JPS63229456A - Color image forming method - Google Patents
Color image forming methodInfo
- Publication number
- JPS63229456A JPS63229456A JP6352787A JP6352787A JPS63229456A JP S63229456 A JPS63229456 A JP S63229456A JP 6352787 A JP6352787 A JP 6352787A JP 6352787 A JP6352787 A JP 6352787A JP S63229456 A JPS63229456 A JP S63229456A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- amount
- gelatin
- color
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 40
- 108010010803 Gelatin Proteins 0.000 claims abstract description 104
- 229920000159 gelatin Polymers 0.000 claims abstract description 104
- 235000019322 gelatine Nutrition 0.000 claims abstract description 104
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 104
- 239000008273 gelatin Substances 0.000 claims abstract description 103
- -1 silver halide Chemical class 0.000 claims abstract description 72
- 229910052709 silver Inorganic materials 0.000 claims abstract description 59
- 239000004332 silver Substances 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 238000011282 treatment Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 82
- 238000005406 washing Methods 0.000 claims description 52
- 238000011161 development Methods 0.000 claims description 25
- 230000006641 stabilisation Effects 0.000 claims description 15
- 238000011105 stabilization Methods 0.000 claims description 15
- 230000000717 retained effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 31
- 239000011248 coating agent Substances 0.000 abstract description 29
- 238000012545 processing Methods 0.000 abstract description 29
- 230000000087 stabilizing effect Effects 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 159
- 239000000839 emulsion Substances 0.000 description 90
- 239000000243 solution Substances 0.000 description 66
- 239000003381 stabilizer Substances 0.000 description 30
- 239000000975 dye Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
- 239000007788 liquid Substances 0.000 description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- 239000007844 bleaching agent Substances 0.000 description 20
- 235000002639 sodium chloride Nutrition 0.000 description 20
- 239000002245 particle Substances 0.000 description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 12
- 230000002265 prevention Effects 0.000 description 11
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 10
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 239000002738 chelating agent Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 235000010265 sodium sulphite Nutrition 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910021612 Silver iodide Inorganic materials 0.000 description 7
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004061 bleaching Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005562 fading Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 6
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 229960003330 pentetic acid Drugs 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 230000033001 locomotion Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- LOIUBRXCXMKWFZ-UHFFFAOYSA-J 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;iron(4+) Chemical compound [Fe+4].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O LOIUBRXCXMKWFZ-UHFFFAOYSA-J 0.000 description 3
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 101100221809 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cpd-7 gene Proteins 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- 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 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 2
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical class O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- WTNULKDCIHSVKN-UHFFFAOYSA-N imidazo[1,2-a]pyridin-2-ol Chemical compound C1=CC=CC2=NC(O)=CN21 WTNULKDCIHSVKN-UHFFFAOYSA-N 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical class C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 125000001909 leucine group Chemical class [H]N(*)C(C(*)=O)C([H])([H])C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical group C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 125000001500 prolyl group Chemical class [H]N1C([H])(C(=O)[*])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical class N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- VNAUDIIOSMNXBA-UHFFFAOYSA-N pyrazolo[4,3-c]pyrazole Chemical class N1=NC=C2N=NC=C21 VNAUDIIOSMNXBA-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- MOODSJOROWROTO-UHFFFAOYSA-N salicylsulfuric acid Chemical compound OC(=O)C1=CC=CC=C1OS(O)(=O)=O MOODSJOROWROTO-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 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
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- QHFDHWJHIAVELW-UHFFFAOYSA-M sodium;4,6-dioxo-1h-1,3,5-triazin-2-olate Chemical compound [Na+].[O-]C1=NC(=O)NC(=O)N1 QHFDHWJHIAVELW-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- MOOINZMWVOZBQO-UHFFFAOYSA-N sulfo 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OS(O)(=O)=O MOOINZMWVOZBQO-UHFFFAOYSA-N 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/396—Macromolecular additives
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はカラー画像形成方法に関するものであシ、更に
詳しくは画像保存性を損なうことなく最終水洗処理液又
は安定化処理液の使用tv大鴫に低減させることができ
る経済的かつ実用上すぐれたカラー画像形成方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a color image forming method. The present invention relates to an economical and practically excellent color image forming method that can reduce the amount of color to black.
(従来技術9
従来、ハロゲン化銀写真感光材料の処理工程には、水洗
工程等が含まれておシ、近年環境保全上又は、水資源上
又は、コスト上の問題から、水量を低減する方向が示唆
されてきた。例えば、ジャーナル オプ ザ ソサエテ
ィ オプ モーション ピクチャー アンド テレビジ
ョン エンジニアズ(Jaurnal of th
e 8ociety ofMotion Pic
ture and TelevisionEngin
eers )第414巻、λ4A r−J j 7頁(
zytt年j月号)の“ウォーター・フローeレイツー
イン・イマージョンもウォシング・オブ・モーション・
ピクチャー・フィルム(WaterFlow Rate
s in Immersion Washingo
f Motion Picture Fi1m″ x
ス、 7−ルeゴールドワイザー(8、R、Goldw
atser)著によれば、水洗タンクを多段にし、水を
向流させることによシ水流水量を削減する方法が提案さ
れている。本方法は、節水に有効な手段として各攬自動
現像機に採用されている。(Prior art 9) Traditionally, the processing process for silver halide photographic materials included a water washing process, but in recent years there has been a trend toward reducing the amount of water due to environmental conservation, water resource, or cost issues. For example, the Journal of the Society of Motion Picture and Television Engineers
e 8ociety of Motion Pic
ture and Television Engine
eers ) Volume 414, λ4A r-J j page 7 (
``Water Flow e Ray-to-In Immersion also Washing of Motion
Picture film (WaterFlow Rate
s in ImmersionWashingo
f Motion Picture Fi1m″ x
S, 7-le Goldweiser (8, R, Goldw
Atser) proposes a method of reducing the amount of water flowing by making the washing tank multi-stage and causing the water to flow counter-currently. This method is adopted in various automatic developing machines as an effective means for saving water.
一万、上記方法とは異なシ、単なる水による処理工程の
代りに各種薬剤を添加した安定液を用いて処理液量を低
下させる方法(特開昭47−J’ j4L1号、同!!
−/1tr311−号、同J7−/321≠z号、同5
r−Ir637号、同JP−1r≠3≠3号など)があ
る。10,000, a method different from the above method is a method in which instead of a simple water treatment process, a stabilizing solution containing various chemicals is used to reduce the amount of treatment solution (Japanese Unexamined Patent Publication No. 1977-J' j4L1, same!!
-/1tr311- issue, same J7-/321≠z issue, same 5
r-Ir No. 637, JP-1r≠3≠3, etc.).
しかしながら上記のいずれの方法においても最終水洗処
理工程又は安定化処理工程の補充ti低減させた場合、
漂白液や漂白定着液中に存在する鉄錯体はもちろん待に
現像液中に存在する現像主薬の洗浄が不充分となり、処
理液保存中にそれらに由来すると思われるイエロー、マ
ゼンタ及びシアンステイ/が上昇するという欠点があつ
念。However, in any of the above methods, if the replenishment ti in the final water washing treatment step or stabilization treatment step is reduced,
Not only the iron complexes present in the bleach and bleach-fix solutions, but also the developing agents present in the developer are not sufficiently washed, and yellow, magenta, and cyan stains that are thought to originate from them occur during storage of the processing solution. The downside is that it rises.
このようなスティンは今に反射材料(例えばカラーペー
パー)の場合、光学的理由から透過材料に比べ数倍に強
調され、微弱なスティンさえも画質全損なう虎めに非常
に!要な要素である。In the case of reflective materials (such as color paper), this kind of stain is emphasized several times more than in transparent materials for optical reasons, and even a weak stain can completely impair the image quality! This is an important element.
(発明が解決しようとする問題点)
従って本発明の目的は画像保存性全損なうことなく、最
終水洗処理液および/又は安定化処理液の使用t’を大
幅に低減させることができるカラー画像形成方法を提供
することにある。(Problems to be Solved by the Invention) Therefore, an object of the present invention is to form a color image that can significantly reduce the use t' of the final washing treatment liquid and/or the stabilization treatment liquid without completely impairing the image preservability. The purpose is to provide a method.
(問題点を解決するための手段)
上記目的は以下に記載された方法により達成さnること
か見い出された。(Means for Solving the Problems) It has been found that the above object can be achieved by the method described below.
芳香族第1級アミン現像主薬の酸化体と反応して色Xt
−形成するカプラーを含み、全塗布ゼラチン量の2jw
t%以上が酸処理ゼラチンであるハロゲン化銀カラー感
光材料全発色現像、脱銀処理したのち水洗処理および/
または安定化処理し、該水洗処理および核安定化処理の
補充量が前浴からの持込tのo、z−to倍であること
を%徴とするカラー画像形成方法。Reacts with the oxidized product of aromatic primary amine developing agent to form color Xt
- 2jw of the total coated gelatin amount, including couplers to be formed.
A silver halide color light-sensitive material in which t% or more is acid-treated gelatin is fully color developed, desilvered, washed with water and/or
Alternatively, a color image forming method in which a stabilization treatment is performed, and the replenishment amount of the water washing treatment and the nuclear stabilization treatment is o, z-to times the carry-in t from the previous bath.
本発明において補充量が前浴からの持込量の0゜j−j
0倍であるとは、脱銀処理と乾燥との間の処理工程の
補充量についてである。ここで、この処理工程が水洗工
程と安定化工程とからなれば共にかかる補充量となって
いることを意味している。In the present invention, the amount of replenishment is 0゜j−j of the amount brought in from the previous bath.
0 times refers to the amount of replenishment in the processing steps between desilvering and drying. Here, if this treatment step consists of a water washing step and a stabilization step, this means that both of them require the same amount of replenishment.
lた水洗工程のみの場合には、水洗工程がかかる補光量
となっていること全意味している。In the case where there is only a water washing step, it means that the water washing step has such a supplementary light amount.
以下に本発明の詳細について説明する。The details of the present invention will be explained below.
本発明における酸処理ゼラチンはコラーゲンからの製造
工程で塩酸などによる処理を伴って製造さnたゼラチン
で通常写真工業界で用いられる石灰などによる処理kj
+うアルカリ処理ゼラチンとは異なるものである。これ
らのゼラチンの製法、性質の詳細はArthur V
eis署 「TheMacromolecular
Cherriistry ofGelatin J
Academic Press、 / 17貞〜2/7
貞(/りぶ蓼年発行)に記載されているが最も大きな相
違は等電点(PI)が酸処理ゼラテ/ではPl=4.θ
〜?、! であるのに対し、アルカリ処理ゼラチンi;
tPI=e、t〜!、3である点である。Acid-treated gelatin in the present invention is gelatin produced by treatment with hydrochloric acid or the like during the production process from collagen, and is treated with lime or the like commonly used in the photographic industry.
+It is different from carboxyl-treated gelatin. For details on the manufacturing method and properties of these gelatins, see Arthur V.
EIS station “The Macromolecular
Cherrystory of Gelatin J
Academic Press, / 17 Sada ~ 2/7
The biggest difference is that the isoelectric point (PI) of acid-treated gelate is 4. θ
~? ,! In contrast, alkali-treated gelatin i;
tPI=e, t~! , 3.
カラー写真感光材料に酸処理ゼラチン金剛いることは特
公昭3/−弘3777号、特開昭j/−?93r号、同
!3−JA24!号等に記載されているが、これらはい
ずれも膜面のレチキュシーション改良に関する事であり
、酸処理ゼラテ/金用いることにより、カラー感光材料
の汚染が著しく防止される4!は全く予想されない事実
であった。Is it true that acid-treated gelatin Kongo is used in color photographic materials? 93r issue, same! 3-JA24! These are all related to improving the reticulation of the film surface, and by using acid-treated gelate/gold, contamination of color photosensitive materials can be significantly prevented 4! This was a completely unexpected fact.
これはカラー現像主薬の酸化物が酸処理ゼラチンに付着
しにくい事に帰因していると推定される。This is presumed to be due to the fact that oxides of color developing agents are difficult to adhere to acid-treated gelatin.
本発明に使用されるカラー感光材料の酸処理ゼラチン含
量は全塗布ゼラチン量に対して26wt%以上であり、
好ましくは30wt%以上である。The content of acid-treated gelatin in the color light-sensitive material used in the present invention is 26 wt% or more based on the total amount of coated gelatin,
Preferably it is 30 wt% or more.
また上限としてはioo%である。Moreover, the upper limit is ioo%.
本発明に使用される酸処理ゼラチンの等電点は6〜5F
、!であシ、好運しくは7〜り、!、より好ましくはr
−r、tである。The isoelectric point of the acid-treated gelatin used in the present invention is 6 to 5F.
,! Well, with good luck it's 7~ri! , more preferably r
-r, t.
また本発明に用いられる酸処理ゼラチンの分子量として
は特に制限はないが好ましくは/万〜20万である。Further, the molecular weight of the acid-treated gelatin used in the present invention is not particularly limited, but is preferably between 10,000 and 200,000.
酸処理ゼラチンと共に併用しうるゼラチンとしては後述
のバインダーとして記載さnたゼラチ/を挙げることが
できる。Examples of gelatin that can be used in combination with acid-treated gelatin include gelatin described below as a binder.
本発明において「全塗布ゼラチン量」は、支持体の両面
のゼラチンを言うが、好ましくは支持体のハロゲン化銀
乳剤層を有した側のゼラテ/lを言う。In the present invention, the "total coated gelatin amount" refers to the gelatin on both sides of the support, preferably gelatin/l on the side of the support having the silver halide emulsion layer.
ここで「全塗布ゼラチン量」としては、好ましくは感光
材料/m 当シ/〜301、より好1し〈はコ〜−〇?
である。Here, the "total coated gelatin amount" is preferably photosensitive material/m 1/~301, more preferably 1/m~-301.
It is.
本発明において酸処理ゼラチン量は、2jwt%以上で
あるが、コ!%に満だなh場合には色汚染を十分に防止
することが困難である。In the present invention, the amount of acid-treated gelatin is 2jwt% or more. %, it is difficult to sufficiently prevent color staining.
本発明の方法は、カラー現像液を使用する処理ならば、
いかなる処理工程にも適用できる。例えばカラーペーパ
ー、カラー反転ペーパー、カラー直接ポジ感元材料、カ
ラーポジフィルム、カラーネガフィルム、カラー反転フ
ィルム等の処理に適用することができるが、待にカラー
ベー/ζ−、カラー反転ペーパーへの適用が好ましい。If the method of the present invention uses a color developer,
It can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, color direct positive sensitive material, color positive film, color negative film, color reversal film, etc., but it is preferably applied to color base/ζ- and color reversal paper. .
本発明に用いられる感光材料のハロゲン化銀乳剤は、沃
臭化銀、臭化銀、塩臭化銀、塩化銀等いかなるハロゲン
組成のものでも使用できる。例えばカラーペーパー等の
迅速処理や低補充処理を行う場合には、塩化銀をぶ0モ
ル%以上含有する塩臭化銀乳剤又は塩化銀乳剤が好まし
く、更には、塩化銀の含有率がto−7ooモル%の場
合が特に好ましい。′!九高g度全必要とし、かつ、製
造時、保存時、及び/又は処理時のカブリをとくに低く
抑える必要がある場合には、臭化銀を30モル%以上含
有する塩臭化銀乳剤又は臭化銀乳剤(3モル%以下の沃
化銀を含有してもよい)が好1しく、更には70モル%
以上が好ましい。撮影用カラー感光材料には、沃臭化銀
、塩沃臭化銀が好ましく、ここで沃化銀含有率は3〜/
jモル第が好ましい。The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. For example, when performing rapid processing or low-replenishment processing of color paper, etc., a silver chlorobromide emulsion or a silver chloride emulsion containing 0 mol% or more of silver chloride is preferable, and furthermore, a silver chloride content of to- Particularly preferred is 70 mol%. ′! When a high-g degree of 9 is required and fog during production, storage, and/or processing needs to be particularly low, silver chlorobromide emulsions containing 30 mol% or more of silver bromide or Silver bromide emulsions (which may contain up to 3 mol% silver iodide) are preferred, more preferably 70 mol%
The above is preferable. Silver iodobromide and silver chloroiodobromide are preferable for color light-sensitive materials for photography, and the silver iodide content is 3 to 1/2.
j mole is preferred.
本発明に用いられるハロゲン化銀粒子は内部と表層が異
なる相tもっていても、接合構造を有するような多相構
造であってもあるいは粒子全体が均一な相から成ってい
てもよい。またそれらが混在していてもよい。The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.
本発明に使用するハロゲン化銀粒子の平均粒子サイズ分
布は狭くても広くてもいずれでもよいが、ハロゲン化銀
乳剤の粒度分布曲線に於る標準偏差値を平均粒子サイズ
で割った値(変動率)が20≦以内、特に好ましくは7
3%以内のいわゆる単分散ハロゲン化銀乳剤を本発明に
使用することが好ましい。また感光材料が目標とする階
調を満足させる丸めに、実質的に同一の感色性を有する
乳剤層において粒子サイズの異なる2種以上の単分散ハ
ロゲン化銀乳剤(単分散性としては前記の変動率をもっ
たものが好ましい)を同一層に混合または別層に重層塗
布することができるつさらに2種以上の多分散ハロゲン
化銀乳剤あるいは単分散乳剤と多分散乳剤との組合わせ
を混合あるいは重層して使用することもできる。The average grain size distribution of the silver halide grains used in the present invention may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size ratio) is within 20≦, particularly preferably 7
So-called monodisperse silver halide emulsions of up to 3% are preferably used in the present invention. Furthermore, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in emulsion layers having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably those with a fluctuation rate) can be mixed in the same layer or coated in separate layers, and furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion are mixed. Alternatively, they can be used in layers.
本発明に使用するハロゲン化銀粒子の形は立方体、八面
体、菱十二面体、十四面体の様な規則的(regula
r)な結晶体七有するものあるいはそれらの共存するも
のでもよく、また球状などのような変則的(irreg
ular)な結晶形をもつものでもよく、ま九これらの
結晶形の複合形管もつものでもよい。ま九平板状粒子で
もよく、特に長さ/厚みの比の値がJ−fまたは2以上
の平板粒子が、粒子の全投影面積の30%以上を占める
乳剤を用いてもよい。これら楕々の結晶形の混合から成
る乳剤であってもよい。The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical ones.
It may have a ular crystal shape, or it may have a composite shape of these crystal shapes. In particular, an emulsion may be used in which tabular grains having a length/thickness ratio of Jf or 2 or more occupy 30% or more of the total projected area of the grains. An emulsion consisting of a mixture of these elliptical crystal forms may also be used.
これら各種の乳剤は潜像を主として表面に形成する表面
潜像型でも、粒子内部に形成する内部潜像型のいずれで
もよい。These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.
本発明に用いられる写真乳剤は、R,ESEARCi(
DI8CL(J8URE vo 1 、 / 70
I ten A/ 74#J(1,■、l)項(/?
7r、12)に記載された方法を用いて調製することが
できる。The photographic emulsion used in the present invention is R, ESEARCi (
DI8CL(J8URE vo 1, /70
I ten A/ 74 #J (1, ■, l) term (/?
7r, 12).
本発明に用いられる乳剤は、通常、物理熟成、化学熟成
および分光増感を行つ九ものを使用する。The emulsions used in the present invention are usually subjected to physical ripening, chemical ripening and spectral sensitization.
このような工程で使用される添加剤はリサーチ・ディス
クロージャー第17ぶ巻、16/74弘3(lり’rr
、i、2月)および同第117巻、A/1yit(iり
7り、17月)に記載されており、その該当個所を後掲
の表にまとめた。Additives used in such processes are described in Research Disclosure Vol. 17, 16/74 Ko 3.
, I, February) and Vol. 117, A/1yit (I, July 17), and the relevant parts are summarized in the table below.
本発明に使用できる公知の写真用添加剤も上記の2つの
りサーチ・ディスクロージャーに記載されており、後掲
の表に記載個所を示し九。Known photographic additives that can be used in the present invention are also listed in the above two search disclosures, and the locations listed are shown in the table below.
添の口剤cR類 R,D/7A≠3
RD/lry/乙1 化学増感剤 23頁
ttr頁右欄2感度上昇剤 同上
3 分光増感剤 コノ−コグ頁 t4tr頁右欄〜4
強色増感剤 ハリ頁右欄5 増
白 斉] コ軸6 かふり防止剤 コ≠
〜2j頁 64L?頁右欄および安定Δす
7 カ プ ラ − 、2J@8
七°f9.浴媒 23頁
9 光吸収剤、フ λj−−乙貝 を弘り瓜右欄
〜イルター呆料 630貞圧欄10
紫外線吸収剤
11 スティン防止剤 λ!貞右欄 120
貞左〜右欄12 色票画像安定剤 −3頁13
硬 膜 剤 −26貝 6j/貞左
欄14 バインダー 26負 同上15
可塑剤、潤滑剤 27貞 430貞右欄
16 蛍石助剤、 コ≦〜27貴 同上表
面活性剤
17 スタチツ名涛止剤 コア貞
同上本発明には種々のカラーカプラー全使用することが
できる。ここでカラーカプラーとは、芳香族第一級アミ
ン現像薬の酸化体とカップリング反応して色素を生成し
うる化合物をいう。有用なカラーカプラーの典型例には
、ナフトールもしくはフェノール系化合物、ピラゾロン
もしくはピラノロアゾール系化合物および開鎖もしくは
複葉環のケトメチレン化合物がある。本発明で使用しう
るこれらのシアン、マゼンタおよびイエローカプラーの
具体例はリサーチ・ディスクロージャ(RD)/744
13(1971年72月)■−り項おXび同/17/
7(/り7?年/1月)に引用さ、れた特許に記載さn
ている。Added mouthwash cR type R, D/7A≠3
RD/lry/Otsu 1 Chemical sensitizer page 23
ttr page right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer Cono-cog page t4tr page right column~4
Supersensitizer Sharpness Page Right Column 5 Increase
Bai Qi] Co-axis 6 Anti-fogging agent Co≠
~2j page 64L? Page right column and stable ΔS7 coupler -, 2J@8
7°f9. Bath medium Page 23 9 Light absorbent, fu λj--Right column - Ilter agent 630 Pressure column 10
Ultraviolet absorber 11 Anti-stain agent λ! Sada right column 120
Tei left to right column 12 Color chart image stabilizer -3 page 13
Hardener -26 Shell 6j/Sada left column 14 Binder 26 negative Same as above 15
Plasticizer, lubricant 27-silicon 430-silicon right column 16 Fluorite auxiliary agent, ko≦~27-ki Same as above Surface active agent 17 Statistic name anti-staining agent Core-silicate
All of the various color couplers can be used in the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyranoloazole compounds, and open chain or bicyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure (RD)/744.
13 (December 1971)
7 (/7?/January) and described in the patent n
ing.
感光材料に内蔵するカラーカプラーは、パラスト基金有
するかまたはポリマー化されることによシ耐拡散性であ
ることが好ブしい。カップリング活性位が水素原子の四
当量カラーカグラーよりも離脱基で置換された二当債カ
ラーカグラーの方が、塗布銀量が低減できる。発色色素
が適度の拡散性を有するようなカプラー、無呈色カプラ
ーまたはカップリング反応に伴って現像抑制剤全放出す
るDIRカプラーもしくは現像促進剤を放出するカプラ
ーもまた使用できる。The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast base or being polymerized. A two-equivalent color kaglar substituted with a leaving group can reduce the amount of coated silver than a four-equivalent color kaglar whose coupling active position is a hydrogen atom. Couplers in which the coloring dye has appropriate diffusivity, colorless couplers, DIR couplers that release all of the development inhibitor or couplers that release the development accelerator upon coupling reaction can also be used.
本発明に使用できるマゼンタカプラーとしては、オイル
プロテクト型の、インダシロン系もしくはシアノアセチ
ル系、好ましくはj−ピラゾロン系およびピラゾロトリ
アゾール類などピラゾロアゾール系のカプラーが挙げら
れる。!−ピラゾaノ系カプラーは3−位がアリールア
ミノ基もしくはアシルアミノ基で置換さルたカプラーが
、発色色素の色相や発色濃度の観点で好ましく、その代
表例は、米国を許@コ、3//、Or−号、同第2゜j
4tJ、703号、同第2.乙θθ、7rJr号、同i
igコ、PC#、j73号、同第3,042.tjJ号
、同第3.l!λ、?96号および同第3゜PI3,0
1J号などに記載されてbる。二当量の!−ピラゾロ/
系カゾラーの離脱基として、米国特許第μ、J10.t
/り号に記載された窒素原子離脱基または米国特許第≠
、331,197号に記載さnたアリールチオ基が好ま
しい。また欧州特許第7j、4Jj号に記載のパラスト
基金有す石!−ピラゾロン系カプラーは高い発色濃度が
得られる。Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as j-pyrazolone and pyrazolotriazoles. ! - As for the pyrazo a-no coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye. /, Or- No. 2゜j
4tJ, No. 703, same No. 2. Otsu θθ, 7r Jr., same i
igco, PC#, j73, same number 3,042. tjJ No. 3. l! λ,? No. 96 and No. 3゜PI3,0
It is described in No. 1J, etc. Two equivalents! -Pirazolo/
As a leaving group for the system cazoler, U.S. Patent No. μ, J10. t
Nitrogen leaving group described in /R issue or U.S. Patent No.≠
, 331,197 is preferred. Also, the stone with the palast foundation described in European Patent Nos. 7j and 4Jj! - Pyrazolone couplers provide high color density.
ピラゾロアゾール系カプラーとしては、米国特許第3.
3&’?、177号記載のピラゾロベンズイミダゾール
類、好運しくに米国特許第3.7.2J、047号に記
載されたピラゾロ(j、/−c、)〔/、コ、4t〕ト
リアゾール類、リサーチ・ディスクロージャーコμココ
0(/り、r弘u月)に記載のピラゾロテトラゾール類
およびリサーチ・ディスクロージャーλ4L23θ(/
P♂≠年を月)に記載のピラゾロピラゾール類が挙げら
れる。発色色素のイエロー副吸収の少なさおよび光堅牢
性の点で欧州特許第1/F、7μ7号に記載のイミダゾ
(/、2−b)ピラゾール類は好ましく、欧州特許第i
iy、rto号に記載のピラゾロ〔/。As a pyrazoloazole coupler, US Patent No. 3.
3&'? , pyrazolobenzimidazoles described in U.S. Pat. Pyrazolotetrazoles described in Disclosure Coμ Coco 0 (/ri, r Hirotsuki) and Research Disclosure λ4L23θ (/
Examples include pyrazolopyrazoles described in P♂≠year (month). Imidazo(/,2-b)pyrazoles described in European Patent No. 1/F, 7μ7 are preferable from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and European Patent No.
Pyrazolo [/.
z−b)(:/、z、4t))リアゾールは特に好まし
い。Particularly preferred are z-b) (:/, z, 4t)) riazoles.
本発明に使用できるシアンカプラーとしては、オイルプ
ロテクト型のナフトール系およびフェノ−ル系のカプラ
ーがあり、米国特許第コ、≠7μ。Cyan couplers that can be used in the present invention include oil-protected naphthol and phenol couplers, US Pat. No. 7, ≠7μ.
λり3号に記載のナフトール系カプラー、好ましくは米
国特許第≠、Ojtλ、λl−号、同第参。3, preferably the naphthol couplers described in U.S. Pat.
/μ6,3り3号、同@グ、コλr、2JJ号および同
第弘、29/s、λOO号に記載された酸素原子離脱型
の二当竜ナフトール系カプラーが代弐例として挙げられ
る。またフェノール系カプラーの具体例は、米国特許第
2,3tテ、222号、同第2,10/、171号、同
第コ、77コ、762号、同第λ、tpj、rコを号な
どに記載されている。湿匿および温度に対し堅牢なシア
ンカプラーは、本発明で好ましく使用され、その典型例
を挙げる々、米国特許第3,772,002号に記載さ
れ友フェノール核のメター位にエチル基以上のアル中ル
基を有するフェノニル系シアンカプラー、米国特許第λ
、77λ、l乙コ号、同第3.7!I、301号、同第
!、/J4.JP4号、同第μ、334L、oii号、
同第参、3コア。/μ6, 3ri No. 3, @gu, koλr, 2JJ, and No. 29/s, λOO, oxygen atom dissociable double-arm naphthol couplers are mentioned as two examples. . Specific examples of phenolic couplers include U.S. Pat. etc. are listed. Cyan couplers that are stable against moisture and temperature are preferably used in the present invention, and typical examples thereof include those described in U.S. Pat. Phenonyl-based cyan coupler having a ru group, U.S. Patent No. λ
, 77λ, l otsuko issue, same number 3.7! I, No. 301, same No.! , /J4. JP No. 4, same No. μ, 334L, oii No.
Same article, 3 cores.
173号、***特許公開第3,3λり、7λり号お゛よ
び特願昭Jf−82ぶ71号などに記載されたコ、J−
ジアシルアミノ置換フェノール系カプラーおよび米国特
許第J、4<!4,4コー号、同第ぴ、333.タタタ
号、同第弘、グzi、 jzり号および同第≠、4A
27,747号などに記載されたコー位にフェニルウレ
イドit有しかつ!−位にアシルアミノ基″It7にす
るフェノール系カプラーなどである。J-
Diacylamino-Substituted Phenolic Couplers and U.S. Patent No. J, 4<! 4,4 Co. No. 4, No. 4, 333. Tatata, No. 1 Hiro, Guzi, Jzuri, and No. ≠, 4A
No. 27,747 etc. has phenylureido in the co-position and! These include phenolic couplers that create an acylamino group "It7" at the - position.
発色色素が適度に拡散性を有するカプラーを併用して粒
状性を改良することができる。このような色素拡散性カ
プラーは、米国特許第≠、J4J。Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in US Patent No. ≠, J4J.
237号および英国特許第2./21,170号にマゼ
ンタカプラーの具体例が、また欧州特許第P6,370
号および***出願公開第3,23≠。No. 237 and British Patent No. 2. Specific examples of magenta couplers are given in European Patent No. P6,370 and European Patent No. P6,370.
No. 3,23≠.
jJJ−Wjにはイエロー、マゼンタもしくはシアンカ
プラーの具体例が記載されている。Specific examples of yellow, magenta or cyan couplers are described in JJJ-Wj.
色素形成カプラーおよび上記の特殊カプラーは、二量体
以上の東合体を形成してもよい。ポリマー化された色素
形成カプラーの典型例は、米国特許第J 、173/
、120号および同第a、oro。The dye-forming couplers and the special couplers described above may form dimers or more east combinations. Typical examples of polymerized dye-forming couplers are U.S. Patent No. J, 173/
, No. 120 and No. a, oro.
277号に記載されている。ポリマー化マゼ/タカプラ
ーの具体例は、英国特許第2,10コ、173号および
米国特許第μ、Jt7.コrコ号に記載されている。It is described in No. 277. Specific examples of polymerized maze/ta couplers are described in British Patent No. 2,10, 173 and US Patent No. μ, Jt7. It is written in the Corco issue.
本発明に使用する各種のカプラーは、感光材料に必要と
される特性を満たすために、感光層の同一層に二種類以
上を併用することもできるし、また同一の化合物會異な
った二層以上に導入することもできる。The various couplers used in the present invention can be used in combination of two or more types in the same layer of the photosensitive layer, or in two or more different layers of the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into
本発明において特に好ましいカプラーはイエローカプラ
ーとしては一般式(1)、マゼンタカプラーとしては一
般式(n)、(lit)、シアンカプラーとしては一般
式CN)及び(V)で表わされる。Particularly preferred couplers in the present invention are represented by general formula (1) for yellow couplers, general formulas (n) and (lit) for magenta couplers, and general formulas CN) and (V) for cyan couplers.
これらのカプラーはいずれも色再現上好ましくまた、使
用する銀量を低下させることができるためコスト上好ま
しいが、特に水洗工程等の補充量を低下させた場合残存
主薬が関与すると思われる 。All of these couplers are preferable in terms of color reproduction and are preferable in terms of cost since they can reduce the amount of silver used; however, it is thought that residual active ingredient may be involved, especially when the amount of replenishment in the water washing step is reduced.
ステイ/が出やすいという欠点を持っていた。しかしな
がら、本発明のゼラチンを使用する事で、上記問題点が
効果的に解決された事は特筆に値する。It had the disadvantage of being prone to Stay/. However, it is noteworthy that the above problems were effectively solved by using the gelatin of the present invention.
ここでイエロー、マゼ/り、シアンカプラーとして一般
式に含まれるもの全同時に用いると一層好ましい。It is more preferable to use all of the yellow, maze/red, and cyan couplers included in the general formula at the same time.
イエローカプラー
一般式(I)
マイ/タカ−プラー
一般式(n)
几5
一般式(III)
ba=bb
シアンカプラー
一般式(fV)
一般式(V)
式中、R1は置換または無置換のN−フェニルカルバモ
イル基金表わし、几2は炭素数μ〜、20個の第3級ア
ルキル基、もしくは置換または無置換のフェニル基を表
わし、
Rおよびル、は置換もしくは無置換のフ二二ル基を表わ
し、
R4は水素原子、脂肪族もしくは芳香族のアシル基、脂
肪族もしくは芳香族スルホニル基kWわし、
R6は水素原子又は置換基上表わし、
R7、ル、。およびR工、は、それぞn脂肪族基、芳香
族基、複素環基、芳香族アミノ基又は複索環アミノ基を
表わし、
凡、は脂肪族基を戎わし、
R8および几、□はそれぞれ水素原子、ハロゲン原子、
脂肪族基、脂肪族オキシ基、又はアシルアミノ基7表わ
し、
Zaおよびzbは、メチン、置換メチン、又は=N−を
我わし、
X□、Y工、Y2、Y3およびY4は現像主薬との酸化
体とのカップリング反応時に離脱可能なit(以下、離
脱基と略す)を表わす。Yellow coupler general formula (I) Mai/Takapler general formula (n) 几5 General formula (III) ba=bb Cyan coupler general formula (fV) General formula (V) In the formula, R1 is substituted or unsubstituted N - represents a phenylcarbamoyl group, 几2 represents a tertiary alkyl group having a carbon number μ~20, or a substituted or unsubstituted phenyl group, and R and R represent a substituted or unsubstituted phenyl group. R4 is a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, R6 is a hydrogen atom or a substituent, and R7 is a substituent. and R represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group, or a polycyclic amino group, respectively; hydrogen atom, halogen atom,
represents an aliphatic group, an aliphatic oxy group, or an acylamino group; Za and zb represent methine, substituted methine, or =N-; It represents an it (hereinafter abbreviated as a leaving group) that can be removed during a coupling reaction with a group.
さらにRR又はXl;kL3%R,、R51〜
2
又はYl;R,、Za、Zb又はY2;几7、RR又は
Y、R,、凡 、R□2又
8% 9 3 10
11はY4で2量体以上の多量体を形成していてもよ
い。Furthermore, RR or Xl; kL3%R,, R51~
2 or Yl; R,, Za, Zb or Y2; 7, RR or Y, R,, ordinary, R□2 or 8% 9 3 10
11 may form a dimer or more multimer with Y4.
ここで述べた脂肪族基とは直鎖状、分岐鎖状もしくは環
状の、アルキル、アルケニル又はアルキニル基を表わす
。)
一般式(1)において好ましいXlとして一般式(■)
、(■)及び(■)があげられる。The aliphatic group mentioned here refers to a linear, branched or cyclic alkyl, alkenyl or alkynyl group. ) In general formula (1), general formula (■) is preferred as Xl
, (■) and (■).
(■) (■)
R、R,、は各々水素原子、ノ10ゲン原子、カルボン
酸エステル基、アミノ基、アルキ暢、アルキルチオ基、
アルコキシ基、アルキルスルホニル基、アルキルフルフ
ィニル基、カルメン酸基、スルホン酸基、無置換もしく
は置換フェニル基または複素環を表わし、こnらの基は
同じでも異ってもよい。(■) (■) R, R, are each a hydrogen atom, a hydrogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group,
It represents an alkoxy group, an alkylsulfonyl group, an alkylfurfinyl group, a carmenic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.
環もしくは6員環を形成するのに要する非金属原子を表
わす。Represents a nonmetallic atom required to form a ring or a 6-membered ring.
以下、一般式(1)で表わされるカプラーの好ましい具
体例を示す。Preferred specific examples of the coupler represented by the general formula (1) are shown below.
(Y−/) C! (Y−λ) (Y−J) (Y−μ) (Y−s) (シ (Y−遥) α (Y−7) α (y−r) l Uに、H,L;2M。(Y-/) C! (Y-λ) (Y-J) (Y-μ) (Y-s) (S (Y-Haruka) α (Y-7) α (yr) l U, H, L; 2M.
(Y−タ) l α (Y−to) (Y−/ /) α CH20H2(JC2H。(Y-ta) l α (Y-to) (Y-/ /) α CH20H2 (JC2H.
(Y−/コ)
t
(Y−/J)
α
(Y−/グ)
α
(Y−/j)
t
α
(Y−/ぶ)
(Y−/7)
(”I
CH3
(Y −/ r )
α
(Y−/り)
α
C1(3
(Y−−l)
(Y−23)
(Y−コダ)
(Y−Jr)
H3
(Y−コt)
α
以下、一般式(n)及び(ill)で表わされるカプラ
ーの好ましい具体例?示す。(Y-/ko) t (Y-/J) α (Y-/g) α (Y-/j) t α (Y-/bu) (Y-/7) ("I CH3 (Y-/r ) α (Y-/ri) α C1(3 (Y--l) (Y-23) (Y-Koda) (Y-Jr) H3 (Y-Kot) α Below, general formula (n) and ( Preferred specific examples of couplers represented by ill) are shown below.
α (M−一) (M刊)、。α (M-1) (published by M).
α
(M−グ)
(M−j)
(M−P)
C8H17(す
(M−//)
に8H1?(す
CM−/ダ)
(M−/4)
(M−/7)
C8H□、(す
(M−1t)
(M−/り)
(M−26)
CH3
(M−Jr)
Ct
(M−コタ)
(M−JO)
(M−3/)
以下、一般式(fV)及び(V)で表わされるカプラー
の好ましい具体例を示す。α (M-g) (M-j) (M-P) C8H17 (su (M-//) ni8H1? (suCM-/da) (M-/4) (M-/7) C8H□, (S(M-1t) (M-/ri) (M-26) CH3 (M-Jr) Ct (M-Kota) (M-JO) (M-3/) Below, the general formula (fV) and ( Preferred specific examples of the coupler represented by V) are shown below.
(C−/) α (C−2) α (C−J) (C−参) α (C−t) α (C−a) (C−7) α (c−r) α (e−P) (C−10) (C−//) α (C−/λ) (’)C5Hll (C−/3) (C−/仏) α (C−/j) (C−/4) (C−t7) α <c−tr) p 、。(C-/) α (C-2) α (C-J) (C-see) α (C-t) α (C-a) (C-7) α (cr) α (e-P) (C-10) (C-//) α (C-/λ) (’)C5Hll (C-/3) (C-/France) α (C-/j) (C-/4) (C-t7) α <c-tr) p,.
(1)05H1l
(C−/り)
〔C−λO〕
(C−2/)
(C−ココ)
(C−コ3)
α
(C−コ−)
(C−コり
(C−λt)
(C−27)
(C−コt)
(t)c、n11
(C−λり)
α
(C−JO)
(C−3t)
(C−3,2)
H
(C−J j )
H
C1□H2,CUN1憬
CC−Jr)
(C−JP)
(c−go)
カラーカプラーの標準的な使用量は、感光性ハロゲン化
銀の1モルあたり0.00/ないし1モルの範囲であシ
、好ましくはイエローカプラーではθ、0/ないし0.
J−モル、マイ/タカプラーでは0.003ないし0.
3モル、またシアンカプラーではθ、002ないし0.
3モルである。(1)05H1l (C-/ri) [C-λO] (C-2/) (C-here) (C-co3) α (C-co-) (C-coli (C-λt) ( C-27) (C-kot) (t)c, n11 (C-λri) α (C-JO) (C-3t) (C-3,2) H (C-J j ) H C1□ H2, CUN1 (CC-Jr) (C-JP) (c-go) The standard usage amount of the color coupler is in the range of 0.00/mol to 1 mol per mol of photosensitive silver halide, Preferably for yellow couplers θ, 0/ to 0.
J-mol, 0.003 to 0.00 for Mai/Ta coupler.
3 moles, and for cyan couplers θ, 002 to 0.
It is 3 moles.
本発明に使用するカプラーは、種々の公知分散方法によ
り感光材料中に導入できる。水中油滴分散法に用いられ
る高沸点有機溶媒の例は、米国特許第、2.322.0
27号などに記載されている。The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high-boiling organic solvents used in oil-in-water dispersion methods include U.S. Patent No. 2.322.0.
It is stated in issue 27 etc.
また、ラテックス分散法の工程、効果、含浸用のラテッ
クスの具体例は、米国特許第@ 、 /?? 。Further, the process and effects of the latex dispersion method, as well as specific examples of latex for impregnation, can be found in US Patent No. @, /? ? .
363号、***特許出願(OLS)第2.!4t/。No. 363, West German Patent Application (OLS) No. 2. ! 4t/.
279号および同第コ、j’l/、230号などに記載
されている。No. 279 and Ko, J'l/, No. 230, etc.
本発明に用いられる写真感光材料は通常用いられている
プラスチックフィルム、(硝酸セルロース、酢酸セルロ
ース、ポリエチレンテレフタレートなど)、紙などの可
撓性支持体またはガラス、などの剛性の支持体に塗布さ
れる。支持体及び塗布方法については詳しくはRESE
ARCHDISCLO8URE / 7 を巻Item
/744tjXV項(p、J7)XW項(p、2/)(
/y7.r年72月号)に記載されている。The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. . For more information on supports and coating methods, please see RESE
ARCHDIS CLO8URE / 7 Item
/744tjXV term (p, J7)XW term (p, 2/) (
/y7. It is described in the July 2011 issue).
本発明においては、反射支持体が好ましく用いられる。In the present invention, a reflective support is preferably used.
「反射支持体」は、反射性を高めてハロゲン化銀乳剤層
に形成された色素画像を鮮明にするものであシ、このよ
うな反射支持体には、支持体上に酸化チタン、酸化亜鉛
、炭酸カルシウム、硫酸カルシウム等の光反射物質を分
散含有する疎水性樹脂を被覆したものや光反射性物質を
分散含有する疎水性樹脂を支持体として用いたものが含
まれる。A "reflective support" is something that enhances the reflectivity to make the dye image formed in the silver halide emulsion layer clearer.Such reflective supports include titanium oxide, zinc oxide, etc. , those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as calcium carbonate or calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support.
以下に本発明のカラー現像液について説明する。The color developer of the present invention will be explained below.
本発明に使用されるカラー現像液中には、公知の芳香族
第一級アミノカラー現像主薬を含有する。The color developer used in the present invention contains a known aromatic primary amino color developing agent.
好ましい例はp−フェニレンジアミン誘導体であり、代
表例を以下に示すがこれらに限定されるものではない。Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.
D−/N、N−ジエチル−p−フェニレンジアミン
D−22−アミノ−よ−ジエチルアミノトルエン
D−32−アミノ−β−(N−エチル−N−ラウリルア
ミノ)トルエン
D−タ グー〔N−エチル−N−(β−ヒドロキシエ
チル)アミノコアニリン
D−r コーメチルーター〔N−エチル−N−〔β
−ヒドロキシエチル)アミンコア
ニリン
D−t 4t−アミノ−3−メチル−N−エチル−
N−(β−(メタンスルホンアミド)エチル〕−アニリ
ン
D−7N−(コーアミノーj−ジエチルアミノフェニル
エチル)メタンスルホンア
ミ ド
D−rN、N−ジメチル−p−フェニレンジアミン
D−94t−アミノ−3−メチル−N−エチル−N−メ
トキシエチルアニリン
D−104t−アミノ−3−メチル−N−エチル−N−
β−エトキシエ゛チルアニリン
D−// 4t−アミノ−3−メチル−N−エチル−
N−β−ブトキシエテルアニリン
上上記−フェニレンジアミン誘導体のうち特に好ましく
はグーアミノ−3−メチル−N−エチル−N−[β−(
メタンスルホンアミド)エチル〕−アニリン(例示化合
物D−6)である。D-/N, N-diethyl-p-phenylenediamine D-22-amino-y-diethylaminotoluene D-32-amino-β-(N-ethyl-N-laurylamino)toluene D-tag [N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-r Comethylrouter [N-ethyl-N-[β
-hydroxyethyl)aminecoaniline D-t 4t-amino-3-methyl-N-ethyl-
N-(β-(methanesulfonamido)ethyl]-aniline D-7N-(co-amino-j-diethylaminophenylethyl)methanesulfonamide D-rN, N-dimethyl-p-phenylenediamine D-94t-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-104t-amino-3-methyl-N-ethyl-N-
β-ethoxyethylaniline D-// 4t-amino-3-methyl-N-ethyl-
Among the above-mentioned -phenylenediamine derivatives, N-β-butoxyetheraniline is particularly preferably guamino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).
また、これらのp−フェニレンジアミン誘導体は硫酸塩
、塩酸塩、亜硫酸塩、p−)ルエンスルホン酸塩などの
塩であってもよい。該芳香族−級アミン現像主薬の使用
量は現像液/l当り好ましくは約0./g〜約20g、
よシ好ましくは約0゜!g〜約10gの濃度である。Moreover, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent used is preferably about 0.0.0. /g ~ about 20g,
Preferably about 0°! g to about 10 g.
又、カラー現像液には保恒剤として、亜硫酸ナトリウム
、亜硫酸カリウム、重亜硫酸ナトリウム、重亜硫酸カリ
ウム、メタ亜硫酸ナトリウム、メタ亜硫酸カリウム等の
亜硫酸塩や、カルボニル亜硫酸付加物を必要に応じて添
加することができる。In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.
又、前記カラー現像主薬を直接保恒する化合物として、
各種ヒドロキシルアミン類、特願昭乙/−/i乙よjり
号記載のヒドロキサム酸類、同6/−7707jt号記
載のヒドラジン類やヒドラジド類、同乙/−//と79
2号及び同6/−2032!3号記載のフェノール類、
同乙/−/!、!?′7Q/号記載のα一記載ロキシケ
トン類やα−アミノケトン類、及び/又は、q6/−/
7067に号記載の各1糖類を添加するのが好ましい。Further, as a compound that directly preserves the color developing agent,
Various hydroxylamines, hydroxamic acids described in Japanese patent application No. 6/-7707j, hydrazines and hydrazides described in Japanese Patent Application No. 6/-7707j, same Otsu/-// and 79
Phenols described in No. 2 and No. 6/-2032!3,
Same girl /-/! ,! ? α-roxyketones and α-aminoketones described in issue '7Q/, and/or q6/-/
It is preferable to add each monosaccharide described in No. 7067.
又、上記化合物と併用して、特願昭≦/−/¥7?、2
3号、同、4;/−/4≦474を号、同6/−/6j
≦2/号、同4/−/4り515号、同6/−7707
,J”9号、及び同6/−7乙r/rり号等に記載のモ
ノアミン類、同≦/−/73!9!号、同、g/ −1
641373号、同6/−7♂65に0号等に記載のジ
アミン類、同4/−/、tjl。In addition, when used in combination with the above compound, the patent application Sho≦/−/¥7? ,2
No. 3, same, 4;/-/4≦474, same 6/-/6j
≦2/ issue, 4/-/4ri issue 515, 6/-7707
, J” No. 9, and monoamines described in No. 6/-7 Otsu r/r, etc., No. ≦/-/73!9!, No. 6/-7, g/-1
Diamines described in No. 641373, No. 6/-7♂65 and No. 0, No. 4/-/, tjl.
27号、及び同6/−/乙り7/り号記載のポリアミン
類、同6/−/776/り号記載のポリアミン類、同乙
/−/?7740号記載のニトロキシラジカル類、同6
/−/J”6j’67号及び6/−/974t/り号記
載のアルコール類、同≦/−/りt??7号記載のオキ
シム類、及び同J/=21sj/’lり号記載の3級ア
ミン類を使用するのが好ましい。No. 27, and polyamines described in No. 6/-/Otsu 7/R, polyamines described in No. 6/-/776/R, No. 6/-/Otsu/-/? Nitroxy radicals described in No. 7740, No. 6
Alcohols described in /-/J''6j'67 and 6/-/974t/ri, oximes described in item ≦/-/rit??7, and J/=21sj/'l Preference is given to using the tertiary amines mentioned.
その他保恒剤として、特開昭j7−44t/g/号及び
同J″7−jj7タヂ号に記載の各種金属類、特開昭!
デー/rO!r♂号記載のサリチル酸類、%開昭r <
t −3j32号記載のアルカノールアミン類、特開昭
!l5−94t34t9号記載のポリエチレンイミン類
、米国特許第3,796,54t41号記載の芳香族ポ
リヒドロキシ化合物等を必要に応じて含有しても良い。Other preservatives include various metals described in JP-A No. J7-44t/g/ and No. J''7-jj7, JP-A-Sho!
Day/rO! Salicylic acids listed in No. r♂, % Kaisho r<
Alkanolamines described in t-3j32, JP-A-Sho! The polyethyleneimine described in No. 15-94t34t9, the aromatic polyhydroxy compound described in U.S. Pat. No. 3,796,54t41, etc. may be contained as necessary.
特に芳香族ポリヒドロキシ化合物の添加が好ましい。Particularly preferred is the addition of an aromatic polyhydroxy compound.
本発明に使用されるカラー現像液は、好ましくはp H
9〜ノ2、より好ましくは9〜//、0であり、そのカ
ラー現像液には、その他に既知の現像液成分の化合物を
含ませることができる。The color developer used in the present invention preferably has a pH of
9-2, more preferably 9-//, 0, and the color developer may contain other known developer component compounds.
上記pHを保持するためには、各種緩衝剤を用いるのが
好ましい。緩衝剤としては、炭酸塩、す/酸塩、ホウ酸
塩、四ホウ酸塩、ヒドロキシ安息香酸塩、グリシン塩、
N、N−ジメチルグリシン塩、ロイシン塩、ノルロイシ
ン塩、グアニン塩、3.4t−ジヒドロキシフェニルア
ラニン塩、アラニン塩、アミノ酪酸塩、コーアミノー2
−メチル−/、3−−1/ロツセンジオール塩、バリン
L プロリン塩、トリスヒドロキシアミンメタン塩、リ
シン塩などを用いることができる。特に炭酸塩、リン酸
塩、四ホウ酸塩、ヒドロキシ安息香酸塩は、溶解性、I
)H? 、o以上の高pH領域での緩衝能に優れ、カラ
ー現像液に添加しても写真性能面への悪影響(カブリな
ど)がなく、安価であるといった利点を有し、これらの
緩衝剤を用いることが特に好ましい。In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, salt, borate, tetraborate, hydroxybenzoate, glycine salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3.4t-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, co-amino-2
-Methyl-/, 3--1/lotusendiol salt, valine L proline salt, trishydroxyamine methane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble, I
)H? The use of these buffers has the advantages of excellent buffering ability in the high pH range of , o or higher, no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and low cost. It is particularly preferable.
これらの緩衝剤の具体例としては、炭酸ナトリウム、炭
酸カリウム、重炭酸ナトリウム、重炭酸カリウム、リン
酸三ナトリウム、リン酸三カリウム、リン酸二ナトリウ
ム、リン酸二カリウム、ホウ酸ナトリウム、ホウ酸カリ
ウム、四ホウ酸ナトリウム(ホウ砂)、四ホウ酸カリウ
ム、0−ヒドロキシ安息香酸ナトリウム(サリチル酸ナ
トリウム)、0−ヒドロキシ安息香酸カリウム、!−ス
ルホーコーヒドロキシ安息香酸ナトリウム(r−スルホ
サリチル酸ナトリウム)、!−スルホー2−ヒドロキシ
安息香酸カリウム(!−スルホサリチル酸カリウム)な
どを挙げることができる。しかしながら本発明は、これ
らの化合物に限定されるものではない。Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate,! -Sodium sulfo-hydroxybenzoate (sodium r-sulfosalicylate),! -Potassium sulfo-2-hydroxybenzoate (!-potassium sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.
該緩衝剤のカラー現像液への添加量は、0.7モル/7
以上であることが好ましく、特にθ、1モル/l〜0.
yモル/lであることが特に好ましい。The amount of the buffer added to the color developer is 0.7 mol/7
It is preferable that it is above, especially θ, 1 mol/l to 0.
Particularly preferred is y mol/l.
その他、カラー現像液中罠はカルシウムやマグネシウム
の沈澱防止剤として、あるいはカラー現像液の安定性向
上のために、各種キレート剤を用いることができる。In addition, various chelating agents can be used in the trap in the color developer to prevent precipitation of calcium or magnesium or to improve the stability of the color developer.
キレート剤としては有機酸化合物が好ましく、例えば特
公昭Q?−304tYt号及び同¥4t−30232号
記載のアミノポリカルボン酸類、特開昭j6−タ734
17号、特公昭j≦−393!9号及び***特許第2,
227,5jり号記載の有機ホスホン酸類、特開昭jコ
ー/θ272乙号、同j3−41.2730号、同64
1−/コ//27号、同jj−/262り7号及び同よ
j−≦!9!θご号等に記載のホスホノカルボン酸類、
その他特開昭!♂−/りjtr4tr号、同j/−コ0
34t4tθ号及び特公昭13−410900号等に記
載の化′合物をあげることができる。以下に具体例を示
すがこれらに限定されるものではない。The chelating agent is preferably an organic acid compound, such as Tokko Sho Q? Aminopolycarboxylic acids described in No.-304tYt and No. ¥4t-30232, JP-A No. 6-ta-734
No. 17, Special Publication Shoj≦-393!9 and West German Patent No. 2,
Organic phosphonic acids described in No. 227,5j, JP-A Shoj Co./θ272 No. 272, J3-41.2730, No. 64
1-/ko//No. 27, same jj-/262, No. 7, and same j-≦! 9! Phosphonocarboxylic acids described in θ, etc.,
Other Tokukai Akira! ♂-/rijtr4tr, samej/-ko 0
Examples include compounds described in No. 34t4tθ and Japanese Patent Publication No. 13-410900. Specific examples are shown below, but the invention is not limited to these.
・ニトリロ三酢酸、・ジエチレントリアミン五酢酸、・
エチレンジアミン四酢酸、・N、N、N−トリメチレン
ホスホン酸、・エチレンジアミン−N、N、N/ 、
N’−テトラメチレンホスホン酸、・トランスシクロヘ
キサンジアミン四酢酸、・/、2−ジアミノプロパン四
酢酸、・グリコールエーテルジアミン四酢酸、・エチレ
ンジアミンオルトヒドロキシフェニル酢酸、・−一ホス
ホノプタンー/、2.’I−)リカルボ/酸、・/−ヒ
ドロキシエチリデン−/、/−ジホスホン酸、・N、N
/−ビス(2−ヒドロキシベンジル)エチレンジアミン
−N、N/−ジ酢酸
これらのキレート剤は必要に応じてコ稽以上併用しても
良い。・Nitrilotriacetic acid, ・Diethylenetriaminepentaacetic acid, ・
Ethylenediaminetetraacetic acid, ・N,N,N-trimethylenephosphonic acid, ・ethylenediamine-N,N,N/,
N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, -monophosphonoptane/, 2. 'I-) Ricarbo/acid, ・/-hydroxyethylidene-/,/-diphosphonic acid, ・N, N
/-bis(2-hydroxybenzyl)ethylenediamine-N,N/-diacetic acid These chelating agents may be used in combination as needed.
これらのキレート剤の添加量はカラー現像液中の金属イ
オンを封鎖するのに充分な量であれば良い。例えば/l
当シ0.7g〜10g程度である。These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
The amount is about 0.7g to 10g.
カラー現像液には、必要によシ任意の現像促進剤を添加
することができる。Any development accelerator may be added to the color developer, if necessary.
現像促進剤としては、特公昭37−760/1号、同3
7−19?7号、同31−7/λ≦号、同4t4を一/
コ3?θ号、同4tj−90/り号及び米国特許第j、
r/J、2417号等に表わされるチオエーテル系化合
物、特開昭jコータ9229号及び同!0−/1j!4
1号に表わされるp−フェニレンジアミン系化合物、特
開昭!θ−/32726号、特公昭Q4t−30074
を号、特開昭!6−/jご/26号及び同j2二4tJ
4tコタ号、等に表わされるダ級アンモニウム塩類、米
国特許第2,4194t、903号、同J 、 /J/
、 112号、同ダ、λ30,7り6号、同J 、
213 、り/り号、特公昭Q/−//4t37号、米
国特許第2、g/J、j4tj号、同コ、!り6.タコ
ご号及び同j 、!/2 、jet号等に記載のアミン
系化合物、特公昭37−/404”2号、同4t、2−
2j20/号、米国特許第j 、/、2F、Ir3号、
特公昭4t/ −114137号、同タコ−23?♂3
号及び米国特許第J、jJ、2.!0/号等に表わされ
るポリアルキレンオキサイド、その他/−フェニルー3
−ピラゾリドン類、イミダゾール類、ベンジルアルコー
ル等を必要に応じて添加することができる。As a development accelerator, Japanese Patent Publication No. 37-760/1, No. 3
7-19?7, 31-7/λ≦, 4t4 1/
Ko3? No. θ, No. 4tj-90/ri and U.S. Patent No. j,
r/J, 2417, etc., JP-A No. 9229 and the same! 0-/1j! 4
The p-phenylenediamine compound represented by No. 1, JP-A-Sho! θ-/32726, special public show Q4t-30074
No. Tokukai Akira! 6-/jgo/26 and j224tJ
4t Kota, etc., U.S. Patent No. 2,4194t, 903, J, /J/
, No. 112, same da, λ30, 7ri No. 6, same J,
213, ri/ri issue, special public show Q/-//4t37, US Patent No. 2, g/J, j4tj issue, co,! 6. Octopus issue and same j,! /2, amine compounds described in jet issue, etc., Japanese Patent Publication No. 37-/404'' No. 2, 4t, 2-
2j20/, U.S. Patent No.j,/, 2F, Ir3,
Special public show 4t/-114137, same octopus-23? ♂3
No. J, jJ, 2. ! Polyalkylene oxide represented by No. 0/, etc./-Phenyl-3
- Pyrazolidones, imidazoles, benzyl alcohol, etc. can be added as necessary.
本発明においては、必要に応じて、任意のカプリ防止剤
を添加できる。カプリ防止剤としては、塩化ナトリウム
、臭化カリウム、沃化カリウムの如きアルカリ金属ハロ
ゲン化物及び有機カブリ防止剤が使用できる。有機カブ
リ防止剤としては、例えばベンゾトリアゾール、6−ニ
ドロベンズイミタソール、!−二トロイソインダゾール
、!−メチルベンゾトリアゾール、!−二トロペンソト
リアゾール、!−クロローベンゾトリアゾール、コーチ
アゾリル−ベンズイミダゾール、λ−チアゾリルメチル
ーベンズイミダゾール、インダゾール、ヒドロキシアザ
インドリジン、アデニンの如き含窒素へテロ環化合物を
代表例としてあげることができる。In the present invention, any anti-capri agent can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrobenzimitasole, and! - ditroisoindazole! -Methylbenzotriazole,! - Nitropensotriazole,! Typical examples include nitrogen-containing heterocyclic compounds such as -chlorobenzotriazole, corchiazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.
本発明に使用されるカラー現像液には、螢光増白剤を含
有するのが好ましい。螢光増白剤としてハ、” + ”
’−シアミノーコ、2′−ジスルホスチルベン系化合
物が好ましい。添加量はo−zg/l好ましくは0./
g−4Fg/lである。The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, "+"
'-cyaminoco and 2'-disulfostilbene type compounds are preferred. The amount added is o-zg/l, preferably 0. /
g-4Fg/l.
又、必要に応じてアルキルスルホン酸、アリールホスホ
ン酸、脂肪族カルボン酸、芳香族カルボン酸等の各種界
面活性剤を添加しても良い。Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.
本発明のカラー現像液の処理温度は20〜!O0C好ま
しくはj O−10°Cである。処理時間は20秒〜!
分好ましくは30秒〜−分である。The processing temperature of the color developer of the present invention is 20~! O0C is preferably j O-10°C. Processing time is 20 seconds!
minutes, preferably 30 seconds to - minutes.
補充量は少ない方が好ましいが、感光材料/m2当シλ
o、tooml好ましくは10〜JOOmlである。更
に好ましくは100m1 S−5−2O0である。It is preferable that the amount of replenishment is small;
o, tooml preferably 10 to JOOml. More preferably, it is 100 m1 S-5-2O0.
本発明においてはカラー現像の後に脱銀処理されるのが
一般的である。In the present invention, desilvering treatment is generally performed after color development.
脱鉄工程は、一般には漂白工程一定着工程、定着工程−
漂白定着工程、漂白工程−漂白定着工程、漂白定着工程
等、いかなる工程を用いても良い。The iron removal process generally includes a bleaching process, a fixing process, and a fixing process.
Any process may be used, such as a bleach-fixing process, a bleach-bleach-fixing process, a bleach-fixing process, etc.
しかしながら本発明の脱銀工程の工程時間は短かい方が
好ましく、又、本発明の効果が顕著である。However, the process time of the desilvering step of the present invention is preferably short, and the effects of the present invention are significant.
一般にば70分以下、より好ましくは30秒〜6分であ
る。Generally, the time is 70 minutes or less, more preferably 30 seconds to 6 minutes.
以下に本発明に用いられる漂白液、漂白定着液及び定着
液を説明する。The bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained below.
本発明に用いられる漂白液又は漂白定着液において用い
られる漂白剤としては、いかなる漂白剤も用いることが
できるが、特に鉄(III)の有機錯塩(例えばエチレ
ンジアミン四酢酸、ジエチレントリアミン五酢酸などの
アミノポリカルボン酸類、アミノポリホスホン酸、ホス
ホノカルボン酸および有機ホスホン酸などの錯塩)もし
くはクエン酸、酒石酸、リンゴ酸などの有機酸;過硫酸
塩;過酸化水素などが好ましい。As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular organic complex salts of iron (III) (e.g., aminopolymers such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. Preferred are carboxylic acids, complex salts of aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, and the like.
これらのうち、鉄(I[[)の有機錯塩は迅速処理と環
境汚染防止の観点から特に好ましい。鉄(I[I)の有
機錯塩を形成するために有用なアミンポリカルボン酸、
アミノポリホスホン酸、もしくは有機ホスホン酸または
それらの塩を列挙すると、エチレンジアミン四酢酸、ジ
エチレントリアミン五酢酸、/、3−ジアミノプロパン
四酢酸、プロピレンジアミン四酢酸、ニトリロ三酢酸、
シクロヘキサンジアミン四酢酸、メチルイミノニ酢酸、
イミノニ酢酸、グリコールエーテルジアミン四酢酸、
などを挙げることができる。Among these, organic complex salts of iron (I[[) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. amine polycarboxylic acids useful for forming organic complex salts of iron(I[I);
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like.
これらの化合物はナトリウム、カリウム、リチウム又は
アンモニウム塩のいずれでも良い。これらの化合物の中
で、エチレンジアミン四酢酸、ジエチレントリアミン五
酢酸、シクロヘキサンジアミン四酢酸、/、3−ジアミ
ノプロパン四酢酸、メチルイミノニ酢酸の鉄(III)
錯塩が漂白刃が高いことから好ましい。These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron(III) ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, /, 3-diaminopropanetetraacetic acid, methyliminodiacetic acid
Complex salts are preferred because they have a high bleaching edge.
これらの第2鉄イオン錯塩は錯塩の形で使用しても良い
し、第コ鉄塩、例えば硫酸第2鉄、塩化第2鉄、硝酸第
2鉄、硫酸第2鉄アンモニウム、燐酸第2鉄などとアミ
ノポリカルボン酸、アミノポリホスホン酸、ホスホノカ
ルボン酸などのキレート剤とを用いて溶液中で第2鉄イ
オン錯塩を形成させてもよい。また、キレート剤を第2
鉄イオン錯塩を形成する以上に過剰に用いてもよい。鉄
錯体のなかでもアミノポリカルボン酸鉄錯体が好ましく
、その添加量はO3θ/〜/、θモル/l好ましくはo
、or−o、tθモル/lである。These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is O3θ/~/, θmol/l, preferably o
, or-o, tθ mol/l.
漂白液、漂白定着液及び/またはこれらの前浴には、漂
白促進剤として種々の化合物を用いることができる。例
えば、米国特許第3.?り3,252号明細書、ドイツ
特許第7.コタθ、♂72号明細書、特開昭53−96
A3θ号公報、リサーチディスクロージャー第17/2
り号(/97!年7月号)に記載のメルカプト基または
ジスルフィド結合を有する化合物や、特公昭Qj−#J
−θ乙号、特開昭!コー20r!2号、同j3−327
3!号、米国特許3.7θg、!67号等に記載のチオ
尿素系化合物、あるいは沃素、臭素イオン等のハロゲン
化物が漂白刃が優れる点で好ましい。Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Patent No. 3. ? No. 3,252, German Patent No. 7. Kota θ, ♂72 specification, JP-A-53-96
A3θ Publication, Research Disclosure No. 17/2
Compounds having a mercapto group or disulfide bond described in the issue (/97! July issue), and
-θ Otsu issue, Tokukai Akira! Ko 20r! No. 2, same j3-327
3! No., U.S. Patent 3.7θg,! Thiourea compounds described in No. 67, etc., or halides such as iodine and bromide ions are preferable because they have excellent bleaching blades.
その他、本発明に用いられる漂白液又は漂白定着液には
、臭化物(例えば、臭化カリウム、臭化ナトリウム、臭
化アンモニラA)または塩化物(例えば、塩化カリウム
、塩化ナトリウム、塩化アンモニウム)または沃化物(
例えば、沃化アンモニウム)等の再ノ10ゲン化剤を含
むことができる。必要に応じ硼酸、硼砂、メタ硼酸ナト
リウム、酢酸、酢酸ナトリウム、炭酸ナトリウム、炭酸
カリウム、亜燐酸、燐酸、燐酸ナトリウム、クエン酸、
クエン酸ナトリウム、酒石酸などのpH緩衝能を有する
/稽類以上の無機酸、有機酸およびこれらのアルカリ金
属またはアンモニウム塩または、硝酸アンモニウム、グ
アニジンなどの腐蝕防止剤などを添加することができる
。In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide A) or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) or iodine. monster(
For example, a reinogenating agent such as ammonium iodide (ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, as required
Inorganic acids having a pH buffering capacity such as sodium citrate and tartaric acid, organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine may be added.
本発明に係わる漂白定着液又は定着液に使用される定着
剤は、公知の定着剤、即ちチオ硫酸ナトリウム、チオ硫
酸アンモニウムなどのチオ硫酸塩;チオシアン酸ナトリ
ウム、チオシアン酸アンモニウムなどのチオシアン酸塩
;エチレンビスチオグリコール酸、3.6−シチアー/
、/−オクタンジオールなどのチオエーテル化合物およ
びチオ尿素類などの水溶性のハロゲン化銀溶解剤であり
、これらを7種あるいはコ種以上混合して使用すること
ができる。また、特開昭6!−/j!!!’I号に記載
された定着剤と多量の沃化カリウムの如きハロゲン化物
などの組み合わせからなる特殊な漂白定着液等も用いる
ことができる。本発明においては、チオ硫酸塩特にチオ
硫酸アンモニウム塩の使用が好ましい。/lあたシの定
着剤の量は、0.3〜2モルが好ましく、更に好ましく
はθ。The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; or ethylene. Bisthioglycolic acid, 3.6-cythia/
, /-octanediol and other water-soluble silver halide solubilizers such as thioureas, and seven or more of these can be used in combination. Also, Tokukai Showa 6! -/j! ! ! It is also possible to use a special bleach-fix solution consisting of a combination of the fixing agent described in No. 'I and a large amount of a halide such as potassium iodide. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per liter is preferably 0.3 to 2 moles, more preferably θ.
j〜/、0モルの範囲である。漂白定着液又は定着液の
pH領域は、3〜/θが好ましく、更には!〜りが特に
好ましい。pHが低すぎると、シアン色素のロイコ化に
伴う濃度低下を引き起こし、またpHが高すぎると脱銀
不良を起こす。j~/, in the range of 0 mol. The pH range of the bleach-fix solution or fix solution is preferably 3 to /θ, and even more! 〜ri is particularly preferable. If the pH is too low, a decrease in concentration occurs due to leucoization of the cyan dye, and if the pH is too high, desilvering failure occurs.
又、漂白定着液には、その他各種の螢光増白剤や消泡剤
あるいは界面活性剤、ポリビニルピロリドン、メタノー
ル等の有機溶媒を含有させることができる。Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.
本発明に於る漂白定着液や定着液は、保恒剤として亜硫
酸塩(例えば、亜硫酸ナトリウム、亜硫酸カリウム、亜
硫酸アンモニウム、など)、重亜硫酸塩(例えば、重亜
硫酸アンモニウム、重亜硫酸ナトリウム、重亜硫酸カリ
ウム、など)、メタ重亜硫酸塩(例えば、メタ重亜硫酸
カリウム、メチ重亜硫酸ナトリウム、メタ重亜硫酸アン
モニウム、など)等の亜硫酸イオン放出化合物を含有す
る。これらの化合物は亜硫酸イオンに換算して約O6O
λ〜0.jOモル/l含有させることが好ましく、更に
好ましくはθ、θq〜0.4tOモル/lである。The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. (e.g., potassium metabisulfite, etc.), metabisulfites (e.g., potassium metabisulfite, sodium methybisulfite, ammonium metabisulfite, etc.). These compounds have approximately O6O in terms of sulfite ions.
λ~0. It is preferable to contain jO mol/l, and more preferably θ, θq to 0.4 tO mol/l.
保恒剤としては、亜硫酸塩の添加が一般的であるが、そ
の他、アスコルビン酸や、カルボニル重亜硫酸付加物、
あるいは、カルボニル化合物等を添加しても良い。Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.
更には緩衝剤、螢光増白剤、キレート剤、消泡剤、防カ
ビ剤等を必要に応じて添加しても良い。Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.
本発明に用いられるハロゲン化銀カラー写真感光材料は
、定着又は漂白定着等の脱銀処理後、水洗及び/又は安
定化処理をするのが一般的である。The silver halide color photographic light-sensitive material used in the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, followed by washing with water and/or stabilizing treatment.
本発明における最終水洗工程又は安定化工程とは前記脱
銀工程の後、乾燥工程までの間に行われる工程であり、
例えば脱銀工程の後の銀回収目的の短時間のリンスある
いは、乾燥の直接に行われる安定処理工程であってもよ
い。以下に具体的な最終水洗工程を示すが、これらに限
定されるものではない。またロコで示した「水洗」は「
安定化」とすることもできる。The final water washing step or stabilization step in the present invention is a step performed after the desilvering step and before the drying step,
For example, it may be a short-time rinse for the purpose of silver recovery after the desilvering step, or a stabilization step performed directly after drying. Specific final water washing steps are shown below, but are not limited thereto. In addition, "washing with water" shown in the loco is "
It can also be referred to as "stabilization".
■ カラー現像−漂白定着一霞一乾燥
@ カラー現像−漂白一定着一困困一乾燥θ カラー現
像−漂白一定着一国国一安定一乾燥
■ カラー現偉−漂白−漂白定着一困国一安定一乾燥
■ カラー現像一定着一漂白定着一困因一乾燥θ 黒白
現像−水洗一反転−カラー現像−促進一漂白一定着一区
因一安定一乾燥
■ 黒白現像−水洗−カラー現像−水洗一漂白定着一区
困一乾燥
水洗工程での水洗水量は、感光材料の特性(例えばカプ
ラー等使用素材による)や用途、水洗水温、水洗タンク
の数(段数)、向流、順流等の補充方式、その他種々の
条件によって広範囲に設定し得る。このうち、多段向流
方式における水洗タンク数と水量の関係は、ジャーナル
オプ ザンサエテイ オプ モーション ピクチャー
アンド テレヴィジョン エンジニアズ(Journ
alof the 5ociety of Mot
ion Pictureand Te1evision
Engineers) 第64を巻、P、 Jり♂
〜2!J (/9.tj−年!月号)に記載の方法で、
もとめることができる。通常多段向流方式における段数
は−〜6が好ましく、特に2〜りが好ましい。■ Color development - Bleach fixing, one drying, one drying @ Color development - Bleach, one color, one color, one drying, one drying θ Color development - Bleach, one color, one country, one stable, one drying ■ Color development - Bleach, one color, one color, one country, one stable 1 drying ■ Color development constant color development 1 bleach fixing 1 difficulty 1 drying θ Black and white development - water washing 1 reversal - color development - acceleration 1 bleaching constant color 1 area 1 stability 1 drying ■ Black and white development - water washing - color development - water washing 1 bleaching The amount of washing water in the drying and washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (stages), the replenishment method such as countercurrent, forwardflow, etc. It can be set over a wide range depending on various conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal Op.
alof the 5ociety of Mot
ion Picture and Television
Engineers) Volume 64, P, Jri♂
~2! By the method described in J (/9.tj-year! month issue),
You can ask for it. Usually, the number of stages in the multistage countercurrent system is preferably from - to 6, particularly preferably from 2 to 2.
水洗水又は安定化液の補充量は、節水の目的で少ない方
が好ましく、本発明においては前浴からの持込み量の0
.1−40倍、好ましくは3倍〜4t0倍である。前浴
からの持込み量は、感光材料の種類やスクイジーの強度
によって異々るが、一般には10m1〜/θ0mAl/
m2程度である。前浴からの持込み量は少ない方が、水
洗水の補充量が低減できるため、より好ましい。The amount of replenishment of washing water or stabilizing liquid is preferably small for the purpose of saving water, and in the present invention, the amount brought in from the previous bath is
.. 1-40 times, preferably 3 times to 4t0 times. The amount brought in from the pre-bath varies depending on the type of photosensitive material and the strength of the squeegee, but generally it is 10m1~/θ0mAl/
It is about m2. It is more preferable to have a smaller amount brought in from the pre-bath because the amount of washing water to be refilled can be reduced.
また、補充1としては、感光材料/m2当り好ましくは
/l以下、より好ましくはJ−Oml〜100θmlで
ある。Further, replenishment 1 is preferably less than /l per m2 of photosensitive material, more preferably J-Oml to 100[theta]ml.
以上のような大幅な節水処理を行なった場合にはタンク
内での水の滞留時間増加により、バクテリアが繁殖し、
生成した浮遊物が感光材料に付着する等の問題が生じる
。本発明のゼラチンは、このような付着物が少ないとい
う点でも優れた効果を示す。又、バクテリアを防止する
手段として特願昭7!;/ −/、17832号に記載
の水中のカルシウム、マグネシウムを低減させる方法を
、極めて有効に用いることができる。また、特開昭j7
−rj412号に記載のインチアゾロン化合物やサイア
ベンダゾール類、同6/−/、20/4tj号に記載の
塩素化インシアヌール酸ナトリウム等の塩素系殺菌剤、
特願昭4O−10j41/7号に記載のベンゾトリアゾ
ール、銅イオンその他堀口博著「防菌防黴剤の化学」、
衛生技術会編「微生物の滅菌、殺菌、防黴技術」、日本
防菌防黴学会編「防菌防黴剤事典」、に記載の殺菌剤を
用いることもできる。When significant water-saving treatments such as those mentioned above are carried out, bacteria proliferate due to the increased residence time of water in the tank.
Problems arise such as the generated floating matter adhering to the photosensitive material. The gelatin of the present invention also exhibits an excellent effect in that it has fewer such deposits. In addition, a special request was made in 1977 as a means to prevent bacteria! ;/-/, the method of reducing calcium and magnesium in water described in No. 17832 can be used very effectively. Also, Unexamined Japanese Patent Publication No. 7
- Chlorine-based disinfectants such as inthiazolone compounds and thiabendazoles described in RJ No. 412, chlorinated sodium incyanurate described in RJ No. 6/-/, 20/4TJ,
Benzotriazole, copper ions, and others described in Japanese Patent Application No. 1987-10J41/7, ``Chemistry of Antibacterial and Antifungal Agents'' by Hiroshi Horiguchi,
It is also possible to use the disinfectants described in "Sterilization, sterilization, and anti-mold technology of microorganisms" edited by the Sanitation Technology Society, and "Encyclopedia of anti-bacterial and anti-mold agents" edited by the Japanese Society of Anti-bacterial and Anti-fungal agents.
更に、水洗水には、水切り剤として界面活性剤や、硬水
軟化剤としてEDTAに代表されるキレート剤を用いる
ことができる。Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.
以上の水洗工程に続くか、又は水洗工程を経ずに直接安
定液で処理することも出来る。安定液には、画像安定化
機能を有する化合物が添加され、例えばホルマリンに代
表されるアルデヒド化合物や、色素安定化に適した膜p
Hに調整するための緩衝剤や、アンモニウム化合物があ
げられる。又、液中でのバクテリアの繁殖防止や処理後
の感光材料に防黴性を付与するため、前記した各種殺菌
剤や防黴剤を用いることができる。The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.
更に、界面活性剤、螢光増白剤、硬膜剤を加えることも
できる。本発明の感光材料の処理において、安定化が水
洗工程を経ることなく直接行われる場合、特開昭17−
rJ−93号、j?−114739号、!デー/193
413号、6Q−コー〇34tj号、60−237/3
2号、6O−2397t4を号、6θ−23タッグ9号
、6/−タθ!り号、4/−///741号等に記載の
公知の方法を、すべて用いることができる。Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the photosensitive material of the present invention, when stabilization is carried out directly without passing through a water washing step,
rJ-93, j? -114739,! Day/193
No. 413, 6Q-Ko 34tj, 60-237/3
No. 2, 6O-2397t4, 6θ-23 tag No. 9, 6/-ta θ! All known methods described in No. 4/-///741 can be used.
その他、/−ヒドロキシエチリデン−/、/−ジホスホ
ン駿、エチレンジアミン四メチレンホスホン酸等のキレ
ート剤、マグネシウムやビスマス化合物を用いることも
好ましい態様である。In addition, it is also a preferred embodiment to use chelating agents such as /-hydroxyethylidene-/, /-diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, and magnesium and bismuth compounds.
本発明の水洗工程又は安定化工程のpHはy〜/Qであ
り、好ましくは!〜rである。温度は感光材量の用途・
特性等で穐々設定し得るが、一般には/j〜夕!0C1
好ましくはコO〜900Cである。時間は任意に設定で
きるが短かい方が本発明の効果がより顕著であり、好ま
しくは30秒〜!分更に好ましくFi30秒〜3分であ
る。補充量は、少ない方が、ランニングコスト、排出量
減、取扱い性等の観点で好ましく、又本発明の効果も大
きい。The pH of the water washing step or stabilization step of the present invention is y~/Q, preferably! ~r. The temperature depends on the usage of the amount of photosensitive material.
It can be set depending on the characteristics etc., but in general /j ~ evening! 0C1
Preferably it is 0 to 900C. Although the time can be set arbitrarily, the effect of the present invention is more noticeable the shorter the time, preferably 30 seconds or more! More preferably, Fi is 30 seconds to 3 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc., and the effects of the present invention are also greater.
水洗及び/又は安定化工程に用いた液は、更に前工程に
用いることもできる。この例として多段向流方式によっ
て削減した水洗水のオーバーツーローを、その前浴の漂
白定着浴に流入させ、漂白定着浴には濃縮液を補充して
、廃液量を減らすことがあげられる。The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water, which has been reduced by a multi-stage countercurrent system, into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid.
本発明の処理において、現像工程に続く脱銀、水洗(ま
たは安定)の総ての工程でpHがj −J’の範囲にあ
る場合に特に発明の効果が顕著に発揮される。即ち、こ
の場合に、白地部の色汚染を起すことなく、良好な画像
濃度と色像堅牢性を得ることが可能となる。In the treatment of the present invention, the effects of the invention are particularly noticeable when the pH is in the range of j-J' in all steps of desilvering and water washing (or stabilization) following the development step. That is, in this case, it is possible to obtain good image density and color image fastness without causing color contamination in the white background area.
(実施例)
以下本発明を実施例により例証するが本発明はこれによ
り限定されるものではない。(Example) The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.
実施例/
ポリエチレンで両面ラミネートした紙支持体の上に以下
に示す層構成の多層カラー印画紙/ −Aを作製した。Example/A multilayer color photographic paper/-A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.
塗布液は下記のよりにして調製した。The coating solution was prepared as follows.
また、ゼラチンはすべて等電点!、0のアルカリ処理ゼ
ラチンを使用した。Also, all gelatin has an isoelectric point! , 0 alkali-treated gelatin was used.
第一層塗布液調製
イエローカプラー(ExY)/り、1gおよび色像安定
剤(Cpd−/)g、ggに酢酸エチル27.2ccお
よび溶媒(Solv−/)7.7ccを加え溶解し、こ
の溶液を/Q%ドデシルベンゼンスルホン酸ナトリウム
tccを含む70%ゼラチン水溶液//leaに乳化分
散させた。一方塊臭化銀乳剤(臭化銀10.0モルチ、
Ag7θg/kg含有)に下記に示す青感性増感色素を
銀1モル当たV)!、0×10−4モル加えたものを調
製した。前記の乳化分散物とこの乳剤とを混合溶解し、
以下に示す組成となるように第一層塗布液を調製した。Preparation of first layer coating solution 27.2 cc of ethyl acetate and 7.7 cc of solvent (Solv-/) were added to 1 g of yellow coupler (ExY) and 1 g of color image stabilizer (Cpd-/), and dissolved. The solution was emulsified and dispersed in a 70% gelatin aqueous solution containing /Q% sodium dodecylbenzenesulfonate tcc//lea. On the other hand, bulk silver bromide emulsion (silver bromide 10.0 molty,
Contains Ag7θg/kg) and the blue-sensitive sensitizing dye shown below per mole of silver V)! , 0x10-4 mol was added. Mixing and dissolving the emulsified dispersion and this emulsion,
A first layer coating solution was prepared to have the composition shown below.
第二層から第七要用の塗布液も第一層塗布液と同様の方
法で調製した。各層のゼラチン硬化剤としては、/−オ
キシ−j、j−ジクロロ−s −)リアジンナトリウム
塩を用いた。Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, /-oxy-j,j-dichloro-s-) riazine sodium salt was used.
各層の分光増感色素として下記のものを用いた。The following spectral sensitizing dyes were used in each layer.
青感性乳剤層
(ハロゲン化銀1モル当たりよ、θX/ 0−4モル)
緑感性乳剤層
(ハロゲン化銀7モル当fcす<t、oxio−4モル
)および
(ハロケン化銀1モル当九F) 7.OX / 0−5
モル)赤感性乳剤層
(ハロゲン化銀1モルa*すO,りX10−4モル)赤
感性乳剤層に対しては、下記の化合物をノ・ロゲ/化銀
1モル当たり2.6x10−aモル添加した。Blue-sensitive emulsion layer (per mol of silver halide, θX/0-4 mol)
Green-sensitive emulsion layer (7 moles of silver halide fc<t, oxio-4 moles) and (9F per mole of silver halide) 7. OX/0-5
mole) Red-sensitive emulsion layer (1 mole of silver halide a*suO, 10-4 mole of silver halide) For the red-sensitive emulsion layer, the following compound was added at a concentration of 2.6 x 10-a per mole of silver halide. Mol added.
また青感性乳剤層、緑感性乳剤層、赤感性乳剤層に対し
、/−(!−メチルウレイドフェニル)−!−メルカプ
トテトラゾールをそれぞれノ\ロゲン化銀1モル当九F
)4t、O×70−6モル、3゜0×10−5モk、/
、0X10−5モル添加した。Also, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(!-methylureidophenyl)-! - Mercaptotetrazole per 1 mole of silver chloride, respectively
) 4t, O x 70-6 mole, 3゜0 x 10-5 mok, /
, 0x10-5 moles were added.
また青感性乳剤層、緑感性乳剤層に対し、グーヒドロキ
シ−t−メチル−i、s、3a、7−チトラザインデン
をそれぞれノーロゲン化銀7モル当たり/、2X70−
2モル、/ 、 /’pl:、10−2モル添加した。In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, goo-hydroxy-t-methyl-i,s,3a,7-titrazaindene was added per 7 mol of silver norogenide/2X70-
2 mol, /, /'pl:, 10-2 mol was added.
イラジェーション防止のために乳剤層に下記の染料を添
加した。The following dyes were added to the emulsion layer to prevent irradiation.
および
(層構成)
以下に各層の組成を示す。数字は塗布fi(g/m 2
)を表す。ハロゲン化銀乳剤は銀換算塗布量を表す。and (layer structure) The composition of each layer is shown below. The numbers are coating fi (g/m2)
) represents. The silver halide emulsion represents the coated amount in terms of silver.
支持体
ポリエチレンラミネート紙
〔第一層側のポリエチレンに白色顔料
(T i 02 )と青味染料(群青)を含む〕第一層
(青感層)
ハロゲン化銀乳剤(Br:10%) 0.2&ゼラ
チン /、t3イx ry
−カブ5−(ExY) 0.13色像安定剤
(Cpd −/) 0./り溶媒(Solv
−/) 0.3j第二層(混色防止層)
ゼラチン 0.29混色防止
剤(Cpd−,2) θ6θ?第三層(緑感
層)
ハロゲン化銀乳剤(Br:J’Qチ) θ、/6ゼラ
チン 7.29マゼンタカ
プラー(ExM) 0.32色像安定剤(Cp
d−3) 0.20色像安定剤(Cpd−9
) θ、o/溶媒(So l v−2)
0 、乙!第四層(紫外線吸収層)
ゼラチン /、!?紫外線吸
収剤(UV−/) o、乙コ混色防止剤(C
pd−、r) o 、or溶媒(Solv−
3) 0.24を第五層(赤感層)
ハロゲン化銀乳剤(Brニア0%) 0..23ゼ
ラチン ハ3グシアンカプラー
(ExC) 0.39色像安定剤(Cpd−
1,) θ、/7ポリマー(Cpd−7)
0.グ0溶媒(Solv−a)
0.23第六層(紫外線吸収層)
ゼラチン θ、j3紫外線
吸収剤(UV−/) θ、2/溶媒(SOI
V−J’) θ、otr第七層(保護層
)
ゼラチン 7.33ポリビ
ニルアルコールのアクリ
ル変性共重合体(変性度/7
チ) o、/y流動パラ
フィン 0.03(ExY)イエ
ローカプラー:Y−/り(E x M )マゼンタカプ
ラー;M−73(ExC)シアンカプラー二〇−//
(Cpd−/)色像安定剤
(Cpd−,2)混色防止剤
H
(Cpd−3)色像安定剤
(Cpd−4t)色像安定剤
(Cpd−t)混色防止剤
(cpa−6)色像安定剤
C4H9(t)
のj:♂:9混合物(重量比)
(Cpd−7)ポリi−
平均分子量to 、oo。Support polyethylene laminate paper [the polyethylene on the first layer side contains a white pigment (T i 02 ) and a blue dye (ulmarine)] First layer (blue-sensitive layer) Silver halide emulsion (Br: 10%) 0. 2 & gelatin /, t3 x ry
-Cub5-(ExY) 0.13 Color image stabilizer (Cpd-/) 0. /Solv
-/) 0.3j Second layer (color mixing prevention layer) Gelatin 0.29 Color mixing prevention agent (Cpd-, 2) θ6θ? Third layer (green-sensitive layer) Silver halide emulsion (Br: J'Q) θ, /6 gelatin 7.29 Magenta coupler (ExM) 0.32 Color image stabilizer (Cp
d-3) 0.20 color image stabilizer (Cpd-9
) θ, o/solvent (Sol v-2)
0, Otsu! Fourth layer (ultraviolet absorption layer) Gelatin /,! ? Ultraviolet absorber (UV-/) o, Otsuko Color mixing prevention agent (C
pd-, r) o, or solvent (Solv-
3) 0.24 as the fifth layer (red-sensitive layer) Silver halide emulsion (Br near 0%) 0. .. 23 Gelatin Ha3 Guccian coupler (ExC) 0.39 Color image stabilizer (Cpd-
1,) θ, /7 polymer (Cpd-7)
0. Solv-a
0.23 Sixth layer (ultraviolet absorbing layer) Gelatin θ, j3 Ultraviolet absorber (UV-/) θ, 2/solvent (SOI
V-J') θ, otr Seventh layer (protective layer) Gelatin 7.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification/7 H) o, /y Liquid paraffin 0.03 (ExY) Yellow coupler: Y -/E x M) Magenta coupler; M-73 (ExC) Cyan coupler 20-// (Cpd-/) Color image stabilizer (Cpd-, 2) Color mixing inhibitor H (Cpd-3) Color image Stabilizer (Cpd-4t) Color image stabilizer (Cpd-t) Color mixing inhibitor (cpa-6) Color image stabilizer C4H9(t) j:♂:9 mixture (weight ratio) (Cpd-7) Poly I - average molecular weight to, oo.
(UV−/)紫外線吸収剤
UH2にH2L;(JLん8M17
の、2:9:/混合物(重量比)
(Solv−/)溶媒
(Solv−2)溶媒
の2二/混合物(容量比)
(Solv−J)溶媒
(Solv−4t)溶媒
試料/ −Aの第1層〜第2層に使用したゼラチンの種
類を塗布量は変更せずに表7のように変更して試料/−
B〜/−Iを作成した。(UV-/) Ultraviolet absorber UH2 to H2L; Solv-J) Solvent (Solv-4t) Solvent sample/-The type of gelatin used in the first to second layers of A was changed as shown in Table 7 without changing the coating amount, and the sample/-
B~/-I was created.
また、第一層、第二層、第五層のカプラーExY、Ex
M、ExCの代わ5にそれぞれY−〇、M−0、C−0
を等モル用いる以外、/−A5/−C及び/−Fと全く
同様にして/−J、/−K、/−Lを作成した。In addition, the couplers ExY, Ex of the first layer, second layer, and fifth layer
Y-〇, M-0, C-0 for 5 instead of M and ExC respectively
/-J, /-K, /-L were prepared in exactly the same manner as /-A5/-C and /-F except that equimolar amounts of were used.
α
さらに第三層のカプラーExMの代わりにM−/を等モ
ル及び下記のM a −/をM−/と等モル用い、かつ
第五層のカプラーExCの代わシにExC:C−/ダ=
/:/(モル比)混合物を等モル用いた以外/−A、/
−C5y−Fと全く同様にして/−M、/−N、 /
−0を作成した。α Further, in place of the coupler ExM in the third layer, M-/ is used in an equimolar amount and the following M a -/ is used in an equimolar amount as M-/, and in place of the coupler ExC in the fifth layer, ExC:C-/D is used. =
/:/(molar ratio) Except using equimolar mixtures/-A, /
-C5y-F in exactly the same way as /-M, /-N, /
-0 was created.
(Ma−/)
C4H9C4H9
試料/−Aを像様露光した後に、下記処理工程にてカラ
ー現像液のタンク容量の2倍補充するまで連続処理を行
なった。6浴の持込量は感光材料/m2当り3rmlで
あった。(Ma-/) C4H9C4H9 Sample/-A was imagewise exposed, and then continuous processing was performed in the following processing steps until twice the tank capacity of the color developer was replenished. The amount of the 6 baths carried in was 3 rml per m2 of light-sensitive material.
カラー現像 3r0c /分4to秒 290m
1 /71漂白定着 30〜34t0C/分oo秒
/JrOml 91水洗■3θ〜34t0C20秒
4tl水洗■30〜34t0C,20秒
<tl水 洗 ■ 30〜34t0C20秒 下記参
照 グl乾 燥 70〜♂θ’Cjg秒
(水洗■→■への3タンク向流方式とした。)水洗■の
補光量は下記3条件にて行なった。Color development 3r0c/min 4to seconds 290m
1/71 bleach fixing 30-34t0C/min oo seconds
/JrOml 91 water wash ■3θ~34t0C, 20 seconds 4tl water wash ■30~34t0C, 20 seconds
<tl water washing ■ 30~34t0C20 seconds See below Gl drying 70~♂θ'Cjg seconds (Washing ■ → ■ 3 tank countercurrent method was used.) The amount of supplementary light for water washing ■ was carried out under the following three conditions. Ta.
(1)/θml (持込量のOl、29倍)(2)
2toml (z 2.4を倍)(3)
210oml(# to倍)各処理液の組成は以下
の通シである。(1)/θml (Ol of brought-in amount, 29 times) (2)
2toml (x 2.4) (3)
The composition of each 210 oml (# to times) treatment solution is as follows.
カラー現像液
水 ♂θ0rnl 700
mlジエチレントリアミ
ン五酢酸 /、0g /、Ofg/−ヒ
ドロキシエチ
リデン−/、/−
ジホスホン酸
(10%) コ、Og 2.0gニトリ
ロ三酢酸 コ、og a、o’gトリエチレ
ンジアミ
ン(/、グージア
ザビシクロ〔コ。Color developer water ♂θ0rnl 700
ml diethylenetriaminepentaacetic acid /, 0g /, Ofg/-hydroxyethylidene-/, /- diphosphonic acid (10%) co, Og 2.0g nitrilotriacetic acid co, og a, o'g triethylenediamine (/, goudiazabicyclo 〔Ko.
λ、コ〕オクタン) r、01g s、0g臭化
カリウム 0.jg −炭酸カリウム
30g jugN−エチル−N−
(β−メタンスル
ホンアミドエチル)
−3−メチル−タ
ーアミノアニリン
硫酸塩 j、jg 7.6gジエチル
ヒドロキシ
ルアミン グ、Og 3.1g螢光増白
剤 ゛
(LIVITEX−CK
チバガイギ製) /、rg 2.0g水を加
えて 7000m1 1000m100Oλs
0c) 10.2.r 10.ごQ漂白定着
液
タンク液 補充液
水 4t00ml 4tOθ
rnlチオ硫酸アンモニウ
ム(7θチ) 2θom7300m1亜硫酸ナトリ
ウム 20g 4tOgエチレンジアミン
四
酢酸鉄(1)ア/
モニウム tOg 720gエチレン
ジアミン四
酢酸二ナトリウム 10g 10g水を加え
て 10100O1000m000mノル ’
C) 7.oo ご、30水洗液
イオン交換水(カルシウム、マグネシウムは各々jpp
m以下)
次に、試料/ −A〜/−0を像様露光した後、上記ラ
ンニンダ液を用いて処理を行なった。ただし/−J〜/
−0については水洗■の補充量は(2)の条件のみ行な
った。処理後♂00C70t4RH10日間経時した時
の白地(Dmin)部のイエロー、マゼンタ及びシアン
スティン濃度及びキセノン光(rjoooLux、距離
till)am)/、2日間照射後のマゼンタ濃度の退
色率(DG=x、O)をマクベス濃度計にて測定した結
果を表2に示した。退色試験は/−A〜/−Iの感材の
み行なった。また、スティン濃度は処理直後に対する増
加分で示した。λ, co]octane) r, 01g s, 0g potassium bromide 0. jg - Potassium carbonate 30g jugN-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-teraminoaniline sulfate j,jg 7.6g diethylhydroxylamine, Og 3.1g fluorescent brightener ゛(LIVITEX-CK manufactured by Ciba Geigi) /, rg Add 2.0g water 7000m1 1000m100Oλs
0c) 10.2. r10. Q: Bleach-fix tank solution Replenisher water 4t00ml 4tOθ
rnl Ammonium thiosulfate (7θti) 2θom7300ml Sodium sulfite 20g 4tOg Ethylenediaminetetraacetate iron (1) ammonium tOg 720g Disodium ethylenediaminetetraacetate 10g Add 10g water 10100O1000m000mnor'
C) 7. oo Go, 30 washing liquid ion exchange water (calcium, magnesium each jpp
m or less) Next, the samples /-A to /-0 were imagewise exposed and then treated using the Laninda solution. However, /-J~/
For -0, the replenishment amount of water washing (2) was carried out only under condition (2). ♂00C70t4RH 10 days after treatment, yellow, magenta and cyan stain density of white background (Dmin) and xenon light (rjoooLux, distance till) am)/, fading rate of magenta density after 2 days of irradiation (DG = x, Table 2 shows the results of measuring O) using a Macbeth densitometer. The fading test was conducted only for the sensitive materials /-A to /-I. In addition, the stain concentration was expressed as an increase compared to immediately after treatment.
表−コから最終水洗工程の補充量が本発明の範囲より少
ない場合ゼラチンの種類によらずイエロー、マゼンタ及
びシアンのスティン濃度増加が著しく(&/〜A?)ま
た多い場合、マゼンタの光退色が多少劣る(&/デ〜2
7)ことがわかる。From Table C, if the replenishment amount in the final water washing step is less than the range of the present invention, the yellow, magenta and cyan stain density increases significantly (&/~A?) regardless of the type of gelatin, and if it is large, magenta photobleaching. is somewhat inferior (&/de~2
7) Understand.
また補充量が本発明の範囲内であυかつ、酸処理ゼラチ
ンの含有量が本発明の範囲内のものがスティン濃度増加
が少なく、マゼンタ光退色も良好であることがわかる(
墓/2〜/7)。さらに酸処理ゼラチンの含有量は!θ
チ以上のものがよυ好ましく (A/4t、 /r)
かつ等電点が2以上のものがよυ好ましい(Al1)こ
とがわかる。It can also be seen that when the replenishment amount is within the range of the present invention and the content of acid-treated gelatin is within the range of the present invention, the increase in stain density is small and the magenta photobleaching is also good (
Tomb/2~/7). Furthermore, what is the content of acid-treated gelatin? θ
υ or more is preferable (A/4t, /r)
It can be seen that those with an isoelectric point of 2 or more are more preferable (Al1).
また、A10、/2、/j、3/、32.33(本発明
の好ましいカプラー使用)とA2F、2デ、3θとを比
較すると酸処理ゼラチンを含有することによるスティン
発生の改良効果は本発明中において特に好ましいカプラ
ーを用いた場合特に顕著であることがわかる。Furthermore, when comparing A10, /2, /j, 3/, 32.33 (using the preferred coupler of the present invention) and A2F, 2de, 3θ, the effect of improving stain generation by containing acid-treated gelatin is significant. It can be seen that this is particularly noticeable when a particularly preferred coupler is used in the invention.
実施例コ
ポリエチレンで両百ラミネートした紙支持体の上に以下
に示す層構成の多層カラー印画紙2−Aを作製した。塗
布液は下記のようにして調製した。EXAMPLE A multilayer color photographic paper 2-A having the layer structure shown below was prepared on a paper support laminated with copolyethylene. The coating solution was prepared as follows.
また、ゼラチンはすべて等電点J−,0のアルカリ処理
ゼラチンを使用した。All gelatin used was alkali-treated gelatin with an isoelectric point of J-.0.
第一層塗布液調製
イエローカプラー(ExY)/9 、/gおよび色像安
定剤(Cpd−/)x、ggに酢酸エチル27.2cc
および溶媒(Solv−/)7.7ccを加え溶解し、
この溶液を/θ係ドデシルベンゼンスルホン酸ナトリウ
ム/CCを含む70%ゼラチン水溶液/♂tccに乳化
分散させた。一方塊臭化銀乳剤(臭化銀/、θモルチ、
Ag;y。First layer coating solution preparation Yellow coupler (ExY)/9, /g and color image stabilizer (Cpd-/) x, gg, ethyl acetate 27.2cc
Add and dissolve 7.7cc of solvent (Solv-/),
This solution was emulsified and dispersed in a 70% gelatin aqueous solution containing /θ sodium dodecylbenzenesulfonate/CC/♂tcc. On the other hand, bulk silver bromide emulsion (silver bromide/, θmolti,
Ag;y.
g/kg含有)に下記に示す青感性増感色素を銀1モル
当たり!、θ×70−4モル加えたものを調製した。前
記の乳化分散物とこの乳剤とを混合溶解し、以下に示す
組成となるように第一層塗布液を調製した。第二層から
第七要用の塗布液も第一層塗布液と同様の方法で調製し
た。各層のゼラチン硬化剤としては、/−オキシ−3,
!−ジクo o −s −トリアジンナトリウム塩を用
いた。g/kg) containing the blue-sensitive sensitizing dye shown below per mole of silver! , θ×70 −4 moles were added. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is /-oxy-3,
! -dikuo-s-triazine sodium salt was used.
各層の分光増感色素としては下記のものを用いた。The following spectral sensitizing dyes were used in each layer.
青感性乳剤層
<M1’y’7化銀1モル当ft−F)j、0×10−
4モル)緑感性乳剤層
(ハロゲン化銀7モル当ftす4A、O×10−4モル
)および
(ハロゲン化銀1モル当たり7.0×10−5モル)赤
感性乳剤層
赤感性乳剤層に対しては、下記の化合物をノ・ロゲン化
銀1モル当たりJ、ご×/θ−3モル添加した。Blue-sensitive emulsion layer<M1'y'ft-F)j, 0x10-
4 moles) green sensitive emulsion layer (7 moles of silver halide per ft 4 A, O x 10-4 moles) and (7.0 x 10-5 moles per mole of silver halide) red sensitive emulsion layer red sensitive emulsion layer The following compound was added in J, x/θ-3 mol per mol of silver halogenide.
また青感性乳剤層、緑感性乳剤層、赤感性乳剤層に対し
、/−(j−メチルウレイドフェニル)−j−メルカプ
トテトラプールをそれぞれノ10ゲン化銀1モル当たり
?、!x10−5モル、2゜7x10−4−E:k、2
、 jX / 0−4モル添加(。Also, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(j-methylureidophenyl)-j-mercaptotetrapool was added per mole of silver 10genide, respectively? ,! x10-5 mol, 2゜7x10-4-E:k, 2
, jX/0-4 mol addition (.
た。Ta.
イラジェーション防止のために乳剤層に下記の染料を添
加した。The following dyes were added to the emulsion layer to prevent irradiation.
および
(層構成)
以下に各層の組成を示す。数字は塗布量(g/m2)を
表す。ハロゲン化銀乳剤は銀換算塗布量を表す。and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver.
支持体
ポリエチレンラミネート紙
〔第一層側のポリエチレンに白色顔料
(Ti02)と青味染料(群青)を含む〕第一層
ハロゲン化銀乳剤(Br1モルチ) θ、3θゼラチ
ン /、/ごイエローカプラ
ー(EXY) 0 、 J’、、2色像安定剤
(Cpd −/) 0./り溶媒(Solv
−/) 0.33第二層(混色防止層)
ゼラチン 0.99混色防止
剤(Cpd−,2) 0.Or第三層(緑感
層)
ハロケン化銀乳剤(B r 1モル%) 0.31
゜ゼラチン /、コグマゼ
ンタカプラー(ExM) 0.3/色像安定剤
(Cpd−、j) 0.2!色像安定剤(c
pa−り) 0./コ溶媒(Solv−J)
0.y2第四層(紫外線吸収層)
ゼラチン /、!♂紫外線
吸収剤(UV−/) o、tr混色防止剤(
Cpd−r) o、or溶媒(Solv−j
) 0.2<1第五層(赤感層)
ハロゲン化銀乳剤(Br1モル%) o、r3ゼラ
チン 7.39シアンカプ
ラー(ExC) 0.39色像安定剤(Cp
d−6) θ、/7ボリマー(Cpd−7)
0.り0溶媒(Solv−g)
0..23第六層(紫外線吸収層)
ゼラチン θ、j3紫外線吸
収剤(UV−/) θ、コ/溶媒(Solv
−3) 0.0!第七層(保護層)
ゼラチン /・33ポリビニル
アルコールのアクリル
変性共重合体(変性度/7係) θ、/7流動パラフ
ィン 0.03(ExY)イエロー
カプラー;Y−/り(E x M )マゼンタカプラー
f
(ExC)シアンカプラー;C−/
(Cpd−/)色像安定剤
(Cpd−2)混色防止剤
(Cpd−j)色像安定剤
(Cpd−タ)色像安定剤
(Cpd−、t)混色防止剤
(cpa−6)色像安定剤
しM2Uki2に<X)b8丘17
のjet:り混合物(重量比)
(Cpd−7)ポリマー
平均分子量♂θ、000
(UV−/)紫外線吸収剤
しM2(、;M2C;(Jす(−;sMtyo、2:り
:/混合物(重量比)
(Solv−/)溶媒
(Solv−2)溶媒
の/:/混合物(容量比)
(Solv−j)溶媒
(Solv−グ)溶媒
試料λ−Aの第1層〜第7層に使用したゼラチンの種類
を塗布量は変更せずに表3のように変更して試料コーB
−コーEを作成した。Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine blue)] First layer silver halide emulsion (Br1 mole) θ, 3θ gelatin /, /Yellow coupler ( EXY) 0, J',, dichroic image stabilizer (Cpd-/) 0. /Solv
-/) 0.33 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-, 2) 0. Or third layer (green-sensitive layer) Silver halide emulsion (Br 1 mol%) 0.31
° Gelatin / Cog magenta coupler (ExM) 0.3 / Color image stabilizer (Cpd-, j) 0.2! Color image stabilizer (c
pa-ri) 0. /Cosolvent (Solv-J)
0. y2 fourth layer (ultraviolet absorption layer) Gelatin /,! ♂Ultraviolet absorber (UV-/) o, tr color mixture prevention agent (
Cpd-r) o, or solvent (Solv-j
) 0.2<1 Fifth layer (red-sensitive layer) Silver halide emulsion (Br 1 mol%) o, r3 gelatin 7.39 Cyan coupler (ExC) 0.39 Color image stabilizer (Cp
d-6) θ, /7 polymer (Cpd-7)
0. 0 solvent (Solv-g)
0. .. 23 Sixth layer (ultraviolet absorbing layer) Gelatin θ, j3 Ultraviolet absorber (UV-/) θ, co/solvent (Solv
-3) 0.0! Seventh layer (protective layer) Gelatin / 33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification / 7th factor) θ, /7 Liquid paraffin 0.03 (ExY) Yellow coupler; Y- / Ri (Ex M ) Magenta coupler f (ExC) Cyan coupler; C-/ (Cpd-/) Color image stabilizer (Cpd-2) Color mixture inhibitor (Cpd-j) Color image stabilizer (Cpd-ta) Color image stabilizer (Cpd- , t) Color mixture prevention agent (cpa-6) Color image stabilizer and M2Uki2 < Ultraviolet absorber M2(,;M2C;(Jsu(-;sMtyo,2:ri:/Mixture (weight ratio) (Solv-/)solvent (Solv-2)/:/Mixture of solvent (volume ratio) Solv-j) Solvent (Solv-j) Solvent Sample Co. B
- Created CoE.
試料コーAを像様露光後、ば−パー処理機を用いて、下
記処理工程にてカラー現像のタンク容量の一倍補充する
まで、連続処理(ランニングテスト)を行った。6浴の
持込量は感光材料/m2当り3!mlであった。After imagewise exposure of Sample Co. A, continuous processing (running test) was carried out using a Bapar processor until one time the capacity of the color development tank was replenished in the processing steps described below. The amount of 6 baths brought in is 3 per m2 of photosensitive material! It was ml.
カラー現像 3s0c es秒 /4/ml
/71品白定着 30〜3乙0C4t!秒 /6/m
l /71水洗■30〜37°Cxo秒 1
01水洗■30〜37°C2θ秒 70!水洗■
30〜37°C−θ秒 101水 洗 ■ 30
〜37°C3o秒 下記参照 io1乾 燥 70
〜lθ’Ctθ秒
−1+感光材料/m2あたり
(水洗■→■へのqタンク向流方式とした。)水洗■の
補充量は下記3条件にて行なった。Color development 3s0c es seconds /4/ml
/71 white fixation 30~3otsu0C4t! seconds /6/m
l /71 water washing ■ 30-37°Cxo seconds 1
01 Wash ■ 30-37°C 2θ seconds 70! Wash with water■
30-37°C-θ seconds 101 water washing ■ 30
~37°C3o seconds See below io1 drying 70
~lθ'Ctθsec-1+photosensitive material/m2 (The q tank countercurrent method was used from washing ■→■.) The amount of replenishment for washing ■ was carried out under the following three conditions.
(1) ioml (持込量tD0.29倍)(
2) 、2tlt!”mil (# 7./倍
)(3)、2/θoml(zto倍)
各処理液の組成は以下の通りである。(1) ioml (amount brought in tD0.29 times) (
2), 2tlt! "mil (#7./times) (3), 2/θoml (zto times) The composition of each treatment liquid is as follows.
カッ−現偉液
水 700m1l 700
m1エチレンジアミン〜
N、N、N、N〜
テトラメチレンホ
スホン酸 /−6g /、jgトリエチ
レンジアミ
ン(/、タージア
ザビシクロ〔コ。Ka-genwei liquid water 700ml 700
m1 Ethylenediamine ~ N, N, N, N ~ Tetramethylenephosphonic acid /-6g /, jg triethylenediamine (/, terdiazabicyclo [co.
2、コクオクタン) j、Og j、0g塩化ナ
トリウム /、41g −炭酸カリウム
2!g 、2!gN−エチルーN−
(β−メタンスル
ホンアミドエチル)
−3−メチル−な
一アミノアニリン
硫酸塩 s、og 7.θgジエチル
ヒドロキシ
ルアミン り、−g 6゜og螢光増白剤
(4t、4t’
一ジアミノスチル
ベン系) λ、og 2.3g水を加え
て ・10100O1000m100Oコj’
c) 10.O!−70,4tj漂白漂白液(タン
ク液と補充液は同じ)水
<toθmJチオ硫酸アンモニウA(70
’lJ) 100m1亜硫酸ナトリウム
/7gエチレンジアミン四酢酸鉄(nl)
アンモニウム 51gエチレンジ
アミン四酢酸二ナト
リウム 7g臭化アン
モニウム 410g氷酢酸
タg水を加えて
1000m100O,2j’C)
s、4t。2. Rich octane) j, Og j, 0g Sodium chloride /, 41g - Potassium carbonate 2! g, 2! gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-monoaminoaniline sulfate s, og 7. θg diethylhydroxylamine ri, -g 6゜og fluorescent brightener (4t, 4t' monodiaminostilbene type) λ, og 2.3g water added ・10100O1000m100Ocoj'
c) 10. O! -70,4tj Bleach Bleach solution (tank solution and refill solution are the same) Water
<toθmJ ammonium thiosulfate A (70
'lJ) 100ml sodium sulfite
/7g ethylenediaminetetraacetic acid iron (nl) Ammonium 51g ethylenediaminetetraacetic acid disodium 7g ammonium bromide 410g glacial acetic acid
Add tag water
1000m100O, 2j'C)
s, 4t.
水洗液(夕/り液と補充液は同じ)
イオン交換水(カルシウム、マグネシウム64799m
以下)
次に試料コーA−2−Eを像様露光した後、上記ランニ
ング液を用いて処理を行なった。処理後100C70%
RH10日間経時した時の白地(Dmin)部のイエロ
ー、マゼンタ及びシアンスティン濃度及びキセノン光(
/ j 000 L u X %距離!θcm)/−日
間照射後のマゼンタ濃度の退色率(DG−=−z、o)
をマクベス濃度計にて測定した結果を表9に示した。ス
ティン濃度は処理直後に対する増加分で示した。Washing liquid (washing liquid and replenishing liquid are the same) Ion exchange water (calcium, magnesium 64799m
(Below) Next, sample code A-2-E was subjected to imagewise exposure and then processed using the above-mentioned running liquid. 100C70% after treatment
Yellow, magenta and cyan stain density of the white background (Dmin) and xenon light (Dmin) after 10 days of RH
/ j 000 L u X % distance! Fading rate of magenta density after irradiation for θcm)/-days (DG-=-z, o)
Table 9 shows the results of measurement using a Macbeth densitometer. The stain concentration was expressed as an increase compared to immediately after treatment.
表−≠から最終水洗工程の補充機及び酸処理ゼラチンの
含有量が本発明の範囲内のものの画像保存性が最も好ま
しいことがわかる(屑g〜10)。From the table ≠, it can be seen that the replenisher in the final water washing step and the content of acid-treated gelatin within the range of the present invention have the most favorable image preservation properties (waste g to 10).
さらに酸処理ゼラチンの含有量が50%以上のものがエ
リ好ましいことがわかる(/i6り、10)。Furthermore, it is found that gelatin containing acid-treated gelatin of 50% or more is preferable (/i6, 10).
実施例 3
コロナ放りa刀目工処理した両面ポリエチレンラミネー
ト紙に、表−jに記載したように第/j−(最上層)〜
第71−(最上層)を塗布し、感光材料3−Aを作成し
た。また、ゼラチンはすべて等′観点!、Qのアルカリ
処理ゼラチンを使用した。Example 3 Double-sided polyethylene laminate paper treated with a corona treatment was coated with layers /j- (top layer) to
The 71st layer (uppermost layer) was applied to prepare a photosensitive material 3-A. Also, all gelatin is from an equal point of view! , Q alkali-treated gelatin was used.
上記第7層目の塗布液は、次のようにして調製した。す
なわち、イエローカプラー20017.退色防止剤73
.3g、高沸点溶媒(2c)iog及び(2d )19
に、補助溶媒として酢酸エチル600 mlを加えた混
合物を60°Cに加熱浴解後、アルカノールB(アルキ
ルナフタレンスルホネート、デュポン社製)の5%水溶
液330rllを含むj%ゼラチン水浴液3300ml
に混合し、コロイドミルを用いて乳化してカプラー分散
液を作製した。この分散液から酢酸エチルを減圧溜去し
、青感性乳剤層用増感色素及び/−メチル−λ−メルカ
プトーj−アセチルアξノー/、3.μ−トリアゾルを
加えた乳剤l弘OOy(Agとして?6゜7g、ゼラチ
ン/ 7017を含む)に添加し、更に10%ゼラチン
水峙液26QOgを加えて塗布液を調製した。The coating liquid for the seventh layer was prepared as follows. That is, yellow coupler 20017. Anti-fading agent 73
.. 3g, high-boiling solvents (2c) iog and (2d) 19
A mixture of 600 ml of ethyl acetate as a co-solvent was dissolved in a heating bath at 60°C, and 3300 ml of a gelatin water bath solution containing 330 rll of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was added.
and emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and /-methyl-λ-mercapto j-acetyl acetate /, 3. A coating solution was prepared by adding μ-triazole to the emulsion 1000 (6.7 g as Ag, containing gelatin/7017) and further adding 26 QO g of a 10% gelatin solution.
第2層〜第7層の塗布lei、は、第7層に準じて調製
した。The coatings of the second to seventh layers were prepared in the same manner as the seventh layer.
イエローカプラー;Y−26
マゼンタカプラー
α
α
シアンカプラー;C−/
C−/r
*Ja2−(コーヒドロキシー3.!−ジーtert−
7ミルフエニル)ペンツトリアゾール
*、2b −一(−一ヒドロキシーJ、j−ジーter
t−iチルフェニル)ベンゾトリアゾール
*2c シ(λ−エテルへキシルンフタジート*コd
ジブチル7タレート
*λe 2.j−ジーtert−アミルフェニル−3
、j−ジーtert−ブチルヒドロキシベンゾエート
*2f2.J−ジーtert−オクチルハイドロキノン
*λg/、弘−ジーtert−アはルーコ、j−ジオク
チルオキンベンゼン
*2h コ、2′−メチレンビス(弘−メチル−6−t
e r t−ブチルフェノール)また各乳剤層の増感
色素として下記の物を用いた。Yellow coupler; Y-26 Magenta coupler α α Cyan coupler; C-/C-/r *Ja2-(Co-hydroxy-3.!-G-tert-
7milphenyl)penztriazole*, 2b-1(-1hydroxy-J, j-ter
t-i tylphenyl) benzotriazole *2c
Dibutyl 7 tallate *λe 2. j-tert-amyl phenyl-3
, j-tert-butyl hydroxybenzoate*2f2. J-G tert-octylhydroquinone *λg/, Hiro-G tert-A is luco,
(ert-butylphenol) Also, the following were used as sensitizing dyes in each emulsion layer.
青感性乳剤層;アンヒドロ−よ−メトキシ−jl−メチ
ル−313′−ジスルフォ
プロビルセレナシアニンヒ)−CIオ
キシド
緑感性乳剤層;アンヒトローターエチル−よ、5′−ジ
フェニル−3,3′−ジスル
フオエチルオキサカルポシアニン
ヒドロオキシド
赤感性乳剤層; j 、 J’−ジエチル−j−メトキ
シータ、り′−(コ、コージメチ
ルー/、!−プロパノ)チアジカ
ルポ7アニンヨージド
また各乳剤層の安定剤として下記の物を用いた。Blue-sensitive emulsion layer; anhydro-methoxy-jl-methyl-313'-disulfoprobyl selenacyanine)-CI oxide; green-sensitive emulsion layer; anhydro-methoxy-jl-methyl-3,3'-CI oxide; -disulfoethyl oxacarpocyanine hydroxide red-sensitive emulsion layer; j, J'-diethyl-j-methoxyta, ri'-(co, cordimethyl-/,!-propano)thiazicarpo-7anine iodide and as a stabilizer for each emulsion layer. The following items were used.
l−メチル−2−メルカプト−よ−アセチルアミノ−/
、J、4!−トリアゾール
またイラジェーション防止染料として下記の物を用いた
。l-Methyl-2-mercapto-yo-acetylamino-/
, J, 4! -The following triazoles and anti-irradiation dyes were used.
μ−(3−カルボキシ−よ−ヒドロキシーダ−(J−(
J−カルボキシ−よ−オキソ−/−(4cmスルホカド
フェニル)−一−ビラソリンー弘−イリチン) −/−
フロベニル)−7−ピラゾリル)ベンゼンスルホカート
−ジ−カリウム塩
N、N’−(IA、r−ジヒドロキジータ、i。μ-(3-carboxy-yo-hydroxyda-(J-(
J-carboxy-yoxo-/-(4cm sulfocadophenyl)-1-virasorin-hiro-iritin) -/-
flobenyl)-7-pyrazolyl)benzenesulfocate-di-potassium salt N,N'-(IA, r-dihydroxedita, i.
−ジオキソ−3,7−ジスルホナトアンスラセン−l、
j−ジイル)ビス(アミノメタンスルホナート)−テト
ラナトリウム塩
また硬膜剤としてl、コービス(ビニルスルホニル)エ
タンを用いた。-dioxo-3,7-disulfonatoanthracene-l,
J-diyl)bis(aminomethanesulfonate)-tetrasodium salt and l,corbis(vinylsulfonyl)ethane were used as a hardening agent.
試料J−Aの第771〜弗7麺に使用したゼラチンの種
類を塗布量は変更せずに表−6のように変更して試料J
−B〜J−Eを作成した。Sample J was prepared by changing the type of gelatin used in the 771st to 7th noodles of Sample J-A as shown in Table 6 without changing the applied amount.
-B to J-E were created.
試料j−Aを像様露光した後に、下記処理工程にてカラ
ー現像液のタンク容量の2倍補充するまで実施例2と同
様にして連続処理を行なった。6浴の持込量は感光材料
/m2当り36m1であった。After sample j-A was imagewise exposed, continuous processing was carried out in the same manner as in Example 2 until twice the tank capacity of the color developer was replenished in the following processing steps. The amount of 6 baths brought in was 36 ml per m2 of light-sensitive material.
カラー現像 JJ−0C4tj秒 /6/縮 /7
1漂白定着 30〜36 °CtAs秒 2/jTl
l /71安定 ■ 30〜37°C2o秒 −
101安定 ■ 30〜37°C20秒 −101
安定 ■ 30−37°C: ao抄 −tol乾
9 70−4!0CIPO秒
*感光材料/m2あたり
(安定■→■への弘タンク向流方式とした。)各処理液
の組成は以下の通りである。Color development JJ-0C4tj seconds /6/shrinkage /7
1 Bleach-fixing 30-36 °CtAs seconds 2/jTl
l /71 stable ■ 30~37°C2o seconds -
101 stable ■ 30~37°C 20 seconds -101
Stable ■ 30-37°C: ao-sho -tol dry 9 70-4!0 CIPO seconds * per photosensitive material/m2 (Hiro tank countercurrent method from stable ■ → ■) The composition of each processing solution is as follows. That's right.
カラー現像液 タンク液 補充液水
100me r00m
lエチレンジアミン四酢酸 2.0g 2.09j
、A−ジヒドロキシベン
ゼンー/12.弘−トリ
スルホン酸 0#9 0.3j;1トリ
エタノールアミン ざ、og r、oy塩化ナ
トリウム /、IQ −炭酸カリウム
コ! g26 9ヘーエチル−N−(β
−メ
タンスルホンアミドエチ
ル)−3−メチル−≠−
アミンアニリン硫酸塩 z、og 7.ogジエ
チルヒドロキシルアミ
ン ≠、2g
b、og螢光増白剤(≠、ψ′−ジ
アミノスチルベン糸) 2.0g λ、rg水を加
えて /θ00rnl 1000m10
0O,2j ’C) 10.0! 10.弘j
漂白定着液(タンク液と補充液は同じ)水
弘oomtチオ硫酸
アンモニウム(70%) /θ0rnl亜硫酸ナトリ
ウム 77gエチレンジアミン四酢
酸鉄(ill)
アンモニウム よjgエチレンジ
アミン四四酢酸二ヒ
トウム sg水を加えて
100100O[((,2j’
CJ J’sμ0安定液
/−ヒドロキシエチリデン−/。Color developer tank liquid replenisher water
100me r00m
l Ethylenediaminetetraacetic acid 2.0g 2.09j
, A-dihydroxybenzene/12. Hiro-trisulfonic acid 0#9 0.3j;1 triethanolamine za, og r, oy sodium chloride /, IQ -potassium carbonate Ko! g26 9h-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl-≠- amine aniline sulfate z, og 7. og diethylhydroxylamine ≠, 2g
b, og fluorescent brightener (≠, ψ′-diaminostilbene thread) 2.0g λ, rg Add water /θ00rnl 1000m10
0O,2j 'C) 10.0! 10. Hiroj
Bleach-fix solution (tank solution and refill solution are the same) water
Ammonium thiosulfate (70%) /θ0rnl Sodium sulfite 77g Iron ethylenediaminetetraacetate (ill) Ammonium yojg Dihydrium ethylenediaminetetraacetate sg Add water 100100O [(,2j'
CJ J'sμ0 stable solution/-hydroxyethylidene-/.
l−ジホスホン酸(60%) /・6扉を塩化ビ
スマス 0.3iポリビニルピロ
リドン 0.3yアンモニア水(26%)
λ、j成ニトリロ三酢酸
/ 、Of:l!−りaローコーメチルー弘−
インチアゾリン−3−オン o、osgλ−オクチ
ル−弘−イソチアゾ
リン−3−オン o、osg螢光増白剤
(弘 p/−シアε
水を加えて 1000rtlpH
(コj’c) 7.7次に、試料3−
A〜3−Eを像様露光した後、上記ランニング液を用い
て処理を行なった。処理後r00c70%RH7O日間
経時した時の白地(Dmin) 部のイエロー、マゼ
ンタ及びシアン濃度及びキセノン光(rroooLux
、距離jOcm)/2日間照射後のマゼンタm度の退
色率(Du=2.O)をマクベス濃度計にて測定し画像
保存性を調べたところ、酸処理ゼラチンの含有量及び最
終水洗処理液の補充量が本発明の範囲内のものが最も好
ましいことがわかった。l-Diphosphonic acid (60%) / 6 doors Bismuth chloride 0.3i Polyvinylpyrrolidone 0.3y Aqueous ammonia (26%)
λ,j-forming nitrilotriacetic acid
/ , Of:l! -ria Roko Methy-Hiro- Inthiazolin-3-one o, osgλ-octyl-Hiro-isothiazolin-3-one o, osg Fluorescent brightener (Hiro p/-Sia ε Add water to 1000rtlpH
(ko j'c) 7.7 Next, sample 3-
After imagewise exposure of A to 3-E, processing was performed using the above running liquid. The yellow, magenta and cyan density of the white background (Dmin) and the xenon light (rroooLux) after processing for r00c70%RH7O days.
, distance jOcm) / magenta degree fading rate (Du = 2.O) after irradiation for 2 days was measured using a Macbeth densitometer to examine image storage stability. It has been found that it is most preferable that the amount of replenishment is within the range of the present invention.
実施例 4
下塗りを施した三酢酸セルロースフィルム支持体上に、
下記に示す工うな組成の各層より゛なる多層カラー感光
材料である試料≠−Aを作成した。Example 4 On a subbed cellulose triacetate film support,
Sample ≠-A, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.
また、ゼラチンは全て等電点S、Oのアルカリ処理ゼラ
チンを使用した。In addition, all gelatin used was alkali-treated gelatin with isoelectric points S and O.
(感光層の組成)
塗布謙はハロゲン化銀およびコロイド銀については銀の
117m2単位で表した量を、またカプラー、添加剤お
よびゼラチンについては97m2単位で表した量を、ま
た増感色素については同一層内のハロゲン化銀1モルあ
たりのモル数で示した。(Composition of the photosensitive layer) The coating composition is the amount expressed in 117 m2 units of silver for silver halide and colloidal silver, the amount expressed in 97 m2 units for couplers, additives and gelatin, and the amount expressed in 97 m2 units for sensitizing dyes. It is expressed as the number of moles per mole of silver halide in the same layer.
第/IF+(ハレーション防止層)
黒色コロイド銀 ・・・0.2ゼラチン
・・・/、3ExM−r
−−−0,04UV−/
−−−o、1UV−λ ・・・
0.2Solv−/ −−−0,0/
5olv−J −−−o、ol第一2
層(中間層)
微粒子臭化銅
(平均粒径0.07m) −−−0,10ゼラチン
・・・/、jUV−/
−
−−o、obUV−2・・・0.0J
ExC−2・・・0.0λ
ExF−/ −−−o、oouSo
lv−/ −−−0,/5ol
v−2−−−o、o5P
第3層(第1赤感乳剤層)
沃臭化銀乳剤(Aglコモル係、内部筒Agl型、球相
当径0.3μ、球相当径の変動係数コタチ、正常晶、双
晶混合粒子、直径/厚み比−0!)
塗布fIi量 ・・・・・・O6μ
ゼラチン ・・・o、1aExS−
/ −−−/ 、0x10−’ExS−2−
−−3,oxio−’
ExS−J /X/(1)−5E
x C−j ・・・o、obEX
C−4−−−0,06
ExC−’y ・・、、、、IAE
xC−2−−−0,0J
Solv−/ −=0.0JSoIv
−j −−−0,0/2第4L層(第
1赤感乳剤層)
沃臭化銀乳剤(Agljモルチ、内部筒Agl型、球相
当径0.7μ、球相当径の変動係数Jj%、正常晶、双
晶混合粒子、直径/厚み比ダン
曽布銀普 ・・・・・・0.7
ゼラチン ・・・λ、jExS−/
1xto−’ExS−s
3xlo−’ExS−31xto−5
E x C−j ・・・0.λ≠E
xC4!
、、、6 、.2 pExに−7−−
−0,044
ExC−2・・・o、o弘
S O凰 v−/
・ ・ ・ 0./jSol
v−J −−−0,0λ第5層(第3
赤感乳剤層)
沃臭化銀乳剤(A g l / oモルチ、内部高Ag
I型、球相当径o、rμ、球相当径の変動係数76%、
正常晶、双晶混合粒子、直径/厚み比1.3)
塗布鎖歓 ・・・・・/、0
ゼラチン ・・・/、0ExS−i
/xyo ’ExS
−、J 3×10 ’E
xS−J /×1O−5E
x C−! ・・・0.OjE x
C−6・・・0./
5olv−/ −−−0,0/5ol
v−2−・−O,OS
第61悄(中間層)
ゼラチン ・・・i、。No./IF+ (antihalation layer) Black colloidal silver...0.2 gelatin
.../, 3ExM-r
---0,04UV-/
---o, 1UV-λ...
0.2Solv-/ ---0,0/
5olv-J ---o, ol 1st 2
Layer (intermediate layer) Fine particle copper bromide (average particle size 0.07 m) ---0,10 gelatin .../, jUV-/
−
--o, obUV-2...0.0J ExC-2...0.0λ ExF-/ ---o, oouSo
lv-/---0,/5ol
v-2---o, o5P 3rd layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (Agl comol ratio, internal cylinder Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter Kotachi, Normal crystal, twin crystal mixed particle, diameter/thickness ratio -0!) Application fIi amount...O6μ Gelatin...o, 1aExS-
/ ---/ , 0x10-'ExS-2-
--3,oxio-' ExS-J /X/(1)-5E
x C-j...o, obEX
C-4---0,06 ExC-'y...,,,,IAE
xC-2---0,0J Solv-/-=0.0JSoIv
-j ---0,0/2 4th L layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (Aglj morch, internal cylinder Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter Jj% , normal crystal, twinned mixed particle, diameter/thickness ratio Dansofu Ginpo ...0.7 Gelatin ...λ, jExS-/
1xto-'ExS-s
3xlo-'ExS-31xto-5 Ex C-j...0. λ≠E
xC4!
,,,6,. 2 pEx-7--
-0,044 ExC-2... o, o Hiro S O 凰 v-/
・ ・ ・ 0. /jSol
v-J ---0,0λ 5th layer (3rd
Red-sensitive emulsion layer) Silver iodobromide emulsion (Ag l/o morch, internal high Ag
Type I, equivalent sphere diameter o, rμ, coefficient of variation of equivalent sphere diameter 76%,
Normal crystal, twinned mixed particle, diameter/thickness ratio 1.3) Coating chain.../, 0 Gelatin.../, 0ExS-i
/xyo 'ExS
−, J 3×10'E
xS-J/×1O-5E
x C-! ...0. OjEx
C-6...0. / 5olv-/ ---0,0/5ol
v-2-・-O, OS No. 61 (middle layer) Gelatin...i,.
(、:pd−/ ・・・0.03S
olv−/ −−−o、oj第7顔(
第2青感乳剤層)
沃臭化銀乳剤1(AgI−2モルチ、内部高AgI型、
球相当径0.3μ、球相当径の変動係数2r%、正常晶
、双晶混合粒子、直径/厚み比λ、j)
塗布銀量 ・・・・・・0.30
ExS−弘 rxio ’ExS
−6・・−0,3XIO−4
ExS−j r×l。(,:pd-/...0.03S
olv-/---o, oj 7th face (
2nd blue-sensitive emulsion layer) Silver iodobromide emulsion 1 (AgI-2 morti, internal high AgI type,
Equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 2r%, normal crystal, twin crystal mixed particle, diameter/thickness ratio λ, j) Coated silver amount...0.30 ExS-Hiro rxio 'ExS
-6...-0,3XIO-4 ExS-j r×l.
ゼラチン ・・・/、OExM−タ
・ ・・O0λExY−/Q
−−−0,03E x M−了
・・・θ、03Solv−/
・・・θ、j弗Ir層(第2青感乳剤層)
沃臭化銀乳剤(Ag I弘モルチ、内部高Agl型、球
相当径o、bμ、球相当径の変動係数3r%、正常晶、
双晶混合粒子、直径/厚み比弘)
塗布銀量 ・・・・・・θ、4L
ゼラチン ・・・θ、にExS−≠
rxio−’ExS−j
λ×10−’ExS−b
−−−o、3x10−’ExM−タ
・・・0.2jExM−r
−−−0,03ExM−/ 0 −
−−0.0/jExY−/≠ ・・・0
.0/5olv−/ −−−0,2
第りII(第3緑感乳剤層)
沃臭化銀乳剤(AgI6モルチ、内部高AgI型、球相
当径1.0μ、球相当径の変動係数10%、正常晶、双
晶混合粒子、直径/厚み比1.2)
塗布銀量 ・・・・・・o、rj
ゼラチン °、−i、。Gelatin.../, OExM-ta...O0λExY-/Q
---0,03E x M-Complete
...θ, 03Solv-/
...θ, j Ir layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag I Hiromoruti, internal high Agl type, equivalent sphere diameter o, bμ, coefficient of variation of equivalent sphere diameter 3r%, normal Akira,
Twin crystal mixed particles, diameter/thickness ratio) Coated silver amount......θ, 4L Gelatin...θ, ExS-≠
rxio-'ExS-j
λ×10-'ExS-b
---o, 3x10-'ExM-ta
...0.2jExM-r
---0,03ExM-/0-
−−0.0/jExY−/≠ ・・・0
.. 0/5olv-/ ---0,2
No. 2 (third green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 molten, internal high AgI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 10%, normal crystal, mixed twin grains, diameter /thickness ratio 1.2) Coated silver amount...o, rj Gelatin °, -i,.
ExS−7−−−J、jX/(7−’
ExS−1−−−/、u×10−’
ExM−// −−−o、otExM
−/2 −−−o、o3ExM−/3
””、2θExM−4−−−o、ox
ExY−ij 、−−o、o2Solv
−i −−−o、2゜5olv−2・
−・0.0j
第/(71悼(イエローフィルタ一層)ゼラチン
°、、/、2黄色コロイド銀
・・・0.0tCpd −−2壷 ・ φ
0 、 /5olv−/
−−−(7,J第//iV!(第/青感乳剤fiJ
沃臭化銀乳剤(AgltAモルチ、高Agl型、球相当
径0.jμ、球相当径の変動係数ijチ、を面体粒子j
広布銀祉 ・・・・・・0.≠
ゼラチン ・・・/、0ExS−タ
2×10−’ExY−/6
・・・OoりExY−tta
−−−0,07Solv−/
−−−0,2第/λ軸(第2青感乳剤層)
沃臭化銀乳剤(AgI/θモルチ、内部高AgI型、球
相当径7.3μ、球相当径め変動係数コjチ、正常晶、
双晶混合粒子、直径/厚み比μ、71
塗布銀量 ・・・・・・O,S
ゼラチン °°°0°6ExS−タ
/X10 ’ExY−/6
−−−0.2jSolv
−/ −−−o、o 7弗
13層(第l保W1層)
ゼラチン ・・・Q、1UV−/
・・・o、1UV−2・・・(
>、、2
Solv−/ −−−0,01Sol
v−2−−−o、oi
第7μ層(第コ保護層)
微粒子臭化銀(平均粒径0.07μ)
e ・ ・ O、j
ゼラチン ・・・Q、μjポリメチ
ルメタクリレート粒子
(直径1.jμ)・・・Q、λ
[−1−/ ・・・Q、弘C
pd−J ・・・O,5Cpd−
参 ・・・O,S各層には上記の成
分の他に、界面活性剤を塗布助剤として添加した。ExS-7---J, jX/(7-' ExS-1---/, u×10-' ExM-// ---o, otExM
-/2 ----o, o3ExM-/3
"", 2θExM-4---o, ox ExY-ij, --o, o2Solv
-i---o, 2゜5olv-2・
-・0.0j/(71st mourning (yellow filter single layer) gelatin
°, , /, 2 yellow colloidal silver
...0.0tCpd --2 jars ・φ
0, /5olv-/
---(7,Jth//iV!(th/Blue-sensitive emulsion fiJ Silver iodobromide emulsion (AgltA morch, high Agl type, equivalent sphere diameter 0.jμ, coefficient of variation of equivalent sphere diameter ij, Particle j Kosenrufu Bank...0.≠ Gelatin.../, 0ExS-ta 2×10-'ExY-/6
・・・OoriExY-tta
---0,07Solv-/
---0, 2nd/λ axis (second blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI/θ morch, internal high AgI type, equivalent sphere diameter 7.3μ, equivalent sphere diameter coefficient of variation Koj , normal crystal,
Twinned mixed particles, diameter/thickness ratio μ, 71 Coated silver amount...O,S Gelatin °°°0°6ExS-ta /X10 'ExY-/6
---0.2jSolv
-/---o, o 7 layers 13 layers (1st layer W1) Gelatin...Q, 1UV-/
...o, 1UV-2...(
>,,2 Solv-/ ---0,01Sol
v-2---o, oi 7th μ layer (protective layer) Fine grain silver bromide (average particle size 0.07 μ) e ・ ・ O, j Gelatin...Q, μj Polymethyl methacrylate particles (diameter 1 .jμ)...Q, λ [-1-/...Q, HiroC
pd-J...O,5Cpd-
Reference: In addition to the above-mentioned components, a surfactant was added as a coating aid to each of the O and S layers.
次に本発明に用いた化合物の化学構造式または化学名を
下に示した。Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.
UV−/
UV−2
・5olv−/ リン酸トリクレジル・5olv−コ
フタル酸ジブチル
・5olv−J フタル酸ビス(コーエチルヘキフル
)
ExY−1
α
ExF−/
ExC−蓼
E x C−6
ExC−7
H2
ExM−タ;M−=7
ExM−/(:)
(Z
ExM−//
ExM−/、2
α
ExM−/ J ;M−rb
ExY−/ 6;Y−214
Cpd−/ Cpd−2E x S
−/
ExS−j
(CH2)asOa)i−N(CzHs)3(CH2)
2SO3Na
ExS−11
ExS−タ
H−/
C1−12=C)l−802−CH2−CONE−1−
CH2CH2=CH−802−CH2−CON[(−C
H2pct−j
1−1t(
Cpd−≠
H
[1
以上の如くして作製した試料をμ−Aとした。UV-/ UV-2 ・5olv-/ Tricresyl phosphate ・5olv- Dibutyl cophthalate ・5olv-J Bis(coethylhexiflu) phthalate ExY-1 α ExF-/ ExC-蓼E x C-6 ExC- 7 H2 ExM-ta;M-=7 ExM-/(:) (Z ExM-// ExM-/, 2 α ExM-/ J ;M-rb ExY-/ 6; Y-214 Cpd-/ Cpd-2E xS
−/ExS-j (CH2)asOa)i-N(CzHs)3(CH2)
2SO3Na ExS-11 ExS-taH-/C1-12=C)l-802-CH2-CONE-1-
CH2CH2=CH-802-CH2-CON[(-C
H2pct-j 1-1t(Cpd-≠H [1 The sample prepared as above was designated as μ-A.
次に試料弘−Aの第/層〜第1μ層に使用したゼラチン
の種類を塗布量は変更せずに表−7のように変更して試
料弘−B−μ−■を作成した。Next, Sample Hiro-B-μ-■ was prepared by changing the type of gelatin used in the 1st layer to the 1 μth layer of Sample Hiro-A as shown in Table 7 without changing the coating amount.
カラー写真感光材料μ−Aを露光したのち、富士写真フ
ィルム■製カラーネガプロセサーFP−3!Qを用い以
下に記載の方法で、(液の累積補充量がその母液タンク
容量の3倍になるまで)処理した。After exposing the color photographic material μ-A, use a color negative processor FP-3 manufactured by Fuji Photo Film ■! Q was treated in the manner described below (until the cumulative replenishment amount of liquor was three times the mother liquor tank volume).
表−処理方法
工程 処理時間 処理温度 補充量 タンク容量発色
現像 3分/j秒 JIoC4Ajxtl ノO!
漂 白 1分00秒 5r0c コOat 4
41漂白定着 3分/j秒 JroCJ(711j
101管方式。Table - Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes/j seconds JIoC4Ajxtl NoO!
Bleach 1 minute 00 seconds 5r0c Ko Oat 4
41 bleach fixing 3 minutes/j seconds JroCJ (711j
101 tube system.
水洗(2)1分00秒 JjoCJOtm ≠!
安 定 4Ao秒 3r 0c 下記参Jfl
l 4’1乾 燥 1分/j秒 j!0C
補充量はJjmm巾/m長さ当たり
尚、上記処理における、濃白定着液の水洗工程への持込
量はJjm/m 巾の感光材料1m長さ当り2Mであ
った。Washing (2) 1 minute 00 seconds JjoCJOtm ≠!
Stable 4Ao seconds 3r 0c See below Jfl
l 4'1 Drying 1 minute/j seconds j! 0C The amount of replenishment was per Jjmm width/m length, and the amount of the dark white fixer brought into the washing process in the above process was 2M per 1m length of the photosensitive material having a width of Jjm/m.
安定工程の液の補充量は下記3条件にて行なった。The amount of liquid replenishment in the stabilization step was carried out under the following three conditions.
(1) o、6rst (持込量の(7,7倍)(
2) 20trl (’ 10倍)(3)
t2oml (# bo倍)次に、処理液
の組成を配子。(1) o, 6rst ((7,7 times the amount brought in) (
2) 20trl ('10 times) (3)
t2oml (#bo times) Next, calculate the composition of the treatment liquid.
(発色現像液)
母液<g> 補充液(I)
ジエチレントリアミン
五酊酸 i、o /、/l−ヒ
ドロキシエチリ
ダン−1,l−ジホ
スホン酸 j、(7J、l亜硫酸ナト
リウム 弘、θ μ、≠炭酸カリ9ム
JO’、0 37.Q臭化カリウム
1.μ b、7ヨウ化カリウム
i、s〜 −ヒドロキシルアミン硫
酸塩 2.4! λ、tμm
(N−エチル−へ
−β−ヒドロキシエ
チルアは〕)−2−
メチルアニリン硫酸
塩 μ、j j、
!水を加えて /、Ol /、Olp[
−110,0110,10
(漂白液) 母液、補充液共通(単位9)エチレンシア
ばン四酢酸
第二鉄アンモニウムニ
水塩 lコ0.0
エチレンジアミン四酢酸
二ナトリウム塩 io、。(Color developer) Mother solution <g> Replenisher (I) Diethylenetriaminepentachoic acid i, o /, /l-hydroxyethyridan-1,l-diphosphonic acid j, (7J, l sodium sulfite Hiroshi, θ μ, ≠ Potassium carbonate 9m
JO', 0 37. Q potassium bromide
1. μ b, 7 potassium iodide
i, s~ -Hydroxylamine sulfate 2.4! λ, tμm
(N-ethyl-to-β-hydroxyethyla is)-2-methylaniline sulfate μ, j j,
! Add water /, Ol /, Olp[
-110,0110,10 (Bleach solution) Common to mother liquor and replenisher (Unit 9) Ethylenethiabanetetraacetic acid ferric ammonium dihydrate lco0.0 Ethylenediaminetetraacetic acid disodium salt io.
臭化アンモニウム ioo、。Ammonium bromide ioo.
硝酸アンモニウム io、。Ammonium nitrate io.
漂白促進剤 o、oozそルアン
七ニア水(コ7チJ / 7 、011水を加え
て / 、Olp[−16・3
(漂白定着液) 母液、補充液共通(単位g)エチレン
ジアミン四酢酸
第二鉄アンモニウムニ
水塩 !0,0
エチレンジアミン四酢酸
二ナトリウム塩 jl
亜硫酸ナトリウム /コ、Oチオ硫酸アンモ
ニウム水
容ff(70To ) 2uo、orxt7
y−v−=7水(27elr ) 6.0rt
rl水を加えて /、0lp)l
7.λ(水洗液) 母液、
補充液共通
水道水をH型強酸性カチオン交換樹脂(ロームアンドハ
ース社製アンバーライトTl(−/λOB)と、OH型
アニオン交換樹脂(同アンバーライトTR−4400)
を充填した温床式カラムに通水してカルシウム及びマグ
ネシウムイオン濃度をJNi/l以下に処理し、続いて
二塩化イソシアヌール酸ナトリウム201n9/lと硫
酸ナトリウム/10ダ/lを添加した。Bleach accelerator o, ooz Soluan 7th aqueous solution (7th J/7, 011 water added /, Olp[-16.3 (bleach-fix solution) Common to mother liquor and replenisher solution (unit: g) Ethylenediaminetetraacetic acid Diiron ammonium dihydrate !0,0 Ethylenediaminetetraacetic acid disodium salt jl Sodium sulfite /co, O ammonium thiosulfate water volume ff (70To) 2uo, orxt7
y-v-=7 water (27elr) 6.0rt
rl Add water /, 0lp)l
7. λ (washing liquid) mother liquor,
Common replenisher tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite Tl (-/λOB) manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite TR-4400 manufactured by Rohm and Haas).
Water was passed through a hotbed column packed with water to reduce the concentration of calcium and magnesium ions to below JNi/l, and then 201 n9/l of sodium isocyanurate dichloride and 10 Da/l of sodium sulfate were added.
この液のpHはす、、f−7,3の範囲にあった。The pH of this solution was in the range of f-7.3.
(安定液) 母液、補充液共通(単位、!i+)ホルマ
リン(37%) 2.0mlポリオキシエチ
レン−p−
モノノニルフェニルニー
チル(′+均ル合度10) Q、Jエチレンジア
ミン四酢酸二
ナトリウム塩 o 、or水を加えて
/、0lpHs、o−r、。(Stable solution) Common to mother solution and replenisher solution (unit, !i+) Formalin (37%) 2.0ml polyoxyethylene-p- monononylphenyl nityl ('+ Uniformity degree 10) Q, J ethylenediaminetetraacetic acid disodium Add salt or water
/,0lpHs,or,.
次に試料μmA−弘一■を像様膳光した後、上記ラン二
ンダ液を用いて処理を行なった。処理後と00C70%
RHJO日間経時した時の巖低譲度fDminJ 部
のイエロー、マゼンタ及びシアンスティン濃度及びto
’<:is日間経時した時のシアン色素の退色率(DR
=/−2)をマクベス濃度計にて測定した。結果を表r
に示した。スティン濃度は処理直後に対する増加分で示
した。Next, the sample .mu.mA-Koichi 1 was subjected to imagewise exposure, and then treated using the above-mentioned Landinda solution. After treatment and 00C70%
Yellow, magenta and cyan stain densities and to
'<:Fading rate of cyan dye after is days (DR
=/-2) was measured using a Macbeth densitometer. Display the results
It was shown to. The stain concentration was expressed as an increase compared to immediately after treatment.
表−gより最終水洗工程の補充量及び酸処理ゼラチンの
含有量が本発明の範囲内のものの画像保存性が最も好ま
しいことがわかる(/16/ J〜/r)。From Table g, it can be seen that the image preservability is most preferable when the amount of replenishment in the final water washing step and the content of acid-treated gelatin are within the range of the present invention (/16/J to /r).
さらに酸処理ゼラチンの含有量がSO%以上のものがエ
リ好ましく(A/4’、/j)、かつ、等電点が2以上
のものがより好ましい(/j6/J、/I)ことがわか
る。Furthermore, it is preferable that the acid-treated gelatin has a content of SO% or more (A/4', /j), and more preferable that the isoelectric point is 2 or more (/j6/J, /I). Recognize.
実施例 5
ポリエチレンで両面ラミネートした紙支持体の上に以下
に示す層構成の多層カラー感光材料j −Aを作製した
。ゼラチンは丁べて等’(IJ、点j、0のアルカリ処
理ゼラチンを使用した。Example 5 A multilayer color photosensitive material j-A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. As for the gelatin, alkali-treated gelatin of IJ, point j, 0 was used.
第Ey層 保護層 第Err偵 紫外線吸収層 第E7rf4 青感乳剤層 第86層 紫外線吸収層 第Es層 イエロフィルタ一層 第Eμ層 紫外線吸収層 第83層 緑感乳剤層 第82層 紫外線吸収層 第E/胸 赤感乳剤層 支持体 ′PIB1層 カーリング防止層 第B2層 保護層 塗布液は次のようにして調製した。Eyth layer Protective layer Detective Err Ultraviolet absorption layer No. E7rf4 Blue-sensitive emulsion layer 86th layer Ultraviolet absorption layer Esth layer yellow filter layer Eμ layer Ultraviolet absorption layer 83rd layer Green-sensitive emulsion layer 82nd layer Ultraviolet absorption layer No. E/Chest Red-sensitive emulsion layer support 'PIB1 layer Anti-curling layer B2 layer Protective layer The coating solution was prepared as follows.
第E/層塗布液調製
シアンカプラー(ExCC−t )/ J 、tapお
よび色像安定M(J(ExSA−/ )6.717およ
びポリマー(ExP−/ )10.7gに酢酸エテルu
occお工び浴媒(ExS−1)y、7aaを加え溶解
し、この溶液な1otsドデシルベンゼンスルホン酸ナ
トリウムzcc、y含む/7%ゼラチン水溶液1rzc
aに乳化分散させた。−1内部潜像型乳剤(Ag6JN
/に、9含有)に下記に示す赤感性増感色素を銀1モル
当たりコ、zxio モル加えたものを調製した。E/Layer Coating Solution Preparation Cyan coupler (ExCC-t)/J, tap and color image stability M (J(ExSA-/) 6.717 and polymer (ExP-/) 10.7 g were mixed with ethyl acetate u.
Add and dissolve occ bath medium (ExS-1) y, 7aa, and this solution contains 1ots sodium dodecylbenzenesulfonate zcc,y/7% gelatin aqueous solution 1rzc
A was emulsified and dispersed. -1 Internal latent image emulsion (Ag6JN
A red-sensitive sensitizing dye shown below was added to the following red-sensitive sensitizing dye in an amount of co, zxio mol per mol of silver.
前記の乳化分散物とこの乳剤とを混合溶解し、以下に示
す組成となるように第一層塗布液を調製した。第82層
から第Eり層および第B/、8.2層用の塗布液%第E
/層塗布液と同様の方法で満製した。各層のゼラチン硬
化剤としては、l−オキシ−3,j−ジクロロ−3−ト
リアジンナトリウム塩を用いた。The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating liquid for 82nd layer to Eth layer and B/, 8.2th layer %E
/ layer coating solution was prepared in the same manner as the coating solution. l-oxy-3,j-dichloro-3-triazine sodium salt was used as the gelatin hardening agent for each layer.
各層の分光増感色素として下記のものを用いた。The following spectral sensitizing dyes were used in each layer.
(ハロケン(IJI 1モル当タリJ、jX/Q モ
ル)(ハロケン化m1モル当たりJ、/X10 モ
ル)青感性乳剤層
嘔
(ハロケン化銀7モル当た+)44.JXlo モ
ルンイラジエーション防止染料として次の染料を用いた
。(Halokene (J, jX/Q mol per 1 mol of IJI) (J, /X 10 mol per mol of halokenide) Blue-sensitive emulsion layer (+ per 7 mol of silver halide) 44. The following dyes were used.
緑感性乳剤層用イラジェーション防止染料赤感性乳剤層
用イラジェーション防止染料(層構成)
以下に各層の組成を示す。数字はm2あたりの塗布量を
表す。ハロゲン化銀乳剤およびコロイド銀は鉋換算塗布
漬を表す。Anti-irradiation dye for green-sensitive emulsion layer Anti-irradiation dye for red-sensitive emulsion layer (layer structure) The composition of each layer is shown below. The numbers represent the coating amount per m2. Silver halide emulsions and colloidal silver represent coating equivalents.
支持体
ポリエチレンジεネート紙
〔第一層側のポリエチレンに白色顔料(TiOz)と青
味染料(群青ンを含む」
第81層
ハロゲン化銀乳剤 0.37gゼラチン
/、3!9シアンカプラー(
ExCC−/] 0.u09色像安定剤(ExSA−
/) 0./7.!9ポリーr−(ExP−/
) o、3−2g浴媒(ExS−/ J
O,2Ji現像現像剤(ExGC−/)
32 In9安定剤 (ExA−/)
!、1 ■造核促進剤(ExZS−/ )
0 、J7即造核剤 (ExZK−/)
タ、りμy第Eコ層
ゼラチン /、6I紫外絢吸収
1ll(ExUV−/ ) 0 、1.29混色防
止剤(ExKB−/ ) 0−0611浴媒
(ExS−2) 0.2弘y第E3層
ハロゲン化銀乳剤 。、ノアyゼラチン
パ7りgマゼンメカブラ−(
ExMC−/)
0.3Jy
色像安定剤(ExSA−/) o 、2oy浴
媒 (ExS−3) 0.lpjg境像調
節剤(ExGC/) 22 rv安定剤
(ExA−7) ’4’ r’9造核促進
剤(ExZS−/ ) 0 、JArn9造核剤
(ExZK−/ ) j 、 It μll
第Eμ層
ゼラチン 0.3311紫外線
吸収剤(ExUV−/) 0.2/i混色防止剤(
ExKB−コ) 0.02/i醪媒(ExS−
コλ θ、ory第Ej#
コロイド銀 0.10ilゼラチ
ン 0.639紫外線吸収剤(
EXUV−/) o、2t、!iI混色防止41(
ExKB−2) o 、o211浴媒 (ExS
−2) 0.019第E61醜
第E≠層と同じ
第87層
ハロゲン化銀乳剤 0.269ゼラチン
i、r3gイエローカプラー
(ExYC−/)
0、IJl
色像安定剤(ExSA−j) 0./99浴媒
(ExS−4’ ) 0 、3117現像
調節剤(EXGC−/) 32 rny安定剤
(ExA−/) 2.タ ■造核促進剤(
ExZS−/) 0.−2 mtp造核剤(Ex
ZK−i ) 2 、6 μll第Eft偵
ゼラチン 0.639紫外線
吸収剤(UV−/) 0.2/fl溶媒(So
lv−j) θ、arp第Eり層
ゼラチン /、J3f;1ポ
リビニルアルコールのアク
リル変性共重合体
(変性度17%) o、/yg流動パラ
フィン 。、03gポリメタクリル酸
メチルのラ
テックス粒子
(平均粒径コ、tμm) 0.Oj第B /
Ili!1
ゼラチン t・7y第Bλ層
第Eり層と同じ
(Ex c: C−/ ) シフyカ/’ラ−; C−
J(ExMC−/ )マゼンPヵiラ−;M−/ J(
ExYC−/)イエローカプラー;/り(ExSA−/
)色像安定剤
C419(t)
の j:r:り混合物(重量比)
(ExSA−2)色像安定剤
(ExSA−j)色像安定剤
(ExP−/)ポリマー
平均分子量 to、oo。Support polyethylene dinate paper [first layer side polyethylene contains white pigment (TiOz) and bluish dye (ultramarine)] 81st layer silver halide emulsion 0.37 g gelatin / 3!9 cyan coupler (
ExCC-/] 0. u09 color image stabilizer (ExSA-
/) 0. /7. ! 9 poly r-(ExP-/
) o, 3-2g bath medium (ExS-/J
O,2Ji developer (ExGC-/)
32 In9 stabilizer (ExA-/)
! , 1 ■Nucleation accelerator (ExZS-/)
0, J7 immediate nucleating agent (ExZK-/)
Ta, Ri μy E-layer gelatin /, 6I ultraviolet absorption 1 liter (ExUV-/) 0, 1.29 Color mixing inhibitor (ExKB-/) 0-0611 Bath medium
(ExS-2) 0.2 hi E3 layer silver halide emulsion. , Noah y gelatin pa7ri g mazenmekabura (
ExMC-/) 0.3Jy Color image stabilizer (ExSA-/) o, 2oy bath medium (ExS-3) 0. lpjg image control agent (ExGC/) 22 rv stabilizer
(ExA-7) '4'r'9 nucleation promoter (ExZS-/) 0, JArn9 nucleation agent (ExZK-/) j, It μll
Eμ layer gelatin 0.3311 Ultraviolet absorber (ExUV-/) 0.2/i Color mixing inhibitor (
ExKB-co) 0.02/i mortar (ExS-
λ θ, ory No. Ej # Colloidal silver 0.10il Gelatin 0.639 Ultraviolet absorber (
EXUV-/) o, 2t,! iI color mixture prevention 41 (
ExKB-2) o, o211 bath medium (ExS
-2) 87th layer silver halide emulsion same as 0.019 E61 Ugly E≠ layer 0.269 Gelatin i, r3g Yellow coupler (ExYC-/) 0, IJl Color image stabilizer (ExSA-j) 0. /99 bath medium
(ExS-4') 0, 3117 Development regulator (EXGC-/) 32 rny stabilizer (ExA-/) 2. ■ Nucleation accelerator (
ExZS-/) 0. -2 mtp nucleating agent (Ex
ZK-i) 2,6 μl Eft gelatin 0.639 Ultraviolet absorber (UV-/) 0.2/fl Solvent (So
lv-j) θ, arp E-layer gelatin /, J3f; 1 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) o, /yg liquid paraffin. , 03g polymethyl methacrylate latex particles (average particle size, tμm) 0. Oj No. B /
Ili! 1 Gelatin t・7y Bλ layer Same as Eth layer (Ex c: C-/) Schiffyka/'ra-; C-
J(ExMC-/) Mazen Pcalar-;M-/J(
ExYC-/) Yellow coupler;/ri (ExSA-/
) Color image stabilizer C419(t) j:r:ri mixture (weight ratio) (ExSA-2) Color image stabilizer (ExSA-j) Color image stabilizer (ExP-/) Polymer average molecular weight to, oo.
(Ext−/)溶媒 (ExS−2)溶媒 (ExS−J)溶媒 の コニl混合物(容量比) (ExS−4’)溶媒 (ExUV−/)紫外線吸収剤 の コ:り:を混合物(1L量比) (ExKB−/)混色防止剤 H (ExKB−コ)混色防止剤 H (ExGC−/)現像調節剤 R (ExA−/)安定剤 弘−ヒドロキシ−6−メチル−/、3.Ja。(Ext-/)solvent (ExS-2) Solvent (ExS-J) Solvent Conil mixture (volume ratio) (ExS-4') Solvent (ExUV-/) Ultraviolet absorber Mixture of (1L volume ratio) (ExKB-/) Color mixing prevention agent H (ExKB-ko) Color mixing prevention agent H (ExGC-/)Development regulator R (ExA-/) stabilizer Hiro-hydroxy-6-methyl-/, 3. Ja.
7−チトラザインデン
(ExZS−/)
λ−(3−ジメチルアミノプロピルチオ)−!メルカプ
ト−7,3,≠−チアジアゾール塩酸塩(ExZK/)
6−ニトキシチオカルボニルアミノーλ−メチル−/−
プロノルギルキノリニウム トリプルオロメタンスルホ
を−ト
また、内部潜像型乳剤は下記のようにして作成した。7-Chitrazaindene (ExZS-/) λ-(3-dimethylaminopropylthio)-! Mercapto-7,3,≠-thiadiazole hydrochloride (ExZK/) 6-nitoxythiocarbonylamino-λ-methyl-/-
An internal latent image type emulsion was prepared using pronorgylquinolinium triple olomethane sulfo as described below.
臭化カリウムと塩化ナトリウムの混合水溶液及び硝酸銀
の水溶液をAg1モル当り0.79の/。A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were mixed at a concentration of 0.79/mole of Ag.
3−ジメチル−/、3−イミダゾリンニス−チオンを添
万Oしたゼラチン水溶液に激しくかくはんしながら6!
0Cで約7分を要して同時に添加し、平均粒径が約0.
2/rnm(臭化銀含量70モル%)単分散の塩臭化銀
乳剤を得た。この乳剤に銀1モル当り/ / 0m9の
チオ硫酸ナトリウムと77In9の塩化金酸(≠水塩)
を加え6!0Cで60分間加熱することにエリ化学増感
処理を行った。こうして得た塩臭化銀粒子をコアとして
、第7回目と同じ沈殿環境でさらに成長させ、最終的に
平均粒径が約Q、6mm(臭化銀含量70モル%)の単
分散のコア/シェル塩臭化銀乳剤を得た。粒子サイズの
変動係数は約72%であった。While vigorously stirring the aqueous gelatin solution to which 3-dimethyl-/3-imidazoline nis-thione had been added, 6!
It took about 7 minutes at 0C to add them simultaneously, and the average particle size was about 0.
A monodisperse silver chlorobromide emulsion with a silver bromide content of 2/rnm (silver bromide content 70 mol %) was obtained. This emulsion contains / / 0 m9 of sodium thiosulfate and 77In9 of chloroauric acid (≠ hydrate) per mole of silver.
Eri chemical sensitization treatment was performed by adding and heating at 6!0C for 60 minutes. Using the thus obtained silver chlorobromide particles as a core, they were further grown in the same precipitation environment as in the seventh precipitation, and finally a monodisperse core with an average particle size of about Q, 6 mm (silver bromide content 70 mol%) was obtained. A shell silver chlorobromide emulsion was obtained. The coefficient of variation in particle size was approximately 72%.
水洗、脱塩後この乳剤に銀1モル当り7.2■のチオ硫
酸ナトリウムと7.2〜の塩化金酸(≠水塩)を加え6
o0Cで60分間加熱して化学増感処理を行い、内部潜
像型・・ロゲン化乳剤を得た。After washing with water and desalting, add 7.2 μ of sodium thiosulfate and 7.2 to 7.2 μ of chloroauric acid (≠ hydrate) per mole of silver to this emulsion.
A chemical sensitization treatment was performed by heating at o0C for 60 minutes to obtain an internal latent image type logenated emulsion.
次に試′prt−AのE/−Eりl@及びB/、B2層
に使用したゼラチンの種類を塗布量は変更せずに表7の
ように変更して試料j−B−j−Eを作成した。Next, the type of gelatin used in the E/-E layer and B/, B2 layer of sample 'prt-A was changed as shown in Table 7 without changing the coating amount, and sample j-B-j- I created E.
上記感光材料j−Aを像様露光後、下記処理工程にてラ
ンニング処理を行なった。6浴の持込量は感光材料1W
L2当りroutであった。After imagewise exposure of the photosensitive material j-A, running processing was performed in the following processing steps. The amount of light-sensitive material brought into 6 baths is 1W.
It was rout per L2.
カラー現像 jr’c /分μO秒JOOd 1
01漂白定着 33℃ 60秒300ゴ j
lリンス■ 30〜3弘’C20秒 −コノリンス■
30〜3≠’C20秒下記参照 21乾燥70−1
0 ’C!0秒
*感光材料17+!2 あたり
(リンス■→■への3タンク向流方式とした。Color development jr'c / minute μO seconds JOOd 1
01 Bleach fixing 33℃ 60 seconds 300g
l Rinse■ 30~3hiro'C20 seconds -Conorinse■
30~3≠'C 20 seconds See below 21 Drying 70-1
0'C! 0 seconds * Photosensitive material 17+! 2 (3-tank countercurrent flow method from rinse ■ to ■).
リンス■の補充祉は下記3条件にて行なった。Replenishment of rinse ■ was carried out under the following three conditions.
(1) /jml(持込量の0.3 倍)(2)
5oo1Ll(# b、o 倍)(3) 3
00tnl(# 60 倍ン各処理液の組成は以
下の通りである。(1) /jml (0.3 times the amount brought in) (2)
5oo1Ll (# b, o times) (3) 3
The composition of each treatment solution is as follows.
カラー現像液 タンク液 補充液水
100m1 r0
0neジエチレントリアミン
五酢酸 i 、og /、09ニト
リロ三酢酸 λ、og a、oyl−ヒ
ドロキシエチリ
デンーi、i−ジホ
スホン酸 コ、Og 2.0gトリエチ
レンジアミン
(/、≠−ジアザビ
シクロ(J、コ、コ〕
オクタン) s、oy s、og
臭化カリウム i、sy −炭酸カリ
ウム 3o 9 30 、Sl) N
−エチル−N−(β
一メタンスルホンミ
ドエチル)−3−メ
チル−μmアミノア
ニリン硫酸塩 !、Ill 7・sgN
、N−ジエチルヒド
ロキシルアミン 3.69 !、31トリ
エタノールアミン to、oI!9 io、og螢
光増白剤(WE−11TEX参B
水を加えて 10001d 10001
4pH(λよ ’C) 10.20 10
.60溢白定着液 タンク液 補充
液水800111 4c00MI
チオ硫酸アンモニウム
(70%) 200rd J00y
d亜硫酸ナトリウム 209 弘opエ
チレンジアミン四酢
酸鉄(ill)アンモニ
ラム 609 /2017エ
チレンジアミン四酢
水を加えて 10100O1000rxl
pH(2j0C) 6.70 6.30リ
ンス液(タンク液と補充液は同じ]
ベンゾトリアゾール / 、09エチレ
ンジアミン−へl N I
N′ 、N′−テトラメチレ
KOHにて p (17、0次に試
料j−A−j−Eを像様露光した後上記ランニング液を
用いて処理を行なった。処理後rO’C70%RH10
日間経時した時の白地(Dmin) 部のイエロー、マ
ゼンタ及びシアンスティン濃度及びキセノン光(Ijo
ooLux 距離sOcm)/λ日間照射後のマゼンタ
myの退色率(Du=−2−i7)をマクベス濃度計に
て測定した結果を表10に示した。スティン濃度は処理
直後に対する増加分で示した。Color developer tank liquid replenisher water
100m1 r0
0ne diethylenetriaminepentaacetic acid i, og /, 09 nitrilotriacetic acid λ, og a, oyl-hydroxyethylidene-i, i-diphosphonic acid co, Og 2.0g triethylenediamine (/, ≠-diazabicyclo (J, co, co) octane) s, oy s, og
Potassium bromide i, sy - Potassium carbonate 3o 9 30 , Sl) N
-Ethyl-N-(β-methanesulfonmidoethyl)-3-methyl-μm aminoaniline sulfate! , Ill 7・sgN
, N-diethylhydroxylamine 3.69! , 31 triethanolamine to, oI! 9 io, og fluorescent whitening agent (WE-11TEX reference B Add water 10001d 10001
4pH (λyo'C) 10.20 10
.. 60 bleach fixer Tank liquid Replenisher water 800111 4c00MI Ammonium thiosulfate (70%) 200rd J00y
d Sodium sulfite 209 Hiroop ethylenediaminetetraacetic acid iron (ill) ammonium 609 /2017 Add ethylenediaminetetraacetic acid water 10100O1000rxl
pH (2j0C) 6.70 6.30 Rinse solution (tank solution and replenishment solution are the same) Benzotriazole / , 09 ethylenediamine-hel N I N' , N'-tetramethylene KOH p (17,0 next sample After imagewise exposure of j-A-j-E, processing was performed using the above running liquid.After processing rO'C70%RH10
Yellow, magenta and cyan stain density of white background (Dmin) and xenon light (Ijo
Table 10 shows the results of measuring the fading rate (Du=-2-i7) of magenta my after irradiation for ooLux distance sOcm/λ days using a Macbeth densitometer. The stain concentration was expressed as an increase compared to immediately after treatment.
表−/Qから最終水洗工程の補充量及び酸処理ゼラチン
含有量が本発明の範囲内のものの画像保存性が最も好ま
しいことがわかる(7g6.r−io)。From Table-/Q, it can be seen that the image preservability is most preferable when the replenishment amount in the final water washing step and the acid-treated gelatin content are within the range of the present invention (7g6.r-io).
さらに酸処理ゼラチンの含有量が50%以上のものがエ
リ好ましいことがわかる(A69,10)。Furthermore, it can be seen that gelatin containing 50% or more of acid-treated gelatin is preferable (A69, 10).
Claims (1)
形成するカプラーを含み、全塗布ゼラチン量の25wt
%以上が酸処理ゼラチンであるハロゲン化銀カラー感光
材料を発色現像、脱銀処理したのち水洗処理および/ま
たは安定化処理し、該水洗処理および該安定化処理の補
充量が前浴からの持込量の0.5〜50倍であることを
特徴とするカラー画像形成方法。Contains a coupler that reacts with the oxidized form of an aromatic primary amine developing agent to form a dye, and contains 25wt of the total coated gelatin amount.
A silver halide color light-sensitive material of which % or more is acid-treated gelatin is subjected to color development and desilvering treatment, followed by water washing and/or stabilization treatment, and the replenishment amount for the water washing treatment and the stabilization treatment is determined by the amount retained from the previous bath. A method for forming a color image, characterized in that the amount is 0.5 to 50 times as large as the amount of color.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6352787A JP2566140B2 (en) | 1987-03-18 | 1987-03-18 | Color image forming method |
US07/169,633 US4830948A (en) | 1987-03-18 | 1988-03-17 | Method of forming color images |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6352787A JP2566140B2 (en) | 1987-03-18 | 1987-03-18 | Color image forming method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63229456A true JPS63229456A (en) | 1988-09-26 |
JP2566140B2 JP2566140B2 (en) | 1996-12-25 |
Family
ID=13231779
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6352787A Expired - Fee Related JP2566140B2 (en) | 1987-03-18 | 1987-03-18 | Color image forming method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2566140B2 (en) |
-
1987
- 1987-03-18 JP JP6352787A patent/JP2566140B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2566140B2 (en) | 1996-12-25 |
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