JPH021294B2 - - Google Patents
Info
- Publication number
- JPH021294B2 JPH021294B2 JP56117169A JP11716981A JPH021294B2 JP H021294 B2 JPH021294 B2 JP H021294B2 JP 56117169 A JP56117169 A JP 56117169A JP 11716981 A JP11716981 A JP 11716981A JP H021294 B2 JPH021294 B2 JP H021294B2
- Authority
- JP
- Japan
- Prior art keywords
- bleach
- solution
- color
- acid
- fixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 claims description 68
- 229910052709 silver Inorganic materials 0.000 claims description 43
- 239000004332 silver Substances 0.000 claims description 43
- 238000012545 processing Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 23
- 238000011161 development Methods 0.000 claims description 22
- 150000007524 organic acids Chemical class 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000003672 processing method Methods 0.000 claims description 7
- 238000004061 bleaching Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 24
- 239000010410 layer Substances 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000975 dye Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 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 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 5
- 229940093915 gynecological organic acid Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 108010010803 Gelatin Proteins 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- ASWXCJULGBPXHT-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;dihydrate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].O.O.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O ASWXCJULGBPXHT-UHFFFAOYSA-N 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical group NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- PBHVCRIXMXQXPD-UHFFFAOYSA-N chembl2369102 Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(=N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)S(O)(=O)=O)=C2N=C1C=C2 PBHVCRIXMXQXPD-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- YCJSKHQFBRCBLH-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methoxyanilino)ethanol;hydrochloride Chemical compound Cl.OCCN(CC)C1=CC=C(N)C(OC)=C1 YCJSKHQFBRCBLH-UHFFFAOYSA-N 0.000 description 1
- HYDLGNNMPHGCPG-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethanesulfonic acid Chemical compound OS(=O)(=O)CCN(CC)C1=CC=C(N)C(C)=C1 HYDLGNNMPHGCPG-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 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
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 1
- ZJOJXRSMJNWWRN-UHFFFAOYSA-N 3-amino-6-[2-(4-aminophenyl)ethenyl]benzene-1,2-disulfonic acid Chemical class C1=CC(N)=CC=C1C=CC1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O ZJOJXRSMJNWWRN-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- HFYPXERYZGFDBD-UHFFFAOYSA-N 4-amino-2,6-dibromophenol Chemical compound NC1=CC(Br)=C(O)C(Br)=C1 HFYPXERYZGFDBD-UHFFFAOYSA-N 0.000 description 1
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 description 1
- JCJRVDVGBXPXMY-UHFFFAOYSA-N 4-n,4-n-diethyl-2-n,2-n-dimethylbenzene-1,2,4-triamine;sulfuric acid;hydrate Chemical compound O.OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C(N(C)C)=C1 JCJRVDVGBXPXMY-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- FFAJEKUNEVVYCW-UHFFFAOYSA-N 4-n-ethyl-4-n-(2-methoxyethyl)-2-methylbenzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(C)=C1 FFAJEKUNEVVYCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GYMLZISALOVMQN-UHFFFAOYSA-L C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].[Na+].[Na+].C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)O)CC(=O)O.C1(=C(C=CC=C1)N(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.C(CN(CCC(=O)O)CCC(=O)O)N(CCC(=O)O)CCC(=O)O Chemical compound C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].[Na+].[Na+].C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)O)CC(=O)O.C1(=C(C=CC=C1)N(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.C(CN(CCC(=O)O)CCC(=O)O)N(CCC(=O)O)CCC(=O)O GYMLZISALOVMQN-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-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
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- JRPKCIKPGXDMRN-UHFFFAOYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].NCCNCCN.[Na+].[Na+].[Na+].[Na+].C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)[O-])CC(=O)[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].NCCNCCN.[Na+].[Na+].[Na+].[Na+].C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)[O-])CC(=O)[O-] JRPKCIKPGXDMRN-UHFFFAOYSA-E 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- DKFFVMCMYIVCMK-UHFFFAOYSA-N azane 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid dihydrate Chemical compound O.[OH-].[NH4+].C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O DKFFVMCMYIVCMK-UHFFFAOYSA-N 0.000 description 1
- 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
- 235000010338 boric acid Nutrition 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical group NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- NPKFETRYYSUTEC-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPKFETRYYSUTEC-UHFFFAOYSA-N 0.000 description 1
- QRBFSNYYMHZRGU-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid;hydrate Chemical compound O.OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 QRBFSNYYMHZRGU-UHFFFAOYSA-N 0.000 description 1
- FMFVYKOQJLUUQK-UHFFFAOYSA-N n-[2-[2-amino-5-(diethylamino)phenyl]ethyl]methanesulfonamide;dihydrochloride Chemical compound Cl.Cl.CCN(CC)C1=CC=C(N)C(CCNS(C)(=O)=O)=C1 FMFVYKOQJLUUQK-UHFFFAOYSA-N 0.000 description 1
- YOUKHKXMLCZXRK-UHFFFAOYSA-N n-[2-amino-5-(diethylamino)phenyl]acetamide Chemical compound CCN(CC)C1=CC=C(N)C(NC(C)=O)=C1 YOUKHKXMLCZXRK-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical class O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 229960002317 succinimide Drugs 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/395—Regeneration of photographic processing agents other than developers; Replenishers therefor
- G03C5/3958—Replenishment processes or compositions, i.e. addition of useful photographic processing 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、更に詳しくは、ハロゲン化銀カ
ラー写真感光材料を自動現像機で、漂白定着液に
よつて連続的に処理する処理方法に関する。
一般に、像様露光されたハロゲン化銀カラー写
真感光材料を自動現像機により連続的に処理して
カラー画像を得るには、発色現像工程の後に、生
成された金属銀を漂白能を有する処理液で処理す
る工程が設けられる。
漂白能を有する処理液としては、漂白液、漂白
定着液が知られている。漂白液が使用される場合
は、通常、漂白工程に次いでハロゲン化銀を定着
剤によつて定着する工程が付け加えられるが、漂
白定着液では漂白及び定着が一工程で行なわれ
る。
漂白工程又は漂白定着工程では、ハロゲン化銀
カラー写真感光材料に付着して持ち込まれる直前
の工程の処理液成分、漂白又は漂白定着によつて
消費される組成物成分、及びハロゲン化銀カラー
写真感光材料から溶出し漂白又は漂白定着液中に
蓄積される成分の漂白又は漂白定着液中の濃度を
常に一定に維持するため、適当な組成の漂白又は
漂白定着補充液が適当量補充される。
ハロゲン化銀カラー写真感光材料の処理におけ
る漂白能を有する処理液には、画像銀を漂白する
ための酸化剤として、赤血塩、重クロム酸塩等の
無機の酸化剤が広く用いられている。
しかし、これらの無機の酸化剤を含有する漂白
能を有する処理液には、いくつかの重大な欠点が
指摘されている。例えば赤血塩及び重クロム酸塩
は画像銀の漂白力という点では比較的すぐれてい
るが、光により分解して人体に有害なシアンイオ
ンや六価のクロムイオンを生成する虞れがあり、
公害防止上好ましくない性質を有している。また
これらの酸化剤はその酸化力が極めて強いため
に、チオ硫酸塩等のハロゲン化銀溶化剤を同一の
処理液中に共存させることが困難で、漂白定着浴
にこれらの酸化剤を用いることはほとんど不可能
であり、このため処理の迅速化および簡素化とい
う目的の達成を難しくしている。さらにこれらの
無機の酸化剤を含む処理液は、処理後の廃液を捨
てることなく再生使用することが困難であるとい
う欠点を有している。
これに対し、公害上の問題も少なく、処理の迅
速化、簡素化、および廃液の再生使用可能等の要
請にかなうものとして、アミノポリカルボン酸金
属錯塩等の有機酸の金属錯塩を酸化剤とした処理
液が使用されるようになつてきた。しかし、有機
酸の金属錯塩を使用した処理液は、酸化力が緩慢
なために、現像工程で形成された画像銀(金属
銀)の漂白速度(酸化速度)が遅いという欠点を
有している。
一般に有機酸の金属錯塩は、中性ないしはアル
カリ性領域に於いてはアルカリ加水分解反応や二
量化反応によつて酸化力が低下したり、拡散性が
低下するため銀漂白力が著しく低下することが知
られている。従つて有機酸の金属錯塩による処理
液の銀漂白能力を高めるためには、処理液のPHを
低下させ、酸性域で使用すれば良いが、PHの低下
は銀漂白等によつて生成した有機酸の金属錯塩の
還元体による発色色素、特にシアン色素の還元反
応を促進しロイコ化する結果、色素画像が赤味を
おびるという重大な障害を生じさせる。
さらにPHの低下は、漂白定着液に於いては、有
機酸の金属錯塩の酸化力を増大させるために、定
着剤や定着剤の保恒剤として使用される亜硫酸イ
オンとの酸化還元反応速度が増加したり、定着剤
として一般的に使用されるチオ硫酸イオンのプロ
トンによる不均化反応が起りやすくなり、漂白定
着液の保存安定性が低下することが知られてい
る。このため漂白液または漂白定着液は、実用的
にはPH6〜PH8の範囲で使用される。
さらにハロゲン化銀カラー写真感光材料を自動
現像機により連続的に処理する際、発色現像工程
後、直接漂白又は漂白定着処理する場合に於いて
は、感光材料に付着して発色現像剤が漂白または
漂白定着液中に持ち込まれることにより、かなり
の濃度の発色現像剤が蓄積する。
こうした条件下で漂白液または漂白定着液をPH
6〜8に維持しながら処理する場合、混入して蓄
積した発色現像剤の還元性成分と反応して有機酸
の金属錯塩が還元され、有機酸の金属錯塩の還元
体が生成するため、銀漂白力が低下すると共に、
上記ロイコ化現象も更に起りやすくなる。又、PH
6未満の漂白又は漂白定着液では銀漂白能力は高
いにもかかわらず、ロイコ化現象が生じやすいと
いう不都合があつた。
一方有機酸の金属錯塩を含有した漂白液または
漂白定着液の銀漂白力を増加させるため、漂白促
進剤の開発等に多大な努力がなされたにもかかわ
らずいまだに充分な結果が得られていないのが実
情である。また上記ロイコ化現象を解消するため
に、漂白または漂白定着後にロイコ化した発色色
素を顕色するための、赤血塩等を含む酸化浴を設
ける例も見られたが、この方法では処理工程を一
つ増やすことになり、処理の迅速化、簡素化とい
う要請に逆行し、また公害発生の危険性があると
いうことからも好ましいものではない。
そこで本発明の第1の目的は、自動現像機によ
つて連続的に発色現像から直接漂白定着処理する
際に、高い銀漂白能力を維持させるようにしたハ
ロゲン化銀カラー写真感光材料の処理方法を提供
することにある。
本発明の第2の目的は、自動現像機によつて連
続的に発色現像から直接漂白定着処理する際に、
色素のロイコ化現象が見られないようにしたハロ
ゲン化銀カラー写真感光材料の処理方法を提供す
ることにある。
本発明の第3の目的は、自動現像機によつて連
続的に発色現像から直接漂白定着する際に、常に
安定した漂白定着能力を維持することができるハ
ロゲン化銀カラー写真感光材料の処理方法を提供
することにある。
本発明の前記目的は、像様露光されたハロゲン
化銀カラー写真感光材料を、自動現像機により芳
香族第一級アミン発色現像主薬を含む発色現像か
ら直接有機酸の金属錯塩を含有する漂白定着液に
よつて連続的に処理する処理方法において、該漂
白定着液に含まれる発色現像液が30%以上であ
り、該漂白定着液のPHが4.5〜5.5であることを特
徴とするハロゲン化銀カラー写真感光材料の処理
方法によつて達成される。
有機酸の金属錯塩を含有する漂白定着液とは、
ハロゲン化銀カラー写真感光材料の発色現像工程
において生成された金属塩を漂白定着できる能力
を有する処理液を意味する。
本発明は特に漂白定着処理する方法に適してい
る。
一般に、自動現像機によつて連続的に発色現像
から直接漂白定着処理する場合、写真感光材料に
付着して持ち込まれることによつて漂白定着液中
に蓄積する発色現像液の量は、発色現像直後のス
クイーズの程度や、漂白定着補充液の量によつて
任意に設定することができる。しかし、漂白定着
液中に持ち込まれる発色現像液を、漂白定着液の
30%以上に、且つ漂白定着液のPHを4.5〜5.5に維
持しながら連続的に処とすることにより、高い銀
漂白力を保ちながら且つロイコ化現象の発生を低
減させることができ、更に漂白定着液の液安定性
を低下させないということは全く知られていな
い。かかる現象の解明は末だ充分になさていない
が、こうした条件下では、漂白定着液中に存在す
る発色現像剤、特に芳香族第一級アミン発色現像
主薬が有効に作用するためと予想される。
漂白定着液中の発色現像液が30%以上でも、漂
白定着液のPHが4.5未満の場合、ロイコ化現象が
生じると共に漂白定着液の液安定性が低下し、漂
白定着液のPHが5.5を越えるとロイコ化現象が生
じる。
さらに漂白定着液のPHが4.5〜5.5であつても、
漂白定着液中の発色現像液が30%未満である場
合、ロイコ化現象が生じると共に漂白定着液の安
定性が低下する。
本発明における有機酸の金属錯塩とは、現像に
よつて生成した金属銀を酸化してハロゲン化銀に
かえる作用を有するもので、その構造はアミノポ
リカルボン酸または蓚酸、クエン酸等の有機酸
で、鉄、コバルト、銅等の金属イオンを配位した
ものである。このような有機酸の金属錯塩を形成
するために用いられる最も好ましい有機酸として
は、たとえば下記一般式〔〕または〔〕で示
されるアミノポリカルボン酸がある。
一般式〔〕
HOCO−A1−Z−A2−COOH
一般式〔〕
〔前記各一般式中、A1、A2、A3、A4、A5および
A6はそれぞれ置換もしくは無置換炭化水素基、
Zは炭化水素基、酸素原子、硫黄原子もしくは
N−A7(A7は炭化水素基もしくは低級脂肪族カル
ボン酸)を表わす〕。
これらのアミノポリカルボン酸はアルカリ金属
塩、アンモニウム塩もしくは水溶性アミン塩であ
つてもよい。前記一般式〔〕または〔〕で示
されるアミノポリカルボン酸の代表的な例として
は次の如きものを挙げることができる。
エチレンジアミンテトラ酢酸
ジエチレントリアミンペンタ酢酸
エチレンジアミン−N−(β−ヒドロオキシエ
チル)−N,N′,N′−トリ酢酸
プロピレンジアミンテトラ酢酸
ニトリロトリ酢酸
シクロヘキサンジアミンテトラ酢酸
イミノジ酢酸
メチルイミノジ酢酸
エチルイミノジ酢酸
ヒドロキシエチルイミノジ酢酸
プロピルイミノジ酢酸
ブチルイミノジ酢酸
ジヒドロキシエチルグリシン
エチルエーテルジアミンテトラ酢酸
グリコールエーテルジアミンテトラ酢酸
エチレンジアミンテトラプロピオン酸
フエニレンジアミンテトラ酢酸
エチレンジアミンテトラ酢酸ジナトリウム塩
エチレンジアミンテトラ酢酸テトラ(トリメチ
ルアンモニウム)塩
エチレンジアミンテトラ酢酸テトラナトリウム
塩
ジエチレントリアミンペンタ酢酸ペンタナトリ
ウム塩
エチレンジアミン−N−(β−ヒドロオキシエ
チル)−N,N′,N′−トリ酢酸ナトリウム塩
プロピレンジアミンテトラ酢酸ナトリウム塩ニ
トリロトリ酢酸ナトリウム塩
シクロヘキサンジアミンテトラ酢酸ナトリウム
塩
本発明に用いられる有機酸の金属錯塩における
金属とは、有機酸と配位結合できる金属であつ
て、例えばクロム、マンガン、鉄、コバルト、ニ
ツケル、銅等があり、本発明に特に好ましいもの
は鉄である。
本発明における有機酸の金属錯塩は、上記の有
機酸と金属のあらゆる組合せが可能であるが、特
に好ましいものはエチレンジアミンテトラ酢酸の
第2鉄塩、例えばエチレンジアミンテトラ酢酸鉄
()ナトリウム、エチレンジアミンテトラ酢酸
鉄()アンモニウムである。また構造を異にす
る2種以上の有機酸の金属錯塩を併用してもよ
い。具体的な使用量は処理液1当り約5〜400
g、特に処理液1当り約10〜200gの範囲で使
用するのが好ましい。
本発明において使用される漂白定着液としては
前記の如き有機酸の金属錯塩(例えば鉄錯塩)を
漂白剤として含有するとともにチオ硫酸塩、チオ
シアン酸塩、チオ尿素類等のハロゲン化銀定着剤
を含有する組成の液が適用される。また、漂白剤
と前記のハロゲン化銀定着剤の他に臭化カリウム
の如きハロゲン化合物を少量添加した組成からな
る漂白定着液、あるいは逆に臭化カリウムの如き
ハロゲン化合物を多量に添加した組成からなる漂
白定着液、さらには漂白剤と多量の臭化カリウム
の如きハロゲン化合物との組合せからなる組成の
特殊な漂白定着液等も用いることができる。
前記のハロゲン化合物としては臭化カリウムの
他に塩化水素酸、臭化水素酸、臭化リチウム、臭
化ナトリウム、臭化アンモニウム、沃化カリウ
ム、沃化アンモニウム等も使用することができ
る。
漂白定着液に含ませるハロゲン化銀定着剤とし
ては通常の定着処理に用いられるようなハロゲン
化銀と反応して水溶性の錯塩を形成する化合物、
たとえばチオ硫酸カリウム、チオ硫酸ナトリウ
ム、チオ硫酸アンモニウムの如きチオ硫酸塩、チ
オシアン酸カリウム、チオシアン酸ナトリウム、
チオシアン酸アンモニウムの如きチオシアン酸
塩、あるいはチオ尿素、チオエーテル、高濃度の
臭化物、ヨウ化物等がその代表的なものである。
なお漂白定着液には硼酸、硼砂、水酸化ナトリ
ウム、水酸化カリウム、炭酸ナトリウム、炭酸カ
リウム、重炭酸ナトリウム、重炭酸カリウム、酢
酸、酢酸ナトリウム、水酸化アンモニウム等の各
種の塩からなるPH緩衝剤を単独であるいは2種以
上組合せて含有せしめることができる。さらにま
た、各種の螢光増白剤や消泡剤あるいは界面活性
剤を含有せしめることもできる。
また、ヒドロキシルアミン、ヒドラジン、亜硫
酸塩、異性重亜硫酸塩、アルデヒドやケトン化合
物の重亜硫酸付加物等の保恒剤、アミノポリカル
ボン酸等の有機キレート剤あるいはニトロアルコ
ール硝酸塩等の一種の安定剤、アルカノールアミ
ン等の可溶化剤、有機アミン等のステイン防止
剤、メタノール、ジメチルフオルムアミド、ジメ
チルスルフオキシド等の有機溶媒を適宜含有せし
めることができる。
本発明に使用される漂白定着液による処理温度
は、通常18℃〜60℃で使用されるが、迅速処理と
しては24℃以上が好ましい。
本発明に使用される発色現像工程は、発色現像
主薬を含有するアルカリ性の発色現像液によつて
行なわれる。発色現像主薬はp−アミノフエノ−
ル、p−フエニレンジアミンまたはp−スルホン
アミドアニリンのような任意の芳香族第一級アミ
ン発色現像主薬が適用できる。使用できる発色現
像主薬に含め得るものとしては3−アセトアミド
−4−アミノ−N,N−ジエチルアニリン、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、N,N−ジエチル−p−フエニ
レンジアミン、2−アミノ−5−ジエチルアミノ
トルエン、N−エチル−N−(β−メタンスルホ
ンアミドエチル)−3−メチル−4−アミノアニ
リン、4−アミノ−N−エチル−3−メチル−N
−(β−スルホエチル)アニリン、2−メトキシ
−4−フエニルスルホンアミドアニリン、2,6
−ジブロモ−4−アミノフエノール等がある。有
用なその他の典型的な発色現像主薬については、
ミーズおよびジエームス著「ザ・セオリー・オ
ブ・ザ・フオトグラフイツク・プロセス」第3
版、1966年マクミラン・カンパニー、ニユーヨー
ク、278〜311頁、米国特許第3813244号および同
第3791827号明細書を参照することができる。本
発明において特に良好な結果を与える芳香族第一
級アミン発色現像主薬は、4−アミノ−N,N−
ジエチルアニリン塩酸塩、4−アミノ−3−メチ
ル−N,N−ジエチルアニリン塩酸塩、4−アミ
ノ−3−メチル−N−エチル−N−(β−メタン
スルホンアミドエチル)アニリンサルフエートハ
イドレート、4−アミノ−3−メチル−N−エチ
ル−N−β−ヒドロキシエチルアニリン硫酸塩、
4−アミノ−3−ジメチルアミノ−N,N−ジエ
チルアニリンサルフエートハイドレート、4−ア
ミノ−3−メトキシ−N−エチル−N−β−ヒド
ロキシエチルアニリン塩酸塩、4−アミノ−3−
(β−メタンスルホンアミドエチル)N,N−ジ
エチルアニリン2塩酸塩および4−アミノ−N−
エチル−N−(2−メトキシエチル)−m−トルイ
ジン2P−トルエンスルホン酸塩である。
本発明において使用される発色現像液は、前記
芳香族第一級アミン発色現像主薬に加えて、更
に、発色現像液に通常添加されている種々の成
分、例えば水酸化ナトリウム、炭酸ナトリウム、
炭酸カリウムなどのアルカリ剤、アルカリ金属亜
硫酸塩、アルカリ金属重亜硫酸塩、アルカリ金属
チオシアン酸塩、アルカリ金属ハロゲン化物、ベ
ンジルアルコール、水軟化剤および濃厚化剤など
を任意に含有することもできる。
この発色現像液のPH値は、通常7以上であり、
最も一般的には約9.5〜約13である。
本発明に係る処理方法においては、発色現像、
漂白定着工程のほかに、画像安定、硬膜、中和、
黒白現像、反転、停止、少量水洗、水洗、リンス
工程等、必要に応じて既知の補助工程が付け加え
られてもよい。
本発明に係る処理方法は、像様露光されたハロ
ゲン化銀カラー写真感光材料を自動現像機により
発色現像から直接有機酸の金属錯塩を含有する漂
白定着液によつて連続的に処理する方法であつ
て、かつ該漂白定着液中に持ち込まれる発色現像
液が、該漂白定着液の30%以上であり、該漂白定
着液のPHが4.5〜5.5であるハロゲン化銀カラー写
真感光材料の処理方法のすべてを包含するが、そ
の好ましい処理方法の代表的具体例を挙げると、
下記の諸工程が含まれる。
〔1〕 発色現像→漂白定着→水洗
〔2〕 発色像→漂白定着→少量水洗→水洗
〔3〕 発色現像→漂白定着→水洗→安定
〔4〕 発色現像→漂白定着→安定
本発明に係る処理方法は、発色剤が写真感光材
料中に含まれている所謂内式現像方式(米国特許
第2376679号、同第2232027号及び同第2801171号
明細書等参照。)のほか、発色剤が発色現像液中
に共存する所謂外式現像方式(米国特許第
2252718号、同第2592243号及び同第2590970号明
細書等参照。)にも適用できる。
本発明に係る処理方法が適用されるカラー写真
感光材料は、基本的には支持体上にそれぞれ感光
波長が異なる少くとも1層のハロゲン化銀乳剤層
を有する。ハロゲン化銀としては臭化銀、塩臭化
銀、沃化銀、沃臭化銀、塩沃臭化銀、塩化銀等の
通常のハロゲン化銀写真乳剤に使用される任意の
ものが包含される。これらは種々の製法、例えば
正混合、同時混合コンバージヨン法等いずれの方
法でつくられたものでも良く、その粒径、晶癖、
混合比等を問わない。
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にはカプラーとして種々な
ものが用いられてもよく、例えばイエローカプラ
ーとしては開鎖ケトメチレン型カプラーを、マゼ
ンタカプラーとしてはピラゾロン系、ピラゾロト
リアゾール系、ピラゾリノベンツイミダゾール
系、イミダゾロン系などの化合物をあげることが
できる。シアンカプラーとしては、ナフトール
系、フエノール系の化合物を挙げることができ
る。
シアンカプラーとしては、下記一般式〔〕、
〔〕または〔〕で示されるシアンカプラーが
好ましい。
一般式〔〕
〔式中、R1はハロゲン原子、水素原子または低
級アルキル基、R2は水素原子、ハロゲン原子ま
たは低級アルキル基、R3は置換基を有しても良
いアシルアミノ基、X1はカツプリング反応に於
いて脱離可能な基(例えば水素原子、ハロゲン原
子、酸素原子、イオウ原子または窒素原子が直接
活性点に結合しているアリールオキシ基、カルバ
モイルオキシ基、カルバモイルメトキシ基、アシ
ルオキシ基、アルキルオキシ基、スルホンアミド
基、ジアゾ基、コハク酸アミド基を示す。〕
一般式〔〕
〔式中、R4は置換基を有してもよいアルキル基
または置換基を有してもよいアリール基、X2は
前記X1と同義である。〕
一般式〔〕
〔式中、R5は前記R1と同義、R6、R7は前記R3と
同義、X3は前記X1と同義である。〕
これら一般式〔〕、〔〕および〔〕で示さ
れるシアンカプラーは、例えば米国特許第
2423730号、同第3998642号、同第3779763号、同
第2447293号、同第2895826号の各明細書、特開昭
55−108662号、同53−109630号、同50−112038
号、同51−6551号、同55−163537号、同56−
29239号の各公報、特願昭55−2305号、同55−
2755号の各明細書等に記載してある一般的な合成
法にて合成できる。
また、本発明に於いては、前記一般式〔〕で
示されるシアンカプラーを用いたハロゲン化銀カ
ラー写真感光材料の処理の際に、とりわけ著しく
好ましい効果を得ることができる。
また、本発明に係る処理方法は、カラーペーパ
ー、カラーネガフイルム、カラーポジフイルム、
スライド用カラー反転フイルム、映画用カラー反
転フイルム、TV用カラー反転フイルム、反転カ
ラーペーパーなどのハロゲン化銀カラー写真感光
材料に適用することができる。
以下、実施例によつて本発明の詳細を説明する
が、これにより本発明の実施の態様が限定される
ものではない。
実施例 1
白色顔料としてアナターゼ型の酸化チタンを含
むポリエチレン層によつて、表面を被覆した紙支
持体上にコロナ放電による前処理を施こした後、
次の各層を順次塗設してカラー印画紙を作つた。
第1層:イエローカプラーとしてα−〔4−(1
−ベンジル−2−フエニル−3,5−ジオキソ−
1,2,4−トリアゾリジル)〕−α−ビバリル−
2−クロロ−5−〔γ−(2,4−ジ−t−アミル
フエノキシ)ブチルアミド〕アセトアニリドを含
有し、5モル%の塩化銀を含む青感性塩臭化銀乳
剤層。
第2層:紫外線吸収剤を含有するゼラチン中間
層。
第3層:マゼンタカプラーとして1−(2,4,
6−トリクロロフエニル)−3−(2−クロロ−5
−オクタテセニルサクシンイミドアニリノ)−5
ピラゾロンを含有し、15モル%の塩化銀を含む緑
感性塩臭化銀乳剤層。
第4層:第2層と同じゼラチン中間層。
第5層:シアンカプラーとして例示化合物−
2を含有し、15モル%塩化銀を含む赤感性塩臭化
銀乳剤層。
第6層:ゼラチン保護層。
上記の各感光性乳剤層は、総体の銀量が100cm2
当り10mgとなるように塗布した。また各感光性乳
剤層に用いたハロゲン化銀写真乳剤はそれぞれチ
オ硫酸ナトリウムにより化学増感を施し、安定
剤、増感色素等通常の添加剤を加えた。またすべ
ての層の塗布液には硬膜剤及び延展剤を添加し
た。
以上のようにして作つたカラー印画紙(ロール
状)を絵焼プリント後、ロール自動現像機で連続
補充処理(以下、ランニング処理と称する。)し
た。
〔基準処理工程〕
1.発色現像 33℃ 3分30秒
2.漂白定着 33℃ 1分30秒
3.水洗 30〜35℃ 3分
4.乾燥 75〜80℃ 約2分
処理液の組成は次の通りである。
〔発色現像タンク液〕
ベンジルアルコール 15ml
エチレングリコール 15ml
亜硫酸カリウム 2.0g
臭化カリウム 0.7g
塩化ナトリウム 0.2g
炭酸カリウム 30.0g
ヒドロキシルアミン硫酸塩 3.0g
ポリリン酸(TPPS) 2.5g
3−メチル−4−アミノ−N−エチル−N−
(β−メタンスルホンアミドエチル)アニリ
ン硫酸塩 5.5g
螢光増白剤(4,4′−ジアミノスチルベンジ
スルホン酸誘導体 1.0g
水酸化カリウム 2.0g
水を加えて1とする。〔発色現像補充液〕
ベンジルアルコール 20ml
エチレングリコール 20ml
亜硫酸カリウム 3.0g
炭酸カリウム 30.0g
ヒドロキシルアミン硫酸塩 4.0g
ポリリン酸(TPPS) 3.0g
3−メチル−4アミノ−Nエチル−N−(β
−メタンスルホンアミドエチル)アニリン硫
酸塩 7.0g
螢光増白剤(4,4′−ジアミノスチルベンジ
ルスホン酸誘導体) 1.5g
水酸化カリウム 3.0g
水を加えて全量を1とする。
〔漂白定着タンク液〕
エチレンジアミンテトラ酢酸第鉄アンモニ
ウム2水塩 30.0g
エチレンジアミンテトラ酢酸 1.8g
チオ硫酸アンモニウム(70%溶液) 100ml
亜硫酸アンモニウム(40%溶液) 27.5ml
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
〔漂白定着補充液(1)−A〕
エチレンジアミンテトラ酢酸第鉄アンモニ
ウム2水塩 78g
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
〔漂白定着補充液(1)−B〕
チオ硫酸アンモニウム(70%溶液) 262ml
亜硫酸アンモニウム(40%溶液) 72ml
エチレンジアミンテトラ酢酸 4.7g
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
〔漂白定着補充液(2)−A〕
エチレンジアミンテトラ酢酸第鉄アンモニ
ウム2水塩 89.5g
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
〔漂白定着補充液(2)−B〕
チオ硫酸アンモニウム(70%溶液) 299ml
亜硫酸アンモニウム(40%溶液) 82ml
エチレンジアミンテトラ酢酸 5.4g
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
〔漂白定着補充液(3)−A〕
エチレンジアミンテトラ酢酸第鉄アンモニ
ウム2水塩 114g
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
〔漂白定着補充液(3)−B〕
チオ硫酸アンモニウム(70%溶液) 382ml
亜硫酸アンモニウム(40%溶液) 105ml
エチレンジアミンテトラ酢酸 6.9g
氷酢酸又はアンモニア水でPHを調整
水を加えて全量を1とする。
自動現像機に上記の発色現像タンク液、漂白定
着タンク液および水を満たし、上記カラー印画紙
を処理しながら、3分間隔毎に上記した発色現像
補充液と漂白定着補充液A、Bを定量カツプを通
じて補充しながら下記第1表に示される(1)〜
(13)のランニング処理テストを行なつた。カラ
ー印画紙1m2当りの発色現像タンクへの補充量は
324mlとした。また漂白定着タンク前後のスクイ
ーズを調整し、カラー印画紙1m2当りの漂白定着
液への発色現像液の持ち込み量及び漂白定着タン
クからの漂白定着液の持ち出し量を共に50.5mlと
した。
漂白定着液補充液A、Bの合計使用量が、漂白
定着浴のタンク容量の4倍になるまでランニング
処理を行ない、漂白定着タンク液の組成を解析
し、発色現像液の蓄積量とPHをチエツクした。
The present invention relates to a method for processing a silver halide color photographic material, and more particularly to a method for processing a silver halide color photographic material continuously with a bleach-fix solution in an automatic processor. Generally, in order to obtain a color image by continuously processing an imagewise exposed silver halide color photographic light-sensitive material using an automatic processor, after the color development step, a processing solution having bleaching ability is used to remove the generated metallic silver. A step of processing is provided. Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added after the bleaching step, but with a bleach-fixing solution, bleaching and fixing are performed in one step. In the bleaching step or bleach-fixing step, components of the processing solution from the previous step that are brought in adhering to the silver halide color photographic light-sensitive material, composition components consumed by bleaching or bleach-fixing, and silver halide color photographic light-sensitive materials are In order to always maintain a constant concentration of components eluted from the material and accumulated in the bleach or bleach-fix solution in the bleach or bleach-fix solution, a suitable amount of a bleach or bleach-fix replenisher having an appropriate composition is replenished. Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in processing silver halide color photographic light-sensitive materials. . However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate have relatively good bleaching power for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body.
It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizing agents such as thiosulfates in the same processing solution, making it difficult to use these oxidizing agents in bleach-fixing baths. is almost impossible, which makes it difficult to achieve the goal of speeding up and simplifying the process. Furthermore, processing liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse the waste liquid after treatment without discarding it. On the other hand, metal complex salts of organic acids, such as aminopolycarboxylic acid metal complex salts, are used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling the reuse of waste liquids. In recent years, treatment solutions have come to be used. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. . In general, in neutral or alkaline environments, the oxidizing power of metal complex salts of organic acids decreases due to alkaline hydrolysis reactions and dimerization reactions, and the diffusivity decreases, resulting in a significant decrease in silver bleaching power. Are known. Therefore, in order to increase the silver bleaching ability of a treatment solution using a metal complex salt of an organic acid, it is sufficient to lower the pH of the treatment solution and use it in an acidic range. As a result of promoting the reduction reaction of coloring dyes, particularly cyan dyes, by reduced forms of acid metal complex salts and converting them into leuco, a serious problem arises in that dye images take on a reddish tinge. Furthermore, a decrease in pH is caused by an increase in the oxidizing power of the metal complex salt of an organic acid in the bleach-fix solution, which reduces the rate of redox reaction with the fixing agent and sulfite ions used as a preservative for the fixing agent. It is known that the storage stability of the bleach-fix solution decreases as a result of the disproportionation reaction caused by protons of thiosulfate ion commonly used as a fixing agent. For this reason, the bleaching solution or bleach-fixing solution is practically used within the range of PH6 to PH8. Furthermore, when silver halide color photographic light-sensitive materials are continuously processed using an automatic processor, and when bleaching or bleach-fixing is performed directly after the color development process, the color developer may adhere to the light-sensitive material and cause bleaching or bleaching. Significant concentrations of color developer accumulate by being carried into the bleach-fix solution. Under these conditions, the bleach or bleach-fix solution should be
When processing while maintaining the temperature of 6 to 8, the metal complex salt of the organic acid is reduced by reacting with the reducing component of the mixed and accumulated color developer, and a reduced form of the metal complex salt of the organic acid is produced. As the bleaching power decreases,
The above-mentioned leucoization phenomenon also becomes more likely to occur. Also, PH
Bleaching or bleach-fixing solutions with a concentration of less than 6 have the disadvantage that leucoization tends to occur even though the silver bleaching ability is high. On the other hand, although great efforts have been made to develop bleaching accelerators to increase the silver bleaching power of bleaching solutions or bleach-fixing solutions containing metal complex salts of organic acids, satisfactory results have not yet been obtained. That is the reality. In addition, in order to eliminate the above-mentioned leuco-formation phenomenon, there have been cases in which an oxidation bath containing red blood salt, etc. is provided to develop the leuco-formed color pigment after bleaching or bleach-fixing. This is not desirable because it goes against the demands of speeding up and simplifying the processing, and there is also the risk of causing pollution. Therefore, the first object of the present invention is to maintain a high silver bleaching ability during continuous color development and direct bleach-fixing processing using an automatic processor. Our goal is to provide the following. A second object of the present invention is to provide continuous bleach-fixing processing from color development to direct bleach-fixing using an automatic processor.
It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material in which the phenomenon of dye leucoization is not observed. A third object of the present invention is a method for processing a silver halide color photographic light-sensitive material that can always maintain a stable bleach-fixing ability during continuous color development and direct bleach-fixing using an automatic processor. Our goal is to provide the following. The object of the present invention is to directly process an imagewise exposed silver halide color photographic light-sensitive material by an automatic processor from color development containing an aromatic primary amine color developing agent to bleach-fixing containing a metal complex salt of an organic acid. A silver halide treatment method in which the bleach-fix solution contains a color developing solution of 30% or more, and the bleach-fix solution has a pH of 4.5 to 5.5. This is achieved by a method for processing color photographic materials. What is a bleach-fix solution containing a metal complex salt of an organic acid?
It refers to a processing solution that has the ability to bleach and fix metal salts produced in the color development process of silver halide color photographic materials. The present invention is particularly suitable for bleach-fixing processes. Generally, when color development and direct bleach-fixing are carried out continuously using an automatic processor, the amount of color developer that accumulates in the bleach-fix solution due to adhesion to the photographic light-sensitive material is It can be set arbitrarily depending on the degree of squeezing immediately after and the amount of bleach-fixing replenisher. However, the color developing solution brought into the bleach-fix solution is
By continuously treating the bleach-fix solution at 30% or more while maintaining the pH of the bleach-fix solution at 4.5 to 5.5, it is possible to maintain high silver bleaching power and reduce the occurrence of leucoization, which further improves bleaching properties. It is not known at all that it does not reduce the liquid stability of the fixer. Although this phenomenon has not yet been fully elucidated, it is expected that under these conditions, the color developing agent present in the bleach-fix solution, especially the aromatic primary amine color developing agent, acts effectively. . Even if the color developer in the bleach-fix solution is 30% or more, if the pH of the bleach-fix solution is less than 4.5, a leuco conversion phenomenon occurs and the stability of the bleach-fix solution decreases, causing the pH of the bleach-fix solution to drop below 5.5. If it is exceeded, a leucoization phenomenon occurs. Furthermore, even if the pH of the bleach-fix solution is 4.5 to 5.5,
If the content of the color developer in the bleach-fix solution is less than 30%, a leuco conversion phenomenon occurs and the stability of the bleach-fix solution decreases. The metal complex salt of an organic acid in the present invention has the effect of oxidizing metallic silver produced by development and converting it into silver halide, and its structure is based on an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid. It is coordinated with metal ions such as iron, cobalt, and copper. The most preferred organic acid used to form such a metal complex salt of an organic acid is, for example, an aminopolycarboxylic acid represented by the following general formula [] or []. General formula [] HOCO−A 1 −Z−A 2 −COOH General formula [] [In each of the above general formulas, A 1 , A 2 , A 3 , A 4 , A 5 and
A 6 is a substituted or unsubstituted hydrocarbon group, respectively;
Z represents a hydrocarbon group, an oxygen atom, a sulfur atom, or N- A7 ( A7 is a hydrocarbon group or a lower aliphatic carboxylic acid)]. These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [] or [] include the following. Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Cyclohexanediaminetetraacetic acid Iminodiacetic acid Methyliminodiacetic acid Ethyliminodiacetic acid Hydroxyethyliminodiacetic acid Propyl Iminodiacetic acid Butyliminodiacetic acid Dihydroxyethylglycine Ethyl etherdiaminetetraacetic acid Glycol etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Phenylenediaminetetraacetic acid Ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriamine penta Acetic acid pentasodium salt Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt Propylenediaminetetraacetic acid sodium salt Nitrilotriacetic acid sodium salt Cyclohexanediaminetetraacetic acid sodium salt Organic material used in the present invention The metal in the metal complex salt of an acid is a metal capable of coordinating with an organic acid, such as chromium, manganese, iron, cobalt, nickel, copper, etc., and iron is particularly preferred in the present invention. The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned organic acid and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, such as sodium iron() ethylenediaminetetraacetate, ethylenediaminetetraacetic acid Iron () ammonium. Further, metal complex salts of two or more organic acids having different structures may be used in combination. The specific amount used is approximately 5 to 400 per treatment solution.
It is particularly preferable to use an amount of about 10 to 200 g per treatment solution. The bleach-fix solution used in the present invention contains a metal complex salt of an organic acid (for example, an iron complex salt) as a bleaching agent, as well as a silver halide fixing agent such as a thiosulfate, a thiocyanate, or a thiourea. A liquid containing a composition is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used. As the halogen compound mentioned above, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can also be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing processing.
For example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. The bleach-fix solution contains a PH buffer consisting of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, organic chelating agents such as aminopolycarboxylic acids, or a type of stabilizer such as nitroalcohol nitrates, A solubilizing agent such as an alkanolamine, a stain inhibitor such as an organic amine, an organic solvent such as methanol, dimethyl formamide, dimethyl sulfoxide, etc. can be appropriately contained. The processing temperature with the bleach-fix solution used in the present invention is usually 18°C to 60°C, but preferably 24°C or higher for rapid processing. The color development step used in the present invention is carried out using an alkaline color developer containing a color developing agent. The color developing agent is p-aminophenol.
Any aromatic primary amine color developing agent can be applied, such as p-phenylenediamine, p-phenylene diamine or p-sulfonamide aniline. Color developing agents that can be used include 3-acetamido-4-amino-N,N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate, N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, N-ethyl-N-(β-methanesulfonamidoethyl )-3-methyl-4-aminoaniline, 4-amino-N-ethyl-3-methyl-N
-(β-sulfoethyl)aniline, 2-methoxy-4-phenylsulfonamide aniline, 2,6
-dibromo-4-aminophenol and the like. Other typical color developing agents that are useful include:
Mees and James, The Theory of the Photographic Process, No. 3
ed., 1966 Macmillan Company, New York, pp. 278-311, US Pat. No. 3,813,244 and US Pat. No. 3,791,827. An aromatic primary amine color developing agent that gives particularly good results in the present invention is 4-amino-N,N-
Diethylaniline hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate,
4-amino-3-dimethylamino-N,N-diethylaniline sulfate hydrate, 4-amino-3-methoxy-N-ethyl-N-β-hydroxyethylaniline hydrochloride, 4-amino-3-
(β-methanesulfonamidoethyl)N,N-diethylaniline dihydrochloride and 4-amino-N-
Ethyl-N-(2-methoxyethyl)-m-toluidine 2P-toluenesulfonate. In addition to the aromatic primary amine color developing agent, the color developing solution used in the present invention further contains various components normally added to color developing solutions, such as sodium hydroxide, sodium carbonate,
It can also optionally contain alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like. The PH value of this color developer is usually 7 or more,
Most commonly from about 9.5 to about 13. In the processing method according to the present invention, color development,
In addition to the bleach-fixing process, image stabilization, hardening, neutralization,
Known auxiliary steps may be added as necessary, such as black and white development, reversal, stopping, washing with a small amount of water, washing with water, and rinsing. The processing method according to the present invention is a method in which an imagewise exposed silver halide color photographic light-sensitive material is continuously processed with a bleach-fix solution containing a metal complex salt of an organic acid directly from color development using an automatic processor. A method for processing a silver halide color photographic light-sensitive material, wherein the color developing solution carried into the bleach-fix solution accounts for 30% or more of the bleach-fix solution, and the pH of the bleach-fix solution is 4.5 to 5.5. Examples of preferred treatment methods include:
The following steps are included. [1] Color development → bleach-fixing → washing [2] Color image → bleach-fixing → washing with a small amount of water → washing with water [3] Color development → bleach-fixing → washing with water → stabilization [4] Color development → bleach-fixing → stabilization Processing according to the present invention Methods include the so-called internal development method in which a color former is contained in the photographic light-sensitive material (see the specifications of U.S. Pat. The so-called external development method (U.S. Patent No.
See specifications of No. 2252718, No. 2592243, No. 2590970, etc. ) can also be applied. A color photographic light-sensitive material to which the processing method according to the present invention is applied basically has at least one silver halide emulsion layer on a support, each layer having a different sensitivity wavelength. Examples of silver halide include silver bromide, silver chlorobromide, silver iodide, silver iodobromide, silver chloroiodobromide, silver chloride, and any other compounds used in ordinary silver halide photographic emulsions. Ru. These may be produced by any of a variety of methods, such as direct mixing and simultaneous mixing conversion methods, and their particle size, crystal habit,
The mixing ratio does not matter. Various couplers may be used in the silver halide color photographic light-sensitive material applied to the processing method according to the present invention. For example, as a yellow coupler, an open-chain ketomethylene coupler is used, and as a magenta coupler, a pyrazolone type or a pyrazolone type coupler is used. Examples include compounds such as zolotriazole, pyrazolinobenzimidazole, and imidazolone. Examples of cyan couplers include naphthol and phenol compounds. As a cyan coupler, the following general formula [],
Cyan couplers represented by [ ] or [ ] are preferred. General formula [] [In the formula, R 1 is a halogen atom, a hydrogen atom or a lower alkyl group, R 2 is a hydrogen atom, a halogen atom or a lower alkyl group, R 3 is an acylamino group which may have a substituent, and X 1 is an acylamino group that may have a substituent. A group that can be removed (for example, an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, an alkyloxy group in which a hydrogen atom, halogen atom, oxygen atom, sulfur atom, or nitrogen atom is directly bonded to the active site) , represents a sulfonamide group, a diazo group, and a succinamide group.] General formula [] [In the formula, R 4 is an alkyl group which may have a substituent or an aryl group which may have a substituent, and X 2 has the same meaning as X 1 above. ] General formula [ ] [In the formula, R 5 has the same meaning as R 1 , R 6 and R 7 have the same meaning as R 3 , and X 3 has the same meaning as X 1 . ] Cyan couplers represented by these general formulas [], [] and [] are disclosed in, for example, US Pat.
Specifications of No. 2423730, No. 3998642, No. 3779763, No. 2447293, and No. 2895826, JP-A-Sho
No. 55-108662, No. 53-109630, No. 50-112038
No. 51-6551, No. 55-163537, No. 56-
Publications No. 29239, Japanese Patent Application No. 55-2305, No. 55-
It can be synthesized by the general synthesis method described in each specification of No. 2755. Further, in the present invention, especially remarkable effects can be obtained when processing a silver halide color photographic light-sensitive material using a cyan coupler represented by the above general formula []. Further, the processing method according to the present invention can be applied to color paper, color negative film, color positive film,
It can be applied to silver halide color photographic materials such as color reversal film for slides, color reversal film for movies, color reversal film for TVs, and color reversal paper. Hereinafter, the details of the present invention will be explained with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 After pretreatment by corona discharge on a paper support coated on the surface with a polyethylene layer containing anatase titanium oxide as white pigment,
Color photographic paper was made by applying each of the following layers in sequence. 1st layer: α-[4-(1
-benzyl-2-phenyl-3,5-dioxo-
1,2,4-triazolidyl)]-α-bivalyl-
A blue-sensitive silver chlorobromide emulsion layer containing 2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide and containing 5 mol% silver chloride. Second layer: gelatin intermediate layer containing UV absorbers. 3rd layer: 1-(2,4,
6-trichlorophenyl)-3-(2-chloro-5
-octatecenyl succinimide anilino)-5
Green-sensitive silver chlorobromide emulsion layer containing pyrazolone and containing 15 mol% silver chloride. 4th layer: gelatin middle layer same as 2nd layer. 5th layer: Exemplary compound as cyan coupler
2 and a red-sensitive silver chlorobromide emulsion layer containing 15 mol% silver chloride. 6th layer: gelatin protective layer. Each of the above photosensitive emulsion layers has a total silver content of 100 cm 2
It was applied at a dose of 10 mg per coat. The silver halide photographic emulsions used in each light-sensitive emulsion layer were chemically sensitized using sodium thiosulfate, and conventional additives such as stabilizers and sensitizing dyes were added. Further, a hardening agent and a spreading agent were added to the coating solution for all layers. After printing the color photographic paper (in roll form) produced as described above, it was subjected to continuous replenishment processing (hereinafter referred to as running processing) using an automatic roll developing machine. [Standard processing steps] 1. Color development 33°C 3 minutes 30 seconds 2. Bleach-fixing 33°C 1 minute 30 seconds 3. Washing 30-35°C 3 minutes 4. Drying 75-80°C approximately 2 minutes The composition of the processing solution is as follows. It is as follows. [Color development tank solution] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4-amino- N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative 1.0g Potassium hydroxide 2.0g Add water to make 1. [Color developer replenisher] Benzyl alcohol 20ml Ethylene glycol 20ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g Polyphosphoric acid (TPPS) 3.0g 3-Methyl-4amino-N-ethyl-N-(β
-Methanesulfonamidoethyl) aniline sulfate 7.0g Fluorescent brightener (4,4'-diaminostilbenzylsulfonic acid derivative) 1.5g Potassium hydroxide 3.0g Add water to bring the total amount to 1. [Bleach-fix tank solution] Ferrous ammonium ethylenediaminetetraacetic acid dihydrate 30.0g Ethylenediaminetetraacetic acid 1.8g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust pH with glacial acetic acid or aqueous ammonia Add water In addition, the total amount is set to 1. [Bleach-fixing replenisher (1)-A] Ferrous ammonium ethylenediaminetetraacetate dihydrate 78g Adjust pH with glacial acetic acid or aqueous ammonia Add water to bring the total volume to 1. [Bleach-fixing replenisher (1)-B] Ammonium thiosulfate (70% solution) 262ml Ammonium sulfite (40% solution) 72ml Ethylenediaminetetraacetic acid 4.7g Adjust the pH with glacial acetic acid or aqueous ammonia Add water to bring the total volume to 1 . [Bleach-fixing replenisher (2)-A] Ferrous ammonium ethylenediaminetetraacetate dihydrate 89.5g Adjust pH with glacial acetic acid or aqueous ammonia Add water to bring the total volume to 1. [Bleach-fix replenisher (2)-B] Ammonium thiosulfate (70% solution) 299ml Ammonium sulfite (40% solution) 82ml Ethylenediaminetetraacetic acid 5.4g Adjust the pH with glacial acetic acid or aqueous ammonia Add water to bring the total volume to 1 . [Bleach-fix replenisher (3)-A] Ferrous ammonium ethylenediaminetetraacetate dihydrate 114g Adjust pH with glacial acetic acid or aqueous ammonia Add water to bring the total volume to 1. [Bleach-fix replenisher (3)-B] Ammonium thiosulfate (70% solution) 382ml Ammonium sulfite (40% solution) 105ml Ethylenediaminetetraacetic acid 6.9g Adjust PH with glacial acetic acid or aqueous ammonia Add water to bring the total volume to 1 . Fill an automatic processor with the color developer tank solution, bleach-fix tank solution, and water, and while processing the color photographic paper, quantify the color developer replenisher and bleach-fix replenisher A and B at 3-minute intervals. As shown in Table 1 below while refilling through the cup (1) ~
We conducted the running processing test (13). The amount to replenish the color developing tank per 1m2 of color photographic paper is
The volume was 324ml. In addition, the squeeze before and after the bleach-fix tank was adjusted so that the amount of color developing solution carried into the bleach-fix solution and the amount of bleach-fix solution taken out from the bleach-fix tank per 1 m 2 of color photographic paper were both 50.5 ml. Perform the running process until the total amount of bleach-fix replenishers A and B becomes four times the tank capacity of the bleach-fix tank, analyze the composition of the bleach-fix tank solution, and calculate the accumulated amount of color developer and pH. I checked.
【表】
ランニングテスト終了時に、処理後のカラーペ
ーパーの黒化部分をPDA−60型光電濃度計〔小
西六写真工業(株)製〕を用いてシアン色素の反射濃
度を測定した。更に螢光X線分析により、処理後
のカラーペーパーの黒化部分の残存銀量を測定し
た。また漂白定着のランニング液を1のビーカ
ーに500mlサンプリングし室温保存してコロイド
銀の発生を経時で観察した。
この結果を下記第2表に示す。[Table] At the end of the running test, the reflection density of the cyan dye was measured on the blackened portion of the processed color paper using a PDA-60 photoelectric densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). Further, the amount of residual silver in the blackened portion of the color paper after treatment was measured by fluorescent X-ray analysis. In addition, 500 ml of the bleach-fixing running solution was sampled into a beaker 1 and stored at room temperature, and the generation of colloidal silver was observed over time. The results are shown in Table 2 below.
【表】【table】
【表】
上記第2表から明らかなように、本発明の処理
方法は本発明以外の比較例に比して脱銀速度が速
く、シアン色素の退色も少ない上に、漂白定着液
の保存安定性も極めて良好であることがわかる。
実施例 2
実施例1と同様にして作成したカラー印画紙を
用いて実施例1と同じ実験を行なつた。ただしこ
こでは、実施例1で使用したシアンカプラーの代
りに、前記例示カプラーV−11を使用した。
ランニング処理テスト終了時に、処理後のカラ
ー印画紙の黒化部分のシアン色素の反射濃度を実
施例1と同様に測定した。この結果を下記第3表
に示す。[Table] As is clear from Table 2 above, the processing method of the present invention has a faster desilvering speed than comparative examples other than the present invention, less fading of cyan dye, and storage stability of the bleach-fix solution. It can be seen that the properties are also extremely good. Example 2 The same experiment as in Example 1 was conducted using color photographic paper prepared in the same manner as in Example 1. However, in place of the cyan coupler used in Example 1, the exemplified coupler V-11 was used here. At the end of the running processing test, the reflection density of the cyan dye in the blackened portion of the processed color photographic paper was measured in the same manner as in Example 1. The results are shown in Table 3 below.
【表】
なお、ランニングテストNo.12および13では実施
例1と同様に脱銀不良が見られた。
上記第3表から明らかなように、本発明の処理
方法では、実施例1で得られたよりも、シアン色
素の退色に対し更に良好な結果が得られることが
わかる。[Table] Note that in running test Nos. 12 and 13, similar to Example 1, poor desilvering was observed. As is clear from Table 3 above, it can be seen that the treatment method of the present invention provides better results against fading of the cyan dye than those obtained in Example 1.
Claims (1)
材料を、自動現像機により芳香族第一級アミン発
色現像主薬を含む発色現像から直接有機酸の金属
錯塩を含有する漂白定着液によつて連続的に処理
する処理方法において、該漂白定着液に含まれる
発色現像液が30%以上であり、該漂白定着液のPH
が4.5〜5.5であることを特徴とするハロゲン化銀
カラー写真感光材料の処理方法。1. The imagewise exposed silver halide color photographic light-sensitive material is directly processed by an automatic processor from color development containing an aromatic primary amine color developing agent to continuous processing using a bleach-fixing solution containing a metal complex salt of an organic acid. In the processing method in which the color developing solution contained in the bleach-fix solution is 30% or more, and the PH of the bleach-fix solution is
4.5 to 5.5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11716981A JPS5818632A (en) | 1981-07-28 | 1981-07-28 | Method for processing silver halide color photosensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11716981A JPS5818632A (en) | 1981-07-28 | 1981-07-28 | Method for processing silver halide color photosensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5818632A JPS5818632A (en) | 1983-02-03 |
JPH021294B2 true JPH021294B2 (en) | 1990-01-11 |
Family
ID=14705147
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11716981A Granted JPS5818632A (en) | 1981-07-28 | 1981-07-28 | Method for processing silver halide color photosensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5818632A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6023857A (en) * | 1983-07-20 | 1985-02-06 | Fuji Photo Film Co Ltd | Method for processing color photosensitive silver halide material |
JPS60256143A (en) * | 1984-06-01 | 1985-12-17 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
JPS6150144A (en) * | 1984-08-18 | 1986-03-12 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
JPH0827506B2 (en) * | 1986-03-31 | 1996-03-21 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
JPH0750327B2 (en) * | 1986-06-06 | 1995-05-31 | 富士写真フイルム株式会社 | Color image forming method and silver halide color photographic light-sensitive material |
JP2849814B2 (en) * | 1987-06-22 | 1999-01-27 | 富士写真フイルム株式会社 | Image forming method |
JP2588717B2 (en) * | 1987-07-14 | 1997-03-12 | 富士写真フイルム株式会社 | Image forming method |
JPH07117721B2 (en) * | 1988-01-21 | 1995-12-18 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3372030A (en) * | 1962-12-14 | 1968-03-05 | Pavelle Corp | Method of shortening the processing time of color photography |
GB1190855A (en) * | 1968-02-02 | 1970-05-06 | Ilford Ltd | Photographic Colour Processing |
JPS50145231A (en) * | 1974-05-14 | 1975-11-21 | ||
JPS54155040A (en) * | 1978-05-26 | 1979-12-06 | Chugai Shashin Yakuhin | Method of reproducing color photographic bleachhfixing liquid |
JPS5577743A (en) * | 1978-12-08 | 1980-06-11 | Oriental Shashin Kogyo Kk | Replenishing method of bleaching agent and fixing agent for color photographic processing |
-
1981
- 1981-07-28 JP JP11716981A patent/JPS5818632A/en active Granted
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3372030A (en) * | 1962-12-14 | 1968-03-05 | Pavelle Corp | Method of shortening the processing time of color photography |
GB1190855A (en) * | 1968-02-02 | 1970-05-06 | Ilford Ltd | Photographic Colour Processing |
JPS50145231A (en) * | 1974-05-14 | 1975-11-21 | ||
JPS54155040A (en) * | 1978-05-26 | 1979-12-06 | Chugai Shashin Yakuhin | Method of reproducing color photographic bleachhfixing liquid |
JPS5577743A (en) * | 1978-12-08 | 1980-06-11 | Oriental Shashin Kogyo Kk | Replenishing method of bleaching agent and fixing agent for color photographic processing |
Also Published As
Publication number | Publication date |
---|---|
JPS5818632A (en) | 1983-02-03 |
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