The bleaching solution or bleach-fixing solution according to the present invention has high solubility and is easy to prepare, and the solution itself is extremely stable. By processing a silver halide color photographic light-sensitive material, some of the silver eluted into the processing bath (bleach bath or bleach-fix bath) according to the present invention is probably dissolved as organic acid silver (silver carboxylate). In fact, when acetic acid is used as the carboxylic acid of the present invention, about 1 to 6 g/g of silver ions can be dissolved in the processing solution. When a photosensitive material is processed in an even larger amount, the silver salt in excess of the soluble amount settles out as very fine precipitates. This ease of sedimentation is significantly enhanced by the presence of organic phosphonic acids or phosphonocarboxylic acids. Therefore, recovery of silver from the treatment bath of the present invention can be carried out continuously and easily by continuous centrifugation, filter filtration, precipitation separation, metal substitution method, etc., and the liquid can be recycled and used repeatedly. Alternatively, by simply making the treatment solution alkaline, all of the silver, precipitated and dissolved silver, can be recovered as silver oxide, and hydrogen peroxide can also be decomposed into water and oxygen at the same time, making it harmless. When the processing solution is made alkaline, waste liquid of an alkaline processing solution such as a developer can be used. Since the processing solution (bleach solution or bleach-fix solution) according to the present invention has a significantly large area of photographic material that can be processed per unit area of the processing solution, the amount of replenishment during continuous processing can be significantly reduced. It also has the advantage that, depending on the case, it is possible to reduce the replenishment amount to such an extent that there is no substantial overflow. Since the bleaching solution or bleach-fixing solution used in the present invention has a sufficiently high oxidation potential, the coloring dye formed does not remain as a leuco dye. In conventional bleaching solutions, especially bleaching solutions and bleach-fixing solutions that use iron()aminopolycarboxylic acid as an oxidizing agent, many couplers are often converted into leuco dyes. In particular, 4-equivalent yellow couplers and 2-equivalent and 4-equivalent cyan couplers are often limited to leuco dyes, posing a major practical problem. Furthermore, in conventional bleaching solutions and bleach-fixing solutions, especially when iron()aminopolycarboxylic acid is used as the oxidizing agent, iron()aminopolycarboxylic acid is produced after oxidizing silver. This substance has a strong reducing property and has the effect of reducing the processing properties of the processing solution and reducing the dye. Since the hydrogen peroxide of the present invention does not produce such a reduced product due to the oxidation reaction of silver, there is no deterioration in processability during use. Since the processing solution (bleach solution or bleach-fix solution) according to the present invention has excellent bleaching or bleach-fixing power as described above, the processing method according to the present invention can be used not only for low-sensitivity silver halide color photographic materials. It can also be effectively applied to processing high-sensitivity silver halide color photographic materials. In particular, because of the nature of the reaction in the processing solution (bleach solution or bleach-fix solution) used in the processing method of the present invention, it can be effectively used in high silver content type photosensitive materials, especially color reversal photosensitive materials. The processing method according to the present invention can be applied to any processing of general silver halide color photographic materials. It can also be applied to silver dye bleaching color processing. The silver halide color photographic light-sensitive material applied to the processing method according to the present invention consists of at least one silver halide emulsion layer coated on a support. Silver halide emulsions are produced by dispersing photosensitive silver halides such as silver chloride, silver iodide, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide, etc. in a hydrophilic colloid binder. . The method of the present invention includes independent steps of development, bleaching, and bleach-fixing, but here, development means black-and-white development and color development, and a method involving only color development or a method including both black-and-white development and color development is also used. . The above steps do not necessarily need to be performed continuously, and various treatment steps can be included before and after each of the above steps. Such a step is called an addition step, and the addition steps include a stop bath, a stop-fix bath, a hardening bath, a neutralization bath, a water wash, a rinse image stabilizing bath, and the like. From the viewpoint of simplifying the processing steps, the bleaching solution or bleach-fixing solution according to the present invention is preferably applied to a processing process in which bleaching or bleach-fixing is performed immediately after color development. However, in the bleach-fix solution of the present invention, it is more preferable that no developing agent or halogen ion is mixed into the bleach-fix solution, and depending on the type of photographic material to be processed and other requirements, washing with water, rinsing, stopping, and stopping after color development. It is more desirable to carry out bleach-fixing after suitably performing one or more treatments such as a fixing treatment, a pre-bleach-fixing bath (a so-called condenser for efficient bleach-fixing), or a hardening treatment. Further, for a special purpose, after the bleach-fixing process, it is optional to perform a separate process with a bleach-fixing solution or a fixing solution that is not according to the present invention. That is, it is optional to place a bleach or bleach-fix solution according to the present invention at any processing process location to remove image silver. The processing using the bleach-fix processing solution of the present invention is preferably a processing step in which no undeveloped silver halide remains. Among the development steps according to the method of the present invention, black and white development is
These are commonly known black-and-white first developing solutions for processing color photographic light-sensitive materials and those used for processing black-and-white photographic materials, and may contain various known additives that are added to black-and-white developing solutions. I can do it. The color developing solution used in the method of the present invention is an alkaline aqueous solution containing a known aromatic primary amine color developing agent, and the color developing agent is a phenylenediamine derivative such as N,N-diethyl-p-
Phenylenediamine sulfate, 4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate, 3-methyl-4-amino-N-ethyl-β-
Methanesulfamide ethylaniline sesquisulfate monohydrade, 3-methyl-4-amino-N-β-hydroxyethylaniline sulfate, 3
-Methyl-4-amino-N,N-diethylaniline hydrochloride, 4-amino-N-ethyl-3-methoxy-N-(β-methoxyethyl)aniline, di-
Examples include p-toluenesulfonate. After processing the bleach-fix solution or bleach-fix solution according to the present invention, a bleach-fix solution may be used for special purposes such as removing stains, but these are bleach-fix solutions or fix solutions with conventional formulations that are not according to the present invention and are known. Any type of bleach-fix and fix solution can be used. For example, ethylenediaminetetraacetic acid iron() complex salt as an oxidizing agent, thiosulfuric acid as a fixing agent,
A bleach-fix solution or a fix solution containing one or more of thioether glycol, thiocyanate, bromide, thiourea, and iodide in combination can be optionally used. When these are used after processing the bleaching solution or bleach-fixing solution used in the processing method of the present invention, the purpose is not to bleach (fix) the image silver by oxidation, so it is about 1/20 to 1/3 of the normal density. is sufficient to achieve the objective. The processing solution (bleach solution or bleach-fix solution) according to the present invention can achieve the objective by combining hydrogen peroxide, lower aliphatic carboxylic acid, and organic phosphonic acid or phosphonocarboxylic acid according to the present invention. , it is possible to further contain additives if necessary. PH consisting of various salts such as sulfuric acid, boric acid, borax, sodium hydroxide, potassium carbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
A buffer may be included. Furthermore,
Contains various fluorescent brighteners, antifoaming agents, various surfactants such as anionic, cationic, and nonionic saponins, and, if necessary, silver halide fixing agents; organic solvents such as methanol and dimethylformamide. You can let it happen. Furthermore, depending on the type of photosensitive material to be processed, hardeners made of various compounds such as brighteners and aldehydes, anti-swelling agents such as magnesium sulfate and sodium sulfate, sulfites, hydrazine, etc. It may also contain a reducing agent. When a conventional fixing agent such as thiosulfate or thiocyanate is added to the processing solution (bleach-fix solution) used in the method of the present invention, undeveloped silver halide is fixed, but the surface activity of the image silver is lost. In addition, hydrogen peroxide may not bleach the silver, and therefore the image silver may not be removed, so in the present invention, it is recommended not to add these conventional fixing agents to the bleach-fix solution of the present invention. desirable. Generally, the processing temperature of the bleaching solution or bleach-fixing solution according to the present invention is preferably within the range of 35 DEG C. to 60 DEG C. for rapid processing. Example 1 1-Hydroxy- as a cyan coupler was added to a red-sensitive silver iodobromide gelatin emulsion containing 9 mol% silver iodide.
A cyan-forming red-sensitive silver halide emulsion prepared by adding 2-n-δ-(2,4-di-t-amylphenoxybutyl)naphthamide and emulsifying it was coated with a silver amount of 2.0.
g/m 2 and 1-(2',4',6'-trichlorophenol)-3''- as a magenta coupler in a green-sensitive silver iodobromide emulsion containing 8 mol% silver iodide.
[2″-chloro-3″-(2″,4″-di-t-amylphenoxyacetamide)anilino]-5-pyrazolone was added and emulsified to form a magenta-forming green-sensitive silver halide emulsion. So that the amount is 2.0g/ m2 ,
Furthermore, α-benzoyl-benzoyl-
A yellow-forming blue-sensitive silver halide emulsion prepared by adding [2-chloro-5-α-(dodecyloxycarbonyl)propyloxycarbonyl]acetanilide and emulsifying it was coated with a silver amount of 2.0 g/m 2 .
Samples of silver halide color photographic light-sensitive materials for color reversal were prepared by coating each on a subbed polyethylene terephthalate film. The obtained sample was exposed to a predetermined amount of light through a light wedge in a conventional manner, and then subjected to the following treatments. Note that the treatment temperature was 38°C. Processing process [1st development (3 minutes 30 seconds)] → [1st stop (30 seconds)]
seconds)] → [1st washing (1 minute)] → [Color development (3 minutes)
40 seconds)] → [2nd stop (1 minute)] → [2nd water wash (1 minute)]
minutes)] → [Bleach-fixing (6 minutes)] → [Stain removal bath (30 seconds)] → [Third washing (1 minute)] → [Stable (1 minute)]
)] Next, the composition of each treatment liquid used is shown. The following bleach-fix solution (a) is a comparative bleach-fix solution not based on the present invention, and bleach-fix solutions (b) to (p) are bleach-fix solutions according to the present invention. [First development] Kardraphos 2.0g Phenidone 0.25g Sodium sulfite (anhydrous) 50.0g Hydroquinone 6.0g Sodium carbonate (monohydrate) 30.0g Potassium bromide 2.0g Sodium thiocyanate 1.3g Sodium glacial oxide 6.0ml Potassium iodide (0.1g) % aqueous solution) 6.0ml 1 in water [1st and 2nd stop] Sodium acetate 10g Glacial acetic acid 36ml 1 in water [Color development] Cardlaphos 5.0g Tertiary sodium phosphate 40.0g Sodium hydroxide 3.0g Ethylenediamine 2.0g Benzyl alcohol 5.8ml t-Butylamine borane 0.1g Sidrazic acid 1.3g Kodatsu CD-3 11.3g Sodium sulfite 5.0g 1 with water [Stain removal bath] Ethylenediaminetetraacetic acid iron () ammonium complex salt 30g Sodium sulfite 7g Ammonium thiosulfate 60g Make 1 with water and hydroxylate Adjusted the pH to 7.5 with ammonium. [Stability bath]
【表】
〔漂白定着液〕
過酸化水素水（35％水溶液） 50ml
氷酢酸 30ml
水で１にし、水酸化ナトリウムでPH4.0に調
整した。
漂白定着液(a)は上記漂白定着液に本発明化合物
の有機ホスホン酸もしくはホスホノカルボン酸を
下記表に示した如く添加した処理液のPHを水酸化
ナトリウムもしくは氷酢酸により4.0に調整し直
して前記処理工程により処理した。
漂白定着液(a)ないし（ｐ）の各処理における処
理性を比較するためクリアリングタイムと泡故障
の発生及び液をステンレスタンクで２ケ月保存し
たときの過酸化水素の分解率をそれぞれ下記第１
表に示した。[Table] [Bleach-fix solution] Hydrogen peroxide (35% aqueous solution) 50 ml Glacial acetic acid 30 ml The pH was adjusted to 1 with water and PH4.0 with sodium hydroxide. Bleach-fix solution (a) is prepared by adding the organic phosphonic acid or phosphonocarboxylic acid of the present invention compound to the above bleach-fix solution as shown in the table below, and adjusting the pH of the processing solution to 4.0 with sodium hydroxide or glacial acetic acid. and was treated according to the treatment steps described above. In order to compare the processability of each bleach-fix solution (a) to (p), the clearing time, occurrence of foam failure, and decomposition rate of hydrogen peroxide when the solution was stored in a stainless steel tank for two months are shown below. 1
Shown in the table.
【表】【table】
【表】
第１表からも明らかな如く本発明によらない比
較用の漂白定着液(a)ではステンレスタンクによる
２ケ月保存での過酸化水素の残存量が非常に低く
分解率が大きい事がわかる。又クリアリングタイ
ムも本発明の処理にくらべると長くなつている。
これにくらべ本発明による処理(b)ないし（ｐ）で
は過酸化水素の残存率が大きく、ほとんど分解し
ない。又クリアリングタイムも短く良好である事
がわかる。又本実施例処理による泡故障は漂白定
着液(a)では著しく発生しているのにくらべ、本発
明の処理(c)ないし（ｒ）では全く発生しなかつ
た。更に泡故障が発生しないためにハイライト部
の透明性も全く問題なく、優れた漂白定着性能を
有している事がわかる。
本処理工程ではステイン除去浴を用いたが、ス
テイン除去浴の有無によるハイライト部のステイ
ン濃度は実質的に差はみられなかつた。また、処
理する試料がコロイド銀ハレーシヨン防止層を有
しているような場合にはこのステイン除去浴の効
果が発揮される事が確認された。さらに、上記処
理の他、漂白定着液のPHを3.5および5.0に硫酸及
び水酸化ナトリウムで調整し処理したが、第１表
と同様の結果が得られた。
本発明漂白定着液(b)ないし（ｐ）を用いて処理
して得られた画像色素は、従来の処理と比較し
て、発色濃度、特性曲線上の直線保有性等写真特
性においてもなんら遜色がないばかりか、得られ
た画像そのものも極めて保存安定性が良い事が確
認された。
このように本発明による漂白定着液(g)〜（ｑ）
は漂白定着性能が非常に優れている。
なお、上記処理において、発色現像を行つた
後、直接漂白定着処理を行つた場合、また、水洗
工程のみを介して漂白定着処理を行つた場合にも
第１表に示した結果と同様の結果が得られた。
さらに、漂白定着処理を60℃で行つたところ本
発明による漂白定着液を用いた処理による泡故障
の防止効果およびクリアリングタイムは第１表に
示した結果より更に良好な結果が得られた。[Table] As is clear from Table 1, the amount of hydrogen peroxide remaining in the comparative bleach-fix solution (a), which is not based on the present invention, after being stored in a stainless steel tank for two months is extremely low, and the decomposition rate is high. Recognize. Also, the clearing time is longer than in the process of the present invention.
In comparison, in the treatments (b) to (p) according to the present invention, the residual rate of hydrogen peroxide is large and it is hardly decomposed. It can also be seen that the clearing time is short and good. In addition, while foam failures caused by the treatments of this example occurred significantly in the bleach-fix solution (a), they did not occur at all in the treatments (c) to (r) of the present invention. Furthermore, since no bubble failure occurs, there is no problem with the transparency of highlighted areas, and it can be seen that it has excellent bleach-fixing performance. Although a stain removal bath was used in this treatment step, there was virtually no difference in the stain concentration in the highlighted area depending on whether a stain removal bath was used or not. It was also confirmed that this stain removal bath is effective when the sample to be treated has a colloidal silver antihalation layer. Furthermore, in addition to the above treatment, the pH of the bleach-fix solution was adjusted to 3.5 and 5.0 with sulfuric acid and sodium hydroxide, and the same results as shown in Table 1 were obtained. The image dyes obtained by processing using the bleach-fix solutions (b) to (p) of the present invention are in no way inferior in photographic properties such as color density and linear retention on characteristic curves, compared to those obtained by conventional processing. It was confirmed that not only was there no problem, but the obtained image itself had extremely good storage stability. In this way, the bleach-fix solutions (g) to (q) according to the present invention
has excellent bleach-fixing performance. In addition, in the above processing, results similar to those shown in Table 1 were obtained when bleach-fixing was performed directly after color development, and when bleach-fixing was performed only through a water washing step. was gotten. Furthermore, when the bleach-fixing process was carried out at 60°C, the effect of preventing bubble failure and the clearing time obtained by the process using the bleach-fixing solution of the present invention were even better than those shown in Table 1.
Claims (1)
材料を発色現像後、 〔〕 １当り0.05〜3.0モルの過酸化水素または
過酸化水素を放出する化合物から選ばれる少な
くとも１種 〔〕 １当り0.05〜3.0モルの下記一般式〔〕
または〔〕で示される低級脂肪族カルボン酸
またはそのアルカリ金属塩（ただし、該カルボ
ン酸またはそのアルカリ金属塩の金属錯塩を除
く。）から選ばれる少なくとも１種 〔〕 １当り0.005〜1.5モルの下記一般式〔〕
ないし〔〕で示される有機ホスホン酸もしく
はホスホノカルボン酸またはその塩から選ばれ
る少なくとも１種を 含みPHが2.0〜5.5である処理浴で処理する工程を
含むことを特徴とするハロゲン化銀カラー感光材
料の処理方法。 一般式〔〕 R1−COOH 〔式中、R1は水素原子または炭素原数１ないし
３のアルキル基であり、該アルキル基は１つ以上
の水素基および／またはアミノ基で置換されてい
てもよい。〕 一般式〔〕 HOOC−（R2）n1−COOH 〔式中、R2は炭素原子数１ないし５のアルキレ
ン基またはアルケニレン基であり、該アルキレン
基またはアルケニレン基は１つ以上の水酸基、低
級アルキル基、カルボキシル基および／またはア
ミノ基で置換されていてもよい。n1は０または１
を示す。〕 一般式〔〕 〔式中、R1は−COOMまたは−PO（OM）2；R2
は水素原子、炭素原子数１ないし４のアルキル基
または−（CH2）nCOOM；R3は水素原子、炭素
原子数１ないし４のアルキル基または −（CH2）nCOOMで表わされる原子または原
子群であり；Ｍは水素原子、アルカリ金属原子ま
たはアンモニウム基、ｍは０または１、ｎは０、
１ないし４の整数を表わす。〕 一般式〔〕 R4N（CH2PO（OM）2）2 〔式中、R4は炭素原子数１ないし４のアルキル
基またはアリール基（これらは−OH、−OR5、−
PO（OM）2、−CH2PO（OM）2、−Ｎ（CH2PO
（OM）2）2、−COOMまたは−Ｎ（CH2COOM）2で
表わされる原子群で置換されてもよい）；Ｍは水
素原子、アルカリ金属原子またはアンモニウム
基；R5は炭素原子数１ないし４のアルキル基を
表わす。〕 一般式〔〕 〔式中、R6およびR7はそれぞれ水素原子、−
COOMで置換されてもよい炭素原子数１ないし
３のアルキル基、ヒドロキシ基または−Ｎ(A)2で
表わされる基（ここでＡは水素原子またはヒドロ
キシ基で置換されてもよいメチル基もしくはエチ
ル基を表わす）；R8は水素原子、炭素原子数１な
いし３のアルキル基、ヒドロキシ基、−PO
（OM）2または−Ｎ(D)2で表わされる基（ここでＤ
は水素原子またはヒドロキシ基で置換されてもよ
いメチル基もしくはエチル基を表わす）；Ｘは−
COOM、−PO（OM）2、またはヒドロキシ基；Ｙ
は水素原子、−COOM、−PO（OM）2、またはヒド
ロキシ基；Ｙは水素原子、−COOM、−PO（OM）2
またはヒドロキシ基（ただしR8がヒドロキシ基
の時はヒドロキシ基ではない）；Ｚは水素原子、
ヒドロキシ基−COOMまたは−PO（OM）2；Ｍは
水素原子、アルカリ金属原子またはアンモニウム
基；ｌは０ないし２の整数を表わす。〕 一般式〔〕 〔式中、R9およびR10はそれぞれ水素原子、アル
カリ金属原子、アンモニウム基、炭素原子数１な
いし12の置換基を有してもよいアルキル基または
アルケニル基；Ｍは水素原子、アルカリ金属原子
またはアンモニウム基を表わす。〕 一般式〔〕 〔式中、R11は炭素原子数１ないし12のアルコキ
シ基、炭素原子数２ないし12のアルキルカルボニ
ル基、炭素原子数２ないし12のジアルキルアミノ
基、アミノ基、炭素原子数１ないし21のアリロキ
シ基、炭素原子数６ないし24のアシルオキシ基；
Q1、Q2およびQ3はそれぞれヒドロキシ基、炭素
原子数１ないし24のアルコキシ基、アラルキルオ
キシ基、アリロキシ基、アミノ基、モルホリノ
基、環状アミノ基、アルキルアミノ基、ジアルキ
ルアミノ基、アリールアミノ基、アシルオキシ基
または−OMで表わされる基；Ｍは水素原子、ア
ルカリ金属原子またはアンモニウム基を表わす。〕[Scope of Claims] 1. After color development of the imagewise exposed silver halide color photographic light-sensitive material, [] at least one selected from hydrogen peroxide or a compound that releases hydrogen peroxide in an amount of 0.05 to 3.0 mol per unit; [] 0.05 to 3.0 mol per unit of the following general formula []
or at least one selected from lower aliphatic carboxylic acids or alkali metal salts thereof (excluding metal complex salts of the carboxylic acids or alkali metal salts thereof) represented by [ ] 0.005 to 1.5 mol per 1 of the following: General formula []
A silver halide color photosensitive film comprising a step of processing in a processing bath containing at least one selected from organic phosphonic acids, phosphonocarboxylic acids, or salts thereof represented by [ ] and having a pH of 2.0 to 5.5. How materials are processed. General formula [] R 1 -COOH [In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the alkyl group is substituted with one or more hydrogen groups and/or amino groups. Good too. ] General formula [] HOOC-(R 2 ) n 1 -COOH [wherein R 2 is an alkylene group or alkenylene group having 1 to 5 carbon atoms, and the alkylene group or alkenylene group has one or more hydroxyl groups, It may be substituted with a lower alkyl group, carboxyl group and/or amino group. n 1 is 0 or 1
shows. ] General formula [ ] [In the formula, R 1 is −COOM or −PO(OM) 2 ; R 2
is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -(CH 2 )nCOOM; R 3 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an atom or atomic group represented by -(CH 2 )nCOOM M is a hydrogen atom, an alkali metal atom or an ammonium group, m is 0 or 1, n is 0,
Represents an integer from 1 to 4. ] General formula [] R 4 N(CH 2 PO(OM) 2 ) 2 [In the formula, R 4 is an alkyl group having 1 to 4 carbon atoms or an aryl group (these are -OH, -OR 5 , -
PO(OM) 2 , -CH 2 PO(OM) 2 , -N(CH 2 PO
(OM) 2 ) 2 , -COOM or -N (CH 2 COOM) 2 ); M is a hydrogen atom, an alkali metal atom or an ammonium group; R 5 has 1 carbon atom Represents 4 to 4 alkyl groups. ] General formula [ ] [In the formula, R 6 and R 7 are hydrogen atoms, −
An alkyl group having 1 to 3 carbon atoms which may be substituted with COOM, a hydroxy group or a group represented by -N(A) 2 (where A is a hydrogen atom or a methyl group or ethyl group which may be substituted with a hydroxy group) (represents a group); R 8 is a hydrogen atom, a C1-C3 alkyl group, a hydroxy group, -PO
(OM) 2 or -N(D) 2 (where D
represents a hydrogen atom or a methyl group or an ethyl group which may be substituted with a hydroxy group);
COOM, -PO(OM) 2 or hydroxy group; Y
is a hydrogen atom, -COOM, -PO(OM) 2 , or a hydroxy group; Y is a hydrogen atom, -COOM, -PO(OM) 2
or a hydroxy group (however, when R 8 is a hydroxy group, it is not a hydroxy group); Z is a hydrogen atom,
Hydroxy group -COOM or -PO(OM) 2 ; M represents a hydrogen atom, an alkali metal atom or an ammonium group; l represents an integer from 0 to 2; ] General formula [ ] [In the formula, R 9 and R 10 are each a hydrogen atom, an alkali metal atom, an ammonium group, an alkyl group or an alkenyl group which may have a substituent having 1 to 12 carbon atoms; M is a hydrogen atom, an alkali metal atom Or represents an ammonium group. ] General formula [ ] [In the formula, R 11 is an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an amino group, or an allyloxy group having 1 to 21 carbon atoms. group, C6-C24 acyloxy group;
Q 1 , Q 2 and Q 3 are each a hydroxy group, a C1-C24 alkoxy group, an aralkyloxy group, an allyloxy group, an amino group, a morpholino group, a cyclic amino group, an alkylamino group, a dialkylamino group, or an arylamino group. group, acyloxy group or -OM; M represents a hydrogen atom, an alkali metal atom or an ammonium group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7104778A JPS54161932A (en) | 1978-06-12 | 1978-06-12 | Processing method for silver halide color photographic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7104778A JPS54161932A (en) | 1978-06-12 | 1978-06-12 | Processing method for silver halide color photographic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54161932A JPS54161932A (en) | 1979-12-22 |
| JPH0115861B2 true JPH0115861B2 (en) | 1989-03-20 |
Family
ID=13449210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7104778A Granted JPS54161932A (en) | 1978-06-12 | 1978-06-12 | Processing method for silver halide color photographic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54161932A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT7925699A0 (en) * | 1978-09-14 | 1979-09-12 | Eastman Kodak Co | PHOTOGRAPHIC COMPOSITIONS OF BIANCA, AND METHODS FOR PHOTOGRAPHIC TREATMENT. |
| JP2684444B2 (en) * | 1989-08-11 | 1997-12-03 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JP2655356B2 (en) * | 1989-11-08 | 1997-09-17 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JP2568924B2 (en) * | 1989-11-13 | 1997-01-08 | 富士写真フイルム株式会社 | Processing method of silver halide color photosensitive material |
| JP2867048B2 (en) * | 1989-12-19 | 1999-03-08 | コニカ株式会社 | Processing method of silver halide color photographic light-sensitive material |
-
1978
- 1978-06-12 JP JP7104778A patent/JPS54161932A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54161932A (en) | 1979-12-22 |
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