CN85104288A - Method for processing color photographic material - Google Patents
Method for processing color photographic material Download PDFInfo
- Publication number
- CN85104288A CN85104288A CN85104288.0A CN85104288A CN85104288A CN 85104288 A CN85104288 A CN 85104288A CN 85104288 A CN85104288 A CN 85104288A CN 85104288 A CN85104288 A CN 85104288A
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- CN
- China
- Prior art keywords
- bleaching
- bath
- group
- grams
- colour
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 126
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000012545 processing Methods 0.000 title claims abstract description 50
- 238000004061 bleaching Methods 0.000 claims abstract description 170
- 229910052709 silver Inorganic materials 0.000 claims abstract description 54
- 239000004332 silver Substances 0.000 claims abstract description 54
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims description 61
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 43
- 238000011161 development Methods 0.000 claims description 29
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 23
- 229910001447 ferric ion Inorganic materials 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000004429 atom Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000001045 blue dye Substances 0.000 claims description 6
- 239000001046 green dye Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000002541 isothioureas Chemical class 0.000 claims description 5
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 claims description 4
- 125000004442 acylamino group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 238000003384 imaging method Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 2
- 150000002843 nonmetals Chemical group 0.000 claims description 2
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 2
- -1 silver halide Chemical class 0.000 abstract description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 53
- 235000002639 sodium chloride Nutrition 0.000 description 47
- 239000000654 additive Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 43
- 230000000996 additive effect Effects 0.000 description 40
- 230000001235 sensitizing effect Effects 0.000 description 32
- 239000000839 emulsion Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000007844 bleaching agent Substances 0.000 description 28
- 230000018109 developmental process Effects 0.000 description 28
- 239000000523 sample Substances 0.000 description 23
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 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 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 239000013068 control sample Substances 0.000 description 12
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 11
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 11
- 235000010265 sodium sulphite Nutrition 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 10
- 230000000087 stabilizing effect Effects 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 9
- 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 8
- 206010070834 Sensitisation Diseases 0.000 description 8
- 229910021612 Silver iodide Inorganic materials 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 230000008313 sensitization Effects 0.000 description 8
- 229940045105 silver iodide Drugs 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 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 7
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 238000013459 approach Methods 0.000 description 7
- 125000004104 aryloxy group Chemical group 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000003203 everyday effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000298 carbocyanine Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000004876 x-ray fluorescence Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- 206010033546 Pallor Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
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- 125000001309 chloro group Chemical group Cl* 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
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- 235000013409 condiments Nutrition 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
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- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 235000007715 potassium iodide Nutrition 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
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- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
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- 125000000547 substituted alkyl group Chemical group 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
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- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- HCXJFMDOHDNDCC-UHFFFAOYSA-N 5-$l^{1}-oxidanyl-3,4-dihydropyrrol-2-one Chemical group O=C1CCC(=O)[N]1 HCXJFMDOHDNDCC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
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- 239000005864 Sulphur Substances 0.000 description 2
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- CSYKLDTVFRFMIT-UHFFFAOYSA-M [Ag]Br.[Cl] Chemical compound [Ag]Br.[Cl] CSYKLDTVFRFMIT-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229960004194 lidocaine Drugs 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- ZJXQWYZBPKDYLS-UHFFFAOYSA-N n-(4-acetylphenyl)benzamide Chemical compound C1=CC(C(=O)C)=CC=C1NC(=O)C1=CC=CC=C1 ZJXQWYZBPKDYLS-UHFFFAOYSA-N 0.000 description 1
- RQIZDDWZOUJENI-UHFFFAOYSA-N n-propylpropane-1-sulfonamide Chemical group CCCNS(=O)(=O)CCC RQIZDDWZOUJENI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 229940069403 pentetate pentasodium Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 125000006248 tosyl amino group Chemical group [H]N(*)S(=O)(=O)C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A process for processing silver halide color photographic material comprising imagewise exposing the material, color developing the exposed material, and then desilvering, the process being characterized in that the desilvering step comprises: the developed material is first processed in a bleaching bath containing a trivalent iron ion complex salt of an aminopolycarboxylic acid, and then the developed material is processed in a bleaching bath containing a trivalent iron ion complex salt of an aminopolycarboxylic acid and a fixer.
Description
This invention relates to one and is used for processing, expose through imaging, fontanelization silver colour photographic sensitive material (hereinafter), the method that is called " color photographic material ", particularly improved the processing of photographic material, can be in the time that has shortened, desilver fully, and produce good colour reproduction.
The basic process of processing color photographic material generally comprises colour development step and desilver step.In the colour development step, the fontanel silver through the imaging exposure is reduced into argent by color developer, and oxidized color developer has then formed chromatic image with colour coupler (being that dyestuff forms agent) reaction.In desilver step thereafter, oxidized dose of (being commonly referred to " bleaching agent ") oxidation of the argent that generates during colour development, silver oxide is dissolved by the silver-colored iron-retention agent that is commonly referred to fixer then.In fact, desilverization step is that dye image is stayed on the color photographic material.
Desilver can be earlier handled in a bleaching bath that contains bleaching agent, and then handles through the fixing bath that contains fixer, also can contain shortly in single bleaching one fixing bath (promptly float and decide bath) that bleaching agent contains fixer again to carry out.
Except that these basic steps, the actual step of colour development process also comprises each additional step, for example the post bake step, suppress step, stabilizing step and washing step, so that obtain to have the dye image of good photographic property and physical property, and the dye image with permanent stability.
The ferricyanide, dichromate, ferric trichloride, aminopolycanboxylic acid's ferric ion complex salt, and persulfate are commonly referred to as bleaching agent.
But, the easy initial ring environment pollution of the ferricyanide and dichromate, the use of this class bleaching agent needs special equipment, so that handle such compound.Also there is variety of issue in ferric trichloride when practical application.For example, it has generated ferric hydroxide, when making purge step afterwards, produces stain.The shortcoming of persulfate is that their bleaching power is very weak, therefore needs very long bleaching time.In this respect, proposed the method for the bleaching power of an improvement or sulfate, Here it is uses persulfate and bleaching accelerator together.But, this method and impracticable because persulfate use and preserve the restriction that will be subjected to fire precautions legislation, so need special stowage arrangement.
The ferric ion complex salt (being aminopolycanboxylic acid's trivalent iron salt) of amino polyacid, the ferric ion complex salt of ethylenediamine tetraacetic acid (being the trivalent iron salt of ethylenediamine tetraacetic acid) particularly, it is the most widely used at present class bleaching agent, because be different from persulfate, above-mentioned complex salt does not almost have the problem of environmental pollution and storage.But, the complex salt that aminopolycanboxylic acid and ferric ion form, its bleaching power may not be always enough strong.When using above-mentioned complex salt bleaching or bleach photographic fixing fontanelization silver color photographic material, and it is when mainly containing the silver of the fontanelization at a slow speed color photographic material of chlorine silver bromide emulsion, and this class complex salt can reach desired desilverization degree.Yet, when this class complex salt being used to process when mainly containing bromo-iodide or bromine chlorosulfonylation silver fast colourful photographic material emulsion and spectral sensitization, especially for the processing color photographic material usefulness of promptly photographing, when containing the color nagatiive film of high silver amount emulsion, the just fully desilver of this class complex salt, be that bleaching time need be very long, just can reach requirement.
For example, to autochromy sensitization negative film, in the bleaching bath of the ferric ion complex salt that contains amino carboxylic acid, the time of bleaching, need 4 minutes at least, and must take the measure of some trouble.As control pH value and promptly ventilate, so that make its bleaching power remain on desired level.Even taked some measure, desilver carry out incomplete situation, neither be rare.
In order to reach the purpose of the desilverization, in bleaching bath, after the processing, must further be placed on material in the fixing bath, handled at least 3 minutes, therefore, press for the time that can shorten the desilverization.
In order to quicken the desilverization, at Deutsche Bundespatent 866, on 605, announced a kind of known bleaching one stop bath, it not only contains aminopolycanboxylic acid's ferric ion complex salt, and contains thiosulfate still, the bleaching power of this solution is very weak, because the aminopolycanboxylic acid of containing in this bleaching one stop bath ferric ion complex salt, the oxidability of itself (or bleaching power) just a little less than, its thiosulfate that contains then has reducing power.Therefore, with this bleaching one stop bath,, be very difficult, so this bleaching one stop bath does not have practical value to carrying out the desilverization with the photograph color sensitive material that contains Gao Yinliang fast.People once did many trials in order to overcome the shortcoming of this bleaching one stop bath.Such example has: in bleach-fixing liquid, add iodide or bromide, this content is published in BrP 926,569, or Japanese patent gazette No.11,854/1978(United States Patent (USP) 4,040,837) on, and, be admixed to triethanolamine in aminopolycanboxylic acid's the ferric ion complex salt solution of high concentration, this content is published in Japanese patent gazette No.95, on 834/1973.But when practical application, in these methods, the neither one method is effectively.
Except its desilverization ability, also there is other critical defect in this bleaching one stop bath, and promptly it is reduced into leuco dye to the cyan dye that forms in the colour development, thereby has influenced colour reproduction.Known, improve the pH value of this bleaching one stop bath, can overcome this shortcoming, this content is published in United States Patent (USP) 3,775, on 510.But from the viewpoint of practicality, this method almost is useless, because improve the pH value of solution, can cause weakening of solution bleaching power.In order to overcome aforesaid drawbacks, at United States Patent (USP) 3,189, a method of announcing on 452 is the certain movie queen of bleaching, with the ferricyanide bleaching liquid leuco dye is oxidized to cyan dye.But using the ferricyanide will cause problem of environmental pollution, and bleach later in bleaching one photographic fixing again, to reducing residual silver amount, almost is invalid.
The alternative method of another that proposes is, for the bleaching power of the ferric ion complex salt that improves the aminopolycanboxylic acid, toward bleaching bath, bleaches in a fixing bath or the prebath, adds various bleaching accelerators.
The example of such accelerator has: at United States Patent (USP) 3,893,858, and BrP 138,842 and Japanese patent gazette No.141, the various sulfhydryl compounds of announcing on 623/1978; In Japanese patent gazette No.95,630/1978(U.S.P.4.169,733) the last compound of announcing that has disulfide bond; At Japanese patent gazette No; 9,854/1978 tetrahydrothiazole derivates of announcing; At Japanese patent gazette No.94,927/1978(United States Patent (USP) 4,144,068) the last isothiourea derivatives of announcing; At Japanese patent gazette NOS, 8506/1970(United States Patent (USP) 3,617,283) and 26,586/1974(United States Patent (USP) 3,809,563) the last thiourea derivative of announcing; At Japanese patent gazette No.42,349/1974(BrP 1,394,357) the last thioamide compound of announcing; And at Japanese patent gazette No.26, the dithiocar-bamate of announcing on 506/1980.
Though certain in the middle of these accelerators is several, be to have certain bleaching to quicken to render a service in the practice,, this effectiveness is not the needs that shorten process time to satisfy.
First purpose of this invention is, provide the method for a processing color photographic material, particularly processing fast and the method for the color photographic material of Gao Yinliang, and this law can make the complete desilverization of material, and produce good colour reproduction in the time that has shortened.
Second purpose of this invention be, the method for the processing color photographic material that is provided, and the storage problem of problem of environmental pollution and employed compound can take place in hardly, so this job operation is easy to implement when practical application.
The inventors of this invention point out, just can reach the purpose of this invention by following step, promptly the color photographic material that exposed through imaging is carried out colour development, the material of processing in the bleaching bath of a ferric ion complex salt that contains the aminopolycanboxylic acid then through developing, then in certain bath of bleaching of a ferric ion complex salt that contains the aminopolycanboxylic acid and fixer, the material that processing has been developed.In other words, inventors point out, use contains the bleaching bath of aminopolycanboxylic acid's ferric ion complex salt, but the bleaching power of this complex salt a little less than, and use and to contain aminopolycanboxylic acid's the ferric ion complex salt and bleaching one fixing bath of fixer, like this and before had, adopt the process technology of bleaching bath and fixing bath to compare, just can in the shorter time, guarantee the desilverization of photographic material, and can make the possibility of the blue or green dyestuff that forms uncolored type reduce to minimum; And this point is being used the already present problem in the fixing bath of bleaching just.These are to exceed unexpected advantage, because it is generally acknowledged a little less than the bleaching power of bleaching one fixing bath, and think and easily process color photographic material, and the color photographic material of particularly high sensitizing degree and Gao Yinliang, normally impossible.
As mentioned above, the bleaching power of aminopolycanboxylic acid's ferric ion complex salt is not always enough strong, in bleaching one fixing bath of complex salt and fixer coexistence, a little less than its bleaching power becomes.Therefore to fast and the color photographic material of Gao Yinliang, when carrying out the desilverization color photographic material often need in bleaching bath, bleach for a long time, and then it be placed in the independent fixing bath handle.Mix in the fixing bath for fear of bleaching liquid, in this method, between blanching step and the photographic fixing step, usually need a water-washing step, thereby hindered the blue or green dyestuff that forms uncolored type, perhaps need to improve the pH value of fixing bath, with the formation of the blue or green dyestuff that prevents white type, foregoing is published in Japanese patent gazette No.
At United States Patent (USP) 3,189, on 452, delivered the method for a desilverization in bleaching one stop bath, it has also been narrated the certain movie queen of bleaching, needs a ferricyanide bleaching bath that contains bleaching power, so that make the blue or green dyestuff that the blue or green dyestuff of uncolored type changes into colour pattern.
According to the general knowledge of stating above, just can not imagine or expect the processing advantage of this invention, and this invention comprises: with the time processing photographic material in bleaching bath that has shortened, consider the formation of the blue or green dyestuff of desilverization ability and uncolored type, then process in bleaching one fixing bath.
Inventors also point out, use job operation of the present invention, processing contain structural formula (I) or (II) can form the color photographic material of cyan dye colour coupler the time, can produce good colour reproduction, can shorten the off-line time again as far as possible:
R in the formula
1, R
2And R
4Be aliphatics, aromatic series or heterocyclic radical (group) that replace or non-replacement; R
3And R
6For hydrogen atom, fontanel plain atom, fat-based replacement or non-replacement, aromatic radical or acylamino-, maybe can form five yuan nitrogenous or a non-metal atom group of hexatomic ring; R
5Be alkyl that replace or non-replacement (preferably having two carbon atoms at least); Z
1And Z
2For hydrogen atom or one with developer generation coupling reaction the time, the group that can be released, and n is 0 or 1.
When use has the cyan coupler of said structure formula,, also can obtain high-quality colour reproduction, and can not weaken the tone of cyan dye image even when shortening the bleaching of time.
Aminopolycanboxylic acid's ferric ion complex salt can be used as in the bleaching bath and bleaching one fixing bath in bleaching agent, this class complex salt is the complex compound that is formed by ferric ion and aminopolycanboxylic acid, or its salt.The bleaching one fixing bath in, used aminopolycanboxylic acid's ferric ion complex salt can be same as or
Be different from this used in bleaching bath class complex salt.
The exemplary of aminopolycanboxylic acid and salt thereof has:
The A-1 ethylenediamine tetraacetic acid
The A-2 disodium ethylene diamine tetraacetate
A-3 ethylenediamine tetraacetic acid two ammoniums
A-4 ethylenediamine tetraacetic acid four (three) first ammoniums
A-5 ethylenediamine tetraacetic acid four potassium
The A-6 tetrasodium ethylenediamine tetraacetate
The A-7 sodium versenate
A-8 diethylene base pentaacetic acid
A-9 diethylene base Pentetate Pentasodium
A-10 ethylenediamine-N-(beta-hydroxyethyl)-and N, N ', N '-triacetic acid
A-11 ethylenediamine-N-(beta-hydroxyethyl)-and N, N ', N '-triacetic acid three ammoniums
A-12 ethylenediamine-N-(beta-hydroxyethyl)-and N, N, N-triacetic acid three ammoniums
A-13 propylene diamine tetraacethyl
A-14 propylene diamine tetraacethyl disodium
The A-15 nitrilotriacetic acid(NTA)
A-16 nitrilotriacetic acid(NTA) trisodium
The A-17 1,2-diaminocyclohexane tetraacetic acid
A-18 1,2-diaminocyclohexane tetraacetic acid disodium
The A-19 iminodiacetic acid
A-20 dihydroxy (base) ethyl glycine
The A-21 ethyl ether diaminetetraacetic acid
A-22 diethanol ether diamine tetraacethyl
The A-23 ethylenediamine tetrapropionic acid
Certainly, enumerate the just explanation for example of above-mentioned these compounds, therefore, other aminopolycanboxylic acid also is applicable to this invention.
In these cited compounds, with A-1, A-2, A-3, A-8, A-17, A-18, A-19 are best.
Employed aminopolycanboxylic acid's ferric ion complex salt can be directly with the compound of complex salt form, also can be that mixed molysite and aminopolycanboxylic acid generate complex salt in solution.Trivalent iron salt wherein is iron sulfate, ferric trichloride, ferric nitrate for example, ammonium ferric sulfate etc.Can be used alone complex salt, or unite use with one or more other complex salt again.When in solution, generating complex salt, then can use one or more aminopolycanboxylic acids and one or more molysite to carry out complex reaction.In all cases, used aminopolycanboxylic acid must be excessive, so that form the complex salt of ferric ion.
Contain the bleaching liquid of ferric ion or bleach a stop bath and can contain beyond the deironing complex salt of other metallic ion, for example complex salt of metallic ion such as cobalt, copper.
The bleaching liquid that the present invention uses also has a heavy fontanelle agent except that containing bleaching agent and above-claimed cpd, bromide for example is as potassium bromide, sodium bromide, ammonium bromide; Or chloride, as potassium chloride, sodium chloride, ammonium chloride.Any condiment that is added in the market bleach liquid all is applicable to the bleaching liquid that the present invention uses, comprise mineral acid, organic acid and salt thereof with PH surge capability, for example, nitrate such as sodium nitrate, ammonium nitrate, boric acid, borax, kodalk, acetate, sodium acetate, sodium carbonate, sal tartari, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartrate or the like.
The amount that contains bleaching agent in 1 liter of bleaching liquid that the present invention uses is 0.1 to 1 mole, preferably 0.2 to 0.5 mole.The pH value of bleaching bath is transferred to 4.0 to 8.0, and preferably 5.0 to 6.5.
The amount that contains bleaching agent in 1 liter of bleach-fixing liquid that the present invention uses is 0.05 to 0.5 mole, is preferably 0.1 to 0.3 mole.
The inventor points out, in the bleaching bath that the present invention uses, at least add a kind of bleaching accelerator that is selected from following compounds, the compound that promptly contains sulfydryl or disulfide bond, isothiourea derivatives and tetrahydrothiazole derivates, if also add identical accelerator in the bleaching liquid of bleaching that technology is arranged earlier and photographic fixing step, then the two is compared, and the former effect is better than the latter.Point out again in addition, compare with the desilverization process that comprises bleaching bath and fixing bath that has earlier.The bleaching acceleration effect that then the present invention obtained and kept is far better.
Floating of the present invention's use decided bath, and suitable fixer has: thiosulfate such as sodium thiosulfate, ATS (Ammonium thiosulphate), sodium thiosulfate ammonium and potassium thiosulfate; Thiocyanate such as sodium thiocyanate, ammonium thiocyanate and potassium rhodanide; Thiocarbamide; Thioether etc.The content of fixer is 0.3 to 3 mole in per 1 liter of stop bath, is preferably 0.5 to 2 mole.
Except that adding above-mentioned bleaching agent and fixer, if necessary, can also in the bleach-fixing liquid that the present invention uses, add any condiment.
For example, can add one or more PH correctivess, as sulphite, for example sodium sulphite, ammonium sulfite etc., boric acid, borax, NaOH, potassium hydroxide, sodium bicarbonate, acetate and sodium acetate.In bleaching one stop bath of the present invention, also can contain various antifoaming agent, surfactant, alkali-metal fontanelle compound such as potassium iodide, ammonium bromide etc., the addition product that fontanel ammonium, azanol, hydrazine or acetaldehyde and bisulfite reaction obtain.
Bleaching one stop bath that the present invention uses, its pH value should be transferred to 5 to 8, and preferably 6 to 7.5.
The present invention, best bleaching time is 20 seconds to 4 minutes.When processing color photographic material, if material contains structural formula can form cyan dye for (I) and (II) colour coupler, the utilization structure formula is the bleaching accelerator of (III) to (IX) (will mention hereinafter) again, then bleaching time be 20 seconds to 2 minutes better.When not using accelerator, then preferably 1 to 4 minute.If the color photographic material of processing, it does not contain the colour coupler that can form cyan dye of structural formula for (I) or (II), and the utilization structure formula is the bleaching accelerator of (III) to (IX), then bleaching time is preferably 40 seconds to 2 minutes, when not using accelerator, then preferably 1.5 to 4 minutes.
In the time of bleaching in one fixing bath, preferably 1 to 5 minute, particularly 1.5 to 3.5 minutes better.When bleaching time is less than 20 seconds,, also cause desilverization effect (very) poor, and when the one photographic fixing time of bleaching is less than 1 minute,, also can cause desilverization weak effect even prolong bleaching time even prolong the one photographic fixing time of bleaching.
The present invention is at blanching step with bleach a water-washing step is arranged between the photographic fixing step.Even when the water-washing step water consumption is few, also without detriment to advantage of the present invention.
In bleaching one fixing bath of the present invention, preferably add additive.Additive contains fundamental component such as bleaching agent or fixer, and it is more convenient that the additive that contains fixer is used.
When process was just carried out, when the bleaching additive was added bleaching bath, the overflowing liquid that is flowed out by bleaching bath can be introduced in bleaching one fixing bath.Doing like this is very economical, because by introducing the overflowing liquid from the front bleaching bath, the bleaching agent in bleaching one fixing bath is remained on the level of requirement.
From the position of prevention environmental pollution, require to reduce the waste liquid amount of photographic material process, because of it has high biochemical oxygen demand (BOD) and high chemical oxygen demand (COD).The way of taking to utilize overflowing liquid and reducing waste liquid amount makes process more economical.
This law adds the additive from the overflowing liquid of bleaching bath in bleaching one fixing bath, be discharged in the processing technology that formerly has, and be to be introduced in bleaching one fixing bath here.Therefore, overflowing liquid plays the effect of solvent, and it is diluted to desired level to the additive component, so, for the additive of bleaching a fixing bath and being provided can be a strong solution, thereby cause having reduced waste liquid amount.
As previously mentioned, in fixing bath, if mix bleaching liquid, will form the blue or green dyestuff of uncolored type, thus grievous injury photographic property, it is useful therefore between blanching step and photographic fixing step a water-washing step being arranged, it has prevented mixing of bleaching liquid.At NEOCOLOR CHEM IST RY FOR C-41 NEGAT IVES, First Wash(is published by the U.S., L.B.RUSSELL CHEM ICALS) point out in the book, inadequate washing can bring more above-mentioned problems, so water-washing step is crucial.
Japanese patent gazette No.70533/1982 points out, when having omitted washing during the step, in order to prevent to form the blue or green dyestuff of uncolored type and the degraded of bleaching liquid, must improve the pH value of bleaching bath.Think then that thus it is very disadvantageous that bleaching liquid mixes in the stop bath.Obviously, the present invention is the way that overflowing liquid and fixer from bleaching bath mix bleaching one stop bath very different or opposite with the technology viewpoint that has earlier.
Among the present invention, be introduced into the amount of the bleaching bath overflowing liquid in bleaching one fixing bath, with can regulate for the body lotion amount that contains bleaching agent of bleaching a fixing bath and being provided, this just makes the bleaching agent in bleaching one fixing bath and the concentration of fixer can remain in the previously described scope.The size of solution amount depends on the concentration of bleaching agent in the overflowing liquid that is introduced into and the concentration of the fixer that provided, and when processing the photographic material of each square metre, solution amount is 150ml to 900ml preferably.
The present invention, for the additive of bleaching a fixing bath and providing can contain any condiment that can be added in the fixing bath, for example, generally Chang Yong fixer such as ATS (Ammonium thiosulphate), sodium thiosulfate etc., sulphite, hydrosulfite, buffering agent and sequestrant.When additive when mixing from the overflow liquid phase of bleaching bath, each component concentrations in these components in the additive all can be regulated, so that form bleaching one stop bath of the concentration that requires, and the concentration in the additive that provides for the fixing bath of generally using always can be provided for every kind of component concentrations.Therefore, it is possible reducing waste liquid amount, so also just reduced the cost that disposes waste liquid.
For bleaching in the additive that a fixing bath provides, the concentration that contains fixer is 0.5 to 4 mol preferably, is more preferably 1 to 3 mol.
The pH value of adding liquid preferably 6 to 10 is more preferably 7 to 9.Add ferric ion complex salt, fontanel ammonium or alkaline metal fontanelle compound that liquid can contain the aminopolycanboxylic acid such as ammonium bromide, sodium bromide, sodium iodide or the like.
The present invention, the overflowing liquid that comes from bleaching bath can directly be introduced into bleaching one fixing bath, for example, the run-down pipe on the bleaching bath is received on bleaching one fixing bath, or with the method for indirectly introducing, for example, overflowing liquid is stored in the container, again it is mixed mutually with the solution that contains fixer, then mixed liquor is introduced in bleaching one fixing bath, or the overflowing liquid and the fixer of storage are introduced respectively in bleaching one fixing bath.
Now, be the colour coupler of the formation cyan dye of (I) or (II) with the structural formula that describes the present invention's use in detail.
In structural formula, R
1, R
2And R
4For the fat-based (group) that contains 1～32 carbon atom as methyl, butyl, tridecyl, cyclohexyl and allyl; Aromatic radical such as phenyl and naphthyl; Or heterocyclic group such as 2-pyridine radicals, 2-imidazole radicals, 2-furyl and 6-quinolyl; And fat-based; aromatic radical and heterocyclic group can be replaced by one or more following groups; it is alkyl; aryl; heterocyclic radical; alkoxy such as methoxyl and 2-methoxyl; aryloxy group is as 2; 4-two tertiary pentyl phenoxy groups; 2-chlorophenoxy and 4-cyano-benzene oxygen; alkenyloxy such as 2-propenyloxy group; acyl group such as acetyl group and benzoyl; ester group such as butoxy carbonic acyl radical; the phenoxy group carbonic acyl radical; acetate; benzoxy; butoxy sulfonyl and tosyl; (acyl) amido such as acetylamino; the ethylamino formoxyl; formyl-dimethylamino; mesyl and butyl sulfamoyl; sulfoamido such as dipropyl sulfonamido; imino group such as succinimido and hydantoins base; urea groups such as phenylcarbamido and dimethyl urea groups; aliphatics or aromatic sulfonyl such as methyl sulphonyl and benzenesulfonyl; ester sulfenyl or sulfo-aromatic radical such as ethylmercapto group and thiophenyl, and hydroxyl; cyano group; carboxyl; nitro; sulfo group; plain atom of fontanel or the like.
In structural formula (I), R
3Be hydrogen atom, the plain atom of fontanel, aliphatic group, aromatic radical, acylamino-or nonmetallic atom group; It and R
2Form five yuan nitrogenous or a hexatomic ring.These groups can be by above-mentioned relevant R
1One or more substituting group of defined replaces.
In (I), n is 0 or 1 in structural formula,
In structural formula (II), R
5Be the alkyl of the replacement that has 2 carbon atoms at least or non-replacement for example ethyl, propyl group, butyl, pentadecyl, the tert-butyl group, cyclohexyl, cyclohexyl methyl, thiophenyl methyl, dodecyloxy thiophenyl methyl, butylamine methyl and methoxy.
In structural formula (I), R
6Be hydrogen atom, the plain atom of fontanel, aliphatic group, aromatic radical or acylamino-.
In structural formula (I) and (II), Z
1And Z
2Respectively be hydrogen atom or release type group; for example; plain atom of fontanel such as fluorine; chlorine and bromine atoms; alkoxy such as ethoxy; dodecyloxy; methoxy ethyl carbamyl ylmethoxy; the carboxyl propoxyl group; with the sulfonyloxy methyl ethoxy; aryloxy group such as 4-chloro phenoxy group; 4-methoxyl phenoxy group and 4-carboxylic phenoxy group; acidic group and acetate; tetradecane acidic group and benzoxy; sulfonyloxy such as sulfonyloxy methyl oxygen base and tosyloxy; amide group and dichloro acetamino; seven fluorine butyrylaminos; amino and the tosyl amino of sulfonyloxy methyl; alkoxy carbonyl oxygen base such as ethoxy carbon ester oxygen base and benzoic acid carbon acyloxy; aryloxy group carbon acyloxy such as phenoxy group carbon acyloxy; aliphatics or fragrance (family) sulfenyl such as ethylmercapto group; thiophenyl and tetrazolium sulfenyl; imino group such as succinimido and hydantoins base, and aromatic azo such as phenylazo.These release type groups can contain to take a picture goes up useful group.
In structural formula (I); R ' is aryl or heterocyclic group preferably, is more preferably an aromatic group that is replaced by the plain atom of fontanel, alkyl, alkoxy, aryloxy group, acylamino-, acyl group, carbamyl, sulfonamide support base, sulfamoyl, sulfonyl, sulfophenyl, carbon acyloxy or cyano group.
In structural formula (I), if R
2And R
3Nonjoinder becomes ring, then a R
2Preferably replace or non-substituted alkyl or aryl, and be more preferably the alkyl that replaces by substituted aryloxy, R
3Be preferably hydrogen atom.
In structural formula (II), R
4Be preferably and replace or non-substituted alkyl or aryl, more preferably by alkyl that substituted aryloxy replaced.
In structural formula (II), R
5Be preferably alkyl or have substituent methyl with 2～15 carbon atoms; And have a carbon atom on its substituting group at least, and substituting group preferably arylthio, alkylthio group, acylamino-, aryloxy group or alkoxy.
In structural formula (II), R
5Be preferably alkyl, more preferably have the alkyl of 2～4 carbon atoms with 2～15 carbon atoms.
In structural formula (II), R
6Be preferably hydrogen atom or fontanel plain atom, more preferably chlorine atom or fluorine atom.
In structural formula (I) and (II), Z
1And Z
2Respectively be the plain atom of hydrogen atom, fontanel, alkoxy, aryloxy group, acyloxy or sulfonamide support.
In structural formula (II), Z
2Be preferably fontanel plain atom, more preferably chlorine atom or fluorine atom.
In structural formula (I), if n is 0, Z then
2Be preferably the plain atom of fontanel, be more preferably chlorine atom or fluorine atom.
Structural formula normally mixes in the fontanelization silver emulsion layer, particularly in the magenta-sensitive emulsion layer for the blue or green fuel colour coupler of (I) or (II).The quality dosage that mixes is 2 * 10
-3～5 * 10
-3Moles/mole Ag, optimised quantity are 1 * 10
-2～5 * 10
-1Moles/mole Ag.
According in U.S. United States Patent (USP) U.S.P.NOS.3,772,002; 4,334,001; 4.32 7,173 and 4,427,767 methods of describing can easily be prepared into the blue or green dye color coupler of structural formula for (I) and (II).
Blue or green dye color coupler, its structural formula is described as follows for the exemplary of (I) and (II), and the present invention is not only limited to following structural formula: (See 42～58 Page)
To describe the bleaching accelerator now in detail.
Mixing the bleaching accelerator in the bleaching bath that the present invention uses, can be any compound with bleaching acceleration capacity.The compound that contains sulfydryl or disulfide bond, tetrahydrothiazole derivates or isothiourea derivatives all can be selected as the bleaching accelerator, and the bleaching accelerator preferably is selected from the compound of structural formula for (III) to (IX).
Wherein, R
1And R
2Can be identical or inequality, it is the low carbon number alkyl of hydrogen atom, replacement or non-replacement; It is better wherein to be preferably the alkyl with 1～5 carbon atom, particularly methyl, ethyl and propyl group; Or for preferably having the acyl group of 1～3 carbon atom, for example acetyl group and propiono, and n is 1,2 or 3.
R1 and R
2Can be merged into a ring.
R1 and R
2Be preferably and replace or non-replacement low carbon number alkyl.
R1 and R
2The substituting group that is contained has for example: hydroxyl, carboxyl, sulfo group and amino.
Wherein, R and R and said structure formula are the R in (I)
1And R
2Described situation is identical, and n is 1,2 or 3.
R
3And R
4Can be merged into a ring.
R
3And R
4Be preferably and replace or non-replacement low carbon number alkyl.
R
3And R
4The substituting group that contains is enumerated as hydroxyl, carboxyl, sulfo group and amino.
In structural formula (V), (VI) and (VII), R
5For the plain atom of hydrogen atom, fontanel such as chlorine or bromine, amino, preferably have replacement or non-replacement low alkyl group, particularly methyl, the ethyl and a propyl group of 1～5 carbon atom and contain amino alkyl such as methylamino, ethylamino, dimethylamino and lignocaine.(structural formula (V), (VI) (VII) See 59 Page)
R
5The substituting group that contains is enumerated as hydroxyl, carboxyl, sulfo group and amino.
In the formula, R
6And R
7Can be identical or different, respectively be hydrogen atom, replacement or non-substituted alkyl, be preferably low alkyl group such as methyl, ethyl and propyl group; Replace or non-substituted-phenyl or replacement or non-substituted heterocyclic radical, the heterocyclic radical that particularly contains one or more heteroatomss such as nitrogen, oxygen and sulphur atom is then better, for example pyridine ring, thiphene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring and imidazole ring.
R
8Be the low alkyl group that preferably contains 1 to 3 carbon atom of hydrogen atom or replacement or non-replacement, for example methyl and ethyl.
R
6, R
7Or R
8The substituting group that can contain is enumerated as hydroxyl, carboxyl, sulfo group, amino and low alkyl group, R
9Be hydrogen atom or carboxyl.
In the formula, R
10R
11And R
12Can be identical or different, it respectively is hydrogen atom or the low alkyl group that preferably has 1～3 carbon atom, for example methyl and ethyl.
R
10And R
11Or R
12Can be merged into a ring.
X is amino, sulfonic group or the carboxyl that contains one or more replacements; For example, low alkyl group such as methyl and acetyl oxyalkyl such as acetoxy-methyl all can.Substituting group as carboxyl.
R
10R
11And R
12Be preferably hydrogen atom, methyl or ethyl, X is preferably amino or dialkylamino.
Exemplary by the compound of structural formula (III) to (IX) representative is described below:
(60～69 pages of structural formula See)
Whole compounds of structural formula (III) to (IX) can be produced with well-known certain methods.For example at U.S.P.4,285,98, G.Schwarzenbach et.al., Helv.chim.Acta., 38,1147(1955) and R.O.Clinton et al., J.Am.Chem.SOC., ZO 950(1948) has described the preparation method of structural formula for the compound of (III) on the document; The preparation method of structural formula for the compound of (IV) described on Japanese patent gazette No.95630/1978; The preparation method of structural formula for the compound of (V) and (IV) described on Japanese patent gazette No.52534/1979; At Japanese patent gazette NOS.68568/1976, the preparation method of structural formula for the compound of (VII) described on 70763/1976 and 50169/1978; At Japanese patent gazette No.9854/1978 and Japanese patent gazette No.214855/1984(United States Patent (USP) 4,508,817) on the preparation method of structural formula for the compound of (VIII) described; The preparation method of structural formula for the compound of (IX) described on Japanese patent gazette No.94927/1978.
In the bleaching liquid that the present invention uses, its amount that contains compound, thiazoline derivative or isothiourea derivatives with sulfydryl or disulfide bond is decided by the kind of processed photographic material; Temperature during rapidoprint; Reach needed time of gratifying processing request and other condition, still, suitable content is 1 * 10
-5～10
-1Mol, optimum is 1 * 10
-4～5 * 10
-3Mol.
Above-mentioned these compounds were dissolved in earlier in solvent such as water, alkali, organic acid organic solvent or the like before the adding bleaching liquid usually.Another kind method is that these compounds are directly added in the bleaching liquid, promptly adds with form of powder, and this is to bleaching acceleration effect without any influence.
Any fontanelization silver all is applicable to the sensitive emulsion layer of the color photographic material that the present invention uses as silver bromide, bromo-iodide, bromine chlorosulfonylation silver, chlorine silver bromide, silver chloride, the fontanelization silver emulsion that color photographic material is used, its amount that contains silver iodide is best up to 15 moles of %, and good especially is 2～12 moles of %
The employed emulsion of photographic material with the present invention's processing can prepare with well-known certain methods, these methods are documented in P.Glafkides, Chimie et physigue Photogra Phigue(Paul Montel, 1967), G.F.Duffin, Photographic Emulsion Chemistry(The Focal Priss, 1960.), V.L.Zelik man et al, Making and Coating Photographic Emulsion(The Focal Press, 1964).
Form or physics between the maturation period at fontanelization silver particle, calcium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, molysite or its complex salt or other similar salt all can allow coexistence.
Usually, fontanelization silver emulsion carries out sensitizing with chemical method, though can be used for emulsion through chemical sensitization (effect) that is so-called primary emulsion.In the book that people such as Glafkides or Zelikman write, or H.Frieser, Drundlagen der Photographischen Prozesse mit Sieberhalogeniden(Akademische Verlagsgesellschaft, 1968) narrated the method for carrying out chemical sensitization in the book.That is, sulphur sensitizing is to use sulfocompound, and it can react with silver ion or active gelatin, reduction sensitization reductibility compound, and noble metal sensitizing is for example used gold separately with noble metal, or two or more noble metals are united use.The sulphur sensitizer has thiosulfate, thiocarbamide, thiazole, rhodamine or the like for example.The example of reduction sensitization agent has tin salt, amine, hydrazine derivate, formamidine sulfinic acid, silane compound or the like.The noble metal complex salt that noble metal sensitizer such as periodic table the 8th revolve, as gold, platinum, iridium and palladium.
Photographic emulsion can carry out spectral sensitization with methine dyes or other similar dyestuff.Be applicable to the blue or green dyestuff of light of the fuel of spectral sensitization such as cyanine dye, merocyanine dyes, complexing, the merocyanine dyes of complexing, full polarity cyanine dye, half cyanine dye, styryl color and (hemioxonol) dyestuff.Useful especially dyestuff is the blue or green dyestuff of portion's light of cyanine dye, merocyanine dyes and complexing.
Except that above-mentioned photonasty fontanelization silver emulsion layer, the fontanelization silver particulate of non-photosensitive in fact also to be arranged, so that improve its granularity or acutance or be used for other purpose.The emulsion layer of this non-photosensitive in fact is positioned on the photonasty fontanelization silver emulsion layer, or is positioned between photonasty fontanelization silver emulsion and the colloidal silver layer (yellow filtering layer or antihalation layer).
The photographic material that the present invention uses can contain polyalkylene oxide or its ether, ester or amine derivative, sulfide compound, thiomorpholine, quaternary ammonium salt, urethane derivant, urea derivatives, imdazole derivatives, 3-pyrazolidone derivant or other similar compound, so that improve sensitizing degree or contrast grade, or quicken to develop.
Though also available other hydrophilic colloid is as the bonding agent of photographic emulsion layer or other layer, it is more favourable to make bonding agent with gelatin.
In the present invention, the photographic material of use can contain as anti-
The all cpds that agent or stabilizing agent are used.These are anti-
The example of agent or stabilizing agent has: azoles is as benzene thiazole salt, nitro indazole, triazole, benzotriazole and benzimidazole (particularly nitro or fontanel are plain replaces); Heterocyclic mercapto compound such as thyroidan, mercaptobenzothiazoler mercaptobenzimidazole, sulfydryl plug diazole, mercapto-tetrazole (particularly 1-phenyl-5-mercapto-tetrazole) and mercaptopyrimidine; The heterocyclic mercapto compound that has hydrophilic group is as band carboxyl and sulfuryl; Thione compounds such as oxazoline thioketones; The azepine indenes such as the purine (particularly (1,3,3a, 7) purine of 4-hydroxyl replacement); Benzene thiosulfonic acid; Benzenesulfinic acid or the like.
To the photographic material that the present invention uses, can contain inorganic or organic hardener in its sensitive emulsion layer and/or other layer.The example of these hardeners has: the compound of chromium such as chrome alum and chromium acetate; Aldehyde such as formaldehyde, glyoxal and glutaraldehyde; N-methylol compound such as dimethylolurea and methylol dimethyl one hydantoins; Two alkane derivatives are as 2,3-two hydroxyl base dioxs; The activation vinyl compound as 1,3,5-three acryloyls-six hydrogen-S-triazine and 1,3-ethene sulphonyl-2-propyl alcohol; The activation halogen compound as 2,4-two chloro-6-hydroxyl-S-triazines; Sticking fontanel acid is as mucochloric acid and glue phenoxy chloric acid.These hardeners can use or unite use separately.
At photographic material of the present invention, its sensitive emulsion layer or other layer can contain various surfactants; Be used for coating assistant, antistatic agent, or be used for improving the chemical reagent that slipping property, emulsibility, dispersiveness, resistance to bond and other photograph character are quickened development, degree of intensifying and sensitizing degree.
To the photographic material that the present invention uses, its sensitive emulsion layer also can contain the colour coupler of other color except that containing above-mentioned cyan colour coupler.So these colour couplers can add lustre to, be because it when the colour development step, with the aromatic primary amine developer, as phenylenediamine derivative and aminophenol derivates with fungicidal property, oxidative coupling takes place and forms coloured dyestuff.The example of these colour couplers has: known cyan colour coupler such as phenols colour coupler and aphthols colour coupler; Pinkish red toner such as 5-pyrazolone colour coupler, pyridine benzimidazole colour coupler, cyanoacetophenone and furans colour coupler and open chain acyl group acetonitrile colour coupler; And yellow colour coupler such as acyl group acetamide colour coupler (for example, benzoyl monoacetylaniline and pivaloyl monoacetylaniline).Structural formula can be united use with the known phenols or the cyan colour coupler of aphthols for the colour coupler of the formation cyan dye of (I) or (II), also can be with the polymerizate of the two.In these colour couplers, have the non-dispersive colour coupler that hydrophobic group also is called the balance group and meet the requirements.With respect to silver ion, colour coupler or four equivalent types or two equivalent types.Also can use colour former agent with color correction effect, or the colour coupler that when developing, can suppress according to development degree released development (so-called DIR colour coupler is except that the DIR colour coupler, also can mix colourless DIR coupling compound, it can generate colourless coupling reaction product, and discharge development restrainer, maybe can mix the DIR redox compound.
Photographic material to the present invention uses can contain developer, and some representative instances of relevant developer are documented in Research Disclosure, and Vol 176, on P.29(1978) " Developioping agents " (title) this section.
The photographic material that the present invention is used can contain the dyestuff of using as colour filter in its sensitive emulsion layer or other belong to, or for the dyestuff that prevents to shine or other purpose is used.At Research Disclesure, Vol 176, P.25～26, and (1978); The example of the relevant this dyestuff of record in " Absorbing and filter dyes " joint.
The photographic material that the present invention uses also can contain antistatic agent, plastifier, take off old agent, lubricant, UV absorbers, fluorescer, antifoggant or the like, Research Dischosure, Vol.176(1078), P.22～27 narrated related content.
Fontanelization silver emulsion layer and/or other layer are to be coated on the support, and at Research Dis closure, P.27～28 Vol.176, has introduced the method that is coated with emulsion layer in (1978) " Coating Procedures " joint.
Job operation of the present invention is convenient to process multilayer negativity color sensitive material, and this material contains the color sensitive material that is suitable for counter-rotary-ing color processing or the colour former agent of combination, in addition, this law also is convenient to process colored X-ray photosensitive material, individual layer rainbow photosensitive material, or contain the color sensitive material of the black and white developer of combination, the photosensitive material that for example contains the 3-pyrazolidone, this content is published in United States Patent (USP) NOS.2,751,297 and 8,902,905, Japanese patent gazette NOS.64339/1981, on 85748/1981 and 85749/1981, the content in conjunction with precursor of relevant color developer is published in United States Patent (USP) NOS.2,478,400,3,342,597,3,342,599,3,719492 and 4,214,047 and Japanese patent gazette No.135628/1978.Even add these colour couplers in developer solution, method of the present invention also is effective.
Use job operation of the present invention, be easy to process the color photographic material that contains Gao Yinliang, for example the silver content of color photographic material be at least 3 the gram/square metre, be preferably 3～15 the gram/square metre.
In the used colour developing solution of the present invention, the aromatic primary amine color developer that it contains has comprised those developers that are widely used in various autochromy processing.These developments have the derivant of amino-phenol and p-phenylenediamine.Normally use the salt of these compounds, for example, oxyhydroxide or sulfate are because salt is more more stable than its free state.Using these compound concentrations is generally: about 0.1 gram is to/1 liter of developer solution of about 30 grams, and preferably concentration is to contain 1 gram in per 1 liter of colour developing solution approximately to 15 gram developers.
The example of amino-phenol developer has: O-aminophenol, para-aminophenol, 5-amino-2-hydroxy-methylbenzene, 2-amino-3-hydroxy-methylbenzene and 2-hydroxyl-3-amino-1,4-dimethylbenzene.
Especially effectively the aromatic primary amine developer is N-dialkyl group-p-phenylenediamine compound, and its alkyl and phenyl can be that replace or non-replacement.Effective example of these compounds has: N, the hydrochloride of N-diethyl-p-phenylenediamine, the hydrochloride of N-methyl-p-phenylenediamine, N, the hydrochloride of N-2 methyl-p-phenylenediamine, 2-amino-5-(N-ethyl-N-+ dialkyl amino)-toluene, the N-ethyl-N-Beta-methyl sulfonamido ethyl 3-methyl-sulfate of 4-amino aniline, N-ethyl-N-beta-hydroxyethyl amino aniline, 4-amino-3-methyl-N, N-diethylaniline and 4-amino-N-(2-methoxy ethyl)-N-ethyl-3-methylaniline-right-toluene sulfonate.
Except that above-mentioned aromatic primary amine color developer, also have alkaline colour developing solution, it can contain added composition in the colour developing solution of common usefulness arbitrarily, for example: bases such as NaOH, sodium carbonate and sal tartari; Alkali-metal sulphite, alkali-metal hydrosulfite, alkali-metal thiocyanate, alkali-metal fontanelle compound, phenmethylol, water softener and thickening agent.It is 7 at least that the pH value of colour developing solution generally is transferred to, and most typical pH value is about 9～13.
Job operation of the present invention is applicable to colour reversal processing.Colour reversal processing black-and-white developer solution has: be used for the counter-rotating processing of color photographic material, be called black-and-white first developer solution and being used to deceives-and-developer solution of Bai photosensitive material processing.That the present invention uses is black-and-the Bai developer solution can contain various well-known adjuvants, and this class adjuvant also is commonly used in common black, the white developer solution.
The example of typical additive has: developer such as 1-phenyl-3-pyridine alkane ketone, Mitouer (registrar woods) and quinhydrones; Preservative agent such as sulphite; Bases accelerator such as NaOH, sodium carbonate and sal tartari; Inorganic or organic inhibitor such as 2-tolimidazole and methylbenzothiazole; Water softener such as polyphosphate; And development restrainer such as a spot of iodide or sulfhydryl compound.
Process of the present invention comprises colour development, bleaches and bleach steps such as a photographic fixing, and this described in front.After the bleaching-photographic fixing, generally also have water-washing step and stabilizing step.But, in process of the present invention, also can use easier job operation, promptly after bleaching-photographic fixing step, carry out stabilizing step and do not have basic water-washing step.
If necessary, in the used washings of water-washing step, can contain known additives.The example of this class adjuvant has; Sequestrant such as inorganic phosphoric acid, aminopolycanboxylic acid and organic phosphoric acid; Be used for suppressing the germifuge of bacterium or algae reproduction; Hardener such as magnesium salts and aluminium salt; And the surfactant that is used for preventing unevenness.At LEWest, in " Water Quality Criteria " book these compounds have been described; At Phot.Sci.and Eng, Val.9 No.6, P.344～359(1965) also on the books on this piece document.If necessary, can use two or more washing baths,, also can adopt the method (for example, adopting the washing of 2 to 9 stage countercurrents) of multi-stage countercurrent washing in order to save the water of washing usefulness.
Can make the stable body lotion of chromatic image can be used as stabilizing agent in the stabilizing step, it is 3～6 buffer solution and the solution of aldehyde-containing type, for example formalin that the example of stabilizing agent has PH.If necessary, stabilizing agent can contain fluorescer, sequestrant, germifuge, hardener and surfactant.
If necessary, can use two or more stabilizer baths,, also can adopt multi-stage countercurrent washing (for example 2 to 9 grades), perhaps also can save water-washing step in order to save stabilizing solution.
Example 1
On the tri acetyl cellulose membrane support of different sheets, make multi layer colour negativity film.Each layer composed as follows:
Ground floor: anti-halo layer
The gelatin layer that contains the black collargol.
The second layer: wall
Contain 2, the gelatin layer of uncle 5-2--octyl group quinhydrones emulsifying dispersant.
The 3rd layer: magenta-sensitive emulsion layer at a slow speed
Silver bromide emulsion-Tu Yinliang is
(silver iodide: 1.6 gram/rice 5 moles of %)
2
Per 1 moles of silver of sensitizing dye 1-
6 * 10
-5Mole
Sensitizing dye II-per 1 moles of silver
1.5 * 10
-5Mole
Colour coupler-per 1 moles of silver
(seeing Table 1) 0.04 mole
Per 1 moles of silver of colour coupler EX-1-
0.003 mole
Per 1 moles of silver of colour coupler EX-2-
0.0006 mole
The 4th layer: quick magenta-sensitive emulsion layer
Bromo-iodide-Tu Yinliang is
(silver iodide: 1.4 gram/rice 10 moles of %)
2
Per 1 moles of silver of sensitizing dye 1-
3 * 10
-5Mole
Sensitizing dye II-per 1 moles of silver
1.2 * 10
-5Mole
Colour coupler-per 1 moles of silver
(illustrated in table 1) 0.02 mole
Per 1 moles of silver of colour coupler EX-1-
0.0016 mole
Layer 5: wall
Identical with the composition of the second layer
Layer 6: quick chlorine sense emulsion layer
Single silver bromide emulsion-Tu Yinliang that disperses is
(silver iodide: 1.2 gram/rice 4 moles of %)
2
Sensitizing dye III-per 1 moles of silver
3 * 10
-5Mole
Sensitizing dye IV-per 1 moles of silver
1 * 10
-5Mole
Per 1 moles of silver of colour coupler EX-3-
9.05 mole
Per 1 moles of silver of colour coupler EX-4-
0.0015 mole
Per 1 moles of silver of colour coupler EX-2-
0.0015 mole
Layer 7: quick edge sense emulsion layer
Silver bromide emulsion-Tu Yinliang is
(silver iodide: 1.3 gram/rice 10 moles of %)
2
Sensitizing dye III-per 1 moles of silver
2.5 * 10
-5Mole
Sensitizing dye IV-per 1 moles of silver
0.8 * 10
-5Mole
Per 1 moles of silver of colour coupler EX-5-
0.017 mole
Per 1 moles of silver of colour coupler EX-4-
0.003 mole
Per 1 moles of silver of colour coupler EX-6-
0.003 mole
The 8th layer: yellow filtering layer
Gelatin layer by yellow collargol and be dissolved in 2.5-two-uncle in the aqueous gelatin solution-
Octyl group quinhydrones emulsifying dispersant is formed.
The 9th layer: blue fast sense emulsifying agent layer
Silver bromide emulsion-Tu Yinliang is
(silver iodide: 0.07 gram/rice 6 moles of %)
2
Per 1 moles of silver of colour coupler EX-7-
0.25 mole
Per 1 moles of silver of colour coupler EX-2-
0.015 mole
The tenth layer: blue fast sense emulsifying agent layer
Silver bromide emulsion-Tu Yinliang is
(silver iodide: 0.6 gram/rice 6 moles of %)
2
Per 1 moles of silver of colour coupler EX-7-
0.06 mole
Eleventh floor: first protective seam
Bromo-iodide-Tu Yinliang is
(1 mole of % of silver iodide) 0.5 gram/rice
Particle mean size 0.07 μ
Gelatin layer contains the emulsifying dispersant of UV absorbers UV-1.
Floor 12: second protective seam
Gelatin layer contains trimethyl methacrylate (salt) particle, and its particle diameter is 1.5 microns.Except that said components, also add gelatin hardener H-1 and/or compound that surfactant＜the preparation component is used〉at each layer
Sensitizing dye 1:
Dehydration-5,5 '-two chloro-3,3 '-two-(8-sulfopropyl)-9-ethyl thiazole
(relevant structural formula See 70～71 Page)
The oxyhydroxide of carbocyanine, pyridiniujm.
The sensitizing dye II:
Dehydration-9-ethyl-3,3 '-two-(γ-sulfopropyl)-4,5,4 ', 5 '-the dibenzo thiophene
The oxyhydroxide of carbocyanine, triethylamine salt.
The sensitizing dye II:
Dehydration-9-ethyl-5,5 '-two chloro-3,3 '-2-(γ-sulfopropyl) the Evil carbocyanine, sodium salt.
The sensitizing dye IV:
Dehydration-5,6,5 ', 6 '-tetrachloro-1,1 '-oxyhydroxide of diethyl-3,3 '-two-{ β-[β-(γ-sulfopropyl ethoxy) ethyl } imidazoles carbocyanine, sodium salt.
The negative film of the colour of making is placed on by a wedge from tungsten lamp 25 centimeters, exposes (by a light filter, the colour temperature of tungsten lamp is tuned to 4800 ° of K), then under 38 ℃ of temperature, carry out colour development by following condition with tungsten lamp:
Method 1(comparative approach)
Colour development 3 minutes 15 seconds
Bleaching illustrated in table 1
Photographic fixing illustrated in table 1
Washed 3 minutes and 15 seconds
Stablized 1 minute and 5 seconds
Method 2(comparative approach)
Colour development 3 minutes and 15 seconds
Bleaching illustrated in table 1
Washed 3 minutes and 15 seconds
Stablized 1 minute and 5 seconds
Method 3(job operation of the present invention)
Colour development 3 minutes and 15 seconds
Bleaching illustrated in table 1
Float accepted argument and brightly see Table 1
Washed 3 minutes and 15 seconds
Stablized 1 minute and 5 seconds
In above steps, the composition of every kind of used process solutions is described as follows:
Colour developing solution
Nitrilotriacetic acid(NTA) trisodium 1.9 grams
Sodium sulphite 4.0 grams
Sal tartari 30.0 grams
Potassium bromide 1.4 grams
1.3 milligrams of potassium iodides
Sulfuric acid hydramine 2.4 grams
4-(N-ethyl-N-β-hydroxyl second 4.5 grams
Amino)-sulfate of 2-aminotoluene
Add water to 1.0 and rise PH10.0
Liquid lime chloride
Ethylenediamine tetraacetic acid, ferric ammonium 100.0 grams
Ethylenediamine tetraacetic acid, disodium salt 8.0 grams
Ammonium bromide 150.0 grams
(28%) 7.0 milliliter of ammoniacal liquor
Add water to 1.0 and rise PH6.0
Stop bath
Sodium tetrapolyphosphate 2.0 grams
Sodium sulphate 4.0 grams
(70%) 175.0 milliliter of thiosulfuric acid aqueous ammonium
Sodium bisulfite 4.6 grams
Add water to 1.0 liter
PH6.6
Float and decide solution
Ethylenediamine tetraacetic acid, ferric ammonium 100.0 grams
Ethylenediamine tetraacetic acid, disodium salt 4.0 grams
(70%) 175.0 milliliter of thiosulfuric acid aqueous ammonium
Sodium sulphite 4.5 grams
15 milliliters of ammoniacal liquor
Add water to 1.0 liters
PH6.8
Stabilizing solution
(40%) 8.0 milliliter of formalin
Polyoxyethylene is right-single nonylplenyl ether, and 5.0 milliliters
0.3 grams per liter
Add water to 1.0 liters
To every kind of photograph software prototyping, measure its minimum density, the suitable sensitizing degree of color harmony through said method processing.Use x-ray fluorescence analysis, be determined at the residual silver amount in the area of maximum colour density.
With the other same film sample of method processing, this method is documented in FUJI COLOR PROCESS CN-16 of FUJI FILM CO., (colour development, 3 minutes and 15 seconds among the LTD.; Bleaching, 6 minutes 30 seconds; Washing, 2 minutes 10 seconds; Photographic fixing, 4 minutes 20 seconds; Washing, 3 minutes 15 seconds; Stablized 1 minute and 5 seconds, then oven dry.Processing temperature is 38 ℃), measure minimum density, the color harmony phase sensitizing degree of finished sample then.The result of measurement result and said method 1 to 3 gained is compared.
Comparative result is listed on the table 1, and listed data are the differences with ratio with the ratio that obtains with contrast method (CN-16 method) of method 1 to 3 gained on the table.Minimum density values is unlisted in table, and this is that the Therefore, omited has been fallen because their difference is too little nonsensical.By table 1 as seen, the absolute figure of the relative sensitizing degree of color harmony is big more, that is big more with the result's of contrast method gained difference, and then photographic property is more bad.
Sensitizing degree and tone are determined as follows relatively:
Relative sensitizing degree:
Difference between the density of expression minimum density and a certain exposure; And on family curve, the control sample minimum density adds that 0.2 density is the density of this exposure.
Tone:
Represent the difference between the density of the density of exposure of above-mentioned definition and a certain exposure; This exposure then is 1.5 times of logH value of above-mentioned definition.
Comparative compound A, B that table 1 is listed and C are the blue or green dye color couplers of following structural formula: (See 72 Page)
Obviously see by table 1, in such time, method of the present invention can the desilverization to goodish level, and bleach a fixation method (comparative example NOS.1～3) or single float all fully desilverizations of the method for deciding (comparative example NOS.4～6).According to relative sensitizing degree difference and the tonal difference between control sample and the example, method of the present invention can obtain good photograph reductibility and not become the blue or green dyestuff of uncolored type, in the present invention, and when the time of the desilverization shortens to 4 minutes and (bleached 1 minute and 30 seconds; Floated fixed 2 minutes and 30 seconds) time, by sample NOS.13 and 14 as seen, descend with the relative sensitizing degree of color harmony of sense red beds under the sorrow of separation condition.But, in general, when uniting use, adopt method of the present invention just can guarantee to obtain good silver-colored effect and fabulous photograph reductibility with the blue or green dye color coupler of structural formula I and II.
Example 2
Being cut into the negative film sample NO.1 of colour wide is 35 millimeters film, sample NO.1 is specified in ((its blue or green dye color coupler is comparative compound A and B) in the table 1, be used in the same procedure of handling sample in the example 1, sample is exposed by wedge successively, adopt automatic developing device, process so that prepare control sample, use automatic developing device according to the CN-16 method, according to the method 1 or 2 of narration on table 2, handle colored negative film sample NO.1 respectively.
Should be noted that under the following conditions to compare that promptly the bleaching time of method 1 is 5 minutes, it equals to bleach in the method 2 and float the summation of fixing time, and sees Table 2.
Colored negative film (is handled 35 mm wides every day, 100 meters are long) be used for field pick-up, process with method 1 and 2 pairs of films respectively then, carry out a wedge-exposure every day with the negative film of same colour, then process with method 1 and 2, these steps were carried out 10 days continuously.
Method 1 and 2 solution compositions of using and additive composition are described below:
Colour developing solution
Original liquid additive
Sodium nitrilo triacetate 10 grams 1.1 grams
Sodium sulphite 4.0 grams 4.4 gram sal tartari
30.0 restrain 32.0 gram potassium bromides
1.4 restrain 0.7 gram Hydroxylamine sulfate
2.4 restrain 2.6 gram 4-(N-ethyl-N-β-hydroxyethylaminos)-
The 2-first
Sulfate 4.5 grams 5.0 grams of base aniline
Add water to 1.0 liters 1.0 liters
PH10.0 PH10.2
Bleaching liquid
Original liquid additive
176 doses of ammonium bromide 160 grams
Ethylenediamine tetraacetic acid, sodium molysite 130 grams 143 grams
Ethylenediamine tetraacetic acid, disodium salt 10 grams 11.5 grams
(28%) 7 milliliter 4 milliliters of ammoniacal liquor
Add water to 1 liter 1 liter
PH6.0 PH5.7
Bleach-fixing liquid
Original liquid additive
Ethylenediamine tetraacetic acid, sodium molysite 70 grams 70 grams
Ethylenediamine tetraacetic acid, disodium salt 4.0 grams 4.0 grams
(70%) 175 milliliter 200 milliliters of thiosulfuric acid aqueous ammoniums
Sodium sulphate 4.5 grams 4.5 grams
(28%) 12 milliliter 13 milliliters of ammoniacal liquor
Add water to 1 liter 1 liter
PH6.8 PH7.0
Stop bath
Original liquid additive
Sodium tetrapolyphosphate 2.0 grams 2.0 grams
Sodium sulphite 4.0 grams 5.0 grams
(70%) 175 milliliter 200 milliliters of thiosulfuric acid aqueous ammoniums
Sodium bisulfite 4.6 grams 5 grams
Add water to 1 liter 1 liter
PH6.6 PH6.6
Stabilizing solution
Original liquid additive
(40%) 5 milliliter 7 milliliters of formalins
Polyoxyethylene is right-single nonylplenyl ether, and 5 milliliters 7 milliliters of 0.3 grams per liters
Add water to 1 liter 1 liter
Table 3
Procedure of processing to per 1 meter film required add dosage
Method 1 method 2
(comparative approach) (the present invention)
40 milliliters 40 milliliters of colour developments
Bleach 15 milliliters 15 milliliters
40 milliliters of photographic fixing-
Bleaching-photographic fixing-40 milliliter
Stablize 40 milliliters 40 milliliters
To usefulness method 1 and 2 processing through the film sample of wedge-exposure, use x-ray fluorescence analysis, measure residual silver-colored the measuring on the maximum colour density area of film sample.Will be with the photographic property of film and the making comparisons of control sample of this method processing.Tone difference between this two classes sample is listed in table 4 with relative sensitizing degree difference.
By table 4 as seen, adopt job operation of the present invention, the desilverization is effective, and obtains the photograph reductibility of high-quality, and can keep the long duration, even carry out the processing of film with automatic developing device, also can obtain above-mentioned good result, yet in comparative approach, its bleaching time is 5 minutes, but desilverization effect and photograph reductibility degenerate in time, by the 10th day, can not carry out the desilverization.That is to say that job operation of the present invention provides the stable desilverization effect and the photograph reductibility of high-quality, these performances have all surpassed the resulting result of comparative approach, and the bleaching time of comparative approach identical with method of the present invention (5 minutes).
Example 3
The negative film NO.10 of colour, the same procedure of being introduced in the use-case 1 after the wedge exposure, then by following step, carry out colour development under 38 ℃ of temperature, and the detailed description of relevant film sample NO.10 sees Table 1:
Method 1(compares)
Colour development 3 minutes and 15 seconds
The bleaching bleaching time sees Table 5
The fixing roller/fixing time sees Table 5
Washed 3 minutes and 15 seconds
Stablized 1 minute and 5 seconds
Method 2(is of the present invention)
Colour development 3 minutes and 15 seconds
The bleaching bleaching time sees Table 5
Bleaching-fixing roller/fixing the time sees Table 5
Washed 3 minutes and 15 seconds
Stablized 1 minute and 5 seconds
Above-mentioned processing solutions employed, except that bleaching liquid contains the bleaching accelerator, the composition of its solution identical with described in the example 1, the title and the consumption of used bleaching accelerator then see Table 5.
Through each sample of processing, the residual silver amount in its maximum colour density area is measured with x-ray fluorescence analysis.
By table 5 as seen,, comprise bleaching step and float and decide the step, add in the bleaching liquid and bleach accelerator job operation of the present invention.Play good effect, and to comparison method, comprise bleaching step and photographic fixing step, the bleaching accelerator has only very little effect.
Example 4
With the method identical with example 1, preparation is as the film sample described in the example 1, but in the example 1 except the colour coupler of the 3rd and the 4th layer of usefulness, and replace it respectively with following colour coupler.
The 3rd layer: magenta-sensitive emulsion layer at a slow speed
Per 1 moles of silver of the comparative compound A-of example 1
0.04 mole
Per 1 moles of silver of colour coupler EX-1-
0.003 mole
Per 1 moles of silver of colour coupler EX-2-
0.0006 mole
The 4th layer: quick magenta-sensitive emulsion layer
Per 1 moles of silver of the comparative compound B-of example 1
0.02 mole
Per 1 moles of silver of colour coupler E-1-
0.0016 mole
The film sample for preparing is cut into the film of 35 mm wides, then it is placed on by wedge from tungsten lamp 25 centimeters, exposing with tungsten lamp, (colour temperature of tungsten lamp is tuned to 4 by light filter, 800 ° of K), (colour development 3 minutes 15 seconds was bleached 6 minutes and 30 seconds to follow the method for introducing according to FUJI COLOR PROESS CN-16 of FUJI PHOTO FILM CO.LTO; Washed 2 minutes and 10 seconds; Photographic fixing 4 minutes and 20 seconds was washed 3 minutes and 15 seconds, stablized 1 minute and 5 seconds, then dried; Processing temperature is 38 ℃), process film so that the preparation control sample with automatic processing machine.Same film sample is used automatic processing machine after exposing by wedge, according in the described three kinds of different processing methods of table 6, under 38 ℃ of temperature, processes respectively.
Above-mentioned job operation solutions employed composed as follows described:
Colour developing solution (method 11～13)
Sodium nitrilo triacetate 1.9 grams
Sodium sulphite 4.0 grams
Sal tartari 30.0 grams
Potassium bromide 1.4 grams
1.3 milligrams of potassium iodides
Hydroxylamine sulfate 2.4 grams
4-(N-ethyl-N-β-hydroxyethylamino)-2-methyl 4.5 grams
1.0 liters in the sulfate of aniline
Add water to PH10.0
Bleaching liquid (method 11～13)
Ethylenediamine tetraacetic acid, ferric ammonium 100.0 grams
Ethylenediamine tetraacetic acid, disodium salt 8.0 grams
Ammonium bromide 150.0 grams
(28%) 7.0 liter of ammoniacal liquor
Add water to 1.0 liters
PH6.0
Stop bath (method 11)
Sodium tetrapolyphosphate 2.0 grams
Sodium sulphite 4.0 grams
(70%) 175.0 milliliter of thiosulfuric acid aqueous ammonium
Sodium bisulfite 4.6 grams
Add water to 1.0 liters
PH6.6
Bleach-fixing liquid (method 12 and 13)
Ethylenediamine tetraacetic acid, ferric ammonium 100.0 grams
Ethylenediamine tetraacetic acid, disodium salt 4.0 grams
(70%) 175.0 milliliter of thiosulfuric acid aqueous ammonium
4.5 milliliters of sodium sulphites
(28%) 15 milliliter of ammoniacal liquor
Add water to 1 liter
Stabilizing solution (method 11～13) PH6.8
(40%) 8.0 milliliter of formalin
Polyoxyethylene is right-single nonylplenyl ether, and 5.0 milliliters of 0.3 grams per liters
Add water to 1.0 liters
Each sample after the measurement processing and the relative sensitizing degree of color harmony of control sample.Measure with the residual silver that x-ray fluorescence analysis is measured in its maximum colour density area.
In method 13, with a pipe, float the end opening of deciding bath from suitable for reading the receiving of the bleaching bath of automatic processing machine, like this, when adding additive in bleaching bath, overflowing liquid is just introduced to float from bleaching bath and is decided the bath.35 milliliters of wide films (every day is with 100 meters) are used for field pick-up, carried out continuously 10 days, when adding worker's solution, process then according to method 13 inch film samples.Simultaneously, the sample that exposed by wedge is also processed every day.＜with respect to the film of per 1 meter long 35 mm wide, needed every kind of consumption of adding liquid 〉
Be added to 40 milliliters of the additive of colour development in bathing
Be added to 20 milliliters of additives in the bleaching bath
Be added to and float 20 milliliters of the additives (containing fixer) decided in the bath
Be added to 40 milliliters of additives in the stabilizer bath
The composition of＜additive 〉
Be added to the additive in the colour development bath
Sodium nitrilo triacetate 1.1 grams
Sodium sulphite 4.4 grams
Carbon sulphur sodium 32.0 grams
Potassium bromide 0.7 gram
Hydroxylamine sulfate 2.6 grams
4-(N-ethyl-N-beta-hydroxyethyl amino)-2-methyl 5.0 grams
The sulfate of aniline
Add water to 1.0 liter
PH10.2
Be added to the additive in the bleaching bath
Ammonium bromide 175.0 grams
(28%) 4.0 milliliter of ammoniacal liquor
Ethylenediamine tetraacetic acid, ferric ammonium 110.0 grams
Ethylenediamine tetraacetic acid, disodium salt 10 grams
Add water to 1.0 liters
PH5.7
Be added to and float the additive of deciding in the bath (containing fixer)
(70%) 400 milliliter of thiosulfuric acid aqueous ammonium
Sodium sulphite 9 grams
(28%) 12 milliliter of ammoniacal liquor
Sodium bisulfite 10.2 grams
Sodium tetrapolyphosphate 4.4 grams add water to
1.0 rise
PH8.1
Be added to the additive in the stabilizer bath
9 milliliters of formalins
Polyoxyethylene is right-single nonylplenyl ether, and 7 milliliters of 0.3 grams per liters
Add water to 1.0 liters
Processing back measurement result is listed in table 7.
Listed relative sensitizing degree difference and tone difference are meant the difference between control sample and the example on table 7.
By table 7 as seen, job operation of the present invention provides the photograph reductibility of high-quality, and obtains good desilver effect in the time that has shortened, these performances and equally matched with the result of contrast method gained, and processing validity of the present invention is very lasting.
Example 5
Repeat the step in the example 4, so that prepare 35 milliliters of wide films, the comparative compound A of the example of in example 4, using with the colour coupler replacement of following structural formula 1 just:
The colour that has prepared is born film, and the method described in the use-case 4 is exposed by wedge, then uses automatic processing machine, processes according to the CN-16 method described in the example 4.
By the film that wedge exposed, the method 14 and 15 described in the table 8 that is used in is respectively processed.
Table 8
Method 14(is relatively) method 15(is of the present invention)
Colour development colour development in 15 seconds in 3 fens 3 minutes and 15 seconds
Bleach bleaching in 40 seconds 40 seconds
Photographic fixing was floated fixed 3 minutes and 15 seconds in 3 minutes 15 seconds
Wash washing in 3 minutes 15 seconds 3 minutes and 15 seconds
Stablize and stablized in 20 seconds 20 seconds
In the described method of table 8, various bleaching accelerators have been used.
Except that following solution, in the working fluid that method on the table 8 is used and the example 4 method 11 and 13 identical:
Bleaching liquid
Ethylenediamine tetraacetic acid, ferric ammonium 100.0 grams
Ethylenediamine tetraacetic acid, disodium salt 8.0 grams
Ammonium bromide 80.0 grams
(28%) 7.0 milliliter of ammoniacal liquor
Bleaching accelerator (as described in Table 9)
Add water to 1.0 liters
PH6.0
Bleach-fixing liquid
Except that not containing any bleaching accelerator,
Other component of solution is identical with above-mentioned bleaching liquid.500 milliliters
(70%) 175 milliliter of thiosulfuric acid ammonia spirit
Sodium sulphite 4.0 grams
Sodium bisulfite 4.6 grams
(28%) 6.0 milliliter of ammoniacal liquor
Sodium tetrapolyphosphate 2.0 grams
This example uses the film (100 meters of every days) of 35 mm wides in field pick-up, carries out continuously 10 days, processes according to method 15 then, adds following working fluid simultaneously.
Simultaneously, make sample, also process every day by after the wedge exposure.
When in bleaching bath, adding additive, adopt similar method in the example 4, the overflowing liquid that flows out from bleaching bath is introduced the bleaching-fixing bath.
The consumption of＜every kind of additive 〉
Identical with in the example 4.
The composition of＜additive 〉
Except that following solution, used identical of other method 13 with example 4.Be added to the additive in the bleaching bath: ethylenediamine tetraacetic acid, ferric ammonium 110 grams
Ammonium bromide 90 grams
(28%) 4 milliliter of ammoniacal liquor
Ethylenediamine tetraacetic acid, disodium salt 10 grams
The bleaching accelerator sees Table 9 described
Add water to 1.0 liters
PH5.7
Processing result is shown in Table 9, by table 9 as seen, method of the present invention provides good photograph reductibility, promoted the useful effect of bleaching accelerator, enable the quick desilverization, and, adopt fixed method is floated in the overflowing liquid introducing of flowing out from bleaching bath, above-mentioned fabulous effect can be kept lastingly.
Example 6
According to example 5 preparation films, the similar approach of use-case 4 makes the film sample expose by wedge, utilizes automatic processing machine then, and CN-16 prepares control sample according to method.
Film is used for outdoor projection (100 meters of every days), carried out continuously 10 days,, and add following working fluid then according to the 15 processing film samples of the method described in the table 8 of example 5.To by the sample after the wedge exposure, also process every day simultaneously.Load onto pipe, make the overflowing liquid that from bleaching bath, flows out introduce to float and decide in the bath.
The composition of＜working fluid 〉
Colour developing solution and additive:
Identical with described in example 4.Bleaching liquid and additive:
Diethylene-triamine pentaacetic acid 174 grams
Ferric chloride hexahydrate 108 grams
Ammonium bromide 90 grams
(37%) 190 milliliter of ammoniacal liquor
Ammonium nitrate 15 grams
Bleaching accelerator (compound IV-1) 2 grams
Add water to 1.0 liters
PH5.8
Bleaching-stop bath
500 milliliters as mentioned above of the compositions of bleaching liquid
Sodium sulphate 10 grams
(70%) 200 milliliter of thiosulfuric acid ammonia spirit
Add water to 1.0 liters
PH7.3
The additive that adds bleaching-fixing bath:
With identical described in the example 4.
Stabilizing solution and additive:
Described identical with example 4
The addition of additive
Be same as example 4 described contents.
Gained the results are shown in table 10, by table 10 as seen, and method of the present invention provides good photograph reductibility, and the desilverization is effective.Table 10 has also illustrated the equally matched of superperformance of the present invention and control sample, and is lasting.
Table 10
The residual silver of the difference of the difference tone of sensitizing degree is measured relatively
Processing fate microgram/centimetre
B G R B G R
0(begins)+0.02+0.01-0.01+0.02 ± 0 ± 0 1.6
10 days+0.01 ± 0 ± 0+0.02 ± 0.01 ± 0.1 1.4
What last table was represented respectively is sample and the relative sensitizing degree difference between the control sample and the difference of tone that the present invention processes.
The composition of＜working fluid 〉
Colour developing solution and additive:
Identical with described in example 4.Bleaching liquid and additive:
Diethylene-triamine pentaacetic acid 174 grams
Ferric chloride hexahydrate 108 grams
Ammonium bromide 90 grams
(37%) 190 milliliter of ammoniacal liquor
Ammonium nitrate 15 grams
Bleaching accelerator (compound IV-1) 2 grams
Add water to 1.0 liters
PH5.8
Bleaching-stop bath
500 milliliters as mentioned above of the compositions of bleaching liquid
Sodium sulphate 10 grams
(70%) 200 milliliter of thiosulfuric acid ammonia spirit
Add water to 1.0 liters
PH7.3
The additive that adds bleaching-fixing bath:
With identical described in the example 4.
Stabilizing solution and additive:
Described identical with example 4
The addition of additive
Be same as example 4 described contents.
Gained the results are shown in table 10, by table 10 as seen, and method of the present invention provides good photograph reductibility, and the desilverization is effective.Table 10 has also illustrated the equally matched of superperformance of the present invention and control sample, and is lasting.
Table 10
The residual silver of the difference of the difference tone of sensitizing degree is measured relatively
Processing fate microgram/centimetre
B G R B G R
0(begins)+0.02+0.01-0.01+0.02 ± 0 ± 0 1.6
10 days+0.01 ± 0 ± 0+0.02 ± 0.01 ± 0.1 1.4
What last table was represented respectively is sample and the relative sensitizing degree difference between the control sample and the difference of tone that the present invention processes.
Claims (4)
1, method that is used to process fontanelization silver color photographic material, this method has comprised the imaging exposure of photographic material, the colour development of the material that exposed, be the desilverization then, it is characterized in that desilverization step comprises: earlier in the bleaching bath of a ferric ion complex salt that contains the aminopolycanboxylic acid, the material that processing has been developed is decided in the bath a ferric ion complex salt and floating of fixer of containing the aminopolycanboxylic acid then, processes developing material.
2, according to the method for claim 1, it is characterized in that wherein fontanelization silver color photographic material contains the blue or green dye color coupler of a kind of structural formula for (I) or (II) at least:
In the formula, R
1, R
2And R
4Expression fatty group, aromatic radical or heterocyclic group that replace or non-replacement, R
3And R
6Be hydrogen atom, the plain atom of fontanel, aliphatic group replacement or non-replacement, aryl or acylamino-, or R
3And R
2For merging the non-metal atom group that forms a nitrogenous five-membered ring or hexatomic ring, R
5Be alkyl that replace or non-replacement, Z
1And Z
2During for hydrogen atom or with developer generation oxidative coupling, the group that can be released, and n is 0 or 1.
It is characterized in that according to the method for claim 1 is described that 3, wherein bleaching bath contains a kind of bleaching accelerator that is selected from following compound at least; Promptly by containing compound, the isothiourea derivatives tetrahydrothiazole derivates that sulfydryl or disulfide bond group are constituted.
4, according to the method for claim 1, it is characterized in that wherein being introduced into to float deciding the bath from the overflowing liquid that bleaching bath flows out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104288 CN1030009C (en) | 1984-09-21 | 1985-06-06 | Method for processing color photographic materials |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19819784A JPS6175352A (en) | 1984-09-21 | 1984-09-21 | Method for processing color photosensitive material |
| CN 85104288 CN1030009C (en) | 1984-09-21 | 1985-06-06 | Method for processing color photographic materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104288A true CN85104288A (en) | 1986-12-03 |
| CN1030009C CN1030009C (en) | 1995-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104288 Expired - Lifetime CN1030009C (en) | 1984-09-21 | 1985-06-06 | Method for processing color photographic materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030009C (en) |
-
1985
- 1985-06-06 CN CN 85104288 patent/CN1030009C/en not_active Expired - Lifetime
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|---|---|
| CN1030009C (en) | 1995-10-11 |
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