JPH0571087B2 - - Google Patents
Info
- Publication number
- JPH0571087B2 JPH0571087B2 JP60185174A JP18517485A JPH0571087B2 JP H0571087 B2 JPH0571087 B2 JP H0571087B2 JP 60185174 A JP60185174 A JP 60185174A JP 18517485 A JP18517485 A JP 18517485A JP H0571087 B2 JPH0571087 B2 JP H0571087B2
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- layer
- halide emulsion
- sensitive
- emulsion layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 claims description 136
- 229910052709 silver Inorganic materials 0.000 claims description 125
- 239000004332 silver Substances 0.000 claims description 125
- 239000000839 emulsion Substances 0.000 claims description 90
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 7
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 115
- 239000000975 dye Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 29
- 238000011161 development Methods 0.000 description 26
- 238000012545 processing Methods 0.000 description 24
- 238000011109 contamination Methods 0.000 description 17
- 108010010803 Gelatin Proteins 0.000 description 16
- 229920000159 gelatin Polymers 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 235000019322 gelatine Nutrition 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- 238000004061 bleaching Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical compound C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- NPKFETRYYSUTEC-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPKFETRYYSUTEC-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical class N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical class O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- FITNPEDFWSPOMU-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-b]pyridin-5-one Chemical compound OC1=CC=C2NN=NC2=N1 FITNPEDFWSPOMU-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- YJQCPPZYIKJFNQ-UHFFFAOYSA-N 2-(4-amino-3-methylanilino)ethanol Chemical compound CC1=CC(NCCO)=CC=C1N YJQCPPZYIKJFNQ-UHFFFAOYSA-N 0.000 description 1
- WEULJWIQMLXOOU-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methoxyanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C(OC)=C1 WEULJWIQMLXOOU-UHFFFAOYSA-N 0.000 description 1
- WFXLRLQSHRNHCE-UHFFFAOYSA-N 2-(4-amino-n-ethylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C=C1 WFXLRLQSHRNHCE-UHFFFAOYSA-N 0.000 description 1
- HYVGFUIWHXLVNV-UHFFFAOYSA-N 2-(n-ethylanilino)ethanol Chemical compound OCCN(CC)C1=CC=CC=C1 HYVGFUIWHXLVNV-UHFFFAOYSA-N 0.000 description 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- 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 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- SIOGKUOINGALLK-UHFFFAOYSA-N 2-pentadecan-3-yloxyethylbenzene Chemical compound CCCCCCCCCCCCC(CC)OCCC1=CC=CC=C1 SIOGKUOINGALLK-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- GKIFPROMYBQIHS-UHFFFAOYSA-N 4-n-ethyl-2-methoxy-4-n-(2-methoxyethyl)benzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(OC)=C1 GKIFPROMYBQIHS-UHFFFAOYSA-N 0.000 description 1
- FFAJEKUNEVVYCW-UHFFFAOYSA-N 4-n-ethyl-4-n-(2-methoxyethyl)-2-methylbenzene-1,4-diamine Chemical compound COCCN(CC)C1=CC=C(N)C(C)=C1 FFAJEKUNEVVYCW-UHFFFAOYSA-N 0.000 description 1
- ARARZLMQLKXONM-UHFFFAOYSA-N 4-n-ethyl-4-n-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-2-methylbenzene-1,4-diamine Chemical compound COCCOCCOCCN(CC)C1=CC=C(N)C(C)=C1 ARARZLMQLKXONM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FUXHWBAPHYPMMU-UHFFFAOYSA-N C(CCC)OC1=C(C(=CC=C1)C(C)CCC)C(C)CCC Chemical compound C(CCC)OC1=C(C(=CC=C1)C(C)CCC)C(C)CCC FUXHWBAPHYPMMU-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical class CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 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
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- DFBLXBPBWVBQJK-UHFFFAOYSA-N n-[2-(4-amino-n,3-dimethylanilino)ethyl]methanesulfonamide Chemical compound CS(=O)(=O)NCCN(C)C1=CC=C(N)C(C)=C1 DFBLXBPBWVBQJK-UHFFFAOYSA-N 0.000 description 1
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 1
- PEIVHTCIMKJVJF-UHFFFAOYSA-N n-[2-amino-5-(dimethylamino)phenyl]acetamide Chemical compound CN(C)C1=CC=C(N)C(NC(C)=O)=C1 PEIVHTCIMKJVJF-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- MTGYZMXZHZOFCT-UHFFFAOYSA-N pentadecoxybenzene Chemical compound CCCCCCCCCCCCCCCOC1=CC=CC=C1 MTGYZMXZHZOFCT-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- BUPJAEYQPRVYDB-UHFFFAOYSA-N sodium;1h-1,3,5-triazin-2-one Chemical compound [Na].O=C1N=CN=CN1 BUPJAEYQPRVYDB-UHFFFAOYSA-N 0.000 description 1
- QGRSLAYMCFPMHW-UHFFFAOYSA-M sodium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [Na+].CC(=C)C(=O)OCCCS([O-])(=O)=O QGRSLAYMCFPMHW-UHFFFAOYSA-M 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- FUFMEQTUGKXEQF-YZNHWISSSA-J tetrasodium 5-[[4-[bis(2-hydroxyethyl)amino]-6-(3-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-2-[(E)-2-[4-[[4-[bis(2-hydroxyethyl)amino]-6-(3-sulfonatoanilino)-1,3,5-triazin-2-yl]amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=C(C=CC=5)S([O-])(=O)=O)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(S([O-])(=O)=O)=C1 FUFMEQTUGKXEQF-YZNHWISSSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000001043 yellow dye 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
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
-
- 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
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
［産業上の利用分野］
本発明はハロゲン化銀カラー写真感光材料に関
し、詳しくは他の処理液成分の混入（所謂バツク
コンタミネーシヨン）耐性が優れたハロゲン化銀
カラー写真感光材料に関する。
一般にハロゲン化銀カラー写真感光材料は支持
体上に青色光、緑色光および赤色光に感光性を有
するように選択的に分光増感された３種の写真用
ハロゲン化銀乳剤層が塗設されている。例えばカ
ラー印画紙用ハロゲン化銀写真感光材料では、一
般に露光される側から赤感性ハロゲン化銀乳剤
層、緑感性ハロゲン化銀乳剤層、青感性ハロゲン
化銀乳剤層の順で塗設されており、特殊の目的で
紫外線吸収層をはじめとする中間層や、保護層等
が設けられている。これらの各ハロゲン化銀乳剤
層は前記とは別の配列で設けられることも知られ
ており、さらに各ハロゲン化銀乳剤層として、
各々の色光に対して実質的に同じ波長域に感光性
を有する２層又はそれ以上の層からなる感光性ハ
ロゲン化銀乳剤層を用いることも知られている。
これらのハロゲン化銀カラー写真感光材料におい
ては、発色現像主薬として、例えば芳香族第１級
アミン系発色現像主薬を用いて、露光されたハロ
ゲン化銀粒子を現像し、生成した発色現像主薬の
酸化体と色素形成性カプラーとの反応により色素
画像が形成される。この方法においては、通常、
シアン、マゼンタおよびイエローの色素画像を形
成するために、それぞれフエノールもしくはナフ
トール系シアンカプラー、５−ピラゾロン系、ピ
ラゾリノベンツイミダゾール系、ピラゾロトリア
ゾール系、インダゾロン系もしくはシアノアセチ
ル系マゼンタカプラーおよびアシルアセトアミド
系イエローカプラーが用いられる。これらの色素
形成性カプラーは感光性ハロゲン化銀乳剤層中も
しくは現像液中に含有される。本発明はこれらの
カプラーが予め非拡散性化されてハロゲン化銀乳
剤層中に含まれているハロゲン化銀カラー写真感
光材料に関するものである。
［従来技術］
感光材料の処理は基本的には発色現像と脱銀の
２工程からなり、脱銀は漂白と定着工程又は漂白
定着工程からなつている。この他に付加的な処理
工程としてリンス処理、安定処理等が加えられ
る。
発色現像において、露光されたハロゲン化銀は
還元されて銀になると同時に酸化された芳香族第
１級アミン系発色現像主薬はカプラーと反応して
色素を形成する。この過程で、ハロゲン化銀の還
元によつて生じたハロゲンイオンが現像液中に溶
出し蓄積する。又別にはハロゲン化銀写真感光材
料中に含まれる抑制剤等の成分も発色現像液中に
溶出して蓄積される。脱銀工程では現像により生
じた銀は酸化剤により漂白され、次いで全ての銀
塩は定着剤により可溶性銀塩として、写真感光材
料中より除去される。なお、この漂白工程と定着
工程をまとめて同時に処理する一浴漂白定着処理
方法も知られている。
近時では、これら現像処理はラボラトリーや店
頭にて自動現像機を用いて連続処理（ランニング
処理）ないし間欠連続処理されているのが一般的
である。
［発明が解決しようとする問題点］
このような自動現像機を用いたランニング処理
ないし間欠連続処理における問題として、他の処
理液成分の混入蓄積の増大がある。これは処理液
補充量が減少しタンク液が補充液で更新される率
が低くなる場合に顕著になり、また液の使用期間
が長くなることも加わると更に顕著になる。上記
「他の処理液の混入」は処理機内での隣りの処理
液のスプラツシユや搬送リーダー、ベルト又はフ
イルムを吊り下げるハンガー等により発色現像液
中に現像直後の処理液成分が持ち込まれる所謂バ
ツクコンタミネーシヨンにより引き起こされる。
これらの蓄積する混入成分のうち、定着剤である
チオ硫塩イオンは現像促進する。即ち、発色現像
後に直接漂白定着処理される場合に特にこの問題
は強く起こる。特に写真特性曲線の肩部を促進す
ることによつて著しいハイコントラスト化を生じ
る。また漂白剤である金属塩、特に第２鉄塩の混
入増大は保恒剤であるヒドロキシルアミンの分解
を促進しアンモニアイオンを生成する。このアン
モニアイオンの発生はチオ硫酸イオンと同様に物
理現像を促進し、ハイコントラスト化する欠点が
あつた。
他の処理液成分の混入による写真性能の変動の
改良の従来技術としては本発明者の知る限り感光
材料において実質的に改良された例はない。一
方、処理液の改良により上記写真性能の変動を改
良する技術もほとんどないのが現状である。しか
しながらわずかに例えば米国特許3839045号、同
3746544号、同4264716号等に記載の如く漂白定着
液に微量に存在する重金属イオンをキレート化す
る技術が挙げられるが、これらの技術では改良巾
は小さくいまだ満足のいくものではない。
そこで、本発明の目的は、他の処理液成分の混
入（所謂バツクコンタミネーシヨン）が起こつて
も処理安定性があり、写真性能が一定に維持され
る安定なハロゲン化銀カラー写真感光材料を提供
することにある。
［問題を解決するための手段］
上記目的は、反射支持体上に、各々塩臭化銀乳
剤を含有する青感性ハロゲン化銀乳剤層、緑感性
ハロゲン化銀乳剤層及び赤感性ハロゲン化銀乳剤
層をこの順序で有すると共に、各乳剤層間に中間
層を有するハロゲン化銀カラー写真感光材料にお
いて、前記青感性ハロゲン化銀乳剤層に相対カプ
リング反応速度が0.3以上の高速反応性イエロー
カプラーを該層の銀１モル当たり２×10-3〜５×
10-1モルを含有し、かつ前記中間層および／また
は青感性ハロゲン化銀乳剤層に相対反応速度が
1.6以上の発色現像主薬の酸化体を失活せしめる
化合物を含有することを特徴とするハロゲン化銀
カラー写真感光材料により達成された。
発色現像主薬の酸化体を失活せしめる化合物
（以下、クエンチヤーという）とは、、発色現像主
薬の酸化体と反応し、失活せしめて、発色現像主
薬の酸化体がカプラーと反応しないようにするも
のである。
本発明によれば、青感性ハロゲン化銀乳剤層お
よび中間層の改良により青感性ハロゲン化銀乳剤
層のみならず緑感性ハロゲン化銀乳剤層及び赤感
性ハロゲン化銀乳剤層の他の処理液成分（例えば
漂白定着成分）の混入による写真性能の安定性も
改善されることは、驚くべき事実であり、本発明
者も予想しなかつたことである。
以下、本発明について更に詳述する。
本発明に係わる青感性ハロゲン化銀乳剤層に用
いられるイエローカプラーは高速反応性イエロー
カプラーであり、これは、相対カプリング反応速
度が0.3以上のイエローカプラーであり、より好
ましくは相対カプリング反応速度が0.5以上のイ
エローカプラーである。
カプラーのカプリング反応速度は相互に明瞭に
分離し得る異つた色素を与える２種類のカプラー
Ｍ及びＮを混合してハロゲン化銀乳剤に添加して
発色現像することによつて得られる色像中のそれ
ぞれの色素量を測定することによつて相対的な値
として決定できる。
カプラーＭの最高濃度（DM）max.、中途段
階では濃度DMの発色を、またカプラーＮについ
てのそれをそれぞれ（DN）max.、DNの発色を
表わすとすれば、両カプラーの反応活性の比
RM／RNは次の式で表わされる。
RM／RN＝log（１−DM／（DM）max.）／log（１−DN／（
DN）max.）
つまり、混合したカプラーを含むハロゲン化銀
乳剤に、種々の段階の露光を与え、発色現像して
得られる数個のDMとDNとの組を直交する２軸
に
log（１−DM／（DM）max.）、log（１−DN／（DN）max.
）
としてプロツトして得られる直線の勾配からカプ
リング活性比RM／RNの値を求められる。
ここで一定のカプラーＮを用いて、各種カプラ
ーについて前記のようにしてRM／RNの値を求
めれば、相対カプリング反応速度の値が求められ
る。
本発明においては上記のカプラーＮとして下記
のカプラーを用いた場合のRM／RN値をいう。
[Industrial Field of Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material that has excellent resistance to contamination with other processing liquid components (so-called back contamination). In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. ing. For example, in a silver halide photographic light-sensitive material for color photographic paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally coated in this order from the exposed side. , intermediate layers such as an ultraviolet absorbing layer, protective layers, etc. are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and each of the silver halide emulsion layers further includes:
It is also known to use a light-sensitive silver halide emulsion layer consisting of two or more layers sensitive to substantially the same wavelength range for each color light.
In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by the reaction of the dye with the dye-forming coupler. In this method, usually
Phenol or naphthol cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indazolone or cyanoacetyl magenta couplers and acylacetamides to form cyan, magenta and yellow dye images, respectively. Yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developer. The present invention relates to a silver halide color photographic light-sensitive material in which these couplers are previously made non-diffusible and are contained in a silver halide emulsion layer. [Prior Art] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps. In color development, the exposed silver halide is reduced to silver, and at the same time, the oxidized aromatic primary amine color developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by reduction of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted into the color developing solution and accumulated. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously. These days, these developing treatments are generally carried out continuously (running processing) or intermittently in a laboratory or at a store using an automatic developing machine. [Problems to be Solved by the Invention] A problem in running processing or intermittent continuous processing using such an automatic processor is an increase in the amount of contamination and accumulation of other processing liquid components. This becomes noticeable when the amount of replenishment of the processing solution decreases and the rate at which the tank solution is renewed with the replenisher becomes low, and becomes even more noticeable when the period of use of the solution becomes longer. The above-mentioned "contamination with other processing solutions" is so-called back contamination, in which processing solution components immediately after development are brought into the color developer by splashes of neighboring processing solutions in the processing machine, transport leaders, belts, hangers for hanging the film, etc. caused by nation.
Among these contaminant components that accumulate, thiosulfate ions, which are fixing agents, accelerate development. That is, this problem occurs particularly when bleach-fixing is performed directly after color development. In particular, by promoting the shoulder of the photographic characteristic curve, a remarkable increase in contrast is produced. Further, increased contamination of metal salts as bleaching agents, especially ferric salts, accelerates the decomposition of hydroxylamine as a preservative, producing ammonia ions. The generation of ammonia ions, like thiosulfate ions, has the disadvantage of accelerating physical development and increasing contrast. As far as the present inventors are aware, there is no example of any substantial improvement in photographic materials as far as the present inventors are aware of the prior art for improving fluctuations in photographic performance due to the mixing of other processing liquid components. On the other hand, there is currently almost no technology for improving the above-mentioned fluctuations in photographic performance by improving processing solutions. However, there are a few examples, such as U.S. Pat.
3746544, 4264716, etc., there are techniques for chelating heavy metal ions present in trace amounts in the bleach-fixing solution, but these techniques provide only a small amount of improvement and are still unsatisfactory. Therefore, an object of the present invention is to provide a stable silver halide color photographic light-sensitive material that has processing stability and maintains constant photographic performance even when mixed with other processing liquid components (so-called back contamination). It is about providing. [Means for Solving the Problem] The above object is to form a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion each containing a silver chlorobromide emulsion on a reflective support. In a silver halide color photographic light-sensitive material having layers in this order and an intermediate layer between each emulsion layer, a fast-reactive yellow coupler having a relative coupling reaction rate of 0.3 or more is added to the blue-sensitive silver halide emulsion layer. 2×10 -3 to 5× per mole of silver
10 -1 mol, and the intermediate layer and/or blue-sensitive silver halide emulsion layer has a relative reaction rate of
This was achieved by a silver halide color photographic light-sensitive material characterized by containing a compound that deactivates the oxidized form of a color developing agent with a molecular weight of 1.6 or more. A compound that deactivates the oxidized form of a color developing agent (hereinafter referred to as a quencher) is a compound that reacts with the oxidized form of the color developing agent, deactivates it, and prevents the oxidized form of the color developing agent from reacting with the coupler. It is something. According to the present invention, by improving the blue-sensitive silver halide emulsion layer and the intermediate layer, other processing liquid components of not only the blue-sensitive silver halide emulsion layer but also the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer can be obtained. It is a surprising fact that the stability of photographic performance is also improved by the incorporation of (for example, bleach-fixing components), and something that the inventors had not anticipated. The present invention will be explained in more detail below. The yellow coupler used in the blue-sensitive silver halide emulsion layer according to the present invention is a fast-reactive yellow coupler, which is a yellow coupler with a relative coupling reaction rate of 0.3 or more, more preferably a relative coupling reaction rate of 0.5. This is the above yellow coupler. The coupling reaction rate of couplers is determined by the rate of the coupling reaction in a color image obtained by mixing two types of couplers M and N that give different dyes that can be clearly separated from each other, and adding the mixture to a silver halide emulsion and color development. By measuring the amount of each dye, it can be determined as a relative value. If we express the maximum concentration (DM) max. of coupler M, the color development of the concentration DM in the middle stage, and the color development of coupler N (DN) max., then the ratio of the reaction activities of both couplers.
RM/RN is expressed by the following formula. RM/RN=log(1-DM/(DM)max.)/log(1-DN/(
DN) max.) In other words, a silver halide emulsion containing a mixed coupler is exposed to light at various stages, and several pairs of DM and DN obtained by color development are expressed as log(1 -DM/(DM)max.), log(1-DN/(DN)max.
) The value of the coupling activity ratio RM/RN can be determined from the slope of the straight line obtained by plotting as follows. Here, by using a constant coupler N and determining the value of RM/RN for various couplers as described above, the value of the relative coupling reaction rate can be determined. In the present invention, it refers to the RM/RN value when the following coupler is used as the above coupler N.
【化】
本発明の高速反応性イエローカプラーの添加量
は、青感性ハロゲン化銀乳剤層の銀１モル当り２
×10-3〜５×10-1モルが好ましく、より好ましく
は１×10-2〜５×10-1モルである。
以下に、本発明の高速反応性イエローカプラー
の具体例を挙げるが、これに限定されるものでは
ない。これらは１種又は２種以上の組合せ使用も
可能である。[Chemical formula] The amount of the fast-reacting yellow coupler of the present invention added is 2 mols of silver per mole of silver in the blue-sensitive silver halide emulsion layer.
The amount is preferably from x10 -3 to 5 x 10 -1 mol, more preferably from 1 x 10 -2 to 5 x 10 -1 mol. Specific examples of the fast-reacting yellow coupler of the present invention are listed below, but the invention is not limited thereto. These may be used alone or in combination of two or more.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
本発明のハロゲン化銀カラー写真感光材料は、
各感光性乳剤層間に中間層（隔離層）が設けられ
ている。本発明のクエンチヤーを含有せしめるこ
とができる中間層はゼラチン、誘導体ゼラチンそ
の他の親水性バインダーを含む親水性コロイド層
であつて感光性乳剤層の間に設けられる隔離層で
あればよいが、好ましくは青感性ハロゲン化銀乳
剤層に隣接し且つ該青感性ハロゲン化銀乳剤層の
上層に位置する中間層である。
中間層の少なくとも１つ及び／又は青感性ハロ
ゲン化銀乳剤層に用いられるクエンチヤーは、相
対反応速度が1.6以上の高速反応性化合物である。
本発明の高速反応性クエンチヤーは、現像主薬
の酸化体と反応した後は、有色であつてもかまわ
ないが、少なくとも各処理は実質的に画像におい
て無色となることが好ましい。
ここで相対反応速度は、前記カプラーＮと混合
して、ハロゲン化銀乳剤に混合して発色現像する
ことによつて得られるカプラーＮの色像の色素量
を測定することによつて相対的な値として決定で
きる。
クエンチヤーとカプラーＮの反応活性の比(R)を
次式で定義する。
Ｒ＝DM／DM′
ここで、
DM：カプラーＮのクエンチヤーを含有しないと
きの発色濃度、
DM′：クエンチヤーをカプラーＮの１／10mol添
加したときのカプラーＮの濃度、
カプラーＮを用いて各種クエンチヤーについて
前記Ｒを求めれば、クエンチヤーの発色現像主薬
酸化体反応速度の相対的な値が決まる。
本発明のクエンチヤーは保存安定性という観点
からＲが15以下のものが好ましい。
高速反応性クエンチヤーの添加量としては、限
定的ではないが、青感性ハロゲン化銀乳剤層に添
加される場合、カプラー１モル当り１×10-4〜５
×10-1モルが好ましい。そして、中間層に添加さ
れる場合、１×10-7〜１×10-1モル／m2が好まし
い。
以下に、本発明のクエンチヤーの具体例を挙げ
るがこれらに限定されるものではない。括弧内に
前記Ｒ値を示す。これらは１種又は２種以上の組
合せ使用も可能である。[Table] The silver halide color photographic light-sensitive material of the present invention is
An intermediate layer (separating layer) is provided between each light-sensitive emulsion layer. The intermediate layer which can contain the quencher of the present invention may be a hydrophilic colloid layer containing gelatin, derivative gelatin or other hydrophilic binder, and is an isolating layer provided between light-sensitive emulsion layers, but preferably It is an intermediate layer located adjacent to the blue-sensitive silver halide emulsion layer and above the blue-sensitive silver halide emulsion layer. The quencher used in at least one of the intermediate layers and/or the blue-sensitive silver halide emulsion layer is a fast-reacting compound with a relative reaction rate of 1.6 or more. The fast-reactive quencher of the present invention may be colored after reacting with the oxidized form of the developing agent, but it is preferable that the image be substantially colorless at least in each treatment. Here, the relative reaction rate is determined by measuring the amount of dye in a color image of coupler N obtained by mixing it with the coupler N and coloring it in a silver halide emulsion. Can be determined as a value. The reaction activity ratio (R) of the quencher and coupler N is defined by the following formula. R=DM/DM' where, DM: Color density of coupler N when no quencher is included, DM': Concentration of coupler N when 1/10 mol of quencher is added to coupler N, Various quenchers using coupler N By determining the above-mentioned R, the relative value of the reaction rate of the quencher to the oxidized color developing agent can be determined. The quencher of the present invention preferably has an R of 15 or less from the viewpoint of storage stability. The amount of the fast-reacting quencher added is not limited, but when added to the blue-sensitive silver halide emulsion layer, it is from 1 x 10 -4 to 5 per mole of coupler.
x10 -1 mol is preferred. When added to the intermediate layer, the amount is preferably 1×10 −7 to 1×10 −1 mol/m 2 . Specific examples of the quencher of the present invention are listed below, but the invention is not limited thereto. The R value is shown in parentheses. These may be used alone or in combination of two or more.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
本発明のハロゲン化銀カラー写真感光材料にお
ける青感性ハロゲン化銀乳剤層の銀量（銀付量）
は0.35g〜0.15g／m2とされるのが好ましい。即
ち、他の処理液成分の混入（所謂バツクコンタミ
ネーシヨン）耐性をもたせるためには0.35g／m2
以下とされることが好ましいが、一方、銀付量が
少ないと最高濃度がでにくいため0.15g／m2以上
がよい。
本発明に好ましく用いられる青感性ハロゲン化
銀乳剤層の膜厚は1.0〜6.0μmが好ましく、膜厚が
厚くなるほど、本発明の他の処理液成分の混入
（所謂バツクコンタミネーシヨン）耐性効果は大
きい。
但し、青感性ハロゲン化銀乳剤層の膜厚が
6.0μm以上であると、現像速度の点で不利にな
る。
本発明に用いられるハロゲン化銀は、平均粒子
サイズが広い範囲に分布している多分散乳剤でも
よいが、単分散乳剤の方が好ましい。
本発明における上記の単分散性のハロゲン化銀
粒子とは、電子顕微鏡写真により乳剤を観察した
ときに大部分のハロゲン化銀粒子が同一形状に見
え、粒子サイズが揃つていて、かつ下記式で定義
される如き粒径分布を有するものである。即ち、
粒径の分布の標準偏差ｓを平均粒径で割つたと
き、その値が0.20以下のものをいい、好ましくは
0.15以下のものである。[Table] Silver amount (silver deposition amount) in the blue-sensitive silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention
is preferably 0.35g/ m2 to 0.15g/m2. In other words, in order to provide resistance to contamination with other treatment liquid components (so-called back contamination), the
On the other hand, if the amount of silver coating is small, it is difficult to achieve the maximum density, so 0.15 g/m 2 or more is preferable. The thickness of the blue-sensitive silver halide emulsion layer preferably used in the present invention is preferably 1.0 to 6.0 μm. big. However, if the film thickness of the blue-sensitive silver halide emulsion layer is
If it is 6.0 μm or more, it will be disadvantageous in terms of development speed. The silver halide used in the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion is preferred. In the present invention, the above-mentioned monodisperse silver halide grains mean that most of the silver halide grains appear to have the same shape when the emulsion is observed using an electron microscope, have uniform grain sizes, and have the following formula: It has a particle size distribution as defined by . That is,
When the standard deviation s of the particle size distribution is divided by the average particle size, the value is 0.20 or less, preferably
0.15 or less.
【化】
ｓ／ｒ≦0.20
ここでいう粒径とは、前記平均粒径について述
べた粒径と同義である。
本発明に好ましく用いられる単分散性のハロゲ
ン化銀粒子は、従来から知られている酸性法、中
性法またはアンモニア法等のいずれの調製法によ
り得られたものでもよい。
また例えば種粒子を酸性法でつくり、更に、成
長速度の速いアンモニア法により成長させ、所定
の大きさまで成長させる方法でもよい。ハロゲン
化銀粒子を成長させる場合に反応釜内のPH、pAg
等をコントロールし、例えば特開昭54−48521号
に記載されているようなハロゲン化銀粒子の成長
速度に見合つた量の銀イオンとハライドイオンを
逐次同時に注入混合することが好ましい。
本発明に係わるハロゲン化銀粒子の調製は以上
のようにして行われる。該ハロゲン化銀粒子を含
有する組成物を以下ハロゲン化銀乳剤という。
これらのハロゲン化銀乳剤は、活性ゼラチン；
硫黄増感剤例えばアリルチオカルバミド、チオ尿
素、シスチン等の硫黄増感剤；セレン増感剤；還
元増感剤例えば第１スズ塩、二酸化チオ尿素、ポ
リアミン等；貴金属増感剤例えば金増感剤剤、具
体的にはカリウムオーリチオシアネート、カリウ
ムクロロオーレート、２−オーロチオ−３−メチ
ルベンゾチアゾリウムクロライド等あるいは例え
ばルテニウム、パラジウム、白金、ロジウム、、
イリジウム等の水溶性塩の増感剤、具体的にはア
ンモニウムクロロパラデート、カリウムクロロプ
ラチネートおよびナトリウムクロロパラデート
（これらの或る種のものは量の大小によつて増感
剤あるいはかぶり抑制剤等として作用する。）等
により単独であるいは適宜併用（例えば金増感剤
と硫黄増感剤の併用、金増感剤とセレン増感剤と
の併用等）して化学的に増感されてもよい。
本発明に係わるハロゲン化銀乳剤は、含硫黄化
合物を添加して化学熟成し、この化学熟成する
前、熟成中、又は熟成後、少なくとも１種のヒド
ロキシテトラザインデンおよびメルカプト基を有
する含窒素ヘテロ還化合物の少なくとも一種を含
有せしめてもよい。
本発明に用いられるハロゲン化銀は、各々所望
の感光波長域に感光性を付与するために、適当な
増感色素をハロゲン化銀１モルに対して５×10-8
〜３×10-3モル添加して光学増感させてもよい。
増感色素としては種々のものを用いることがで
き、また各々増感色素を１種又は２種以上組合せ
て用いることができる。本発明において有利に使
用される増感色素としては例えば次の如きものを
挙げることができる。
即ち、青感性ハロゲン化銀乳剤層に用いられる
増感色素としては、例えば西独特許929080号、米
国特許2231658号、同2493748号、同2503776号、
同2519001号、同2912329号、同3656959号、同
3672897号、同3694217号、同4025349号、同
4046572号、英国特許1242588号、特公昭44−
14030号、同52−24844等に記載されたものを挙げ
ることができる。また緑感光性ハロゲン化銀乳剤
に用いられる増感色素としては、例えば米国特許
1939201号、同2072908号、同2739149号、同
2945763号、英国特許505979号等に記載されてい
る如きシアニン色素、メロシアニン色素または複
合シアニン色素をその代表的なものとして挙げる
ことができる。さらに、赤感光性ハロゲン化銀乳
剤に用いられる増感色素としては、例えば米国特
許2269234号、同2270378号、同2442710号、同
2454629号、同2776280号等に記載されている如き
シアニン色素、メロシアニン色素または複合シア
ニン色素をその代表的なものとして挙げることが
できる。更にまた米国特許2213995号、同2493748
号、同2519001号、西独特許929080号等に記載さ
れている如きシアニン色素、メロシアニン色素ま
たは複合シアニン色素を緑感光性ハロゲン化銀乳
剤または赤感光性ハロゲン化銀乳剤に有利に用い
ることができる。
これらの増感色素は単独で用いてもよく、また
これらを組合せて用いてもよい。増感色素の組合
せは得に強色増感の目的でしばしば用いられる。
その代表例は米国特許2688545号、同2977229号、
同3397060号、同3522052号、同3527641号、同
3617293号、同3628964号、同3666480号、同
3672898号、同3679428号、同3703377号、同
3769301号、同3814609号、同3837862号、同
4026707号、英国特許1344281号、同1507803号、
特公昭43−4936号、同53−12375号、特開昭52−
110618号、同52−109925号に記載されている。
本発明のハロゲン化銀カラー写真感光材料に
は、親水性コロイド層にフイルター染料として、
あるいはイラジエーシヨン防止その他種々の目的
で、水溶性染料を含有してもよい。このような染
料にはオキソノール染料、ヘミオキソノール染
料、メロシアニン染料及びアゾ染料が包含され
る。中でもオキソノール染料、ヘミオキソノール
染料及びメロシアニン染料が有用である。用い得
る染料の具体例は、英国特許584609号、同
1277429号、特開昭48−85130号、同49−99620号、
同49−114420号、同49−129537号、同52−108115
号、同59−25845号、米国特許2274782号、同
2533472号、同2956879号、同3125448号、同
3148187号、同3177078号、同3247127号、同
3540887号、同3575704号、同3653905号、同
3718472号、同4071312号、同4070352号に記載さ
れている。
本発明に係わる青感光性ハロゲン化銀乳剤には
前記高速反応性イエローカプラーが用いられる
が、他のイエローカプラーが併用されてもよい。
または緑感光性ハロゲン化銀乳剤層及び赤感光性
ハロゲン化銀乳剤層にはそれぞれマゼンタカプラ
ー及びシアンカプラー、即ち、発色現像主薬の酸
化体と反応してマゼンタ及びシアン色素を形成し
得る化合物を含有させることができる。
本発明においては、上記カプラーとして各種マ
ゼンタカプラーおよびシアンカプラーを用いるこ
とができる。これらのカプラーはいわゆる２当量
型であつてもよいし４当量型カプラーであつても
よく、またこれらのカプラーに組合せて、拡散性
色素放出型カプラー等を用いることも可能であ
る。
本発明の青感光性ハロゲン化銀乳剤に併用でき
るイエローカプラーとしては、閉鎖ケトメチレン
化合物さらにいわゆる２当量型カプラーと称され
る活性点−ｏ−アリール置換カプラー、活性点−
ｏ−アシル置換カプラー、活性点ヒダントイン化
合物置換カプラー、活性点ウラゾール化合物置換
カプラーおよび活性点コハク酸イミド化合物置換
カプラー、活性点フツ素置換カプラー、活性点塩
素あるいは臭素置換カプラー、活性点−ｏ−スル
ホニル置換カプラー等が有効なイエローカプラー
として用いることができる。併用し得るイエロー
カプラーの具体例としては、米国特許2875057号、
同3265506号、同3408194号、同3551155号、同
3582322号、同3725072号、同3891445号、西独特
許1547868号、西独出願公開2219917号、同
2261361号、同2414006号、英国特許1425020号、
特公昭51−10783号、特開昭47−26133号、同48−
73147号、同51−102636号、同50−6341号、同50
−123342号、同50−130442号、同51−21827号、
同50−87650号、同52−82424号、同52−115219
号、同58−95346号等に記載されたものを挙げる
ことができる。
前記マゼンタカプラーとしては、ピラゾロン
系、ピラゾロトリアゾール系、ピラゾリノベンツ
イミダゾール系、インダゾロン系の化合物を挙げ
ることができる。これらのマゼンタカプラーは４
当量型カプラーだけでなく、２当量型カプラーで
あつてもよい。マゼンタカプラーの具体例として
は米国特許2600788号、同2983608号、同3062653
号、同3127269号、同3311476号、同3419391号、
同3519429号、同3558319号、同3582322号、同
3615506号、同3834908号、同3891445号、西独特
許1810464号、西独特許出願（OLS）2408665号、
同2417945号、、同2418959号、同2424467号、特公
昭40−6031号、特開昭51−20826号、同52−58922
号、同49−129538号、同49−74027号、同50−
159336号、同52−42121号、同49−74028号、同50
−60233号、同51−26541号、同53−55122号、特
願昭55−110943号等に記載されたものを挙げるこ
とができる。
前記アシンカプラーとしては、例えばフエノー
ル系、ナフトール系カプラー等を挙げることがで
きる。そしてこれらのシアンカプラーは４当量型
カプラーだけでなく、２当量型カプラーであつて
もよい。シアンカプラーの具体例としては米国特
許2369929号、同2434272号、同2474293号、同
2521908号、同2895826号、同3034892号、同
3311476号、同3458315号、同3476563号、同
3583971号、同3591383号、同3767411号、同
4004929号、西独特許出願（OLS）2414830号、
同2454329号、特開昭48−59838号、同51−26034
号、同48−5055号、同51−146827号、同52−
69624号、同52−90932号、同58−95346号等に記
載のものを挙げることができる。
本発明の高速反応性イエローカプラーその他の
カプラーを本発明に係わる青感性ハロゲン化銀乳
剤その他のハロゲン化銀乳剤中に含有せしめるに
は、該カプラーがアルカリ可溶性である場合に
は、アルカリ性溶液として添加してもよく、油溶
性である場合には、例えば米国特許第2322027号、
同第2801170号、同第2801171号、同第2272191号
および同第2304940号各明細書に記載の方法に従
つてカプラーを高沸点溶媒に、必要に応じて低沸
点溶媒を併用して溶解し、微粒子状に分散してハ
ロゲン化銀乳剤に添加するのが好ましい。このと
き必要に応じて他のハイドロキノン誘導体、紫外
線吸収剤、褪色防止剤等を併用してもさしつかえ
ない。また２種以上のカプラーを混合して用いて
もさしつかえない。さらに本発明において好まし
いカプラーの添加方法を詳述するならば、１種ま
たは２種以上の該カプラーを必要に応じて他のカ
プラー、ハイドロキノン誘導体、褪色防止剤や紫
外線吸収剤等と共に有機酸アミド類、カルバメー
ト類、エステル類、ケトン類、尿素誘導体、エー
テル類、炭化水素類等、特にジ−ｎ−ブチルフタ
レート、トリークレジルホスフエート、トリフエ
ニルホスフエート、ジ−イソオクチルアゼレー
ト、ジ−ｎ−ブチルセバケート、トリ−ｎ−ヘキ
シルホスフエート、Ｎ，Ｎ−ジ−エチル−カプリ
ルアミドブチル、Ｎ，Ｎ−ジエチルラウリルアミ
ド、ｎ−ペンタデシルフエニルエーテル、ジ−オ
クチルフタレート、ｎ−ノニルフエノール、３−
ペンタデシルフエニルエチルエーテル、２，５−
ジ−sec−アミルフエニルブチルエーテル、モノ
フエニル−ジ−ｏ−クロロフエニルホスフエート
あるいはフツ素パラフイン等の高沸点溶媒、およ
び／または酢酸メチル、酢酸エチル、酢酸プロピ
ル、酢酸ブチル、プロピオン酸ブチル、シクロヘ
キサノール、ジエチレングリコールモノアセテー
ト、ニトロメタン、四塩化炭素、クロロホルム、
シクロヘキサンテトラヒドロフラン、メチルアル
コール、アセトニトリル、ジメチルホルムアミ
ド、ジオキサン、メチルエチルケトン等の低沸点
溶媒に溶解し、アルキルベンゼンスルホン酸およ
びアルキルナフタレンスルホン酸の如きアニオン
系界面活性剤および／またはソルビタンセスキオ
レイン酸エステルおよびソルビタンモノラウリル
酸エステルの如きノニオン系界面活性剤および／
またはゼラチン等の親水性バインダーを含む水溶
液と混合し、高速回転ミキサー、コロイドミルま
たは超音波分散装置等で乳化分散し、ハロゲン化
銀乳剤に添加される。
この他、上記カプラーはラテツクス分散法を用
いて分散してもよい。ラテツクス分散法およびそ
の効果は、特開昭49−74538号、同51−59943号、
同54−32552号各公報やリサーチ・デイスクロー
ジヤー1976年８月、No.14850、77〜79頁に記載さ
れている。
適当なラテツクスは、例えばスチレン、アクリ
レート、ｎ−ブチルアクリレート、ｎ−ブチルメ
タクリレート、２−アセトアセトキシエチルメタ
クリレート、２−（メタクリロイルオキシ）エチ
ルトリメチルアンモニウムメトサルフエート、３
−（メタクリロイルオキシ）プロパン−１−スル
ホン酸ナトリウム塩、Ｎ−イソプロピルアクリル
アミド、Ｎ−〔２−（２−メチル−４−オキソペン
チル）〕アクリルアミド、２−アクリルアミド−
２−メチルプロパンスルホン酸等のようなモノマ
ーのホモポリマー、コポリマーおよびターポリマ
ーである。
本発明のクエンチヤーの添加方法については、
前記カプラーの添加方法を参照すればよい。
本発明のハロゲン化銀カラー写真感光材料には
他に各種の写真用添加剤を含有せしめることがで
きる、例えばリサーチ・デイスクロージヤー誌
17643号に記載されているカブリ防止剤、安定剤、
紫外線吸収剤、色汚染防止剤、蛍光増白剤、色画
像褪色防止剤、帯電防止剤、硬膜剤、界面活性
剤、可塑剤、湿潤剤等を用いることができる。本
発明のハロゲン化銀カラー写真感光材料におい
て、乳剤を調製するために用いられる親水性コロ
イドには、ゼラチン、誘導体ゼラチン、ゼラチン
と他の高分子とのグラフトポリマー、アルブミ
ン、カゼイン等の蛋白質、ヒドロキシエチルセル
ロース誘導体、カルボキシメチルセルロース等の
セルロール誘導体、澱粉誘導体、ポリビニルアル
コール、ポリビニルイミダゾール、ポリアクリル
アミド等の単一あるいは共重合体の合成親水性高
分子等の任意のものが包含される。
本発明のハロゲン化銀カラー写真感光材料の反
射支持体としては、例えばバライタ紙、ポリエチ
レン被覆紙、ポリプロピレン合成紙、反射層を併
設した、又は反射体を併用する透明支持体、例え
ばガラス板、セルロースアセテート、セルロース
ナイトレート又はポリエチレンテレフタレート等
のポリエステルフイルム、ポリアミドフイルム、
ポリカーボネートフイルム、ポリスチレンフイル
ム等があり、これらの反射支持体は感光材料の使
用目的に応じて適宜選択される。
本発明において用いられる乳剤層及びその他の
構成層の塗設には、デイツピング塗布、エアード
クター塗布、カーテン塗布、ホツパー塗布等種々
の塗布方法を用いることができる。また米国特許
2761791号、同2941898号に記載の方法による２層
以上の同時塗布法を用いることもできる。
本発明においては、支持体側から順次青感性ハ
ロゲン化銀乳剤層、緑感性ハロゲン化銀乳剤層、
赤感性ハロゲン化銀乳剤層の配列とする。
本発明の感光材料において、本発明の中間層の
他に、目的に応じて適当な厚さの非感光性親水性
コロイド層を設けることは任意であり、フイルタ
ー層、カール防止層、保護層、アンチハレーシヨ
ン層等の種々の構成層として適宜組合せて用いる
ことができる。これらの構成層には結合剤として
前記のような乳剤層に用いることのできる親水性
コロイドを同様に用いることができ、またその層
中には前記の如き乳剤層中に含有せしめることが
できる種々の写真用添加剤を含有せしめることが
できる。本発明の中間層がフイルター層やアンチ
ハレーシヨン層等を兼ねてもよい。
本発明に係わるハロゲン化銀乳剤を用いた写真
感光材料の処理方法については特に制限はなく、
あらゆる処理方法が適用できる。例えば、その代
表的なものとしては、発色現像後、漂白定着処理
を行い必要ならさらに水洗および／または安定処
理を行う方法、発色現像後、漂白と定着を分離し
て行い、必要に応じさらに水洗および／または安
定処理を行う方法；あるいは前硬膜、中和、発色
現像、停止定着、水洗、漂白、定着、水洗、後硬
膜、水洗の順で行う方法、発色現像、水洗、補足
発色現像、停止、漂白、定着、水洗、安定の順で
行う方法、発色現像によつて生じた現像銀をハロ
ゲネーシヨンブリーチをしたのち、再度発色現像
をして生成色素量を増加させる現像方法等、いず
れの方法を用いて処理してもよい。
本発明のハロゲン化銀乳剤の処理に用いられる
発色現像液は、発色現像主薬を含むPHが好ましく
は８以上、更に好ましくはPHが９〜12のアルカリ
性水溶液である。この発色現像主薬としての芳香
族第１級アミン現像主薬は、芳香族環上に第１級
アミノ基を持ち露光されたハロゲン化銀を現像す
る能力のある化合物であり、さらに必要に応じて
このような化合物を形成する前駆体を添加しても
よい。
上記発色現像主薬としてはｐ−フエニレンジア
ミン系のものが代表的であり、次のものが好まし
い例として挙げられる。
４−アミノ−Ｎ，Ｎ−ジエチルアニリン、３−
メチル−４−アミノ−Ｎ，Ｎ−ジエチルアニリ
ン、４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキ
シエチルアニリン、３−メチル−４−アミノ−Ｎ
−β−ヒドロキシエチルアニリン、３−メチル−
４−アミノ−Ｎ−エチル−Ｎ−β−メトキシエチ
ルアニリン、３−メチル−４−アミノ−Ｎ−メチ
ル−Ｎ−β−メタンスルホンアミドエチルアニリ
ン、３−メトキシ−４−アミノ−Ｎ−エチル−Ｎ
−β−ヒドロキシエチルアニリン、３−メトキシ
−４−アミノ−Ｎ−エチル−Ｎ−β−メトキシエ
チルアニリン、３−アセトアミド−４−アミノ−
Ｎ，Ｎ−ジメチルアニリン、Ｎ−エチル−Ｎ−β
−〔β−（β−メトキシエトキシ）エトキシ〕エチ
ル−３−メチル−４−アミノアニリン、Ｎ−エチ
ル−Ｎ−β−（β−メトキシエトキシ）エチル−
３−メチル−４−アミノアニリンや、これらの塩
例えば硫酸塩、塩酸塩、亜硫酸塩、ｐ−トルエン
スルホン酸塩等である。
さらに、例えば特開昭48−64932号、同50−
131526号、同51−95849号およびベント等のジヤ
ーナル・オブ・ジ・アメリカン・ケミカル・ソサ
エテイー、73巻、3100〜3125頁（1951年）記載の
ものも代表的なものとして挙げられる。
これらの芳香族第１級アミノ化合物の使用量
は、現像液の活性度をどこに設定するかできまる
が、活性度を上げるためには使用量を増加してや
るのが好ましい。使用量としては0.0002モル／
から0.7モル／までの範囲で用いられる。また
目的によつて２つ以上の化合物を適宜組合せて使
用することができる。例えば３−メチル−４−ア
ミノ−Ｎ，Ｎ−ジエチルアニリンと３−メチル−
４−アミノ−Ｎ−エチル−Ｎ−β−メタンスルホ
ンアミドエチルアニリン、３−メチル−４−アミ
ノ−Ｎ−エチル−Ｎ−β−メタンスルホンアミド
エチルアニリンと３−メチル−４−アミノ−Ｎ−
エチル−Ｎ−β−ヒドロキシエチルアニリン等の
組合せ等目的に応じて自由に組合せ使用し得る。
本発明において用いられる発色現像液には、更
に通常添加されている種々の成分、例えば水酸化
ナトリウム、炭酸ナトリウム等のアルカリ剤、ア
ルカリ金属亜硫酸塩、アルカリ金属亜硫酸水素
塩、アルカリ金属チオシアン酸塩、アルカリ金属
ハロゲン化物、ベンジルアルコール、水軟化剤、
濃厚化剤および現像促進剤等を任意に含有させる
こともできる。
上記発色現像液に添加される上記以外の添加剤
としては、例えば臭化カリウム、臭化アンモニウ
ム等の臭化物、沃化アルカリ、ニトロベンゾイミ
ダゾール、メルカブトベンゾイミダゾール、５−
メチル−ベンゾトリアゾール、１−フエニル−５
−メルカプトテトラゾール等の迅速処理液用化合
物を始めとして、ステイン防止剤、スラツジ防止
剤、保恒剤、重層効果促進剤、キレート剤等があ
る。
漂白工程の漂白液もしくは漂白定着液に用いら
れる漂白剤としては、アミノポリカルボン酸また
は蓚酸、クエン酸等の有機酸で鉄、コバルト、銅
等の金属イオンを配位したものが一般に知られて
いる。そして上記のアミノポリカルボン酸の代表
的な例としては次のものを挙げることができる。
エチレンジアミンテトラ酢酸
ジエチレントリアミンペンタ酢酸
プロピレンジアミンテトラ酢酸
ニトリロトリ酢酸
イミノジ酢酸
エチルエーテルジアミンテトラ酢酸
エチレンジアミンテトラプロピオン酸
エチレンジアミンテトラ酢酸ジナトリウム塩
ジエチレントリアミンペンタ酢酸ペンタナトリ
ウム塩
ニトリロトリ酢酸ナトリウム塩
漂白液は上記の漂白剤と共に種々の添加剤を含
有してもよい。また漂白工程に漂白定着液を用い
る場合には、前記漂白剤のほかにハロゲン化銀定
着剤を含有する組成の液が適用される。また漂白
定着液には更に例えば臭化カリウムの如きハロゲ
ン化合物を含有させてもよい。そして前記の漂白
液の場合と同様に、その他の各種の添加剤、例え
ばPH緩衝剤、蛍光増白剤、消泡剤、界面活性剤、
保恒剤、キレート剤、安定剤、有機溶媒等を添
加、含有させてもよい。
なおハロゲン化銀定着剤としては、例えばチオ
硫酸ナトリウム、チオ硫酸アンモニウム、チオシ
アン酸カリウム、チオシアン酸ナトリウム、また
はチオ尿素、チオエーテル等の通常の定着処理に
用いられるようなハロゲン化銀と反応して水溶性
の銀塩を形成する化合物を挙げることができる。
本発明のハロゲン化銀カラー写真感光材料の発色
現像、漂白定着（又は漂白、定着）、更に必要に
応じて行われる水洗、安定化、乾燥等の各種処理
工程の処理温度は迅速処理の見地から30℃以上で
行われるのが好ましい。
本発明のハロゲン化銀カラー写真感光材料は特
開昭58−14834号、同58−105145号、同58−
134634号及び同58−18631号並びに特願昭58−
2709号及び同59−89288号等に示されるような水
洗代替安定化処理を行つてもよい。
［発明の効果］
本発明によれば、他の処理液の混入（バツクコ
ンタミネーシヨン）耐性が非常に改良される。本
発明により改良される理由として本発明者は次の
ように考えている。
漂白定着成分の混入による写真性能の変化、特
に肩ガンマーの硬調化は、漂白定着成分の混入が
ない現像液において、現像主薬の酸化体により漂
白を受け現像されないハロゲン化銀が、漂白定着
成分の混入がある現像液において現像が開始され
ることに起因する。
漂白定着成分の混入がない現像液において、漂
白を受けるハロゲン化銀の割合は、各感光性乳剤
層中における現像主薬の酸化体濃度により決定さ
れる。即ち、現像主薬の酸化体の濃度が高いほど
漂白を受け現像されないハロゲン化銀の割合は高
い。
一方、感光性乳剤層中における現像主薬の酸化
体の濃度は、各感光性乳剤層間で相互に影響を及
ぼしており、本発明の高速イエローカプラーおよ
び高速反応性クエンチヤーを用いることにより青
感性ハロゲン化銀乳剤層中の現像主薬の酸化体の
濃度だけでなく緑感性ハロゲン化銀乳剤層及び赤
感性ハロゲン化銀乳剤層中の現像主薬の酸化体濃
度も低くなつていると考えられる。
よつて漂白定着成分の混入がない現像液におい
て、漂白を受けるハロゲン化銀の割合が少ないた
めに、漂白定着成分の混入が起こつても現像を開
始するハロゲン化銀の割合は漂白定着成分の混入
がない現像液の場合と同じであり、写真性能が一
定に維持されると考えられる。
［実施例］
以下に本発明の具体的実施例を述べるが、本発
明の実施の態様はこれらに限定されない。
実施例 １
ポリエチレンをラミネートした紙支持体上に、
下記の各層を支持体側より順次塗設し、ハロゲン
化銀カラー写真感光材料試料No.１〜６を作成し
た。
層１………1.6g／m2のゼラチン、0.32g／m2
（銀換算、以下同じ）の青感性塩臭化銀乳剤（90
モル％の臭化銀含有並びに平均粒径は0.5μm）、
0.50g／m2のジオクチルフタレートに溶解した
0.80g／m2の前記高速反応性イエローカプラー
（Ｙ−６）を含有する層。
層２………0.7g／m2のゼラチン及び0.1g／m2の
ジオクチルフタレートに溶解した0.4g／m2の高速
反応性クエンチヤー（Ｑ−６）からなる中間層。
層３………1.25g／m2のゼラチン、0.22g／m2の
緑感性塩臭化銀乳剤（70モル％の臭化銀含有並び
に平均粒径は0.35μm）、0.30g／m2のジオクチル
フタレートに溶解した0.62g／m2の下記マゼンタ
カプラー（Ｍ−１）を含有する層。
層４………1.2g／m2のゼラチンからなる中間
層。
層５………1.4g／m2のゼラチン、0.20g／m2の
赤感性塩臭化銀乳剤（70モル％の臭化銀含有並び
に平均粒径は0.35μm）、0.20g／m2のジオクチル
フタレートに溶解した0.45g／m2の下記シアンカ
プラー（Ｃ−１）を含有する層。
層６………1.0g／m2のゼラチン及び0.20g／m2
のジオクチルフタレートに溶解した0.30g／m2の
下記紫外線吸収剤UV−１を含有する層。
層７………0.5g／m2のゼラチンを含有する層。
試料No.１の高速反応性イエローカプラー（Ｙ−
６）及び高速反応性クエンチヤー（Ｑ−６）に代
えて下記表１に示す化合物を用いて、試料No.２〜
６を作成した。[Chemical formula] s/r≦0.20 The particle size here has the same meaning as the particle size described above regarding the average particle size. The monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. PH and pAg in the reaction vessel when growing silver halide grains
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A No. 54-48521. The silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is hereinafter referred to as a silver halide emulsion. These silver halide emulsions contain activated gelatin;
Sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers. Agents, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or such as ruthenium, palladium, platinum, rhodium, etc.
Sensitizers of water-soluble salts such as iridium, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these can be used as sensitizers or fog suppressors depending on the amount) chemically sensitized by using sensitizers alone or in appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). It's okay. The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, the silver halide emulsion contains at least one hydroxytetrazaindene and a nitrogen-containing heterozygous compound having a mercapto group. It may contain at least one kind of reducing compound. The silver halide used in the present invention contains an appropriate sensitizing dye at a rate of 5 x 10 -8 per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be achieved by adding up to 3×10 −3 mol.
Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929080, US Patent No. 2231658, US Patent No. 2493748, US Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example,
No. 1939201, No. 2072908, No. 2739149, No.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, US Patent No. 2213995, US Patent No. 2493748
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. In the silver halide color photographic light-sensitive material of the present invention, a filter dye is added to the hydrophilic colloid layer.
Alternatively, a water-soluble dye may be contained for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609;
No. 1277429, Japanese Patent Publication No. 48-85130, No. 49-99620,
No. 49-114420, No. 49-129537, No. 52-108115
No. 59-25845, U.S. Patent No. 2274782, Id.
No. 2533472, No. 2956879, No. 3125448, No.
No. 3148187, No. 3177078, No. 3247127, No. 3148187, No. 3177078, No. 3247127, No.
No. 3540887, No. 3575704, No. 3653905, No. 3540887, No. 3575704, No. 3653905, No.
It is described in No. 3718472, No. 4071312, and No. 4070352. Although the above-mentioned fast-reactive yellow coupler is used in the blue-sensitive silver halide emulsion according to the present invention, other yellow couplers may also be used in combination.
Alternatively, the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer each contain a magenta coupler and a cyan coupler, that is, compounds that can react with the oxidized product of a color developing agent to form magenta and cyan dyes. can be done. In the present invention, various magenta couplers and cyan couplers can be used as the couplers. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers. Yellow couplers that can be used in combination with the blue-sensitive silver halide emulsion of the present invention include closed ketomethylene compounds, active point -o-aryl substituted couplers called so-called 2-equivalent type couplers, and active point -
o-acyl substituted couplers, active point hydantoin compound substituted couplers, active point urazole compound substituted couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -o-sulfonyl Substitution couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used in combination include U.S. Patent No. 2875057;
Same No. 3265506, No. 3408194, No. 3551155, Same No.
No. 3582322, No. 3725072, No. 3891445, West German Patent No. 1547868, West German Patent Application No. 2219917,
No. 2261361, No. 2414006, British Patent No. 1425020,
Special Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 48-
No. 73147, No. 51-102636, No. 50-6341, No. 50
−123342, No. 50-130442, No. 51-21827,
No. 50-87650, No. 52-82424, No. 52-115219
No. 58-95346. Examples of the magenta coupler include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers are 4
Not only an equivalent type coupler but also a two-equivalent type coupler may be used. Specific examples of magenta couplers include U.S. Patent No. 2600788, U.S. Patent No. 2983608, and U.S. Patent No. 3062653.
No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, No. 3558319, No. 3582322, Same No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1977, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
Examples include those described in No. 60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983. Examples of the acine couplers include phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent couplers but also 2-equivalent couplers. Specific examples of cyan couplers include U.S. Patent Nos. 2369929, 2434272, 2474293, and
No. 2521908, No. 2895826, No. 3034892, No. 2521908, No. 2895826, No. 3034892, No.
No. 3311476, No. 3458315, No. 3476563, No.
No. 3583971, No. 3591383, No. 3767411, No.
No. 4004929, West German Patent Application (OLS) No. 2414830,
JP-A No. 2454329, JP-A-48-59838, JP-A No. 51-26034
No. 48-5055, No. 51-146827, No. 52-
Examples include those described in No. 69624, No. 52-90932, No. 58-95346, and the like. In order to incorporate the fast-reacting yellow coupler of the present invention and other couplers into the blue-sensitive silver halide emulsion and other silver halide emulsions of the present invention, when the couplers are alkali-soluble, they are added as an alkaline solution. If it is oil-soluble, for example, US Pat. No. 2,322,027,
Dissolving the coupler in a high boiling point solvent and, if necessary, using a low boiling point solvent in accordance with the method described in the specifications of the same No. 2801170, the same No. 2801171, the same No. 2272191 and the same No. 2304940, It is preferable to disperse it in the form of fine particles and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. It is also possible to use a mixture of two or more couplers. Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to an organic acid amide along with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. , carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n- -butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3 −
Pentadecyl phenylethyl ether, 2,5-
High-boiling solvents such as di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate or fluorine paraffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol , diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform,
Dissolved in a low boiling point solvent such as cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate and sorbitan monolauryl. Nonionic surfactants such as acid esters and/or
Alternatively, it is mixed with an aqueous solution containing a hydrophilic binder such as gelatin, emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc., and then added to a silver halide emulsion. Alternatively, the above couplers may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538 and JP-A-51-59943.
54-32552 and Research Disclosure, August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3
-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like. Regarding the method of adding the quencher of the present invention,
Please refer to the above method for adding couplers. The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as those published in Research Disclosure Magazine.
Antifoggants, stabilizers, as described in No. 17643;
Ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Any of cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included. Examples of the reflective support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports provided with a reflective layer or combined with a reflective material, such as glass plates, cellulose Polyester films such as acetate, cellulose nitrate or polyethylene terephthalate, polyamide films,
Examples include polycarbonate film and polystyrene film, and these reflective supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also US patent
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2761791 and No. 2941898. In the present invention, from the support side, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer,
Arrangement of red-sensitive silver halide emulsion layers. In the photosensitive material of the present invention, in addition to the intermediate layer of the present invention, it is optional to provide a non-photosensitive hydrophilic colloid layer with an appropriate thickness depending on the purpose, such as a filter layer, an anti-curl layer, a protective layer, They can be used in appropriate combinations as various constituent layers such as antihalation layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included. The intermediate layer of the present invention may also serve as a filter layer, an antihalation layer, etc. There are no particular restrictions on the method of processing photographic materials using the silver halide emulsion according to the present invention.
Any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are carried out separately after color development, followed by further washing with water if necessary. and/or a method of stabilizing; or a method of prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, supplementary color development , a method in which stopping, bleaching, fixing, washing, and stabilizing are performed in this order; a developing method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of produced dye, etc. The treatment may be performed using any method. The color developing solution used for processing the silver halide emulsion of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added. The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples. 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-β-hydroxyethylaniline, 3-methyl-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-methyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl- N
-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-
N,N-dimethylaniline, N-ethyl-N-β
-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-
These include 3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like. Furthermore, for example, JP-A-48-64932, JP-A No. 50-
No. 131526, No. 51-95849, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples. The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used is 0.0002 mol/
It is used in the range from 0.7 mol/ to 0.7 mol/. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-
4-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-
Combinations such as ethyl-N-β-hydroxyethylaniline can be freely used depending on the purpose. The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, Alkali metal halides, benzyl alcohol, water softeners,
A thickening agent, a development accelerator, etc. can also be optionally included. Examples of additives other than those mentioned above that are added to the color developing solution include bromides such as potassium bromide and ammonium bromide, alkali iodide, nitrobenzimidazole, mercabutobenzimidazole, 5-
Methyl-benzotriazole, 1-phenyl-5
- Compounds for rapid processing solutions such as mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, etc. Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following. Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium salt Bleaching solution can be used with various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. And, as in the case of the bleaching solution mentioned above, various other additives such as PH buffers, optical brighteners, antifoaming agents, surfactants,
Preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained. The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.
The processing temperatures for various processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water, stabilization, drying, etc. performed as necessary for the silver halide color photographic light-sensitive material of the present invention are determined from the viewpoint of rapid processing. Preferably, it is carried out at a temperature of 30°C or higher. The silver halide color photographic material of the present invention is disclosed in JP-A-58-14834, JP-A-58-105145, and JP-A-58-58-1.
No. 134634 and No. 58-18631 and patent application No. 1983-
Stabilization treatment as an alternative to washing may be performed as shown in No. 2709 and No. 59-89288. [Effects of the Invention] According to the present invention, resistance to contamination with other processing liquids (back contamination) is greatly improved. The present inventor believes that the reason for the improvement achieved by the present invention is as follows. Changes in photographic performance due to the contamination of bleach-fixing components, especially the sharpening of shoulder gamma, are caused by the fact that in a developing solution that does not contain bleach-fixing components, the silver halide that is not developed after being bleached by the oxidized form of the developing agent is caused by the incorporation of bleach-fixing components. This is due to the fact that development is started in a developer with contamination. In a developer solution free of bleach-fix components, the proportion of silver halide that undergoes bleaching is determined by the concentration of the oxidized form of the developing agent in each light-sensitive emulsion layer. That is, the higher the concentration of the oxidized form of the developing agent, the higher the proportion of silver halide that is bleached and not developed. On the other hand, the concentration of the oxidized developing agent in the light-sensitive emulsion layer affects each other between the light-sensitive emulsion layers. It is considered that not only the concentration of the oxidized developing agent in the silver emulsion layer but also the concentration of the oxidized developing agent in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is lowered. Therefore, in a developing solution that is not contaminated with bleach-fixing components, the proportion of silver halide that undergoes bleaching is small, so even if bleach-fixing components are mixed in, the proportion of silver halide that starts development will be lower than that of the bleach-fixing components. It is considered that the photographic performance is maintained constant. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare silver halide color photographic light-sensitive material samples Nos. 1 to 6. Layer 1...1.6g/ m2 gelatin, 0.32g/ m2
Blue-sensitive silver chlorobromide emulsion (90
mol% silver bromide content and average grain size 0.5 μm),
Dissolved in 0.50g/ m2 dioctyl phthalate
A layer containing 0.80 g/m 2 of the fast-reacting yellow coupler (Y-6). Layer 2: Intermediate layer consisting of 0.4 g/m 2 of a fast-reacting quencher (Q-6) dissolved in 0.7 g/m 2 of gelatin and 0.1 g/m 2 of dioctyl phthalate. Layer 3: 1.25 g/m 2 of gelatin, 0.22 g/m 2 of green-sensitive silver chlorobromide emulsion (containing 70 mol% silver bromide and having an average grain size of 0.35 μm), 0.30 g/m 2 A layer containing 0.62 g/m 2 of the following magenta coupler (M-1) dissolved in dioctyl phthalate. Layer 4: Intermediate layer consisting of 1.2 g/m 2 of gelatin. Layer 5...1.4 g/ m2 gelatin, 0.20 g/ m2 red-sensitive silver chlorobromide emulsion (70 mol% silver bromide content and average grain size 0.35 μm), 0.20 g/ m2 A layer containing 0.45 g/m 2 of the following cyan coupler (C-1) dissolved in dioctyl phthalate. Layer 6...1.0g/ m2 gelatin and 0.20g/ m2
A layer containing 0.30 g/m 2 of the ultraviolet absorber UV-1 below dissolved in dioctyl phthalate. Layer 7: Layer containing 0.5 g/m 2 of gelatin. Sample No. 1 fast-reactive yellow coupler (Y-
6) and the fast-reactive quencher (Q-6) using the compounds shown in Table 1 below, samples No. 2 to
6 was created.
【表】【table】
【表】
なお、硬膜剤として、２，４−ジクロロ−６−
ヒドロキシ−Ｓ−トリアジンナトリウムを層２、
４及び７中に、それぞれゼラチン1g当り0.017gに
なるように添加した。
上記感光材料試料No.１〜６各々を光学ウエツジ
を通して露光後、下記現像処理工程に従つて処理
した。
現像処理工程（38℃）
発色現像 ３分30秒
漂白定着 １分
水 洗 １分
乾 燥 60〜80℃ ２分
各処理液の組成は下記の通りである。
［発色現像液］
純 水 800ml
ベンジルアルコール 15ml
硫酸ヒドロキシアミン 2.0g
臭化カリウム 1.5g
塩化ナトリウム 1.0g
亜硫酸カリウム 2.0g
トリエタノールアミン 2.0g
Ｎ−エチル−Ｎ−β−メタンスルホンアミド
エチル−３−メチル−４−アミノアニリン硫
酸塩 4.5g
１−ヒドロキシエチリデン−１，１−ジホス
ホン酸（60％水溶液） 1.5ml
炭酸カリウム 32g
whitex BB（50％水溶液） ２ml
（蛍光増白剤住友化学工業社製）
純水を加えて１とし20％水酸化カリウム又は
10％希硫酸でPH＝10.1に調整する。
該発色現像液１に０ml、0.2ml、0.4ml、0.6ml
の下記漂白定着液を加えて用いる。
［漂白定着液］
純 水 550ml
エチレンジアミン四酢酸鉄（）
アンモニウム 65g
チオ硫酸アンモニウム 85g
亜硫酸水素ナトリウム 10g
メタ重亜硫酸ナトリウム 2g
エチレンジアミン四酢酸−２ナトリウム 20g
臭化ナトリウム 10g
純水を加えて１とし、アンモニア水又は希硫
酸にてPH＝7.0に調整する。
下記に基き漂白定着成分のバツクコンタミネー
シヨンのによる写真性能の変動の評価を行つた。
即ち、漂白定着液を発色現像液１に対して０
ml、0.2ml、0.4ml、0.6ml加えたときのガンマーの
変動巾で評価を行つた。ガンマーの変動巾の結果
を表２に示す。ここで△γ＝（γの最大値）−（γ
の最小値）である。[Table] As a hardening agent, 2,4-dichloro-6-
layer 2 of sodium hydroxy-S-triazine;
4 and 7 in an amount of 0.017g per 1g of gelatin, respectively. Each of the photosensitive material samples Nos. 1 to 6 was exposed through an optical wedge and then processed according to the following development process. Development process (38°C) Color development 3 minutes 30 seconds Bleach fixing 1 minute Washing 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows. [Color developer] Pure water 800ml Benzyl alcohol 15ml Hydroxyamine sulfate 2.0g Potassium bromide 1.5g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-Aminoaniline sulfate 4.5g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5ml Potassium carbonate 32g whitex BB (50% aqueous solution) 2ml (Fluorescent brightener manufactured by Sumitomo Chemical Co., Ltd.) Pure Add water to 1 and make 20% potassium hydroxide or
Adjust the pH to 10.1 with 10% dilute sulfuric acid. 0ml, 0.2ml, 0.4ml, 0.6ml to the color developer 1
Add the following bleach-fix solution and use. [Bleach-fix solution] Pure water 550ml Iron ethylenediaminetetraacetate () Ammonium 65g Ammonium thiosulfate 85g Sodium hydrogen sulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetic acid 20g Sodium bromide 10g Add pure water to make 1, and add ammonia water or Adjust the pH to 7.0 with dilute sulfuric acid. The variation in photographic performance due to back contamination of bleach-fixing components was evaluated based on the following.
That is, the ratio of bleach-fix solution to 1 part color developer is 0.
Evaluation was made based on the range of gamma variation when adding ml, 0.2ml, 0.4ml, and 0.6ml. Table 2 shows the results of the gamma variation range. Here, △γ = (maximum value of γ) - (γ
).
【表】
Ｒ：青感性ハロゲン化銀乳剤層
Ｏ：緑感性ハロゲン化銀乳剤層
Ｐ：赤感性ハロゲン化銀乳剤層
上記結果より、本発明の試料は漂白定着成成分
のバツクコンタミネーシヨンがおこつてもガンマ
ーの変動巾が小さく、写真性能が一定に維持され
ていることがわかる。即ち、高速イエローカプラ
ーのみを用いた試料No.２および試料No.４は、、ど
ちらも用いない試料No.３と比較するとガンマーの
変動巾は小さいものの、その改良巾は小さい。一
方、高速イエローカプラーおよび高速反応性クエ
ンチヤーを用いた本発明の試料No.１、５、６は青
感性ハロゲン化銀乳剤層のみならず、、緑感性ハ
ロゲン化銀乳剤層及び赤感性ハロゲン化銀乳剤層
のガンマーの変動巾が大巾に改良されていること
がわかる。
実施例 ２
実施例１の試料No.１において層１及び層２のみ
を下記のように代えて試料No.７を作成した。
層１………1.6g／m2のゼラチン、0.32g／m2
（銀換算、以下同じ）の青感性塩臭化乳剤（90モ
ル％の臭化銀含有並びに平均粒径は0.5μm）、
0.50g／m2のジオクチルフタレートに溶解した
0.80g／m2の前記高速反応性イエローカプラー
（Ｙ−６）及び50mg／m2の前記高速反応性クエン
チヤー（Ｑ−12）を含有する層。
層２………0.7g／m2のゼラチン及び0.1g／m2の
ジオクチルフタレートに溶解した50mg／m2の（Ｑ
−Ａ）からなる中間層。
上記試料No.７において、層２の（Ｑ−Ａ）を本
発明の高速反応性クエンチヤー（Ｑ−６）に代え
たことのみ異ならせて試料No.８を作成した。
実施例１の試料No.１並びに上記試料No.７及び試
料No.８を実施例１と同じく露光後、現像処理し
て、漂白定着液成分のバツクコンタミネーシヨン
による写真性能の評価を行つた。また、漂白定着
液を加えない発色現像液で処理した場合のDm
（最大濃度）を測定し、表３に示した。[Table] R: Blue-sensitive silver halide emulsion layer O: Green-sensitive silver halide emulsion layer P: Red-sensitive silver halide emulsion layer From the above results, the samples of the present invention are free from back contamination of bleach-fixing components. It can be seen that the range of variation in gamma is small, and photographic performance is maintained constant. That is, Sample No. 2 and Sample No. 4 using only the high-speed yellow coupler have a smaller range of variation in gamma than Sample No. 3 using neither, but the range of improvement is small. On the other hand, samples Nos. 1, 5, and 6 of the present invention using a high-speed yellow coupler and a fast-reactive quencher have not only a blue-sensitive silver halide emulsion layer, but also a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. It can be seen that the gamma variation width of the emulsion layer has been greatly improved. Example 2 Sample No. 7 was prepared by replacing only layer 1 and layer 2 of sample No. 1 of Example 1 as shown below. Layer 1...1.6g/ m2 gelatin, 0.32g/ m2
Blue-sensitive chlorobromide emulsion (contains 90 mol% silver bromide and has an average grain size of 0.5 μm) (in terms of silver, the same applies hereinafter),
Dissolved in 0.50g/ m2 dioctyl phthalate
A layer containing 0.80 g/m 2 of the fast-reacting yellow coupler (Y-6) and 50 mg/m 2 of the fast-reacting quencher (Q-12). Layer 2: 50 mg / m 2 ( Q
- an intermediate layer consisting of A); Sample No. 8 was prepared with the only difference from Sample No. 7 above that (Q-A) in layer 2 was replaced with the fast-reacting quencher (Q-6) of the present invention. Sample No. 1 of Example 1, Sample No. 7, and Sample No. 8 were exposed and developed in the same manner as in Example 1, and the photographic performance was evaluated based on back contamination of the bleach-fixing solution components. . In addition, Dm when processed with a color developing solution without adding bleach-fix solution.
(maximum concentration) was measured and shown in Table 3.
【表】
試料No.１、試料No.７、試料No.８を比較するとガ
ンマーの変動巾は試料No.８が若干改良されている
ものの、試料No.１、試料No.７、試料No.８でほとん
ど変らず、層２の中間層のみに該高速反応性クエ
ンチヤーを含有せしめた試料（No.１）、青感性ハ
ロゲン化銀乳剤層にのみ該高速反応性クエンチヤ
ーを含有せしめた試料（No.７）および層２の中間
層および青感性ハロゲン化銀乳剤層の両方に含有
せしめた試料（No.８）のいずれの試料でも、漂白
定着液成分のバツクコンタミネーシヨンによる写
真性能変動が改良されていることがわかる。
しかしながら、青感性ハロゲン化銀乳剤層の
Dmについては青感性ハロゲン化銀剤層に高速反
応性クエンチヤーを含有せしめた試料No.７、試料
No.８において若干の低下があり、高速反応性クエ
ンチヤーを中間層に含有せしめる方がこの点で若
干有利であることがわかる。
比較例
特開昭60−60647号公報実施例１の試料Ｇにつ
いて、第１層のBL−２のハイドロキノン誘導体
HQ−１を同量の29頁記載のHQ−11に換えた以
外は前記試料Ｇと同様にして比較試料１を作成し
た。また、同じく試料について、第１層のBL
−５のハイドロキノン誘導体HQ−１を同量の29
頁記載のHQ−11に換えた以外は前記試料と同
様にして比較試料２を作成した。
得られた試料について本発明の実施例１と同様
の評価を行いγ（ガンマー）の変動幅を求めた。
結果を表４に示す。[Table] Comparing Sample No. 1, Sample No. 7, and Sample No. 8, although Sample No. 8 has slightly improved gamma variation range, Sample No. 1, Sample No. 7, and Sample No. 8, there was almost no difference in the sample in which the fast-reacting quencher was contained only in the intermediate layer of layer 2 (No. 1), and the sample in which the fast-reacting quencher was contained only in the blue-sensitive silver halide emulsion layer (No. 1). .7) and the sample (No. 8) in which it was contained in both the intermediate layer of layer 2 and the blue-sensitive silver halide emulsion layer, the fluctuation in photographic performance due to back contamination of bleach-fixing solution components was improved. I can see that it is being done. However, the blue-sensitive silver halide emulsion layer
Regarding Dm, Sample No. 7 containing a fast-reactive quencher in the blue-sensitive silver halide agent layer;
There was a slight decrease in No. 8, indicating that it is slightly more advantageous in this respect to include a fast-reacting quencher in the intermediate layer. Comparative example Regarding sample G of Example 1 of JP-A-60-60647, the hydroquinone derivative of BL-2 in the first layer
Comparative Sample 1 was prepared in the same manner as Sample G except that HQ-1 was replaced with the same amount of HQ-11 described on page 29. Also, regarding the same sample, the BL of the first layer
-5 hydroquinone derivative HQ-1 in the same amount 29
Comparative sample 2 was prepared in the same manner as the above sample except that the sample was replaced with HQ-11 as described on the page. The obtained sample was evaluated in the same manner as in Example 1 of the present invention to determine the variation range of γ (gamma).
The results are shown in Table 4.
【表】
表４からも明らかなように、たとえ本発明の相
対反応速度が1.6以上の発色現像主薬の酸化体を
失活せしめる化合物を使用しても、本発明の高速
反応性イエローカプラーに該当しないイエローカ
プラーを使用した比較試料１及び２は、本発明の
効果が得られない。[Table] As is clear from Table 4, even if a compound that deactivates the oxidized color developing agent with a relative reaction rate of 1.6 or more is used, it still falls under the fast-reactive yellow coupler of the present invention. Comparative samples 1 and 2 using a yellow coupler that does not have the same effect as those of the present invention cannot be obtained.
Claims (1)
る青感性ハロゲン化銀乳剤層、緑感性ハロゲン化
銀乳剤層及び赤感性ハロゲン化銀乳剤層をこの順
序で有すると共に、各乳剤層間に中間層を有する
ハロゲン化銀カラー写真感光材料において、前記
青感性ハロゲン化銀乳剤層に相対カプリング反応
速度が0.3以上の高速反応性イエローカプラーを
該層の銀１モル当たり２×10-3〜５×10-1モル含
有し、かつ前記中間層および／または青感性ハロ
ゲン化銀乳剤層に相対反応速度が1.6以上の発色
現像主薬の酸化体を失活せしめる化合物を含有す
ることを特徴とするハロゲン化銀カラー写真感光
材料。1. On a reflective support, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer each containing a silver chlorobromide emulsion are provided in this order, and there is a space between each emulsion layer. In a silver halide color photographic light-sensitive material having an intermediate layer, a fast-reactive yellow coupler having a relative coupling reaction rate of 0.3 or more is added to the blue-sensitive silver halide emulsion layer in an amount of 2×10 -3 to 5 per mole of silver in the layer. x10 -1 mol, and the intermediate layer and/or blue-sensitive silver halide emulsion layer contains a compound that deactivates the oxidized form of a color developing agent and has a relative reaction rate of 1.6 or more. Silver chemical color photographic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18517485A JPS6249349A (en) | 1985-08-23 | 1985-08-23 | Silver halide color photograph sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18517485A JPS6249349A (en) | 1985-08-23 | 1985-08-23 | Silver halide color photograph sensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6249349A JPS6249349A (en) | 1987-03-04 |
| JPH0571087B2 true JPH0571087B2 (en) | 1993-10-06 |
Family
ID=16166127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18517485A Granted JPS6249349A (en) | 1985-08-23 | 1985-08-23 | Silver halide color photograph sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6249349A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156933A (en) * | 1982-03-11 | 1983-09-19 | Fuji Photo Film Co Ltd | Color photographic sensitive material |
| JPS595247A (en) * | 1982-06-18 | 1984-01-12 | イ−ストマン・コダツク・カンパニ− | Color photographic element |
| JPS6060647A (en) * | 1983-09-13 | 1985-04-08 | Fuji Photo Film Co Ltd | Method for bleach fixing silver halide color photosensitive material |
| JPS60108843A (en) * | 1983-11-18 | 1985-06-14 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
-
1985
- 1985-08-23 JP JP18517485A patent/JPS6249349A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58156933A (en) * | 1982-03-11 | 1983-09-19 | Fuji Photo Film Co Ltd | Color photographic sensitive material |
| JPS595247A (en) * | 1982-06-18 | 1984-01-12 | イ−ストマン・コダツク・カンパニ− | Color photographic element |
| JPS6060647A (en) * | 1983-09-13 | 1985-04-08 | Fuji Photo Film Co Ltd | Method for bleach fixing silver halide color photosensitive material |
| JPS60108843A (en) * | 1983-11-18 | 1985-06-14 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6249349A (en) | 1987-03-04 |
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