JPS6126055B2 - - Google Patents
Info
- Publication number
- JPS6126055B2 JPS6126055B2 JP4201281A JP4201281A JPS6126055B2 JP S6126055 B2 JPS6126055 B2 JP S6126055B2 JP 4201281 A JP4201281 A JP 4201281A JP 4201281 A JP4201281 A JP 4201281A JP S6126055 B2 JPS6126055 B2 JP S6126055B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- layer
- carbon atoms
- silver halide
- photographic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 silver halide Chemical class 0.000 claims description 80
- 150000001875 compounds Chemical class 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 58
- 239000000839 emulsion Substances 0.000 claims description 48
- 229910052709 silver Inorganic materials 0.000 claims description 46
- 239000004332 silver Substances 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- DNTVKOMHCDKATN-UHFFFAOYSA-N pyrazolidine-3,5-dione Chemical compound O=C1CC(=O)NN1 DNTVKOMHCDKATN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- IBTDNBUTNOKAQD-UHFFFAOYSA-N cyclohex-3-ene-1,2-dione Chemical compound O=C1CCC=CC1=O IBTDNBUTNOKAQD-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 109
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 239000000975 dye Substances 0.000 description 24
- 238000009792 diffusion process Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 238000012546 transfer Methods 0.000 description 18
- 238000012545 processing Methods 0.000 description 17
- 239000006097 ultraviolet radiation absorber Substances 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000006096 absorbing agent Substances 0.000 description 15
- 239000004816 latex Substances 0.000 description 15
- 229920000126 latex Polymers 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000006386 neutralization reaction Methods 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 230000003068 static effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 230000003595 spectral effect Effects 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- CBXGIYSFAJVJOB-UHFFFAOYSA-N 1-[4,6-di(prop-2-enoyl)triazin-5-yl]prop-2-en-1-one Chemical compound C=CC(=O)C1=NN=NC(C(=O)C=C)=C1C(=O)C=C CBXGIYSFAJVJOB-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- SZABDZQEJIVBIB-UHFFFAOYSA-N 2-pentadecylbenzene-1,4-diol;sodium Chemical compound [Na].CCCCCCCCCCCCCCCC1=CC(O)=CC=C1O SZABDZQEJIVBIB-UHFFFAOYSA-N 0.000 description 2
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 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
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- BUNYBPVXEKRSGY-ONEGZZNKSA-N (1e)-buta-1,3-dien-1-amine Chemical class N\C=C\C=C BUNYBPVXEKRSGY-ONEGZZNKSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- OJNXPAPLAAGFBJ-UHFFFAOYSA-N (4-methylphenyl) prop-2-enoate Chemical compound CC1=CC=C(OC(=O)C=C)C=C1 OJNXPAPLAAGFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- OCKYCCVSWVDVAL-UHFFFAOYSA-N 1,2-dimethylpyrazolidine-3,5-dione Chemical compound CN1N(C)C(=O)CC1=O OCKYCCVSWVDVAL-UHFFFAOYSA-N 0.000 description 1
- XDPKQGKEOCYMQC-UHFFFAOYSA-N 1,2-diphenylpyrazolidine-3,5-dione Chemical compound O=C1CC(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 XDPKQGKEOCYMQC-UHFFFAOYSA-N 0.000 description 1
- VVSASNKOFCZVES-UHFFFAOYSA-N 1,3-dimethyl-1,3-diazinane-2,4,6-trione Chemical compound CN1C(=O)CC(=O)N(C)C1=O VVSASNKOFCZVES-UHFFFAOYSA-N 0.000 description 1
- BQEYXXWHAVECGB-UHFFFAOYSA-N 1-ethyl-3-octyl-1,3-diazinane-2,4,6-trione Chemical compound CCCCCCCCN1C(=O)CC(=O)N(CC)C1=O BQEYXXWHAVECGB-UHFFFAOYSA-N 0.000 description 1
- ACUSQXRCSPCTIF-UHFFFAOYSA-N 1-methyl-3-octyl-1,3-diazinane-2,4,6-trione Chemical compound CCCCCCCCN1C(=O)CC(=O)N(C)C1=O ACUSQXRCSPCTIF-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- MECMQZBUZCGXQW-UHFFFAOYSA-N 1-phenyl-1,3-diazinane-2,4,6-trione Chemical compound O=C1NC(=O)CC(=O)N1C1=CC=CC=C1 MECMQZBUZCGXQW-UHFFFAOYSA-N 0.000 description 1
- ZKEGGSPWBGCPNF-UHFFFAOYSA-N 2,5-dihydroxy-5-methyl-3-(piperidin-1-ylamino)cyclopent-2-en-1-one Chemical compound O=C1C(C)(O)CC(NN2CCCCC2)=C1O ZKEGGSPWBGCPNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- BQULIJPCVADMIR-UHFFFAOYSA-N 3-(1-phenyltetrazol-5-yl)sulfanylbutanenitrile Chemical compound N#CCC(C)SC1=NN=NN1C1=CC=CC=C1 BQULIJPCVADMIR-UHFFFAOYSA-N 0.000 description 1
- RSNJQTJXJWHGTK-UHFFFAOYSA-N 3-[3-[2,4-bis(2-methylbutan-2-yl)phenoxy]propyl]-6-ethoxy-5h-pyrimidine-2,4-dione Chemical compound O=C1CC(OCC)=NC(=O)N1CCCOC1=CC=C(C(C)(C)CC)C=C1C(C)(C)CC RSNJQTJXJWHGTK-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- UWOZQBARAREECT-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-(4-methylphenyl)pyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1NC(=O)C(C)(CO)C1 UWOZQBARAREECT-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- VUUNCMULTZRHHS-UHFFFAOYSA-N 5,5-diethylcyclohexane-1,3-dione Chemical compound CCC1(CC)CC(=O)CC(=O)C1 VUUNCMULTZRHHS-UHFFFAOYSA-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
- VPFRSJOYWJRYOI-UHFFFAOYSA-N 6-ethoxy-3-ethyl-5h-pyrimidine-2,4-dione Chemical compound CCOC1=NC(=O)N(CC)C(=O)C1 VPFRSJOYWJRYOI-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- LDKDGDIWEUUXSH-UHFFFAOYSA-N Thymophthalein Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C LDKDGDIWEUUXSH-UHFFFAOYSA-N 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 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 1
- 239000001273 butane Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- COPHVUDURPSYBO-UHFFFAOYSA-N butyl dioctyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCC)OCCCCCCCC COPHVUDURPSYBO-UHFFFAOYSA-N 0.000 description 1
- BNHLMVOPTDTRFK-UHFFFAOYSA-N butyl prop-2-enoate;n-(hydroxymethyl)prop-2-enamide;prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.OCNC(=O)C=C.C=CC1=CC=CC=C1.CCCCOC(=O)C=C BNHLMVOPTDTRFK-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- FIQMGTUXVVDDHS-UHFFFAOYSA-N dodecyl 2-(benzenesulfonyl)acetate Chemical compound CCCCCCCCCCCCOC(=O)CS(=O)(=O)C1=CC=CC=C1 FIQMGTUXVVDDHS-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- LOCAIGRSOJUCTB-UHFFFAOYSA-N indazol-3-one Chemical compound C1=CC=C2C(=O)N=NC2=C1 LOCAIGRSOJUCTB-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- FCVOMRWPTGPIJC-UHFFFAOYSA-N octyl 3-(3-ethyl-2,4,6-trioxo-1,3-diazinan-1-yl)propanoate Chemical compound CCCCCCCCOC(=O)CCN1C(=O)CC(=O)N(CC)C1=O FCVOMRWPTGPIJC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- XOQRNNDIPPJGLV-UHFFFAOYSA-M sodium;2,5-dihydroxy-4-pentadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCC1=CC(O)=C(S([O-])(=O)=O)C=C1O XOQRNNDIPPJGLV-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- XOKPOPWYLRKXEA-UHFFFAOYSA-N trihexylazanium;chloride Chemical compound Cl.CCCCCCN(CCCCCC)CCCCCC XOKPOPWYLRKXEA-UHFFFAOYSA-N 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 238000004383 yellowing Methods 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
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Description
本発明はハロゲン化銀写真感光材料に関し、さ
らに詳しくは紫外線吸収剤をハロゲン化銀写真感
光材料に含有せしめることにより、ハロゲン化銀
写真感光材料の製造時発生するスタチツクマーク
を防止する方法に関する。
紫外線が写真感光材料に有害な影響を与えるこ
とは周知である。写真感光材料は一般に三酢酸セ
ルローズ、ポリエチレンテレフタレート、ポリス
チレンあるいはポリカーボネートからなるフイル
ム支持体、及びこれらで被覆されたラミネート紙
のように比較的電気絶縁性の高い支持体上に、ハ
ロゲン化銀を主体とする感光性写真乳剤が塗布さ
れており、写真感光材料の表面はかなり高い電気
絶縁性をもつている。このため、写真感光材料の
製造時や取り扱い中にその表面が同種又は異種の
材質の物体と接触し、次いで摩擦又は剥離する際
に電荷が発生する。この現象は帯電と称され、こ
の帯電による静電気の蓄積がある限界量に達する
と瞬間的に空中放電を起し、同時に放電火花を発
生する。この放電発生によつて、写真感光材料が
感光した場合、現像処理後に、樹枝状、羽毛状、
点状、放射状の画像が現れる。このような原因に
よつて得られる画像を写真業界でスタチツクマー
クと称している。スタチツクマークを生ぜしめる
この種の放電発生の分光エネルギー分布が200nm
〜550nmであり、特に300nm〜400nmにかけての
強度が著しく、この範囲の光エネルギーがスタチ
ツクマーク発生の原因になつていることが知られ
ている。従つて従来より、例えば、特公昭50−
10726号公報、特開昭51−26021号明細書、仏国特
許第2036679号明細書、等に記載されているよう
に、紫外線吸収剤により、特に300〜400nmの紫
外線光を遮光することによりスタチツクマーク発
生を防止する試みがなされてきた。
このような目的のために、例えば、米国特許
3253921号等に記載されているベンゾトリアゾー
ル系化合物、米国特許3707375号、同3705805号等
に記載されている桂皮酸系化合物、米国特許
4195999号等に記載されているアミノブタジエン
系化合物等がこれまで広く紫外線吸収剤として写
真用感光材料に利用されているが、どれも300〜
400nmの吸収特性が悪く、特に300〜330nmの波
長領域の吸光係数が低かつた。これまでに写真用
感光材料に利用されている紫外線吸収剤には300
〜330nmの波長領域を吸収する化合物はあるが、
どれもバインダーとの混和性が悪かつたり、層間
の移動が大きいために他端へ拡散して悪影響を及
ぼしたり、乳化物が不安定で結晶が析出したり、
それ自身が紫外線、熱、湿度に対して十分安定と
はいえないために着色してステインとなつたりし
て前記用途に十分適しているとは到底いえなかつ
た。したがつて、このような欠点をもたない紫外
線吸収剤を見い出すことが従来より強く望まれて
いた。
一方写真撮影時、すなわち露光時の紫外線も写
真感光材料に有害な影響を与えることも周知であ
る。ハロゲン化銀乳化剤は紫外域にも感度(固有
感度)をもつており、紫外線が含まれた露光をす
ると完成した画像は実際の視感度と異なるため、
奇異な写真画像となることはよく知られている。
これを防止するために紫外線吸収剤が用いられ
300〜400nmの紫外線を遮断する試みがなされて
きた。この目的のためには、特に長波側すなわち
400nm付近の吸収がシヤープな紫外線吸収剤が望
ましい。
現在までに紫外線吸収剤を2種類以上混合して
用いることは既に知られており、例えば、特公昭
48−5496、米国特許3705805、特公昭49−26138、
特公昭48−31255、特公昭48−30493、特公昭48−
31255、などに記載されている。特に米国特許
3705805にはケイヒ酸エステル系化合物をベンゾ
トリアゾール系化合物と併用することが記載され
ているが、これらの特許の化合物では、
長波長端即ち390〜400nm付近の吸収がシヤ
ープでなく、ハロゲン化銀乳剤に対する紫外線
のカツトが不充分である。
塗布膜中で、紫外線吸収剤が移動し易く、特
に前述のカラー拡散転写法写真要素においては
カバーシートの中和タイミング時間への影響が
著しい。
短波長端即ち300〜340nm付近の吸収が充分
でないため、スタチツクマークが発生し易い。
ベンゾトリアゾール系、ヒドロキシベンゾフ
エノン系はアルカリ条件下で黄色着色し、耐拡
散性が不充分のため拡散してステインになる、
などの欠点を有している。
本発明の第1の目的は、300〜400nmの吸収特
性がよく、特に300〜330nmの波長領域の吸収係
数が高い紫外線吸収剤を含む、スタチツクマーク
発生を防止したハロゲン化銀写真感光材料を提供
することにある。
本発明の第2の目的は、層間の移動が非常に少
なく他端への拡散による悪影響のない紫外線吸収
剤を含むハロゲン化銀写真感光材料を提供するこ
とにある。例えば、リサーチ・デイスクロージヤ
ーNo.151,15162(1976年11月発行)に記載の如
き支持体上に少なくとも1つの色像供与化合物
と組み合わさつたハロゲン化銀乳剤層、および受
像層、白色反射層、遮光層をそれぞれ1層以上有
する感光シート、別の支持体上に少なくとも1
つの中和層と中和タイミング層を有するカバーシ
ート、上記感光シートとカバーシートとの間に
展開されるアルカリ性処理液からなるカラー拡散
転写用写真要素においては、紫外線吸収剤はハロ
ゲン化銀乳剤に対して感光シートの支持体と反対
側の最上層に含有せしめることは既に知られてい
るが、上記感光シートとカバーシートはそれぞれ
の塗布面が重ね合わされ、特開昭50−153628に記
載の如き形態でリサーチ・デイスクロージヤー
No.187,18714(1979年11月発行)に記載の如き
パツクに装填されたまま写真撮影までの期間保存
される。即ち、感光シート最上層の紫外線吸収剤
含有層とカバーシート最上層の中和タイミング層
は相互に強く接触したまま長期間保存されるので
ある。このような写真要素において従来から知ら
れている紫外線吸収剤を用いる場合、紫外線吸収
剤は中和タイミング層に移動し易く、この結果中
和タイミング層のアルカリに対する抵抗性が変化
し中和タイミング時間が短かくなるため画像形成
が十分進行しないまま中和されることにより最大
濃度が低下するという欠点があつた。本発明の目
的は、このような欠点をとりのぞくことのできる
紫外線吸収剤を含むカラー拡散転写用写真要素を
提供することにある。
本発明の第3の目的は、乳化剤の安定性に優れ
長期間保存しても結晶が析出し難い紫外線吸収剤
を含むハロゲン化銀写真感光材料を提供すること
にある。
本発明の第4の目的は、紫外線、熱、湿度に対
して十分安定である紫外線吸収剤を含むハロゲン
化銀写真感光材料を提供することにある。
本発明の第5の目的は、感度、カブリ等の写真
性、接着等の膜の物理性に影響がない紫外線吸収
剤を含むハロゲン化銀写真感光材料を提供するこ
とにある。
鋭意検討した結果、本発明者らは、一般式
()で表わされる化合物の少なくとも1種と、
一般式()で表わされる化合物の少なくとも1
種を組合わせて用いることにより上記目的を達成
した写真感光材料が得られることを見い出した。
式中、R1は水素原子、炭素数1〜5のアルキ
ル基(例えば、メチル基、エチル基、n―プロピ
ル基、イソプロピル基、n―ブチル基、t―ブチ
ル基、n―アミル基、t―アミル基、メトキシエ
チル基、エトキシプロピル基、ヒドロキシエチル
基、クロロプロピル基、シアノエチル基等)、又
はハロゲン原子(例えば、塩素原子、臭素原子
等)を表わし、R2は水素原子、炭素数1〜5の
アルキル基(例えば、メチル基、エチル基、n―
プロピル基、イソプロピル基、n―ブチル基、n
―アミル基等)、又は炭素数6〜20のアリール基
(例えば、フエニル基、トリル基、メシチル基、
クロロフエニル基等)、又R3は炭素数12〜18のア
ルキル基(例えば、n―ドデシル基、n―トリデ
シル基、n―テトラデシル基、n―ペンタデシル
基、n―ヘキサデシル基、n―ヘプタデシル基、
n―オクタデシル基等)を表わす。
nは1又は2の整数である。R4とR5は各々水
素原子、炭素数1〜20のアルキル基(例えば、メ
チル基、エチル基、n―ブチル基、n―ヘキシル
基、シクロヘキシル基、n―デシル基、n―ドデ
シル基、n―オクタデシル基、エイコシル基、メ
トキシエチル基、エトキシプロピル基、2―エチ
ルヘキシル基、ヒドロキシエチル基、クロロプロ
ピル基、N,N―ジエチルアミノプロピル基、シ
アノエチル基、フエネチル基、ベンジル基、p―
t―ブチルフエネチル基、p―t―オクチルフエ
ノキシエチル基、3―(2,4―ジ―t―アミル
フエノキシ)プロピル基、エトキシカルボニルメ
チル基、2―(2―ヒドロキシエトキシ)エチル
基、2―フリルエチル基等)、又は炭素数6〜20
のアリール基(例えば、トリル基、フエニル基、
アニシル基、メシチル基、クロロフエニル基、
2,4―ジ―t―アミルフエニル基、ナフチル基
等)を表わし、更にR4とR5は互いに同一もしく
は異つていてもよいが、同時に水素原子を表わす
ことはない。更にR4とR5は結合して一体化して
もよく、その場合は環状アミノ基(例えば、ピペ
リジノ基、モルホリノ基、ピロリジノ基、ヘキサ
ヒドロアゼピノ基、ピペラジノ基等)を形成する
のに必要な原子団を表わす。R6はシアノ基、―
COOR8,―COR8又は―SO2R8を表わし、R7はシ
アノ基、―COOR9,―COR9,―SO2R9を表わ
し、R8とR9は各々炭素数1〜20のアルキル基、
又は炭素数6〜20のアリール基を表わし、R4又
はR5が表わすアルキル基、アリール基と同意義
である。更にR8とR9は結合して一体化してもよ
く、一体化した場合は1,3―ジオキソシクロヘ
キサン環(例えば、ジメドン、1,3―ジオキソ
ー5,5―ジエチルシクロヘキサン等)、1,3
―ジアザー2,4,6―トリオキソシクロヘキサ
ン環(例えば、バルビツール酸、1,3―ジメチ
ルバルビツール酸、1―フエニルバルビツール
酸、1―メチル―3―オクチルバルビツール酸、
1―エチル―3―オクチルバルビツール酸、1―
エチル―3―オクチルオキシカルボニルエチルバ
ルビツール酸等)、1,2―ジアザー3,5―ジ
オキソシクロペンタン環(例えば、1,2―ジア
ザー1,2―ジメチル―3,5―ジオキソシクロ
ペンタン、1,2―ジアザー1,2―ジフエニル
―3,5―ジオキソシクロペンタン等)、又は
2,4―ジアザー1―アルコキシ―3,5―ジオ
キソシクロヘキセン環(例えば、2,4―ジアザ
ー1―エトキシ―4―エチル―3,5―ジオキソ
シクロヘキセン、2,4―ジアザー1―エトキシ
ー4―〔3―(2,4―ジ―t―アミルフエノキ
シ)プロピル〕―3,5―ジオキソシクロヘキセ
ン等)を形成するのに必要な原子団を表わす。n
が2のときは、R4,R5,R8は各々更にアルキレ
ン基(例えば、メチレン基、エチレン基、デカメ
チレン基等)又はアリーレン基(例えば、フエニ
レン基等)を表わし、R4,R5及びR8の少くとも
一つはアルキレン基又はアリーレン基を表わし、
二量体を形成しうる。
一般式()において好ましくはR1は炭素数
1〜5のアルキル基であり、R2は水素原子を表
わし、R3は炭素数12〜18のアルキル基を表わ
す。又、一般式()において好ましくはn=1
であり、R4とR5は各々炭素数1〜20のアルキル
基を表わし、R6はシアノ基、―SO2R8を表わし、
R7はシアノ基、―COOR9を表わす。R8とR9は
各々炭素数1〜20のアルキル基又は、炭素数6〜
20のアリール基を表わし、R4,R5,R8,R9の炭
素総数は12〜80であることが好ましい。
一般式()において特に好ましくはR1は炭
素数1〜5のアルキル基であり、R2は水素原子
を表わし、R3は炭素数12〜18のアルキル基を表
わす。又、一般式()において特に好ましくは
n=1であり、R4とR5は各々炭素数1〜6のア
ルキル基を表わし、R6は―SO2R8を表わし、R7
は―COO.9を表わす。R8は置換してもよいフエ
ニル基(例えば、フエニル基、トリル基等)を表
わし、R9は炭素数12〜20のアルキル基を表わ
し、R4,R5,R9の炭素総数は20〜52であること
が特に好ましい。
本発明の上記第二の目的は好ましくは、(1)支持
体上に色像供与化合物が組合わさつたハロゲン化
銀乳剤層を少くとも一つ含み、かつ該支持体から
最も遠い層として、前記一般式()で表わされ
る化合物の少くとも1種と前記一般式()で表
わされる化合物の少くとも1種との組合せを含む
紫外線吸収剤含有層を含む感光シート、及び(2)別
の支持体上に中和層を有し、その支持体より実質
的に最も遠い側にポリマーラテツクスから形成さ
れたバリヤー層を含むカバーシート、が互いに支
持体とは反対側の面で接触する様に配置され、該
感光シートと該カバーシートとの間に処理組成物
を均一に展開するに適したカラー拡散転写用写真
感光材料により達成される。
上記のポリマーラテツクスから形成されたバリ
ヤー層は特開昭54−155837号公報に記載のバリヤ
ー層が有利に用いられる。
本発明のカラー拡散転写法写真感光材料の好ま
しい態様例としては、いわゆる“積層一体型”写
真フイルム・ユニツトと呼ばれるもので、具体的
には透明支持体上に受像層、白色反射層、遮光
層、色像供与化合物と組み合わさつた少なくとも
1層のハロゲン化銀乳剤層、紫外線吸収剤含層が
この順序に塗設されており、更にこの上に、別の
透明支持体上に中和層、中和タイミング層、前記
のバリヤー層がこの順序に塗設されたカバーシー
トを重ねて構成された感光性ユニツトであつて、
しかもこの感光性ユニツトには、アルカリ処理組
成物(現像主薬と遮光剤を含む)で満された破裂
可能容器(袋)が組み込まれているものを挙げる
事げできる。この容器は前記のバリヤー層や紫外
線吸収剤含有層の外側にあつてこれらに接してお
り、しかも、この容器の破裂予定口がこれらの層
の間にアルカリ処理組成物を延長しうるような位
置に配置されているのが好ましい。
積層一体型写真フイルムユニツトについてはベ
ルギー特許757959、あるいはリサーチ・デイスク
ロージヤー(Research Disclosur)誌151巻
No.15162に記載されている。
ここでバリヤー層は、アルカリ処理組成物の透
過性の温度に対する依存性が大きく、巾広い処理
温度範囲においてすぐれた色画像を得ることを目
的としたものである。バリヤー層とは別に中和タ
イミング作用を有するいわゆる中和タイミング層
を設けることができるのは上記の如くである。
以下に本発明の前記一般式(),()で表わ
される化合物の代表例を示すがこれによつて本発
明の化合物が限定されるものではない。
一般式()の例示化合物
本発明に用いる化合物は、例えば米国特許
4200464号、Beilsteins Handbuchder
Organischen Chemie(第4版)10巻521頁
(1942年)等に記載の方法に従い、対応するシア
ノ酢酸エステルと置換ベンズアルデヒド又はケト
ンとから容易に合成することができるが、以下に
参考までにその合成例を挙げる。
合成法―1(例示化合物−3)
トルアルデヒド(50.0g)とシアノ酢酸エチル
エステル(49.0g)と酢酸(7.5ml)と酢酸アン
モニウム(3.5g)をエチルアルコール(165ml)
中で2時間加熱還流する。反応後、減圧下にエチ
ルアルコールを80mlまで濃縮し、室温下放置後沈
澱物を吸引過し、水と少量のエチルアルコール
で洗うと、94〜95℃で溶融するエチル―2―シア
ノ―3―(4―メチルフエニル)―アクリレート
を80gの収量で得る。この化合物(32.2g)とセ
チルアルコール(43.5g)とテトラブトキシチタ
ン(1.5ml)を混合し、減圧下110℃で3時間加熱
撹拌する。反応液を酢酸エチルとメチルアルコー
ルから再結晶すると62〜63℃の溶融する白色結晶
を得る。IR,NMR,元素分析結果により目的物
を確認した。
合成法―2(例示化合物―6)
p―クロルベンズアルデヒド(35.4g)とシア
ノ酢酸エチルエステル(29.7g)と酢酸(5ml)
と酢酸アンモニウム(2.2g)をエチルアルコー
ル(100ml)中で、2時間加熱還流する。反応後
エチルアルコールを50mlまで濃縮し、室温下放置
後沈澱物を吸引過し、少量のエチルアルコール
で洗うと、88〜89℃で溶融するエチル―2―シア
ノ―3―(4―クロルフエニル)―アクリレート
を51gの収量で得る。この化合物(47.1g)とセ
チルアルコール(58.1g)とテトラブトキシチタ
ン(2ml)を混合し、減圧下110℃で3時間加熱
撹拌する。反応液にメチルアルコールを入れ加熱
溶解させ再結晶すると、57〜58℃で溶融する白色
結晶を得る。IR,NMR、元素分析結果により目
的物を確認した。
一般式()の例示化合物
本発明に用いる化合物は、例えば米国特許
4195999号、特開昭51−56620号等に記載の方法に
従い、容易に合成することができるが、以下に参
考までにその合成例を挙げる。
合成法―1(例示化合物−8)
3―アニリノアクロレインアニル(13.3g)と
ドデシルフエニルスルホニルアセテート(23.1
g)を無水酢酸(40ml)中で85〜90℃に2時間加
熱する。減圧下に無水酢酸を除き、エチルアルコ
ール(40ml)とジエチルアミン(9.5g)を加え
て2時間還流する。エチルアルコールを留去し、
残渣をカラムクロマト(メルク社製Kieselgel
60)にかけ、ベンゼン留出物を集め、エチルアル
コールより再結晶すると、69℃で溶融する目的物
13gを得る。IR,NMR、元素分析結果により目
的物を確認した。
合成法―2(例示化合物―10)
3―アニリノアクロレインアニル(12.8g)と
マロノニトリル(4.8g)を無水酢酸(50ml)中
で85〜90℃に2時間加熱する。減圧下に無水酢酸
を除き、エチルアルコール(50ml)とジブチルア
ミン(15.0g)を加え1時間還流する。反応後エ
チルアルコールを留去し、残渣を157℃、0.03mm
Hgで蒸留すると、目的物を5.0g得る。IR,
NMR、元素分析結果により目的物を確認した。
本発明の特徴を以下記述する。
一般式()の化合物の長波長端がシヤープ
であるため、ハロゲン化銀乳剤に対する紫外線
の影響がなく、良好な画像が得られる。
一般式()の化合物の吸収域(長波)に対
して、一般式()の化合物の吸収域(短波)
が非常に適当な領域にあり、両者の混合によつ
て300〜400nmの波長領域を充分吸収できる理
想的な紫外線吸収能力が得られる。このため
に、スタチツクマークを生ぜしめる放電発光の
分光エネルギー領域である300〜400nmの波長
領域、特に従来十分吸収されているとはいえな
かつた300〜330nmの波長領域をも十分吸収で
きるためスタチツクマークの発生を防止でき
る。p―アルコキシ置換したケイ皮酸エステル
系(一般式()のR1がp―アルコキシ)は
知られているが、吸収域が長波であため、短波
側が充分カバーできない。この点で一般式
()と一般式()の化合物を混合する方法
は大きな特徴を有する。
一般式()および一般式()の化合物は
塗布膜層中での他層への移動が非常に少ないも
のである。特にカラー拡散転写写真要素の場合
には、タイミング層へ移動しないので中和タイ
ミング時間に対する悪影響(通常中和タイミン
グ時間が短かくなる)がない。
乳化物安定性に優れており、長期間保存して
も結晶が析出し難い。
熱、湿度に対しても本願発明に用いる紫外線
吸収化合物は安定である。
ステインの原因にならない他、画像形成過程
(例えば現像抑制するとか)においても悪影響
を及ぼさない。
など従来から知られている紫外線吸収剤またはそ
の使用法の欠点がない優れた特徴をもつ写真感光
材料が得られた。
これらの特徴は一般写真感光材料は無論のこと
特にカラー拡散転写用写真要素において有効に生
かされる。
本発明において、一般式()と一般式()
の化合物の混合比は放電発光の分布に応じて決め
られ、必要に応じて3種以上を混合することもで
きるが、好ましくは()/()=0.4〜1.5
(モル比)の2種混合で、特に好ましくは0.6〜
1.2(モル比)である。
本発明の紫外線吸収剤の塗布量は、300〜
400nmにおける透過濃度の最大値が0.5〜3.0にな
る量が好ましく、さらに好ましくは0.8〜2.0にな
る量である。
本発明に用いる化合物かハロゲン化銀感光要素
中に添加するには以下の分散方法を適用すること
ができる。
たとえば、実質的に水に不溶な高沸点有機溶媒
例えば、フタール酸のアルキルエステル(例え
ば、ジブチルフタレート、ジオクチルフタレート
など)、トリメリト酸エステル(例えば、トリ―
t―オクチルトリメリテート)、芳香族エーテ
ル、燐酸エステル(例えば、ジフエニルフオスフ
エート、トリフエニルフオスフエート、トリクレ
ジルフオスフエート、ジオクチルブチルフオスフ
エート)、クエン酸エステル(例えば、アセチル
クエン酸トリブチル)、アルキルアミド(例え
ば、N,N―ジエチルラウリルアミド)等に溶解
し、得られる溶液を親水性有機コロイド水溶液中
に乳化分散する方法(例えば、米国特許2322027
号、等)、補助溶媒(例えば、メタノール、アセ
トン、メチルセロソルブ、等の水溶性溶媒、酢酸
エチル、酢酸ブチル等の実質的に水に不溶な溶
媒)をさらに併用する水不溶性高沸点有機溶媒を
用いた乳化分散方法(例えば、米国特許2739888
号、同3351681号、特開昭51−59943号、等参
照)、本発明に用いる化合物を、有機溶媒(実質
的に水不溶性の高沸点有機溶媒、実質的に水不溶
性の低沸点有機溶媒、水混和性有機溶媒、等)に
溶かし(又はそれ自体油状物であればそのままで
もよい)、それをポリマーラテツクス水性分散液
中又は親水性コロイドを含有するポリマーラテツ
クス中に添加して、本発明に用いる化合物をポリ
マーラテツクス粒子中に含浸させた状態で分散す
るラテツクス分散方法(例えば、特公昭51−
39853号、特開昭51−59942号、同51−59943
号、)、本発明に用いる化合物を水に可溶な溶媒
(例えば、アセトン、メチルセロソルブ、メタノ
ール、エタノール等)に溶解し、感光性ハロゲン
化銀感光材料の親水性有機コロイド塗布液中に直
接分散する方法、本発明に用いる化合物自体が常
温で油状物である場合はそれ自体を親水性有機コ
ロイド溶液中に乳化分散して写真用塗布液に添加
する方法、等を挙げることができる。とくに、実
質的に水不溶性の高沸点有機溶媒に溶解するか、
又はさらに補助溶媒を併用して溶解し、親水性有
機コロイド水溶液中に乳化分散する方法又はラテ
ツクス分散方法が好ましい。
本発明に用いる紫外線吸収化合物は、1g当り
乳化分散用高沸点有機溶媒約0.1〜約10mlを用
い、好ましくは、0.2〜4mlを用いて乳化分散す
る。また、本発明に用いる紫外線吸収化合物と分
散用ポリマーラテツクスの重量比を約0.1〜約10
g、好ましくは0.2〜4gの範囲で用いてラテツ
クス分散する。
このような種々の分散方法において、一般式
()および()の化合物をそれぞれ単独で分
散した後、2つの分散物を混合して使用すること
もできるし、一方2種類以上の化合物を同時に分
散しても良い。
本発明に用いる紫外線吸収化合物は、ハロゲン
化銀感光材料上での塗布量を約5〜約1500mg/m2
の範囲で用いることができる。とくにプリント用
カラー感光材料(例えば、カラーペーパー、カラ
ーポジフイルム)では好ましくは約50〜約1500
mg/m2、撮影用カラー感光材料(例えば、カラー
ネガフイルム、カラーレバーサルフイルム)では
好ましくは約5〜約650mg/m2。
本発明に用いる化合物をハロゲン化銀感光材料
に含める場合、従来の紫外線吸収剤より少量でか
つ良好な効果が得られるため、膜の軟化、多層構
成写真感光材料での層間密度を悪化させないし、
又写真感光材料間の表面での接着をひきおこすこ
ともない。本発明に用いる化合物の乳化分散物、
水に可溶な有機溶媒に溶解した溶液は粒子の疎大
化又は結晶析出がおこらず安定であり、これらを
感光性ハロゲン化銀乳剤または、非感光性親水性
コロイド層(例えば、ゼラチン層)に添加しても
不透明化しない。ハロゲン化銀感光要素中で本発
明に用いる化合物は熱に対して安定である。
本発明に用いる化合物は、米国特許3253921
号、同3707375号、同3705805号、同3271156号、
同3754919号、同3794493号、英国特許1338265
号、特公昭50−25337号公報、米国特許3692525
号、同3738837号、同3698907号、特公昭49−
26138号公報、同49−26139号、米国特許3936305
号、同3687671号、同3694211号等に記載されてい
る公知の写真用の紫外線吸収剤、公知の写真用酸
化防止剤(例えば、ハイドロキノン誘導体、カテ
コール誘導体、アミノフエノール誘導体、没食子
酸誘導体、等)及び公知のカラー画像形成剤とと
もに使用することもできる。
本発明に用いる親水性有機コロイドとしては、
例えば、ゼラチン、ゼラチン誘導体(例えば、フ
タル化ゼラチン、等)、カルボキシセルローズ誘
導体、スルホセルローズ誘導体、ポリアクリルア
ミド類、ポリビニルアルコール類、ポリビニルピ
ロリドン類、等を挙げることができる。
本発明に用いる紫外線吸収化合物を含めるハロ
ゲン化銀写真感光材料の写真層としては以下の如
き親水性有機コロイド層を挙げることができる。
例えば、感光性ハロゲン化銀乳剤層、非感光層
(例えば、表面保護層、バツク層、アンチハレー
シヨン層、中間層、下引き層、等)を挙げること
ができる。本発明に用いる紫外線吸収化合物は白
黒感光材料においては表面保護層、バツク層、ア
ンチハレーシヨン層、カラー感光材料において
は、最上層(例えば、表面保護層)、中間層、ア
ンチハレーシヨン層、支持体から最も遠い感光性
ハロゲン化銀乳剤層に含めるのが好ましい。
本発明に用いるハロゲン化銀写真感光材料は、
支持体、少なくとも1つのハロゲン化銀乳剤層と
少なくとも1つの非感光層からなつている。
本発明には支持体上に少なくとも2つの異なる
分光感度を有する多層多色写真感光材料が適用で
きる。多層カラー写真感光材料は、通常支持体上
に赤感性乳剤層、緑感性乳剤層、および青感性乳
剤層を各々少なくとも一つ有する。これらの層の
順序は必要に応じて任意にえらべる。赤感性乳剤
層にシアン形成カプラーを、緑感性乳剤層にマゼ
ンタ形成カプラーを、青感性乳剤層にイエロー形
成カプラーをそれぞれ含むのが通常であるが、場
合により異なる組合せをとることもできる。さら
に非感光層として、保護層、中間層、アンチハレ
ーシヨン層、バツク層、下引き層、等を設けるこ
とができる。米国特許3726681号、同3516831号、
英国特許923045号、***特許出願(OLS)
2018341号、等に記載の多層カラー写真感光材料
にも適用できる。
本発明に用いられるハロゲン化銀としては、臭
化銀、塩化銀、沃臭化銀、塩臭化銀、塩沃臭化
銀、等が使用でき、ハロゲン化銀乳剤は公知の
種々の製法で得られる。このハロゲン化銀乳剤は
化学増感剤(例えば、チオ尿素、アリルチオカル
バミド、アリルイソチオシアナート、シスチン等
の硫黄増感剤、カリウムクロロオーレート、オー
リツクトリクロライド、カリウムオーリツクチオ
シアネート、等の金化合物、他の多くの貴金属増
感剤、等)、公知の多くの還元増感剤、等で増感
することができる。さらに、これらのハロゲン化
銀乳剤にはトリアゾール類、イミダゾール類、ア
ザインデン類等の公知の安定剤又はカブリ防止剤
が添加されうる。
さらにカラー写真感光材料には、種々のカラー
画像形成剤が用いられる。例えば、ベンゾイルア
セトアニリド系及びピバロイルアセトアニリド系
の2当量あるいは4当量のイエローカプラー、ピ
ラゾロン系、インダゾロン系、あるいはシアノア
セチル系の2当量又は4当量のマゼンタカプラ
ー、フエノール系、ナフトール系の2当量又は4
当量のシアンカプラー、シアン又はマゼンタ発色
のカラードカプラーがある(前記2当量のイエロ
ー、マゼンタ、又はシアンカプラーは、DIRカプ
ラーであつてもよい。)。これらのカプラーは耐拡
散性であることが望ましい。
その他、通常用いられる公知の添加剤(例え
ば、分光増感剤、カラーステイン防止剤、褪色防
止剤、硬膜剤、界面活性剤、帯電防止剤、等)を
適用することもできる。
本発明のハロゲン化銀感光材料としては、特に
B/W高感度撮影フイルム、マイクロ用フイル
ム、印刷感材用フイルム(リスフイルム等)、カ
ラーネガテイブフイルム、カラーレバーサルフイ
ルム、カラーダイレクトポジフイルム、カラーポ
ジペーパー、カラー拡散転写法写真感光材料等を
あげることができる。特にカラー拡散転写用感光
材料において本発明は著しい効果を上げることが
できる。
カラー拡散転写法写真感光材料については、例
えばベルギー特許732985、同757959、特公昭48−
33697などに記載されており、さらに詳しくは、
リサーチ・デイスクロージヤー(Research
Disclosure)No.151,15162(1976年11月発行)
に記載されている。カラー拡散転写に用いられる
色像供与化合物としては、各種の化合物が使用で
きるが、色素放出性レドツクス化合物やカプラー
などが特に有用である。
色素放出レドツクス化合物のうち、酸化を受け
た化合物がアルカリ加水分解して色素を放出する
ものとしては、下記の文献に記載のものを挙げる
ことができる。
米国特許4053312号、同4055428号、同4076529
号、同4152153号、同4135929号、特開昭53−
149328号、同51−104343号、同53−46730号、同
54−130122号、同53−3819号、特開昭56−12642
号、同56−16130号、同56−16131号、等
このうち、イエロー色素を放出するもの:
米国特許4013633号、特開昭53−149328号、同
51−114930号、特願昭54−148237号、リサーチ・
デイスクロージヤー(Research Disclosure)
17630(′78)、同16475(′77)等
マゼンタ色素を放出するもの:
米国特許3954476号、同3931144号、同3932308
号、特開昭53−23628号、同52−106727号、同54
−65034号、同54−161332号、同55−4028号、同
55−36804号、特願昭54−149777号、同54−
146655号、同54−42848号、***特許出願
(OLS)2847371号、等
シアン色素を放出するもの:
米国特許3942987号、同3929760号、同4013635
号、特開昭51−109928号、同53−149328号、同52
−8827号、同53−143323号、同53−47823号、特
願昭54−146654号、等
また、酸化を受けなかつた方の化合物が閉環す
るなどして色素を放出するレドツクス化合物とし
ては、下記の文献に記載のものを挙げることがで
きる。
米国特許4139379号、同3980479、同3908479
号、***特許出願(OLS)2402900号、同
2448811号、英国特許1464104号、同1464105号又
はベルギー特許8644656号、等。
又、本発明に使用されるカプラーは、例えば
The Theory of Photographic Process(第4
版、1977年、T.H.James編)第12章に記載され
ている。
本発明のカラー拡散転写法写真感光材料に使用
されるハロゲン化銀乳剤は、塩化銀、臭化銀、塩
臭化銀、沃臭化銀、塩沃臭化銀もしくはこれらの
混合物の親水性コロイド状分散物であつて、ハロ
ゲン組成は感光材料の使用目的と処理条件に応じ
て選択されるが、臭化銀、沃臭化銀又は塩沃臭化
銀が特に好ましい。但し、沃化物含量は10mol%
以下、塩化物含量は30mol%以下である。この場
合には表面潜像を形成するネガ型乳剤でも、直接
反転型乳剤でも使用できる。後者の乳剤として
は、内部潜像型乳剤や予めカブらせた直接反転型
乳剤がある。
内部潜像型ハロゲン化銀乳剤が有利に使用で
き、この型の乳剤としては例えば米国特許
2592250号、同3206313号、同3447927号、同
3761276号、及び同3935014号等に記載があるコン
バージヨン型乳剤、コア/シエル型乳剤、異種金
属を内蔵させた乳剤等を挙げることができる。
この型の乳剤の造核剤としては、米国特許
2588982号、同2563785号に記載されたヒドラジン
類;同3227552号に記載されたヒドラジド類とヒ
ドラゾン類;英国特許1283835号、特公昭49−
38164号、米国特許3734738号、同3719494号、同
3615615号に記載された四級塩化合物;米国特許
3718470号に記載された、かぶらせ作用のある
(nucleating)置換基を色素分子中に有する増感
色素;米国特許4030925号、同4031127号に記載さ
れたアシルヒドラジノフエニルチオ尿素系化合物
が代表的なものである。
本発明に使用されるハロゲン化銀乳剤は、所望
に応じて分光増感色素によつて拡大された感色性
をもち得る。分光増感色素としては、シアニン色
素やメロシアニン色素等を適宜使用できる。
本発明のカラー拡散転写法写真感光材料の処理
に用いられる現像薬は、アルカリ性処理組成物の
中に含ませてもよいし、写真要素の適当な層に含
ませてもよい。本発明において使用しうる現像薬
の例をあげると次の通りである。
特開昭56−16131号に記載のハイドロキノン
類、アミノフエノール類、フエニレンジアミン
類、ピラゾリジノン類〔例えばフエニドン、1―
フエニル―3―ピラゾリジノン、ジメゾン(1―
フエニル―4,4―ジメチル―3―ピラゾリジノ
ン)、1―p―トリル―4―メチル―4―オキシ
メチル―3―ピラゾリジノン、1―(4′―メトキ
シフエニル)―4―メチル―4―オキシメチル―
3―ピラゾリジノン、1―フエニル―4―メチル
―4―オキシメチル―3―ピラゾリジノン〕な
ど。
色素放出レドツクス化合物を用いる場合には、
ここにあげたもののなかで、フエニレンジアミン
類などのカラー現像薬よりも一般に受像層のステ
イン形成を軽減する性質を具えている白黒現像剤
(なかでもピラゾリジノン類)が、特に好まし
い。
本発明のカラー拡散転写法写真感光材料を処理
するのに使用するアルカリ処理組成物は、水酸化
ナトリウム、水酸化カリウム、炭酸ナトリウム、
リン酸ナトリウムのような塩基を含みpH約9以
上であることが適当であり、好ましくは11.5以上
のアルカリ強度を持つ、処理組成物は亜硫酸ナト
リウム、アスコルビン酸塩、ピペリジノヘキソー
ズレダクトンの如き酸化防止剤を含有してもよい
し、又臭化カリウムのような銀イオン濃度調節剤
を含有し得る。又ヒドロキシエチルセルロース、
ナトリウムカルボキシメチルセルロースの如き粘
度増加化合物が含有してもよい。
又本アルカリ性処理組成物中には現像促進もし
くは色素の拡散を促進する如き化合物を含ませて
もよい(たとえばベンジルアルコールの如き化合
物)。
減色法による天然色の再現には、ある波長範囲
に選択的分光感度をもつ乳剤と同波長範囲に選択
的な分光吸収をもつ色像供与化合物との組合せの
少くとも二つからなる感光材料が使用される。
特に青感性ハロゲン化銀乳剤と黄色色素放出レ
ドツクス化合物との組合せ、緑感性乳剤とマゼン
タ色素放出レドツクス化合物との組合せ並びに赤
感性乳剤とシアン色素放出レドツクス化合物との
組合せからなる感光要素は有用である。これら乳
剤と色素放出レドツクス化合物との組合せ単位は
感光材料中で面対面の関係で層状に重ねて塗布さ
れてもよいし、或いは各粒子状(色素放出レドツ
クス化合物とハロゲン化銀粒子が同一粒子中に存
在する)に形成されて混合して一層として塗布さ
れてもよい。
中間層と色像供与化合物を含有する層の間に特
開昭55−52056号に記載されるように隔離層を設
けてもよい。又中間層中に特願昭54−144155号に
記載されるようにハロゲン化銀乳剤を加えてもよ
い。
本発明のカラー拡散転写法写真感光材料に使用
しうる受像層は特開昭50−61228号、同51−73440
号、同52−64533号、同53−30328号、同54−
128336号などに記載された受像層が用いられる。
白色反射層については特開昭50−6337号、同55−
73042号などに記載されたものが用いられる。遮
光層については特開昭50−6337号、特願昭55−
56424号などに記載されたものが用いられる。
本発明のハロゲン化銀感光材料は、よく知られ
た現像処理方法あるいは、感光材料中に内蔵され
たDIRカラー処理液による方法等が適用される。
例えば、“Journal of the Society of Motion
Picture and Television Engineers”61巻(1953
年)、667〜701頁に記載されている方法等が適用
できる。
色素放出レドツクス化合物を用いて、カラー拡
散転写画像を得るためのプロセスについては、
Photographic Science and Engineering誌、
vol20、No.4,p155〜164,July/August 1976に
記載されている。又色素現像剤を用いた場合のカ
ラー画像を得るためのプロセスについては特公昭
49−26896号公報などに記載されている。
本発明のハロゲン化銀写真感光材料によれば、
製造中及び保存中に発生するスタチツクによるカ
ブリが生じないだけでなく、撮影時の被写体の紫
外線を効果的にカツトされたことにより鮮明な画
像を与える。特にカラー感光材料ではカメラレン
ズの紫外線吸収の差による色再現のばらつきがな
くなつた本当の色再現をした画像を与える。又、
形成された染料画像の光退色、変色も少なく、さ
らに乳化物安定性が良いという効果が得られる。
前記効果が得られる一方、感度、カブリ、接着、
等の写真性、物理性に好ましくない影響を生じな
い。特にカラー拡散転写用写真要素においては、
タイミング層への悪影響がなく保存性を著しく改
良する。
実施例−1
以下のようにして、カラー拡散転写用写真感光
材料に用いる感光シート、カバーシート、処理液
を作成した。
ポリエチレンテレフタレート透明支持体上に、
次の如き各層を塗布して感光シート1〜8を作つ
た。
感光シート:
(1) コポリ〔スチレン―N―ビニルベンジル―
N,N,N―トリヘキシルアンモニウムクロリ
ド〕3.0g/m2、ゼラチン3.0g/m2を含有する
受像層。
(2) 二酸化チタン20g/m2、ゼラチン2.0g/m2
を含有する白色反射層。
(3) カーボンブラツク2.0g/m2とゼラチン1.5
g/m2を含有する遮光層。
(4) 下記のシアン色素放出レドツクス化合物0.44
g/m2、トリシクロヘキシルホスフエート0.09
g/m2、2,5―ジ―tペンタデシルハイドロ
キノン0.008g/m2、およびゼラチン0.8g/m2
を含有する層。
(5) 赤感性内潜型直接ポジ臭化銀乳剤(銀の量で
1.03g/m2)、ゼラチン1.2g/m2、下記の造核
剤0.04mg/m2および2―スルホ―5―n―ペン
タデシルハイドロキノン・ナトリウム塩0.13
g/m2を含有する赤感性乳剤層。
(6) 2,5―ジ―t―ペンタデシルハイドロキノ
ン0.43g/m2、トリヘキシルホスフエート0.1
g/m2およびゼラチン0.4g/m2を含有する
層。
(7) 下記構造式のマゼンタ色素放出レドツクス
化合物(0.21g/m2)、構造式のマゼンタ色
素放出レドツクス化合物(0.11g/m2)、トリ
シクロヘキシルホスフエート(0.08g/m2)、
2,5―ジ―t―ペンタデシルハイドロキノン
(0.009g/m2)及びゼラチン(0.9g/m2)を
含有する層。
(8) 緑感性内潜型直接ポジ臭化銀乳剤(銀の量で
0.82g/m2)、ゼラチン(0.9g/m2)、層(5)と
同じ造核剤(0.03mg/m2)および2―スルホ―
5―n―ペンタデシルハイドロキノン・ナトリ
ウム塩(0.08g/m2)を含有する緑感性乳剤
層。
(9) (6)と同一の層。
(10) 下記構造のイエロー色素放出レドツクス化合
物(0.53g/m2)、トリシクロヘキシルホスフ
エート(0.13g/m2)、2,5―ジ―t―ペン
タデシルハイドロキノン(0.014g/m2)およ
びゼラチン(0.7g/m2)を含有する層。
(11) 青感性内潜型直接ポジ臭化銀乳剤(銀の量で
1.09g/m2)、ゼラチン(1.1g/m2)、層(5)と
同じ造核剤(0.04mg/m2)および2―スルホ―
5―n―ペンタデシルハイドロキノン・ナトリ
ウム塩(0.07g/m2)を含有する青感性乳剤
層。
(12) 表1に示す紫外線吸収剤(各々4×
10-4mol/m2)をトリス(2―エチルヘキシ
ル)ホスフエート(0.02g/m2)を用いて乳化
分散した、ゼラチン(1.0g/m2)、ポリメチル
メタアクリレートラテツクス(0.06g/m2)お
よび硬膜剤としてトリアクロイルトリアジン
(0.02g/m2)を含む紫外線吸収剤含有層。
試料1〜8をそれぞれ下記カバーシートと面対
面で重ね合せて、接触面積100cm2当り1.5Kgの圧力
をかけたまま50℃、相対湿度50%、3日間放置
(接触加熱経時)した後それぞれのカバーシート
の中和タイミング時間を測定した。
中和タイミング時間は指示薬としてチモールフ
タレインを白色顔料層に分散・塗布したシートと
所望のカバーシートを重ね合わせ、アルカリ性処
理液を展開した後、指示薬の分光濃度が処理接後
の半分の濃度になる時間を測定する方法で求めら
れる。この結果を表1に示す。
カバーシートの構成
透明なポリエチレンテレフタレート支持体上に
順次、以下の層1′〜3′を塗布してカバーシート
を作製した。
(1)′ アクリル酸とアクリル酸ブチルの80対20
(重量比)の共重合体(22g/m2)および1,
4―ビス(2,3―エポキシプロポキシ)―ブ
タン(0.44g/m2)を含有する層。
(2)′ アセチルセルロース(100gのアセチルセル
ロースを加水分解して、39.4gのアセチル基を
生成するもの)(3.8g/m2)およびスチレンと
無水マレイン酸の60対40(重量比)の共重合体
(分子量約5万)のメタノール開環物(0.23
g/m2)および5―(2―シアノ―1―メチル
エチルチオ)―1―フエニルテトラゾール
(0.154g/m2)を含有する層。
(3)′ スチレン―n―ブチルアクリレート―アク
リル酸―N―メチロールアクリルアミドの49.7
対42.3対3対5(重量比)共重合体ラテツクス
とメチルメタアクリレート―アクリル酸―N―
メチロールアクリルアミドの93対4対3(重量
比)共重合体ラテツクスを前者のラテツクスと
後者のラテツクスの固形分比が6対4になるよ
うに混合して塗布して厚さ2μの層。
処理液の組成
1―p―トリル―4―ヒドロキシメチル―4―
メチル―3―ピラゾリドン 6.9g
メチルハイドロキノン 0.3g
5―メチルベンゾトリアゾール 3.5g
亜硫酸ナトリウム(無水) 0.2g
カルボキシメチルセルロースNa塩 58g
水酸化カリウム(28%水溶液) 200cc
ベンジルアルコール 1.5cc
カーボンブラツク 150g
水 685cc
表1から明らかな様に、本発明の感光シートを
用いた場合、従来の感光シートに比べてカバーシ
ートの中和タイミング時間が短くならない利点を
有する。
The present invention relates to silver halide photographic materials, and more particularly to a method for preventing static marks that occur during the production of silver halide photographic materials by incorporating an ultraviolet absorber into the silver halide photographic materials. It is well known that ultraviolet radiation has a detrimental effect on photographic materials. Photographic light-sensitive materials are generally made of silver halide as a main component on a relatively highly electrically insulating support such as a film support made of cellulose triacetate, polyethylene terephthalate, polystyrene, or polycarbonate, or a laminated paper coated with these. The surface of the photographic material has fairly high electrical insulation properties. For this reason, during manufacturing or handling of a photographic material, the surface of the material comes into contact with an object made of the same or different material, and then when the material is rubbed or peeled off, an electric charge is generated. This phenomenon is called electrification, and when the accumulation of static electricity due to this electrification reaches a certain limit, an air discharge occurs instantaneously, and discharge sparks are generated at the same time. When the photographic light-sensitive material is exposed to light due to the occurrence of this electric discharge, it may become dendritic, feather-like, or
A dotted or radial image appears. Images obtained due to such causes are called static marks in the photographic industry. The spectral energy distribution of this type of discharge that causes static marks is 200 nm.
~550nm, and the intensity is particularly significant between 300nm and 400nm, and it is known that light energy in this range is the cause of static mark generation. Therefore, conventionally, for example,
As described in Japanese Patent Application Laid-open No. 10726, Japanese Patent Application Laid-open No. 51-26021, French Patent No. 2036679, etc., UV absorbers can be used to block ultraviolet light, especially in the wavelength range of 300 to 400 nm. Attempts have been made to prevent the occurrence of tick marks. For such purposes, e.g.
Benzotriazole compounds described in US Pat. No. 3253921, etc., cinnamic acid compounds described in US Pat. No. 3707375 and US Pat.
Aminobutadiene compounds such as those described in No. 4195999 have been widely used as ultraviolet absorbers in photographic materials, but none of them have
The absorption characteristics at 400 nm were poor, and the extinction coefficient in the wavelength range of 300 to 330 nm was particularly low. Up to now, there are 300 ultraviolet absorbers used in photographic materials.
Although there are compounds that absorb in the wavelength region of ~330 nm,
In either case, the miscibility with the binder is poor, the movement between layers is large and it diffuses to the other end and has an adverse effect, the emulsion is unstable and crystals precipitate,
Since it itself is not sufficiently stable against ultraviolet rays, heat, and humidity, it may become colored and become a stain, so it cannot be said to be sufficiently suitable for the above-mentioned uses. Therefore, there has been a strong desire to find ultraviolet absorbers that do not have these drawbacks. On the other hand, it is also well known that ultraviolet rays during photographing, that is, during exposure, have a harmful effect on photographic materials. Silver halide emulsifiers have sensitivity (inherent sensitivity) in the ultraviolet region, and when exposed to ultraviolet light, the resulting image differs from the actual visibility.
It is well known that this results in strange photographic images.
UV absorbers are used to prevent this.
Attempts have been made to block ultraviolet light between 300 and 400 nm. For this purpose, especially on the long wave side i.e.
A UV absorber with sharp absorption around 400 nm is desirable. It has already been known to use a mixture of two or more types of ultraviolet absorbers; for example,
48-5496, U.S. Patent No. 3705805, Special Publication No. 49-26138,
Tokuko Sho 48-31255, Tokuko Sho 48-30493, Tokko Sho 48-
31255, etc. especially US patents
3705805 describes the use of cinnamic acid ester compounds in combination with benzotriazole compounds, but the compounds in these patents do not have sharp absorption at the long wavelength end, i.e. around 390 to 400 nm, and are similar to silver halide emulsions. UV rays are insufficiently blocked. The ultraviolet absorber easily moves in the coating film, and this has a significant effect on the neutralization timing of the cover sheet, especially in the above-mentioned color diffusion transfer photographic element. Static marks are likely to occur because absorption at the short wavelength end, ie, around 300 to 340 nm, is insufficient. Benzotriazole and hydroxybenzophenone have drawbacks such as yellowing under alkaline conditions and insufficient diffusion resistance, which causes them to diffuse and become stains. The first object of the present invention is to provide a silver halide photographic light-sensitive material which prevents the generation of static marks and contains an ultraviolet absorber having good absorption characteristics in the wavelength range of 300 to 400 nm, and particularly a high absorption coefficient in the wavelength range of 300 to 330 nm. It is about providing. A second object of the present invention is to provide a silver halide photographic light-sensitive material containing an ultraviolet absorber that exhibits very little interlayer movement and has no adverse effects due to diffusion to the other end. For example, a silver halide emulsion layer in combination with at least one color image-providing compound on a support as described in Research Disclosure No. 151, 15162 (published November 1976), and an image-receiving layer, a white reflective layer. , a photosensitive sheet each having one or more light-shielding layers, and at least one light-shielding layer on another support.
In a photographic element for color diffusion transfer consisting of a cover sheet having two neutralizing layers and a neutralizing timing layer, and an alkaline processing liquid developed between the photosensitive sheet and the cover sheet, the ultraviolet absorber is added to the silver halide emulsion. On the other hand, it is already known that the photosensitive sheet is contained in the uppermost layer on the side opposite to the support, but the photosensitive sheet and the cover sheet have their coated surfaces overlapped, as described in JP-A-153628-1983. Research disclosure in form
No. 187, 18714 (published in November 1979), it is stored in a pack until the photo is taken. That is, the ultraviolet absorber-containing layer on the top layer of the photosensitive sheet and the neutralization timing layer on the top layer of the cover sheet are kept in strong contact with each other for a long period of time. When using conventionally known UV absorbers in such photographic elements, the UV absorber tends to migrate into the neutralization timing layer, which changes the resistance of the neutralization timing layer to alkali and increases the neutralization timing time. This has the disadvantage that the maximum density decreases due to neutralization occurring before image formation has sufficiently progressed due to the shortening of the image formation. It is an object of the present invention to provide a photographic element for color diffusion transfer containing an ultraviolet absorber which can eliminate these drawbacks. A third object of the present invention is to provide a silver halide photographic light-sensitive material containing an ultraviolet absorber which has excellent emulsifier stability and is resistant to precipitation of crystals even after long-term storage. A fourth object of the present invention is to provide a silver halide photographic material containing an ultraviolet absorber that is sufficiently stable against ultraviolet rays, heat, and humidity. A fifth object of the present invention is to provide a silver halide photographic light-sensitive material containing an ultraviolet absorber that does not affect the photographic properties such as sensitivity and fog, and the physical properties of the film such as adhesion. As a result of extensive studies, the present inventors discovered that at least one compound represented by the general formula () and
At least one of the compounds represented by the general formula ()
It has been discovered that a photographic material that achieves the above objectives can be obtained by using a combination of species. In the formula, R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-amyl group, t -amyl group, methoxyethyl group, ethoxypropyl group, hydroxyethyl group, chloropropyl group, cyanoethyl group, etc.), or a halogen atom (for example, chlorine atom, bromine atom, etc.), R 2 is a hydrogen atom, and has 1 carbon atom ~5 alkyl groups (e.g. methyl, ethyl, n-
Propyl group, isopropyl group, n-butyl group, n
-amyl group, etc.), or an aryl group having 6 to 20 carbon atoms (e.g., phenyl group, tolyl group, mesityl group,
chlorophenyl group, etc.), and R3 is an alkyl group having 12 to 18 carbon atoms (e.g., n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group,
n-octadecyl group, etc.). n is an integer of 1 or 2. R 4 and R 5 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, n-butyl group, n-hexyl group, cyclohexyl group, n-decyl group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N,N-diethylaminopropyl group, cyanoethyl group, phenethyl group, benzyl group, p-
t-Butylphenethyl group, pt-octylphenoxyethyl group, 3-(2,4-di-t-amylphenoxy)propyl group, ethoxycarbonylmethyl group, 2-(2-hydroxyethoxy)ethyl group, 2- (furylethyl group, etc.), or carbon number 6-20
aryl group (e.g. tolyl group, phenyl group,
Anisyl group, mesityl group, chlorophenyl group,
2,4-di-t-amyl phenyl group, naphthyl group, etc.), and R 4 and R 5 may be the same or different from each other, but do not simultaneously represent a hydrogen atom. Furthermore, R 4 and R 5 may be combined and integrated, and in that case, the cyclic amino group (e.g., piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group, etc.) represents an atomic group. R 6 is a cyano group, -
COOR 8 , --COR 8 or --SO 2 R 8 , R 7 represents a cyano group, --COOR 9 , --COR 9 , --SO 2 R 9, R 8 and R 9 each have 1 to 20 carbon atoms. alkyl group,
Or it represents an aryl group having 6 to 20 carbon atoms, and has the same meaning as the alkyl group or aryl group represented by R 4 or R 5 . Furthermore, R 8 and R 9 may be combined and integrated, and when integrated, a 1,3-dioxocyclohexane ring (for example, dimedone, 1,3-dioxo-5,5-diethylcyclohexane, etc.), 1, 3
-diaza 2,4,6-trioxocyclohexane ring (e.g. barbituric acid, 1,3-dimethylbarbituric acid, 1-phenylbarbituric acid, 1-methyl-3-octylbarbituric acid,
1-ethyl-3-octylbarbituric acid, 1-
ethyl-3-octyloxycarbonylethylbarbituric acid, etc.), 1,2-diaza 3,5-dioxocyclopentane ring (e.g. 1,2-diaza 1,2-dimethyl-3,5-dioxocyclopentane) , 1,2-diaza 1,2-diphenyl-3,5-dioxocyclopentane, etc.), or 2,4-diaza 1-alkoxy-3,5-dioxocyclohexene ring (for example, 2,4-diaza 1 -Ethoxy-4-ethyl-3,5-dioxocyclohexene, 2,4-diaza1-ethoxy4-[3-(2,4-di-t-amylphenoxy)propyl]-3,5-dioxocyclohexene, etc. ) represents the atomic group necessary to form. n
is 2, R 4 , R 5 , and R 8 each further represent an alkylene group (e.g., methylene group, ethylene group, decamethylene group, etc.) or an arylene group (e.g., phenylene group, etc.), and R 4 , R 5 and at least one of R 8 represents an alkylene group or an arylene group,
Can form dimers. In the general formula (), R 1 preferably represents an alkyl group having 1 to 5 carbon atoms, R 2 represents a hydrogen atom, and R 3 represents an alkyl group having 12 to 18 carbon atoms. Further, in the general formula (), preferably n=1
, R 4 and R 5 each represent an alkyl group having 1 to 20 carbon atoms, R 6 represents a cyano group, -SO 2 R 8 ,
R 7 represents a cyano group, -COOR 9 . R 8 and R 9 are each an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms.
The total number of carbon atoms in R 4 , R 5 , R 8 and R 9 is preferably 12 to 80. In general formula (), R 1 is particularly preferably an alkyl group having 1 to 5 carbon atoms, R 2 is a hydrogen atom, and R 3 is an alkyl group having 12 to 18 carbon atoms. Further, in the general formula (), particularly preferably n = 1, R 4 and R 5 each represent an alkyl group having 1 to 6 carbon atoms, R 6 represents -SO 2 R 8 , and R 7
- represents COO. 9 . R 8 represents an optionally substituted phenyl group (e.g., phenyl group, tolyl group, etc.), R 9 represents an alkyl group having 12 to 20 carbon atoms, and the total number of carbon atoms in R 4 , R 5 , and R 9 is 20 -52 is particularly preferred. The above second object of the present invention is preferably achieved by: (1) comprising at least one silver halide emulsion layer in combination with a color image-providing compound on a support, and as the layer furthest from the support; A photosensitive sheet including an ultraviolet absorber-containing layer containing a combination of at least one compound represented by general formula () and at least one compound represented by general formula (2), and (2) another support. a cover sheet having a neutralizing layer on the body and a barrier layer formed from a polymer latex on its side substantially furthest from the support, such that the cover sheets are in contact with each other on their sides opposite the support; This is achieved by a photographic material for color diffusion transfer that is arranged and suitable for uniformly spreading the processing composition between the photosensitive sheet and the cover sheet. As the barrier layer formed from the above polymer latex, the barrier layer described in JP-A-54-155837 is advantageously used. A preferred embodiment of the color diffusion transfer photographic light-sensitive material of the present invention is a so-called "laminated integrated" photographic film unit, in which an image-receiving layer, a white reflective layer, and a light-shielding layer are provided on a transparent support. , at least one silver halide emulsion layer combined with a color image-providing compound, and a layer containing an ultraviolet absorber are coated in this order, and on top of this, a neutralizing layer is coated on another transparent support. A photosensitive unit constituted by stacking cover sheets on which a sum timing layer and the above-mentioned barrier layer are coated in this order,
Furthermore, the photosensitive unit may include a rupturable container (bag) filled with an alkaline processing composition (including a developing agent and a light shielding agent). This container is located outside and in contact with the barrier layer and the ultraviolet absorber-containing layer, and is located such that the intended rupture opening of the container can extend the alkaline treatment composition between these layers. It is preferable that the Belgian patent 757959 for laminated integral photographic film units or Research Disclosure, volume 151
Described in No.15162. Here, the barrier layer is used because the permeability of the alkaline processing composition is highly dependent on temperature, and the purpose of the barrier layer is to obtain an excellent color image over a wide processing temperature range. As mentioned above, a so-called neutralization timing layer having a neutralization timing function can be provided separately from the barrier layer. Representative examples of the compounds represented by the general formulas () and () of the present invention are shown below, but the compounds of the present invention are not limited thereto. Exemplary compounds of general formula () Compounds used in the present invention may be used, for example, in the U.S. patent
No. 4200464, Beilsteins Handbuchder
It can be easily synthesized from the corresponding cyanoacetate and a substituted benzaldehyde or ketone according to the method described in Organischen Chemie (4th edition), Vol. 10, p. 521 (1942). Give an example. Synthesis method-1 (Exemplary compound-3) Tolualdehyde (50.0g), cyanoacetic acid ethyl ester (49.0g), acetic acid (7.5ml), and ammonium acetate (3.5g) are mixed with ethyl alcohol (165ml).
Heat under reflux for 2 hours. After the reaction, concentrate the ethyl alcohol to 80ml under reduced pressure, leave it at room temperature, filter the precipitate under suction, and wash with water and a small amount of ethyl alcohol to obtain ethyl-2-cyano-3- which melts at 94-95℃. A yield of 80 g of (4-methylphenyl)-acrylate is obtained. This compound (32.2 g), cetyl alcohol (43.5 g) and tetrabutoxytitanium (1.5 ml) were mixed and heated and stirred at 110° C. for 3 hours under reduced pressure. The reaction solution is recrystallized from ethyl acetate and methyl alcohol to obtain white crystals that melt at 62-63°C. The target product was confirmed by IR, NMR, and elemental analysis results. Synthesis method-2 (Exemplary compound-6) p-chlorobenzaldehyde (35.4g), cyanoacetic acid ethyl ester (29.7g), and acetic acid (5ml)
and ammonium acetate (2.2 g) in ethyl alcohol (100 ml) are heated under reflux for 2 hours. After the reaction, the ethyl alcohol was concentrated to 50 ml, and after being left at room temperature, the precipitate was filtered under suction and washed with a small amount of ethyl alcohol. Ethyl-2-cyano-3-(4-chlorophenyl) melted at 88-89°C. A yield of 51 g of acrylate is obtained. This compound (47.1 g), cetyl alcohol (58.1 g) and tetrabutoxytitanium (2 ml) were mixed and heated and stirred at 110° C. for 3 hours under reduced pressure. When methyl alcohol is added to the reaction solution and heated to dissolve and recrystallize, white crystals that melt at 57-58°C are obtained. The target product was confirmed by IR, NMR, and elemental analysis results. Exemplary compounds of general formula () Compounds used in the present invention may be used, for example, in the U.S. patent
It can be easily synthesized according to the methods described in No. 4195999, JP-A No. 51-56620, etc., and examples of its synthesis are listed below for reference. Synthesis method-1 (Exemplary compound-8) 3-anilinoacroleinanyl (13.3g) and dodecylphenylsulfonylacetate (23.1g)
g) in acetic anhydride (40ml) at 85-90°C for 2 hours. Acetic anhydride was removed under reduced pressure, ethyl alcohol (40 ml) and diethylamine (9.5 g) were added, and the mixture was refluxed for 2 hours. Distill the ethyl alcohol,
The residue was purified by column chromatography (Merck Kieselgel)
60), collect the benzene distillate, and recrystallize from ethyl alcohol to obtain the desired product, which melts at 69℃.
Get 13g. The target product was confirmed by IR, NMR, and elemental analysis results. Synthesis method-2 (Exemplary compound-10) 3-anilinoacroleinanyl (12.8 g) and malononitrile (4.8 g) are heated to 85-90°C for 2 hours in acetic anhydride (50 ml). Acetic anhydride was removed under reduced pressure, ethyl alcohol (50 ml) and dibutylamine (15.0 g) were added, and the mixture was refluxed for 1 hour. After the reaction, ethyl alcohol was distilled off and the residue was heated to 157℃ and 0.03mm.
Distillation with Hg yields 5.0g of the desired product. IR,
The target product was confirmed by NMR and elemental analysis results. The features of the present invention will be described below. Since the long wavelength end of the compound of general formula () is sharp, there is no influence of ultraviolet rays on the silver halide emulsion, and good images can be obtained. The absorption range (short wave) of the compound of general formula () compared to the absorption range (long wave) of the compound of general formula ()
is in a very appropriate range, and by mixing the two, an ideal ultraviolet absorption ability that can sufficiently absorb the wavelength range of 300 to 400 nm can be obtained. For this reason, it is possible to sufficiently absorb the wavelength region of 300 to 400 nm, which is the spectral energy region of discharge luminescence that causes static marks, and especially the wavelength region of 300 to 330 nm, which cannot be said to have been sufficiently absorbed in the past. It is possible to prevent the occurrence of tick marks. Although p-alkoxy-substituted cinnamate esters (R 1 in the general formula () is p-alkoxy) are known, their absorption range is at long wavelengths, so they cannot sufficiently cover the short wavelength side. In this respect, the method of mixing the compounds of general formula () and general formula () has a significant feature. The compounds of general formula () and general formula () migrate to other layers in the coating film layer very little. Particularly in the case of color diffusion transfer photographic elements, there is no adverse effect on neutralization timing time (usually resulting in shorter neutralization timing time) since there is no migration into the timing layer. It has excellent emulsion stability, and crystals do not easily precipitate even after long-term storage. The ultraviolet absorbing compound used in the present invention is stable against heat and humidity. In addition to not causing staining, it does not have any adverse effects on the image forming process (for example, inhibiting development). A photographic light-sensitive material with excellent characteristics free from the drawbacks of conventionally known ultraviolet absorbers or their methods of use was obtained. These characteristics can be effectively utilized not only in general photographic materials but also in particular in photographic elements for color diffusion transfer. In the present invention, general formula () and general formula ()
The mixing ratio of the compounds is determined according to the distribution of discharge light emission, and three or more types can be mixed if necessary, but preferably ()/() = 0.4 to 1.5
A mixture of two types (molar ratio), particularly preferably 0.6 to
1.2 (molar ratio). The coating amount of the ultraviolet absorber of the present invention is 300~
The amount is preferably such that the maximum transmission density at 400 nm is 0.5 to 3.0, more preferably 0.8 to 2.0. The following dispersion method can be applied to add the compound used in the present invention into a silver halide photosensitive element. For example, high-boiling organic solvents that are substantially insoluble in water, such as alkyl esters of phthalic acid (e.g., dibutyl phthalate, dioctyl phthalate, etc.), trimellitic acid esters (e.g., tri-
t-octyl trimellitate), aromatic ethers, phosphoric acid esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), alkylamide (e.g., N,N-diethyl laurylamide), etc., and emulsifying and dispersing the resulting solution in an aqueous solution of a hydrophilic organic colloid (e.g., US Pat. No. 2,322,027
water-insoluble high-boiling organic solvents that are further combined with auxiliary solvents (e.g., water-soluble solvents such as methanol, acetone, methyl cellosolve, etc., and substantially water-insoluble solvents such as ethyl acetate, butyl acetate). Emulsification and dispersion methods used (e.g., U.S. Pat. No. 2,739,888
No. 3,351,681, JP-A No. 51-59943, etc.), the compound used in the present invention can be used in organic solvents (substantially water-insoluble high-boiling organic solvents, substantially water-insoluble low-boiling organic solvents, Water-miscible organic solvent, etc.) (or if it is an oil itself, it may be used as is) and added to an aqueous polymer latex dispersion or a polymer latex containing a hydrophilic colloid. A latex dispersion method in which the compound used in the invention is dispersed in a state in which it is impregnated into polymer latex particles (for example,
No. 39853, JP-A No. 51-59942, JP-A No. 51-59943
), the compound used in the present invention is dissolved in a water-soluble solvent (e.g., acetone, methyl cellosolve, methanol, ethanol, etc.) and directly added to the hydrophilic organic colloid coating solution of the photosensitive silver halide photosensitive material. If the compound used in the present invention is oily at room temperature, it may be emulsified and dispersed in a hydrophilic organic colloid solution and added to a photographic coating solution. In particular, it is soluble in a substantially water-insoluble high-boiling organic solvent;
Alternatively, a method of emulsifying and dispersing in a hydrophilic organic colloid aqueous solution by dissolving it in combination with an auxiliary solvent, or a latex dispersion method is preferable. The ultraviolet absorbing compound used in the present invention is emulsified and dispersed using about 0.1 to about 10 ml, preferably 0.2 to 4 ml, of a high-boiling organic solvent for emulsification and dispersion per gram. In addition, the weight ratio of the ultraviolet absorbing compound used in the present invention to the dispersing polymer latex is about 0.1 to about 10.
g, preferably in the range of 0.2 to 4 g, to disperse the latex. In these various dispersion methods, the compounds of general formulas () and () can be dispersed individually and then the two dispersions can be mixed and used, or on the other hand, two or more types of compounds can be dispersed simultaneously. You may do so. The ultraviolet absorbing compound used in the present invention has a coating amount of about 5 to about 1500 mg/m 2 on the silver halide photosensitive material.
It can be used within the range of In particular, it is preferably about 50 to about 1500 for color photosensitive materials for printing (e.g. color paper, color positive film).
mg/m 2 , preferably about 5 to about 650 mg/m 2 for color photosensitive materials for photography (for example, color negative film, color liver film). When the compound used in the present invention is included in a silver halide light-sensitive material, it is used in a smaller amount than conventional ultraviolet absorbers, and a better effect can be obtained, so that it does not soften the film or deteriorate the interlayer density in a multilayer photographic material.
Furthermore, it does not cause adhesion on the surfaces between photographic materials. Emulsified dispersion of the compound used in the present invention,
A solution dissolved in a water-soluble organic solvent is stable without causing particle enlargement or crystal precipitation, and can be used as a photosensitive silver halide emulsion or a non-photosensitive hydrophilic colloid layer (e.g. gelatin layer). It does not become opaque even when added to. The compounds used in the present invention in silver halide photosensitive elements are stable to heat. The compound used in the present invention is disclosed in US Pat. No. 3,253,921.
No. 3707375, No. 3705805, No. 3271156,
No. 3754919, No. 3794493, British Patent No. 1338265
No., Special Publication No. 50-25337, U.S. Patent No. 3692525
No. 3738837, No. 3698907, Special Publication No. 1973-
Publication No. 26138, No. 49-26139, U.S. Patent No. 3936305
Known photographic ultraviolet absorbers and known photographic antioxidants (e.g., hydroquinone derivatives, catechol derivatives, aminophenol derivatives, gallic acid derivatives, etc.) described in No. 3687671, No. 3694211, etc. It can also be used together with known color image forming agents. The hydrophilic organic colloid used in the present invention includes:
Examples include gelatin, gelatin derivatives (eg, phthalated gelatin, etc.), carboxycellulose derivatives, sulfocellulose derivatives, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, and the like. Examples of the photographic layer of the silver halide photographic material containing the ultraviolet absorbing compound used in the present invention include the following hydrophilic organic colloid layers.
Examples include a photosensitive silver halide emulsion layer and a non-photosensitive layer (eg, a surface protective layer, a back layer, an antihalation layer, an intermediate layer, an undercoat layer, etc.). The ultraviolet absorbing compound used in the present invention is a surface protective layer, a back layer, an antihalation layer in a black-and-white light-sensitive material, and a top layer (e.g., a surface protective layer), an intermediate layer, an antihalation layer, a support layer in a color light-sensitive material. It is preferably included in the light-sensitive silver halide emulsion layer furthest from the body. The silver halide photographic material used in the present invention is
The support consists of at least one silver halide emulsion layer and at least one non-light sensitive layer. A multilayer, multicolor photographic material having at least two different spectral sensitivities on a support can be applied to the present invention. A multilayer color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. Further, as a non-photosensitive layer, a protective layer, an intermediate layer, an antihalation layer, a back layer, an undercoat layer, etc. can be provided. U.S. Patent No. 3726681, U.S. Patent No. 3516831,
British Patent No. 923045, West German Patent Application (OLS)
It can also be applied to multilayer color photographic materials described in No. 2018341, etc. As the silver halide used in the present invention, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. can be used, and the silver halide emulsion can be prepared by various known methods. can get. This silver halide emulsion contains chemical sensitizers (e.g., sulfur sensitizers such as thiourea, allylthiocarbamide, allyl isothiocyanate, cystine, potassium chloroaurate, auricul trichloride, potassium auriculitiocyanate, etc.). gold compounds, many other noble metal sensitizers, etc.), many known reduction sensitizers, and the like. Furthermore, known stabilizers or antifoggants such as triazoles, imidazoles, and azaindenes may be added to these silver halide emulsions. Furthermore, various color image forming agents are used in color photographic materials. For example, 2 or 4 equivalents of benzoylacetanilide and pivaloylacetanilide type yellow couplers, 2 or 4 equivalents of pyrazolone, indazolone or cyanoacetyl type magenta couplers, 2 or 2 equivalents of phenolic or naphthol type couplers. 4
There are equivalent cyan couplers, colored couplers that develop cyan or magenta (the two equivalents of yellow, magenta, or cyan couplers may be DIR couplers). It is desirable that these couplers be diffusion resistant. In addition, commonly used known additives (for example, spectral sensitizers, color stain inhibitors, antifading agents, hardeners, surfactants, antistatic agents, etc.) can also be applied. The silver halide photosensitive materials of the present invention include, in particular, B/W high-sensitivity photographic films, microscopic films, films for printing sensitive materials (lithographic films, etc.), color negative films, color reversible films, color direct positive films, and color positive films. Examples include paper, color diffusion transfer photographic materials, and the like. In particular, the present invention can bring about remarkable effects in light-sensitive materials for color diffusion transfer. For color diffusion transfer photographic materials, for example, Belgian patents 732985, 757959, and Belgian patents 1973-
33697, etc., and for more details,
Research Disclosure
Disclosure) No. 151, 15162 (issued November 1976)
It is described in. Various compounds can be used as the color image-providing compound used in color diffusion transfer, but dye-releasing redox compounds and couplers are particularly useful. Among dye-releasing redox compounds, compounds that undergo oxidation and release dyes through alkaline hydrolysis include those described in the following literature. U.S. Patent No. 4053312, U.S. Patent No. 4055428, U.S. Patent No. 4076529
No. 4152153, No. 4135929, Japanese Unexamined Patent Publication No. 1973-
No. 149328, No. 51-104343, No. 53-46730, No.
No. 54-130122, No. 53-3819, JP-A-56-12642
No. 56-16130, No. 56-16131, etc. Among these, those that emit yellow pigment: U.S. Patent No. 4013633, JP-A No. 53-149328, No. 56-16131, etc.
No. 51-114930, Patent Application No. 148237, Research
Research Disclosure
17630 ('78), 16475 ('77), etc. Those that emit magenta dye: U.S. Patent Nos. 3954476, 3931144, and 3932308
No. 53-23628, 52-106727, 54
−65034, No. 54-161332, No. 55-4028, No.
No. 55-36804, Patent Application No. 149777, No. 54-
No. 146655, No. 54-42848, West German Patent Application (OLS) No. 2847371, etc. Those that emit cyan dye: U.S. Patent No. 3942987, No. 3929760, No. 4013635
No. 51-109928, No. 53-149328, No. 52
-8827, No. 53-143323, No. 53-47823, Japanese Patent Application No. 54-146654, etc. In addition, redox compounds that release dyes when the compound that is not oxidized undergoes ring closure, etc. Those described in the following documents can be mentioned. U.S. Patent No. 4139379, U.S. Patent No. 3980479, U.S. Patent No. 3908479
No., West German Patent Application (OLS) No. 2402900,
2448811, British Patent No. 1464104, British Patent No. 1464105 or Belgian Patent No. 8644656, etc. Further, couplers used in the present invention include, for example,
The Theory of Photographic Process (Part 4)
(Ed., 1977, edited by TH James), Chapter 12. The silver halide emulsion used in the color diffusion transfer photographic light-sensitive material of the present invention is a hydrophilic colloid of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof. The halogen composition of the dispersion is selected depending on the purpose of use of the light-sensitive material and processing conditions, but silver bromide, silver iodobromide or silver chloroiodobromide is particularly preferred. However, the iodide content is 10mol%
Below, the chloride content is 30 mol% or less. In this case, either a negative emulsion that forms a surface latent image or a direct reversal emulsion can be used. The latter emulsion includes an internal latent image type emulsion and a pre-fogged direct reversal type emulsion. Internal latent image type silver halide emulsions can be advantageously used; emulsions of this type are described, for example, in U.S. Pat.
No. 2592250, No. 3206313, No. 3447927, No. 3447927, No. 3206313, No. 3447927, No.
Examples include conversion type emulsions, core/shell type emulsions, and emulsions incorporating different metals, which are described in Nos. 3761276 and 3935014. As a nucleating agent for this type of emulsion, the U.S. patent
Hydrazines described in No. 2588982 and No. 2563785; Hydrazides and hydrazones described in No. 3227552; British Patent No. 1283835, Japanese Patent Publication No. 1973-
38164, U.S. Patent No. 3734738, U.S. Patent No. 3719494, U.S. Pat.
Quaternary salt compounds described in No. 3615615; US patent
Representative examples include sensitizing dyes having a nucleating substituent in the dye molecule, as described in US Pat. It is something like that. The silver halide emulsions used in the present invention can have color sensitivity expanded by spectral sensitizing dyes, if desired. As the spectral sensitizing dye, cyanine dyes, merocyanine dyes, etc. can be used as appropriate. The developer used in processing the color diffusion transfer photographic material of the present invention may be included in the alkaline processing composition or in an appropriate layer of the photographic element. Examples of developing agents that can be used in the present invention are as follows. Hydroquinones, aminophenols, phenylenediamines, pyrazolidinones [e.g. phenidone, 1-
Phenyl-3-pyrazolidinone, dimezone (1-
phenyl-4,4-dimethyl-3-pyrazolidinone), 1-p-tolyl-4-methyl-4-oxymethyl-3-pyrazolidinone, 1-(4'-methoxyphenyl)-4-methyl-4-oxy Methyl
3-pyrazolidinone, 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidinone], etc. When using a dye-releasing redox compound,
Of these, black and white developers (among them pyrazolidinones) are particularly preferred, as they generally have properties that reduce stain formation in the image-receiving layer more than color developers such as phenylene diamines. The alkaline processing composition used for processing the color diffusion transfer photographic material of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate,
Suitably the treatment composition contains a base such as sodium phosphate and has a pH of about 9 or higher, preferably an alkaline strength of 11.5 or higher, containing sodium sulfite, ascorbate, piperidinohexose reductone. It may also contain antioxidants such as, and silver ion concentration regulators such as potassium bromide. Also hydroxyethyl cellulose,
Viscosity increasing compounds such as sodium carboxymethyl cellulose may also be included. The alkaline processing composition may also contain compounds that promote development or dye diffusion (eg, compounds such as benzyl alcohol). To reproduce natural colors by the subtractive color method, a photosensitive material consisting of at least two combinations of an emulsion with selective spectral sensitivity in a certain wavelength range and a color image-providing compound with selective spectral absorption in the same wavelength range is used. used. Especially useful are light-sensitive elements comprising a combination of a blue-sensitive silver halide emulsion and a yellow dye-releasing redox compound, a combination of a green-sensitive emulsion and a magenta dye-releasing redox compound, and a combination of a red-sensitive emulsion and a cyan dye-releasing redox compound. . The combined units of these emulsions and dye-releasing redox compounds may be coated in layers in a face-to-face relationship in the light-sensitive material, or in the form of individual grains (the dye-releasing redox compound and the silver halide grains are in the same grain). ) may be mixed and applied as a single layer. A separating layer may be provided between the intermediate layer and the layer containing the color image-providing compound as described in JP-A-55-52056. Furthermore, a silver halide emulsion may be added to the intermediate layer as described in Japanese Patent Application No. 144155/1983. The image-receiving layer that can be used in the color diffusion transfer photographic material of the present invention is disclosed in Japanese Patent Application Laid-Open Nos. 50-61228 and 51-73440.
No. 52-64533, No. 53-30328, No. 54-
The image receiving layer described in No. 128336 and the like is used.
Regarding the white reflective layer, see JP-A Nos. 50-6337 and 55-
The one described in No. 73042 etc. is used. Regarding the light-shielding layer, see Japanese Patent Application Laid-Open No. 1983-6337 and Japanese Patent Application No. 1987-
The one described in No. 56424 etc. is used. The silver halide photosensitive material of the present invention can be processed by a well-known development method or a method using a DIR color processing liquid incorporated in the photosensitive material.
For example, “Journal of the Society of Motion
Picture and Television Engineers” Volume 61 (1953
The method described in 2010), pp. 667-701 can be applied. For a process for obtaining color diffusion transfer images using dye-releasing redox compounds, see
Photographic Science and Engineering magazine,
vol 20, No. 4, p 155-164, July/August 1976. In addition, the process for obtaining color images using dye developers is described in Tokko Sho.
It is described in Publication No. 49-26896, etc. According to the silver halide photographic material of the present invention,
Not only does it not cause fog due to static that occurs during manufacturing and storage, but it also effectively blocks out ultraviolet rays from the subject when photographing, giving a clear image. In particular, color photosensitive materials provide images with true color reproduction that eliminates variations in color reproduction due to differences in ultraviolet absorption of camera lenses. or,
The dye image formed is less subject to photobleaching and discoloration, and furthermore, the emulsion stability is good.
While the above effects can be obtained, sensitivity, fog, adhesion,
There is no unfavorable effect on photographic properties and physical properties. Especially in photographic elements for color diffusion transfer.
Significantly improves storage stability without adversely affecting the timing layer. Example 1 A photosensitive sheet, a cover sheet, and a processing liquid for use in a photographic material for color diffusion transfer were prepared in the following manner. On a polyethylene terephthalate transparent support,
Photosensitive sheets 1 to 8 were prepared by coating the following layers. Photosensitive sheet: (1) Copoly [styrene-N-vinylbenzyl-
An image-receiving layer containing 3.0 g/m 2 of N,N,N-trihexylammonium chloride and 3.0 g/m 2 of gelatin. (2) Titanium dioxide 20g/m 2 , gelatin 2.0g/m 2
A white reflective layer containing. (3) Carbon black 2.0g/ m2 and gelatin 1.5
A light shielding layer containing g/m 2 . (4) The following cyan dye-releasing redox compound 0.44
g/m 2 , tricyclohexyl phosphate 0.09
g/m 2 , 2,5-di-tpentadecylhydroquinone 0.008 g/m 2 , and gelatin 0.8 g/m 2
A layer containing. (5) Red-sensitive latent type direct positive silver bromide emulsion (depending on the amount of silver)
1.03g/m 2 ), gelatin 1.2g/m 2 , the following nucleating agent 0.04mg/m 2 and 2-sulfo-5-n-pentadecylhydroquinone sodium salt 0.13
A red-sensitive emulsion layer containing g/m 2 . (6) 2,5-di-t-pentadecylhydroquinone 0.43g/m 2 , trihexyl phosphate 0.1
g/m 2 and a layer containing 0.4 g/m 2 of gelatin. (7) A magenta dye-releasing redox compound having the following structural formula (0.21 g/m 2 ), a magenta dye-releasing redox compound having the structural formula (0.11 g/m 2 ), tricyclohexyl phosphate (0.08 g/m 2 ),
Layer containing 2,5-di-t-pentadecylhydroquinone (0.009 g/m 2 ) and gelatin (0.9 g/m 2 ). (8) Green-sensitive latent type direct positive silver bromide emulsion (depending on the amount of silver)
0.82g/m 2 ), gelatin (0.9g/m 2 ), the same nucleating agent as layer (5) (0.03mg/m 2 ), and 2-sulfo-
A green-sensitive emulsion layer containing 5-n-pentadecylhydroquinone sodium salt (0.08 g/m 2 ). (9) Same layer as (6). (10) A yellow dye-releasing redox compound with the following structure (0.53 g/m 2 ), tricyclohexyl phosphate (0.13 g/m 2 ), 2,5-di-t-pentadecylhydroquinone (0.014 g/m 2 ), and Layer containing gelatin (0.7g/m 2 ). (11) Blue-sensitive latent type direct positive silver bromide emulsion (depending on the amount of silver)
1.09g/m 2 ), gelatin (1.1g/m 2 ), the same nucleating agent as layer (5) (0.04mg/m 2 ), and 2-sulfo-
A blue-sensitive emulsion layer containing 5-n-pentadecylhydroquinone sodium salt (0.07 g/m 2 ). (12) Ultraviolet absorbers shown in Table 1 (4×
Gelatin (1.0 g/m 2 ), polymethyl methacrylate latex ( 0.06 g/ m 2 ) and an ultraviolet absorber-containing layer containing triacryloyltriazine (0.02 g/m 2 ) as a hardening agent. Samples 1 to 8 were stacked face-to-face with the following cover sheets, and left at 50°C and relative humidity 50% for 3 days (contact heating time) while applying a pressure of 1.5 kg per 100 cm 2 of contact area. The neutralization timing time of the cover sheet was measured. The neutralization timing is determined by overlapping a sheet in which thymolphthalein as an indicator is dispersed and applied to a white pigment layer and a desired cover sheet, and after spreading an alkaline treatment solution, the spectral density of the indicator becomes half the concentration after treatment contact. It is determined by a method that measures the amount of time. The results are shown in Table 1. Construction of Cover Sheet A cover sheet was prepared by sequentially applying the following layers 1' to 3' on a transparent polyethylene terephthalate support. (1)′ Acrylic acid and butyl acrylate 80:20
(weight ratio) copolymer (22 g/m 2 ) and 1,
Layer containing 4-bis(2,3-epoxypropoxy)-butane (0.44g/m 2 ). (2)′ Acetylcellulose (100g of acetylcellulose is hydrolyzed to produce 39.4g of acetyl groups) (3.8g/m 2 ) and a 60:40 (weight ratio) combination of styrene and maleic anhydride. Methanol ring-opened product (0.23) of polymer (molecular weight approximately 50,000)
g/m 2 ) and 5-(2-cyano-1-methylethylthio)-1-phenyltetrazole (0.154 g/m 2 ). (3)′ Styrene-n-butyl acrylate-acrylic acid-N-methylolacrylamide 49.7
42.3:3:5 (weight ratio) copolymer latex and methyl methacrylate-acrylic acid-N-
A 93:4:3 (weight ratio) copolymer latex of methylol acrylamide was mixed and applied so that the solid content ratio of the former latex and the latter latex was 6:4, and the layer was coated to a thickness of 2 μm. Composition of treatment liquid 1-p-tolyl-4-hydroxymethyl-4-
Methyl-3-pyrazolidone 6.9g Methylhydroquinone 0.3g 5-methylbenzotriazole 3.5g Sodium sulfite (anhydrous) 0.2g Carboxymethylcellulose Na salt 58g Potassium hydroxide (28% aqueous solution) 200cc Benzyl alcohol 1.5cc Carbon black 150g Water 685cc Table 1 As is clear from the above, when the photosensitive sheet of the present invention is used, there is an advantage that the neutralization timing time of the cover sheet is not shortened compared to the conventional photosensitive sheet.
実施例―2
実施例―1で作製した感光シート2,5(本発
明)および6,7(比較用)をそれぞれ実施例1
と同様にカバーシートと接触加熱経時した。感光
シートを通常の写真ウエツジを用いて露光し次に
これらの感光シートとカバーシートの間に実施例
1の処理液を15℃で展開した。なお接触加熱経時
していない写真要素も同様に処理した。1時間後
にこれらの反射濃度を測定し、表2にはB,G,
Rの各々の最大濃度値(Dmax)を示した。
表2から、本発明の感光シートは処理前の経時
安定性が著しく改良されていることが明確であ
る。 Example-2 Photosensitive sheets 2, 5 (invention) and 6, 7 (for comparison) prepared in Example-1 were used in Example 1, respectively.
It was heated in contact with the cover sheet in the same manner as above. The photosensitive sheets were exposed using a conventional photographic wedge, and then the processing solution of Example 1 was developed at 15° C. between the photosensitive sheets and the cover sheet. Photographic elements that had not been subjected to contact heating were also processed in the same manner. After one hour, these reflection densities were measured, and Table 2 shows B, G,
The maximum concentration value (Dmax) of each R is shown. From Table 2, it is clear that the photosensitive sheet of the present invention has significantly improved stability over time before processing.
【表】
実施例―3
次のように透明支持体から順に塗布して試料9
〜12を作成した。
層1〜5は実施例―1に同じ。
層6は表3に示す紫外線吸収剤(各々4×
10-4mol/m2を用いた他は実施例―1の層12に
同じ。
試料9〜12に最低濃度になる量の光
(10CMS)を当てた後実施例―1と同じカバーシ
ート及び処理液を用いて同様に展開処理した。直
後から3時間までの反射濃度計Bフイルターの濃
度を記録し、その最大値を表3に示した。
試料11,12(比較用)はアルカリ条件下で黄色
着色した紫外線吸収剤が拡散してイエロー着色す
るのに対し、本発明の試料9,10はこの着色が全
く認められない。[Table] Example-3 Sample 9 was coated in the following order starting from the transparent support.
~12 created. Layers 1 to 5 are the same as in Example-1. Layer 6 contains the ultraviolet absorbers shown in Table 3 (4×
The same as layer 12 of Example-1 except that 10 -4 mol/m 2 was used. Samples 9 to 12 were exposed to an amount of light (10 CMS) that gave the lowest concentration, and then developed in the same manner as in Example 1 using the same cover sheet and processing solution. The density of the reflection densitometer B filter was recorded immediately after the test and for up to 3 hours, and the maximum value is shown in Table 3. In Samples 11 and 12 (for comparison), the ultraviolet absorber colored yellow under alkaline conditions diffuses and becomes yellow colored, whereas in Samples 9 and 10 of the present invention, this coloring is not observed at all.
【表】【table】
実施例―4
次の如く層(1)〜(12)を塗布し、感光シート13,
14,15を作成した。但し、層(1)〜(11)は実施例1と
同じである。
層(12) 表4に示す紫外線吸収剤(各々4×
10- 4mol/m2)トリス(2―エチルヘキシル)ホ
スフエート(0.02g/m2)を用いて乳化分散した
ゼラチン(1.0g/m2)、ポリメチルメタアクリレ
ートラテツクス(0.06g/m2)および硬膜剤とし
てトリアクリロイルトリアジン(0.02g/m2)を
含む紫外線吸収剤含有層。
感光シート1,2,3,8,13,14,15をそれ
ぞれ次の様にしてスタチツクマーク発生の頻度を
テストした。ステンレス製ローラー2本とゴムロ
ーラー1本で3角形の頂点を作り、暗室内で感光
シートをこのローラーにループ状にかけ、先端と
後端を接合した後1本のローラーにモーターを連
結し、毎分25mの速度で1時間回転させた後、感
光シートを取り外し、未露光のまま実施例1に記
載と同じカバーシートと処理液を用いて展開処理
し、白灯下で各試料のスタチツクマークを観察
し、同一面積あたりの数を数えて評価した。この
結果を表4に示す。
表4から明らかなように、スタチツクマークを
抑えるには一般式()と一般式()の化合物
を併用することが顕著な効果を示し、特に−3
と−8の併用ではスタチツクマークの発生は認
められなかつた。 Example-4 Layers (1) to (12) were coated as follows, and the photosensitive sheet 13,
14 and 15 were created. However, layers (1) to (11) are the same as in Example 1. Layer (12) Ultraviolet absorber shown in Table 4 (4×
10 - 4 mol/m 2 ) Gelatin (1.0 g/m 2 ) emulsified and dispersed using tris(2-ethylhexyl) phosphate (0.02 g/m 2 ), polymethyl methacrylate latex (0.06 g/m 2 ) and a UV absorber-containing layer containing triacryloyltriazine (0.02 g/m 2 ) as a hardening agent. Photosensitive sheets 1, 2, 3, 8, 13, 14, and 15 were tested for the frequency of static marks in the following manner. Two stainless steel rollers and one rubber roller make the apex of a triangle, and a photosensitive sheet is looped around these rollers in a dark room. After joining the front and rear ends, a motor is connected to one roller, and each After rotating at a speed of 25 m/min for 1 hour, the photosensitive sheet was removed and unexposed using the same cover sheet and processing solution as described in Example 1. were observed and evaluated by counting the number per same area. The results are shown in Table 4. As is clear from Table 4, the combined use of compounds of general formula () and general formula () has a remarkable effect in suppressing static marks, especially -3
No static marks were observed in the combined use of -8 and -8.
【表】【table】
Claims (1)
剤層及び少なくとも1つの非感光層を含むハロゲ
ン化銀写真感光材料において、下記一般式()
で表わされる紫外線吸収化合物の少なくとも1つ
と下記一般式()で表わされる紫外線吸収化合
物の少なくとも1つとの組合せを含有することを
特徴とするハロゲン化銀写真感光材料。 式中、R1は水素原子、炭素数1〜5のアルキ
ル基、又はハロゲン原子を表わし、R2は水素原
子、炭素数1〜5のアルキル基、又は炭素数6〜
20のアリール基を表わす。R3は炭素数12〜18の
アルキル基を表わす。nは1又は2の整数であ
る。R4とR5は各々水素原子、炭素数1〜20のア
ルキル基又は炭素数6〜20のアリール基を表わ
し、更にR4とR5は互いに同一もしくは異つてい
てもよいが、同時に水素原子を表わすことはな
い。更に又R4とR5は結合して一体化してもよく
その場合は環状アミノ基を形成するのに必要な原
子団を表わす。R6はシアノ基、―COOR8,―
COR8又は―SO2R8を表わし、R7はシアノ基、―
COOR9,―COR9又は―SO2R9を表わし、R8とR9
は各々炭素数1〜20のアルキル基、又は炭素数6
〜20のアリール基を表わし、更にR8とR9は結合
して一体化してもよく、一体化した場合は1,3
―ジオキソシクロヘキサン、バルビツール酸、
1,2―ジアザー3,5―ジオキソシクロペンタ
ン又は2,4―ジアザー1―アルコキシ―3,5
―ジオキソシクロヘキセンの核を形成するのに必
要な原子団を表わす。nが2のときは、R4,
R5,R8は各々更にアルキレン基又はアリーレン
基を表わし、R4,R5及びR8の少なくとも一つは
アルキレン基又はアリーレン基である。[Scope of Claims] 1. A silver halide photographic material comprising at least one silver halide emulsion layer and at least one non-photosensitive layer on a support, comprising the following general formula ()
1. A silver halide photographic material comprising a combination of at least one ultraviolet absorbing compound represented by the formula () and at least one ultraviolet absorbing compound represented by the following general formula (). In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and R 2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 6 to 5 carbon atoms.
represents 20 aryl groups. R 3 represents an alkyl group having 12 to 18 carbon atoms. n is an integer of 1 or 2. R 4 and R 5 each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 4 and R 5 may be the same or different from each other, but at the same time hydrogen It does not represent atoms. Furthermore, R 4 and R 5 may be combined and integrated, in which case they represent an atomic group necessary to form a cyclic amino group. R 6 is a cyano group, -COOR 8 , -
Represents COR 8 or -SO 2 R 8 , R 7 is a cyano group, -
COOR 9 , -COR 9 or -SO 2 R 9 , R 8 and R 9
are each an alkyl group having 1 to 20 carbon atoms or 6 carbon atoms
~20 aryl groups, and R 8 and R 9 may be combined to form a single unit, and when combined, 1,3
-Dioxocyclohexane, barbituric acid,
1,2-diaza 3,5-dioxocyclopentane or 2,4-diaza 1-alkoxy-3,5
-Represents the atomic group necessary to form the nucleus of dioxocyclohexene. When n is 2, R 4 ,
R 5 and R 8 each further represent an alkylene group or an arylene group, and at least one of R 4 , R 5 and R 8 is an alkylene group or an arylene group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4201281A JPS57157236A (en) | 1981-03-23 | 1981-03-23 | Photographic sensitive silver halide material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4201281A JPS57157236A (en) | 1981-03-23 | 1981-03-23 | Photographic sensitive silver halide material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57157236A JPS57157236A (en) | 1982-09-28 |
JPS6126055B2 true JPS6126055B2 (en) | 1986-06-18 |
Family
ID=12624262
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4201281A Granted JPS57157236A (en) | 1981-03-23 | 1981-03-23 | Photographic sensitive silver halide material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57157236A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1181384B (en) * | 1983-06-07 | 1987-09-23 | Minnesota Mining & Mfg | ULTRAVIOLET ABSORBER AND PHOTOGRAPHIC MATERIAL THAT INCLUDES IT |
-
1981
- 1981-03-23 JP JP4201281A patent/JPS57157236A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57157236A (en) | 1982-09-28 |
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