JPH0254268A - Photopolymerizable composition - Google Patents
Photopolymerizable compositionInfo
- Publication number
- JPH0254268A JPH0254268A JP20590388A JP20590388A JPH0254268A JP H0254268 A JPH0254268 A JP H0254268A JP 20590388 A JP20590388 A JP 20590388A JP 20590388 A JP20590388 A JP 20590388A JP H0254268 A JPH0254268 A JP H0254268A
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl group
- denotes
- formula
- aryl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract 2
- 229920000620 organic polymer Polymers 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 6
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000003094 microcapsule Substances 0.000 abstract description 2
- -1 trichloromethyl compound Chemical class 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 21
- 238000011282 treatment Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- QOXRFMBDPXGIKL-UHFFFAOYSA-N 6-methyl-1,3-benzoselenazole Chemical compound CC1=CC=C2N=C[se]C2=C1 QOXRFMBDPXGIKL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BREUOIWLJRZAFF-UHFFFAOYSA-N 1,3-benzothiazol-5-ol Chemical compound OC1=CC=C2SC=NC2=C1 BREUOIWLJRZAFF-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 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
- KOAOGWOLJJHLPN-UHFFFAOYSA-N 2-sulfanyl-3h-1,2-benzothiazole Chemical compound C1=CC=C2SN(S)CC2=C1 KOAOGWOLJJHLPN-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- WQJKBLBBLUDZEW-UHFFFAOYSA-N 4-ethoxy-1,3-benzothiazole Chemical compound CCOC1=CC=CC2=C1N=CS2 WQJKBLBBLUDZEW-UHFFFAOYSA-N 0.000 description 1
- DUMYZVKQCMCQHJ-UHFFFAOYSA-N 5-chloro-1,3-benzoselenazole Chemical compound ClC1=CC=C2[se]C=NC2=C1 DUMYZVKQCMCQHJ-UHFFFAOYSA-N 0.000 description 1
- YTSFYTDPSSFCLU-UHFFFAOYSA-N 5-chloro-1,3-benzothiazole Chemical compound ClC1=CC=C2SC=NC2=C1 YTSFYTDPSSFCLU-UHFFFAOYSA-N 0.000 description 1
- PNJKZDLZKILFNF-UHFFFAOYSA-N 5-methoxy-1,3-benzothiazole Chemical compound COC1=CC=C2SC=NC2=C1 PNJKZDLZKILFNF-UHFFFAOYSA-N 0.000 description 1
- UBIAVBGIRDRQLD-UHFFFAOYSA-N 5-methyl-1,3-benzoxazole Chemical compound CC1=CC=C2OC=NC2=C1 UBIAVBGIRDRQLD-UHFFFAOYSA-N 0.000 description 1
- AAKPXIJKSNGOCO-UHFFFAOYSA-N 5-phenyl-1,3-benzothiazole Chemical compound C=1C=C2SC=NC2=CC=1C1=CC=CC=C1 AAKPXIJKSNGOCO-UHFFFAOYSA-N 0.000 description 1
- NIFNXGHHDAXUGO-UHFFFAOYSA-N 5-phenyl-1,3-benzoxazole Chemical compound C=1C=C2OC=NC2=CC=1C1=CC=CC=C1 NIFNXGHHDAXUGO-UHFFFAOYSA-N 0.000 description 1
- AIBQGOMAISTKSR-UHFFFAOYSA-N 6-chloro-1,3-benzothiazole Chemical compound ClC1=CC=C2N=CSC2=C1 AIBQGOMAISTKSR-UHFFFAOYSA-N 0.000 description 1
- AHOIGFLSEXUWNV-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazole Chemical compound COC1=CC=C2N=CSC2=C1 AHOIGFLSEXUWNV-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RRARBJLDZRQCPP-UHFFFAOYSA-M C(C)C(=O)C.[OH-].[K+] Chemical compound C(C)C(=O)C.[OH-].[K+] RRARBJLDZRQCPP-UHFFFAOYSA-M 0.000 description 1
- IPSNGXBRIGUEJG-UHFFFAOYSA-N C=C.C=C.C=C.C=C.OCC(CO)(CO)CO Chemical group C=C.C=C.C=C.C=C.OCC(CO)(CO)CO IPSNGXBRIGUEJG-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical compound C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- BPTYDLGBSQCMFR-UHFFFAOYSA-N bis[4-(dipropylamino)phenyl]methanone Chemical compound C1=CC(N(CCC)CCC)=CC=C1C(=O)C1=CC=C(N(CCC)CCC)C=C1 BPTYDLGBSQCMFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- MXOAEAUPQDYUQM-UHFFFAOYSA-N chlorphenesin Chemical group OCC(O)COC1=CC=C(Cl)C=C1 MXOAEAUPQDYUQM-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- GPKUICFDWYEPTK-UHFFFAOYSA-N methoxycyclohexatriene Chemical group COC1=CC=C=C[CH]1 GPKUICFDWYEPTK-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000001544 thienyl group Chemical group 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は不飽和単量体と光重合開始剤と有機硼素化合物
とを含み、さらに必要により線状有機高分子重合体を含
む光重合性組成物に関し、特に印刷用原版の作製、プリ
ント基板作製用レジストまたはフォトマスク、白黒また
はカラーの転写発色用シートや発色シート作製などの用
途に用いることのできる高感度な光重合性組成物に関す
るものである。Detailed Description of the Invention [Industrial Application Field] The present invention provides a photopolymerizable material containing an unsaturated monomer, a photopolymerization initiator, an organoboron compound, and, if necessary, a linear organic polymer. Regarding compositions, in particular, highly sensitive photopolymerizable compositions that can be used for purposes such as the production of printing original plates, resists or photomasks for producing printed circuit boards, and the production of monochrome or color transfer coloring sheets and coloring sheets. It is.
重合可能なエチレン性不飽和化合物と、光重合開始剤と
、更に必要に応じて適当な皮膜形成能を有する線状有機
高分子重合体、熱重合防止剤等を混和させたものを感光
性組成物として写真的手法によって画像複製を行なう方
法は現在広く知られるところである。すなわち特公昭３
５−５０９３号公報、特公昭３５−８４９５号公報等に
記載される様に該感光性組成物は活性光線の照射により
光重合を起し、不溶化する。従って、感光性組成物を適
当な皮膜となし、所望の画像の陰画を通して活性光線の
照射を行い、適当な溶媒により未感光部のみを除去する
（以下単に現像とよぶ。）ことにより所望の光重合画像
を形成させることができる。このタイプの感光性組成物
は印刷板、プルーフ、ドライレジスト、塗料、ＵＶイン
キ、転写証録材料やマイクロレジスト等の感光剤として
極めて有用である。A photosensitive composition is a mixture of a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and, if necessary, a linear organic polymer having an appropriate film-forming ability, a thermal polymerization inhibitor, etc. 2. Description of the Related Art Methods of copying images using photographic methods are now widely known. In other words, Tokko Sho 3
As described in Japanese Patent Publication No. 5-5093 and Japanese Patent Publication No. 35-8495, the photosensitive composition undergoes photopolymerization and becomes insolubilized by irradiation with actinic rays. Therefore, by forming a photosensitive composition into a suitable film, irradiating active light through the negative of the desired image, and removing only the unexposed areas with an appropriate solvent (hereinafter simply referred to as development), the desired light can be produced. A polymerized image can be formed. This type of photosensitive composition is extremely useful as a photosensitive agent for printing plates, proofs, dry resists, paints, UV inks, transfer recording materials, microresists, and the like.
従来より、重合可能なエチレン性不飽和化合物の光重合
開始剤として、ベンジル、ベンゾイン、ベンゾインエチ
ルエーテノベミヒラーケトン、アンスラキノン、アクリ
ジン、フェナジン、ベンゾフェノン、２−エチルアンス
ラキノン等が代表的なものとして知られている。しかし
ながらこれらの開始剤は、実用上必ずしも充分な光重合
開始能力を示さず、光照射による画像形成には多くの時
間を要した。この欠点を改良するために通常ラジカル発
生剤に光吸収剤を組み合せることが提案されている。た
とえば本発明の一般式（Ｉ）で表わされるＳ−）リアジ
ン化合物のトリクロロメチル化合物に、特公昭５９−２
８３２８号公報に示される芳香族チアゾール化合物、特
開昭５４−１５１０２４号公報に示されるメロシアニン
色素、特開昭５８−４０３０２号公報に示される芳香族
チオピリリウム塩や芳香族ピリリウム塩、その他９−フ
ェニルアクリジン、
（式中、Ｒはアルキル基である。）
等の光吸収剤を組み合せ、更にはこれらの組み合せにＮ
−フェニルグリシン、２−メルカプトベンゾチアゾール
Ｎ／、Ｎ／ −ジメチルアミノ安息香酸エチル等の水
素供与体等を組み合せることによって、優れた光重合開
始能力を示すことが知られている。しかしこれらのラジ
カル発生剤と光吸収剤との組み合せでは実用系で用いた
場合必ずしも感度的には満足するものではなく、長時間
の露光を必要としたりあるいは強力な光源を必要とした
。Conventionally, representative photopolymerization initiators for polymerizable ethylenically unsaturated compounds include benzyl, benzoin, benzoin ethylethenobemichler ketone, anthraquinone, acridine, phenazine, benzophenone, and 2-ethyl anthraquinone. known as. However, these initiators do not necessarily exhibit sufficient photopolymerization initiation ability for practical use, and it takes a long time to form an image by light irradiation. In order to improve this drawback, it has been proposed to combine a radical generator with a light absorber. For example, in the trichloromethyl compound of the S-) riazine compound represented by the general formula (I) of the present invention,
Aromatic thiazole compounds shown in JP-A No. 8328, merocyanine dyes shown in JP-A-54-151024, aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-58-40302, and other 9-phenyl Acridine, (in the formula, R is an alkyl group) and other light absorbers are combined, and these combinations are further combined with N.
-Phenylglycine, 2-mercaptobenzothiazole N/, N/-It is known that excellent photopolymerization initiation ability is exhibited by combining hydrogen donors such as ethyl dimethylaminobenzoate. However, when these combinations of radical generators and light absorbers are used in practical systems, they are not necessarily satisfactory in terms of sensitivity, requiring long-time exposure or a powerful light source.
従って本発明は、より高感度な印刷用原版、プリント基
板作製用レジストまたはフォトマスク、白黒またはカラ
ーの転写発色用シートや発色シートに用いる感光性マイ
クロカプセルに有用な光重合性組成物を堤供することを
目的とする。Therefore, the present invention provides a photopolymerizable composition useful for highly sensitive printing original plates, resists or photomasks for producing printed circuit boards, and photosensitive microcapsules used in monochrome or color transfer coloring sheets and coloring sheets. The purpose is to
本発明者らは、上記のような技術の現状に鑑み、鋭意研
究の結果、光重合性組成物において、光重合開始剤とし
てトリアジン系化合物、有機硼素化合物および光によっ
てそれ自体で重合を開始する能力を有している特定の増
感剤の３者を組み合せることによって、より優れた光重
合開始能力を示すことができるという知見を得、これに
基づき、本発明をなすに至った。In view of the current state of the technology as described above, the present inventors have conducted intensive research and found that in a photopolymerizable composition, a triazine compound and an organic boron compound are used as a photopolymerization initiator, and the polymerization itself is initiated by light. We have obtained the knowledge that a combination of three specific sensitizers having this ability can exhibit superior photopolymerization initiation ability, and based on this, we have accomplished the present invention.
すなわち本発明は、活性光線により光重合が可能な少な
くとも１個のエチレン性不飽和基をもつ単量体と光重合
開始剤と、必要とするならば線状有機高分子重合体とを
含む光重合性組成物において、光重合開始剤として
（ａ） 少なくとも１種の下記一般式（１）：（Ｘは
ハロゲン原子を表わす。Ｙは−Ｃｘ３、−Ｎｌ２、−Ｎ
ＨＲ’ −ＮＲ２’又は−ＯＲ’を表わす。ここでＲ
′はアルキル基又はアリール基を表わす。またＲはアル
キル基、アリール基、−ＣＬ基又は千ＣＨ＝ＣＨ＋ｒ
Ｒ’を表わす。ここでＲ′はアリール基又は複素環基を
、ｎは１〜３の整数を表わす。）ら）少なくとも１種の
下記一般式（■）：（ＲＩＳＲ２、Ｒ３およびＲ４は同
じでも異っていてもよく、アルキル基、アリール基、ア
ラルキル基、アルカリール基、アルケニル基、アリサイ
クリック基、アリル基又は複素環基を表わし、Ｒ１、Ｒ
２、Ｒ３およびＲ４はその２個以上の基が結合している
環状構造であってもよい。ただしＲ１，Ｒ２、Ｒ３およ
びＲ４のうち少なくとも１つは、アルキル基である。Ｘ
○はアルカリ金属又はＳ
す。ここでＲ５、Ｒ６、Ｒ’およびＲ８は同じであって
も異っていてもよく水素、アルキル基、アリール基、ア
ラルキル基、アルカリール基、アルケニル基、アルキニ
ル基、アリサイクリック基又はアリル基を表わす。）、
および
（Ｃ） 少なくとも１種のビス（ジアルキルアミノ）
ベンゾフェノン又は下記一般式（■）：（２は窒素を含
む５員環の複素環核を形成するのに必要な非金属原子群
を表わし、該複素環はＳ、Ｓｅ又は０のいずれかを異項
原子として含有し、かつ縮合環となっている。Ｒ９はア
ルキル基を表わす。ＲＩＯはアルキル基、アリール基ま
たはチエ口
ニル基を表わす。Ｒ１１は水素又は−〇−Ｒ１０を表わ
す。）の組み合せを用いることを特徴とする光重合性組
成物である。That is, the present invention provides a photopolymer containing a monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic light, a photopolymerization initiator, and, if necessary, a linear organic polymer. In the polymerizable composition, as a photopolymerization initiator (a) at least one type of the following general formula (1): (X represents a halogen atom, Y represents -Cx3, -Nl2, -N
HR' represents -NR2' or -OR'. Here R
' represents an alkyl group or an aryl group. R is an alkyl group, an aryl group, a -CL group, or a thousand CH=CH+r
Represents R'. Here, R' represents an aryl group or a heterocyclic group, and n represents an integer of 1 to 3. ), etc.) At least one of the following general formula (■): (RISR2, R3 and R4 may be the same or different, and are an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alicyclic group) , represents an allyl group or a heterocyclic group, R1, R
2, R3 and R4 may be a cyclic structure in which two or more groups thereof are bonded. However, at least one of R1, R2, R3 and R4 is an alkyl group. X
○ indicates alkali metal or S. R5, R6, R' and R8 may be the same or different and may be hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group or an allyl group. represents. ),
and (C) at least one bis(dialkylamino)
Benzophenone or the following general formula (■): (2 represents a nonmetallic atomic group necessary to form a nitrogen-containing 5-membered heterocyclic nucleus, and the heterocyclic ring has either S, Se, or 0. (R9 represents an alkyl group. RIO represents an alkyl group, an aryl group, or a thienoyl group. R11 represents hydrogen or -〇-R10.) This is a photopolymerizable composition characterized by using.
本発明に使用される「活性光線により光重合が可能な少
なくとも１個のエチレン性不飽和基を有する単量体」は
、常圧で沸点１ｏｏｔ：以上の、少なくとも１分子中に
１個、より好ましくは２個以上の付加重合可能なエチレ
ン性不飽和基を有する分子量ｉｏ、ｏｏｏ以下のモノマ
ー又はオリゴマーである。このようなモノマー又はオリ
ゴマーとしては、ポリエチレングリコールモノ （メタ
）アクリレート、ポリプロピレングリコールモノ （メ
タ）アクリレート、フェノキシエチル（メタ）アクリレ
ート等の単官能のアクリレートやメタクリレート；ポリ
プロレングリコールジ（メタ）アクリレート、ポリプロ
ピレンジ（メタ）アクリレート、トリメチロールエタン
トリ （メタ）アクリレート、ネオペンチルグリコール
ジ（メタ）アクリレート、ペンタエリスリトールトリ
（メタ）アクリレート、ペンタエリスリトールテトラ
（メタ）アクリレート、ジペンタエリスリトールヘキサ
（メタ）アクリレート、ヘキサンジオールジ（メタ）ア
クリレ−）、）ＩＪ（アクリロイロキシエチル）インシ
アヌレート、クリセリンやトリメチロールエタン等の多
価アルコールにエチレンオキサイドやプロピレンオキサ
イドを付加させた後（メタ）アクリレート化したもの、
特公昭４１１１−４１７０８号、特公昭５０−６０３７
号、特開昭５１−３７１・９３号各公報に記載されてい
るようなウレタンアクリレート類、特開昭４８−６４１
８３号、特公昭４９−４３１９１号、特公昭５２−３０
４９０号各公報に記載されているポリエステルアクリレ
ート類、エポキシ樹脂と（メタ）アクリル酸を反応させ
たエポキシアクリレート類等の多官能のアクリレートや
メタクリレートをあげることができる。The "monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic rays" used in the present invention has a boiling point of 100:00 or more at normal pressure, and at least one per molecule, or more. Preferably, it is a monomer or oligomer having two or more addition-polymerizable ethylenically unsaturated groups and having a molecular weight of less than io or ooo. Such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, and phenoxyethyl (meth)acrylate; polyprolene glycol di(meth)acrylate, polypropylene Di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate
(meth)acrylate, pentaerythritol tetra
Ethylene oxide and (meth)acrylate after adding propylene oxide,
Special Publication No. 4111-41708, Special Publication No. 50-6037
Urethane acrylates as described in JP-A-51-371/93, JP-A-48-641
No. 83, Special Publication No. 49-43191, Special Publication No. 52-30
Examples include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid, which are described in each publication of No. 490.
さらに日本接着協会誌Ｖａｔ、２０、Ｎｏ、 ７．３０
０〜３０８ページに光硬化性モノマー及びオリコマ−と
して紹介されているものも使用することができる。Furthermore, Japan Adhesive Association Journal Vat, 20, No. 7.30
Those introduced as photocurable monomers and oligomers on pages 0 to 308 can also be used.
本発明で用いる一般式（１）
で表わされる化合物としては、２．４．６−）Ｕ（トリ
クロルメチル）−３−）リアジン、２（ｐ−アセチルフ
ェニル）−４，６−ビス（トリクロルメチル）−３−）
リアジン、２−メチル−４，６−ビス（トリクロルメチ
ル）−３−）リアジン、
や若林ら著、Ｂｕｌｌ、 Ｃｈｅｍ、Ｓａｃ、 Ｊａｐ
ａｎ、土ヱ、２９２４ （１９６９）記載の化合物、た
とえば、２−フェニル−４，６−ビス（トリクロルメチ
ル）−８−トリアジン、２−（ｐ−クロルフェニル）−
４，６−ビス（トリクロルメチル）−３−トリアジン、
２−（ｐ−）リル）−４，６−ビス（トリクロルメチル
）−３−）リアジン、２−（ｐ−メトキシフェニル）−
４，６−ビス（トリクロルメチル）−３−）リアジン、
２− （２’ 、４’ジクロルフエニル）−４，６−ビ
ス（トリクロルメチル）−３−）リアジン等が挙げられ
る。その他、英国特許１３８８４９２号明細書記載の化
合物、たとえば、２−スチリル−４，６−ビス（トリク
ロルメチル）−３−）リアジン、２−（ｐ−メチルスチ
リル）−４，６−ビス（トリクロルメチル）−３−）リ
アジン、２−（ｐ−メトキシスチリル）−４，６−ビス
（トリクロルメチル）−３−）リアジン等、特開昭５３
−１３３４２８号公報記載の化合物、たとえば、２−
（４−メトキシ−ナフト−１−イル）−４，６−ビス−
トリクロルメチル−Ｓ−）リアジン、２−（４−エトキ
シ−ナフト−１−イル）−４，６−ビス−トリクロルメ
チル−Ｓ−トリアジン、２− ［：４− （２−二トキ
シエチル）−ナフト−１−イル：ｌ−４，６−ビス−ト
リクロルメチル−Ｓ−）リアジン、２−（４゜７−ジメ
トキシ−ナフトー１−イル）−４，６−ビス−トリクロ
ルメチル−Ｓ−）リアジン、２−（アセナフト−５−イ
ル）−４，６−とスートリクロルメチルーＳ−）リアジ
ン等、特公昭５９−１２８１号公報記載の化合物、たと
えば等
特開昭６２−５８２４１号公報記載の化合物、たとえば
狭量特許３３３７０２４号明細書記載の化合物たとえば
、
等や、
特開昭６３−１５３５４２号公報記載の化合物、たとえ
ば
では
等をあげることが出来る。The compounds represented by the general formula (1) used in the present invention include 2.4.6-)U(trichloromethyl)-3-)riazine, 2(p-acetylphenyl)-4,6-bis(trichloromethyl) )-3-)
Riazine, 2-methyl-4,6-bis(trichloromethyl)-3-) riazine, Ya Wakabayashi et al., Bull, Chem, Sac, Jap
Compounds described in An, Satue, 2924 (1969), such as 2-phenyl-4,6-bis(trichloromethyl)-8-triazine, 2-(p-chlorophenyl)-
4,6-bis(trichloromethyl)-3-triazine,
2-(p-)lyl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-methoxyphenyl)-
4,6-bis(trichloromethyl)-3-)riazine,
Examples include 2-(2',4'dichlorophenyl)-4,6-bis(trichloromethyl)-3-)riazine. Other compounds described in British Patent No. 1388492, such as 2-styryl-4,6-bis(trichloromethyl)-3-)riazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl) )-3-) riazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-3-) riazine, etc., JP-A-1973
-133428, for example, 2-
(4-methoxy-naphth-1-yl)-4,6-bis-
Trichloromethyl-S-)riazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-[:4-(2-ditoxyethyl)-naphtho- 1-yl: l-4,6-bis-trichloromethyl-S-) liazine, 2-(4゜7-dimethoxy-naphthol-1-yl)-4,6-bis-trichloromethyl-S-) riazine, 2 -(acenaphth-5-yl)-4,6- and sootrichloromethyl-S-)riazine, etc. Compounds described in Japanese Patent Publication No. 59-1281, e.g. Compounds described in JP-A No. 62-58241, e.g. Compounds described in Japanese Patent No. 3337024, such as, and compounds described in JP-A-63-153542, such as, can be mentioned.
本発明で用いられる一般式
で表わされる化合物としては、式中のＲ１へＲ４が炭素
数１〜１８のものが好ましい。特に好ましいものは炭素
数１〜６のアルキル基、フェニル基、置換フェニル基及
びベンジル基である。ＸＯはア（ｅ）
（、Ｃ−Ｈ５） −８−
Ｎ” （、、Ｃ，Ｈ，） 。The compound represented by the general formula used in the present invention is preferably one in which R1 to R4 have 1 to 18 carbon atoms. Particularly preferred are alkyl groups having 1 to 6 carbon atoms, phenyl groups, substituted phenyl groups, and benzyl groups. XO is a(e) (,C-H5)-8-N'' (,,C,H,).
Ｒ′ としては炭素数１〜６のアルキル基が好ましい。R' As such, an alkyl group having 1 to 6 carbon atoms is preferable.
一般式（ＩＩ）で表わされる具体的な化合物とし等をあ
げることが出来る。Specific examples of the compound represented by the general formula (II) include the following.
本発明で用いられるビス（ジアルキルアミノ）ベンゾフ
ェノンとしては４，４′−ビス（ジメチルアミノ）ベン
ゾフェノン、４．４’ −ビス（ジエチルアミノ）ベン
ゾフェノン、４．４’ −ビス（ジプロピルアミノ）ベ
ンゾフェノン等をあげることが出来る。Examples of the bis(dialkylamino)benzophenone used in the present invention include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(dipropylamino)benzophenone. I can give it to you.
本発明で用いられる一般式（［［）
で表わされる化合物としては、Ｒ９がアルキル基（たと
えばメチル基、エチル基、プロピル基など）又は置換ア
ルキル基（たとえば２−ヒドロキシエチル基、２−メト
キシエチル基、カルボキシメチル基、２−カルボキシエ
チル基、３−カルボキシプロピル基、２−スルホエチル
基、３−スルホプロピル基、２−カルボメトキシエチル
基、ベンジル基、フェネチル基、Ｐ−スルホフェネチル
基、Ｐ−カルボキシフェネチル基、ビニルメチル基など
）、Ｒ”がアルキル基（例えばメチル基、エチル基、プ
ロピル基など）またはアリール基（例えばフェニル基、
Ｐ−ヒドロキシフェニル基、Ｐ−メトキシフェニル基、
Ｐ−クロロフェニル基、ナフチル基など）もしくはチエ
ニル基、Ｚが通常シアニン色素で用いられる窒素を含む
５員環の複素環核を形成するのに必要な非金属原子群を
表わし、該複素環は５ＳＳｅもしくは０のいずれかを異
項原子として含有し、かつ縮合環となっているもの、た
とえばベンゾチアゾール類（ベンゾチアゾール、５−ク
ロロベンゾチアゾール、６−クロロベンゾチアゾール、
４−メチルベンゾチアゾーノベ６メチルベンゾチアゾー
ル、５−フェニルベンゾチアゾール、６−メドキシベン
ゾチアゾーノベ４−エトキシベンゾチアゾール、５−メ
トキシベンゾチアゾール、５−ヒドロキシベンゾチアゾ
ール、５．６−シメチルベンゾチアゾール、５．６−シ
メトキシベンゾチアゾールなど）、ナフトチアゾール類
（α−ナフトチアゾール、β−ナフトチアゾールなど）
、ベンゾセレナゾール＠（ベンゾセレナゾール、５−ク
ロロベンゾセレナソール、６−メチルベンゾセレナゾー
ル、６−メチルベンゾセレナゾールなど）、ナフトセレ
ナゾール類（α−ナフトセレナゾール、β−ナフトセレ
ナゾールなど）、ベンゾオキサゾール類（ベンゾオキサ
ゾール、５−メチルベンゾオキサゾール、５−フェニル
ベンゾオキサゾール、６−メトキシベンゾチアゾールな
ど）、ナフトオキサゾール類（α−ナフトオキサゾール
、β−ナフトオキサゾールなど）であるものをあげるこ
とが出来る。In the compound represented by the general formula ([[) used in the present invention, R9 is an alkyl group (e.g., methyl group, ethyl group, propyl group, etc.) or a substituted alkyl group (e.g., 2-hydroxyethyl group, 2-methoxyethyl group, etc.). group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 2-carbomethoxyethyl group, benzyl group, phenethyl group, P-sulfophenethyl group, P- carboxyphenethyl group, vinylmethyl group, etc.), R'' is an alkyl group (e.g. methyl group, ethyl group, propyl group, etc.) or an aryl group (e.g. phenyl group,
P-hydroxyphenyl group, P-methoxyphenyl group,
P-chlorophenyl group, naphthyl group, etc.) or thienyl group, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing 5-membered heterocyclic nucleus usually used in cyanine dyes, and the heterocycle is 5SSe. or 0 as a foreign atom and a fused ring, such as benzothiazoles (benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole,
4-Methylbenzothiazole 6-methylbenzothiazole, 5-phenylbenzothiazole, 6-medoxybenzothiazole 4-ethoxybenzothiazole, 5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5.6-dimethyl benzothiazole, 5,6-simethoxybenzothiazole, etc.), naphthothiazoles (α-naphthothiazole, β-naphthothiazole, etc.)
, benzoselenazole @ (benzoselenazole, 5-chlorobenzoselenazole, 6-methylbenzoselenazole, 6-methylbenzoselenazole, etc.), naphthoselenazole (α-naphthoselenazole, β-naphthoselenazole, etc.) ), benzoxazole (benzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methoxybenzothiazole, etc.), and naphthoxazole (α-naphthoxazole, β-naphthoxazole, etc.). I can do it.
これらの光重合開始剤の使用濃度は通常わずかなもので
あり、不適当に多い場合には有効光線の遮蔽等好ましく
ない結果を生じる。本発明における光重合開始剤の組み
合せの合計量は光重合可能なエチレン性不飽和化合物と
必要とするなら線状有機高分子重合体との合計に対して
０．０１重量％から２０重量％の範囲で充分であり、更
に好ましくは１重量％から１０重量％で良好なる結果を
得る。また前記の一般式（Ｉ）の化合物、一般式（ＩＩ
）の化合物とビス（ジアルキルアミノ）ベンゾフェノン
は一般式（ＩＩＩ）の化合物の全光重合開始剤に対する
割合は、それぞれ６０〜１０重量％、１０〜６０重量％
および３０〜７０重徽％であることが望ましい。The concentration of these photopolymerization initiators used is usually small, and if the concentration is inappropriately high, undesirable effects such as blocking of effective light rays will occur. The total amount of the photopolymerization initiator combination in the present invention is 0.01% to 20% by weight based on the total of the photopolymerizable ethylenically unsaturated compound and, if necessary, the linear organic polymer. A range of 1% to 10% by weight is more preferable, and good results are obtained. Also, the compound of the general formula (I), the general formula (II)
) and bis(dialkylamino)benzophenone, the proportions of the compound of general formula (III) to the total photopolymerization initiator are 60 to 10% by weight and 10 to 60% by weight, respectively.
and 30 to 70% by weight.
更に本発明で用いる光重合開始剤に必要に応じてＮ−フ
ェニルグリシン、２−メルカプトベンゾチアゾール、Ｎ
、Ｎ−ジアルキル安息香酸アルキルエステル等の水素供
与性化合物を与えることによって更に光重合開始能力を
高めることができる。Furthermore, N-phenylglycine, 2-mercaptobenzothiazole, N
The ability to initiate photopolymerization can be further enhanced by providing a hydrogen-donating compound such as N-dialkylbenzoic acid alkyl ester.
本発明において必要に応じて添加する「線状有機高分子
重合体」としては当然光重合可能なエチレン性不飽和化
合物と相溶性を有しているものを選択しなければならな
い。光重合可能なエチレン性不飽和化合物と相溶性のあ
る線状有機高分子重合体である限り、どれを使用しても
構わないが、望ましくは水現像あるいは弱アルカリ水現
像を可能とする様な線状有機高分子重合体を選択すべき
である。線状有機高分子重合体は、該組成物の皮膜形成
剤としてだけではなく、水、弱アルカリ水あるいは有機
溶剤等、使用される現像剤に応じて使用される。たとえ
ば水可溶性有機高分子重合体を用いると水現像が可能と
なる。この様な線状有機高分子重合体としては、側鎖に
カルボン酸を有する付加重合体、たとえばメタクリル酸
共重合体、アクリル酸共重合体、イタコン酸共重合体、
クロトン酸共重合体、マレイン酸共重合体、部分エステ
ル化マレイン酸共重合体等があり、また同様に側鎖にカ
ルボン酸を有する酸性セルロース誘導体がある。この池
水酸基を有する付加重合体に環状酸無水物を付加させた
もの等が有用である。この他に水溶性線状有機高分子重
合体としてポリビニルピロリドンやポリエチレンオキサ
イド等が有用である。また硬化皮膜の強度をあげるため
にアルコール可溶性ナイロンや２．２−ビス−（４−ヒ
ドロキシフェニル）−プロパンとエビクロロヒドリンの
ポリエーテル等も有用である。これらの線状有機高分子
重合体は全組成中に任意な量、例えば光重合可能なエチ
レン性不飽和基を有する単量体１００重量部当り、１０
０〜９００重量部の割合で混和させることができるが、
９０重量％を超えることは形成される画像強度等の点で
好ましい結果を与えない。In the present invention, as the "linear organic polymer" added as necessary, it is necessary to select one that is compatible with the photopolymerizable ethylenically unsaturated compound. Any linear organic polymer can be used as long as it is compatible with the photopolymerizable ethylenically unsaturated compound, but it is preferable to use a linear organic polymer that can be developed with water or weakly alkaline water. A linear organic high molecular weight polymer should be selected. The linear organic polymer is used not only as a film-forming agent in the composition, but also depending on the developer used, such as water, weak alkaline water, or an organic solvent. For example, water development becomes possible when a water-soluble organic polymer is used. Examples of such linear organic polymers include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers,
These include crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, as well as acidic cellulose derivatives having carboxylic acid in their side chains. An addition polymer having a hydroxyl group to which a cyclic acid anhydride is added is useful. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis-(4-hydroxyphenyl)-propane and shrimp chlorohydrin are also useful. These linear organic high-molecular polymers can be used in any amount in the total composition, for example, 10 parts by weight per 100 parts by weight of monomers having a photopolymerizable ethylenically unsaturated group.
It can be mixed in a proportion of 0 to 900 parts by weight,
If it exceeds 90% by weight, it will not give favorable results in terms of the strength of the image formed.
さらに本発明においては以上の基本成分の他に光重合性
組成物の製造中あるいは保存中において重合可能なエチ
レン性不飽和化合物の不要な熱重合を阻止するために少
量の熱重合防止剤を添加することが望ましい。適当な熱
重合防止剤としてはハイドロキノン、ｐ−メトキシフェ
ノール、ジｔ−フチルーｐ−クレゾール、ピロガロール
、ｔ−ブチルカテコール、ベンツ゛キノン、４．４’チ
オビス（３−メチル−６−ｔ−ブチルフェノール）、２
．２’ −メチレンビス（４−メチル−６−ｔ−ブチル
フェノール）、２−メルカプトベンゾイミダゾール、Ｎ
−ニトロソフェニルヒドロキシアミン第一セリウム塩等
があげられる。また、場合によっては、硬化皮膜の物性
を改良する目的で無機光てん剤を加えてもよい。Furthermore, in the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds during the production or storage of the photopolymerizable composition. It is desirable to do so. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-phthyl-p-cresol, pyrogallol, t-butylcatechol, benzenequinone, 4,4'thiobis(3-methyl-6-t-butylphenol), 2
．． 2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N
- Nitrosophenylhydroxyamine cerous salt, etc. In some cases, an inorganic brightening agent may be added for the purpose of improving the physical properties of the cured film.
本発明の光重合性組成物は、例えば、２−メトキシエタ
ノール、２−メトキシエチルアセテート、プロピレング
リコールモノメチルエーテル、３メトキシプロパツール
、３−メトキシプロピルアセテート、メチルエチルケト
ン、エチレンジクロライドなどの適当な溶剤の単独また
はこれらを適当に組合せた混合溶媒に溶解して支持体上
に塗設することができる。その被覆量は乾燥後の重量で
約０．１ｇ／ｍ’〜約１０．ｇ／ｍ’の範囲が適当であ
り、より好ましくは０．５〜５ ｇ ／ ｍ’である。The photopolymerizable composition of the present invention can be prepared using a suitable solvent such as, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone, or ethylene dichloride. Alternatively, they can be coated on a support by dissolving them in an appropriate mixed solvent. The coating amount is about 0.1 g/m' to about 10.0 g/m' after drying. A suitable range is g/m', more preferably 0.5 to 5 g/m'.
さらにまた、本発明の光重合性組成物は、所期の目的を
達成するための公知の他の添加剤（例えば、焼出し剤等
）を含み得る。Furthermore, the photopolymerizable composition of the present invention may contain other known additives (eg, printing out agents, etc.) to achieve the intended purpose.
上記支持体としては、寸度的に安定な板状物が用いられ
る。このような寸度的に安定な板状物としては、従来印
刷版の支持体として使用されたものが含まれ、それらを
好適に使用することができる。かかる支持体としては、
紙、プラスチック（例えばポリエチレン、ポリプロピレ
ン、ポリスチレンなど）がラミネートされた紙、例えば
アルミニウム（アルミニウム合金も含む。）、亜鉛、銅
などのような金属の板、例えば二酢酸セルロース、三酢
酸セルロース、プロピオン酸セルロース、酪酸セルロー
ス、酢酸酪酸セルロース、硝酸セルロース、ポリエチレ
ンテレフタレート、ポリエチレン、ポリスチレン、ポリ
プロピレン、ポリカーボネート、ポリビニルアセタール
などのようなプラスチックのフィルム、上記の如き金属
がラミネートもしくは蒸着された紙もしくはプラスチッ
クフィルムなどが含まれる。これらの支持体のうち、ア
ルミニウム板は寸度的に著しく安定であり、しかも安価
であるので特に好ましい。更に、特公昭４８−１８３２
７号公報に記されているようなポリエチレンテレフタレ
ートフィルム上にアルミニウムシートが結合された複合
体シートも好ましい。As the support, a dimensionally stable plate-like material is used. Such dimensionally stable plate-like materials include those conventionally used as supports for printing plates, and these can be suitably used. Such supports include:
Paper, paper laminated with plastics (e.g. polyethylene, polypropylene, polystyrene, etc.), plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., e.g. cellulose diacetate, cellulose triacetate, propionic acid Includes plastic films such as cellulose, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with the above metals, etc. It will be done. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. In addition, the special public official 1832-1832
Also preferred is a composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 7.
また金属、特にアルミニウムの表面を有する支持体の場
合には、砂目立て処理、珪酸ソーダ、弗化ジルコニウム
酸カリウム、燐酸塩等の水溶液への浸漬処理、あるいは
陽極酸化処理などの表面処理がなされていることが好ま
しい。また、米国特許第２．７１４．０６６号明細書に
記載されている如く、砂目立てしたのちに珪酸ナトリウ
ム水溶液に浸漬処理されたアルミニウム板、特公昭４７
−５１２５号公報に記載されているようにアルミニウム
板を陽極酸化処理したのちに、アルカリ金属珪酸塩の水
溶液に浸漬処理したものも好適に使用される。In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably. In addition, as described in U.S. Pat.
As described in Japanese Patent No. 5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.
上記陽極酸化処理は、例えば、燐酸、クロム酸、硫酸、
硼酸等の無機酸、若しくは蓚酸、スルファミン酸等の有
機酸またはこれらの塩の水溶液又は非水溶液の単独又は
二種以上を組み合わせた電解液中でアルミニウム板を陽
極として電流を流すことにより実施される。The above anodic oxidation treatment can be performed using, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution consisting of an aqueous or non-aqueous solution of an inorganic acid such as boric acid, an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. .
また、米国特許第３．６５８．６６２号明細書に記載さ
れているようなシリケート電着も有効である。Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.
更に特公昭４６−２７４８１号公報、特開昭５２−５８
６０２号公報、特開昭５２−３０５０３号公報に開示さ
れているような電解ダレインを施した支持体と、上記陽
極酸化処理及び珪酸ソーダ処理を組合せた表面処理も有
用である。Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-58
Also useful is a surface treatment that combines a support subjected to electrolytic duplexing and the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in JP-A-602 and JP-A-52-30503.
更には、特開昭５６−２８８９３号公報に開示されてい
るような、ブラシダレイン、電解ダレイン、陽極酸化処
理さらに珪酸ソーダ処理をｊ頃に行ったものも好適であ
る。Furthermore, those which have been subjected to brush darein, electrolytic darein, anodic oxidation treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.
更にこれらの処理を行った後に、水溶性の樹脂、たとえ
ばポリビニルフォスホン酸、スルホン酸基を側鎖に有す
る重合体及び共重合体、ポリアクリル酸等を下塗りした
ものも好適である。Furthermore, after these treatments, it is also suitable to apply an undercoat with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, or the like.
これらの親水化処理は、支持体の表面を親水性とするた
めに施されるものであるが、その上に設けられる光重合
性組成物と支持体との間の有害な反応を防ぐため、更に
は感光層の密着性の向上部のために施されるものでもあ
る。These hydrophilic treatments are performed to make the surface of the support hydrophilic, but in order to prevent harmful reactions between the photopolymerizable composition provided thereon and the support, Furthermore, it is applied to improve the adhesion of the photosensitive layer.
支持体上に設けられた光重合性組成物の層の上には、空
気中の酸素による重合禁止作用を完全に防止するため、
例えばポリビニルアルコール、特にケン化度９９％以上
のポリビニルアルコール、酸性セルロース頚などのよう
な酸素遮断性に優れたポリマーよりなる保護層を設けて
もよい。この様な保護層の塗布方法については、例えば
米国特許第３．４５８．３１１号、特公昭５５−４９７
２９号公報に詳しく記載されている。On the layer of the photopolymerizable composition provided on the support, in order to completely prevent the polymerization inhibition effect caused by oxygen in the air,
For example, a protective layer made of a polymer with excellent oxygen barrier properties such as polyvinyl alcohol, especially polyvinyl alcohol with a degree of saponification of 99% or more, acidic cellulose, etc., may be provided. A method for applying such a protective layer is described, for example, in U.S. Pat.
It is described in detail in Publication No. 29.
本発明の光重合性組成物を支持体上に設けた感光性プレ
ートをメタルハライドランプ、高圧水銀灯などのような
紫外線に富んだ光源を用いて画像露光し、現像液で処理
して感光層の未露光部を除去し、最後にガム液を塗布す
ることにより印刷板が得られる。上記現像液として好ま
しいものは、ベンジルアルコール、２−フェノキシエタ
ノール、２−ブトキシェタノールのような有機溶媒を少
量含むアルカリ水溶液であり、例えば米国特許第３、４
７５．１７１号及び同３．６１５．４８０号に記載され
ているものを挙げることができる。A photosensitive plate provided with the photopolymerizable composition of the present invention on a support is imagewise exposed using a light source rich in ultraviolet rays such as a metal halide lamp or a high-pressure mercury lamp, and then treated with a developer to remove the photosensitive layer. A printing plate is obtained by removing the exposed areas and finally applying a gum solution. Preferably, the developer is an alkaline aqueous solution containing a small amount of an organic solvent such as benzyl alcohol, 2-phenoxyethanol, or 2-butoxyethanol, such as U.S. Pat.
Examples include those described in No. 75.171 and No. 3.615.480.
更に、特開昭５０−２６６０１号、特公昭５６−３９４
６４号、同５６−４２８６０号の各公報に記載されてい
る現像液も上記感光性プレートの現像液として優れてい
る。Furthermore, Japanese Patent Publication No. 50-26601, Japanese Patent Publication No. 56-394
64 and No. 56-42860 are also excellent as developers for the photosensitive plate.
以下実施例をもって本発明を説明するが本発明はこれに
限定されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
厚さ０．３０１１１（Ｏのアルミニウム板をナイロンブ
ラシと４００メツシユのパミストンの水懸濁液とを用い
その表面を砂目立てした後、よく水で洗浄した。１０％
水酸化ナトリウムに７０℃で６０秒間浸漬してエツチン
グした後、流水で水洗後２０％ＨＮＯ３で中和洗浄し、
次いで水洗した。これをＶＡ＝ １２．７ Ｖの条件下
で正弦波の交番波形電流を用いて１％硝酸水溶液中で１
６０ク一ロン／ｄｍ’の陽極特電気量で電解粗面化処理
を行った。その表面粗さを測定したところ、０．６μ（
Ｒ，表示）であった。ひきつづいて３０％の８２Ｓ口。Example 1 The surface of an aluminum plate with a thickness of 0.30111 (O) was grained using a nylon brush and a water suspension of 400 mesh pumice stone, and then thoroughly washed with water.
After etching by immersing in sodium hydroxide at 70°C for 60 seconds, washing with running water and neutralizing with 20% HNO3,
Then, it was washed with water. This was heated to 1% in a 1% nitric acid aqueous solution using a sinusoidal alternating current waveform under the condition of VA = 12.7 V.
Electrolytic surface roughening treatment was carried out using an anode special electricity amount of 60 corons/dm'. When the surface roughness was measured, it was found to be 0.6 μ(
R, indicated). 82S mouth continues to be 30%.
水溶液中に浸漬し５０℃で２分間デスマットした後、２
０％Ｈ＝ＳＯ４水溶液中、電流密度２Ａ／ｄｍ２におい
て厚さが２．７ｇ／ｍ”になるように２分間陽極酸化処
理した。After immersing in an aqueous solution and desmutting at 50°C for 2 minutes,
It was anodized for 2 minutes in a 0% H=SO4 aqueous solution at a current density of 2 A/dm2 to a thickness of 2.7 g/m''.
このように処理されたアルミニウム板上に、下記組成の
光重合性組成物からなる感光液を乾燥塗布重量が１．５
ｇ／ｍ’となるように塗布し、１００℃で２分間乾燥さ
せ感光性プレートを得た。A photosensitive solution consisting of a photopolymerizable composition having the following composition was applied onto the aluminum plate treated in this way to a dry coating weight of 1.5.
g/m' and dried at 100°C for 2 minutes to obtain a photosensitive plate.
光重合開始剤
銅フタロシアニン顔料
ｇ
Ｏ１２ｇ
１にケイ酸カリウム
水酸化カリウム
メチルエチルケトン
０ ｇ
この感光層上にポリビニルアルコール（ケン化度８６．
５〜８９モル％、重合度１．０００）の３重量％の水溶
液を乾燥塗布重量が２ｇ／ｒｎ″となるように塗布し、
１００℃／２分間乾燥させた。Photopolymerization initiator copper phthalocyanine pigment g O 12 g 1 potassium silicate potassium hydroxide methyl ethyl ketone 0 g Polyvinyl alcohol (saponification degree 86.
Apply a 3% by weight aqueous solution of 5 to 89 mol%, degree of polymerization 1.000) so that the dry coating weight is 2 g/rn'',
It was dried at 100°C for 2 minutes.
このようにして得られた感光性平版印刷版上に富士写真
フィルム■製の富士ＰＳステップガイド（ΔＤ＝０．１
５で不連続に透過濃度が変化するグレースケール）を密
着させ、その上に３８０ｎｍ以下の光をカットするフィ
ルターフィルムを置いて、その上から露光した。光源は
１００Ｗの高圧水銀灯で、フィルターを通過した後での
版面での光強度は０．０１ ｍＷ／ ｃｍ ’であった
。感度としてはプレートを現像した後グレースケールの
６段目が残存している時の露光量を、実用感度として表
示した。A Fuji PS step guide (ΔD=0.1 manufactured by Fuji Photo Film ■) was placed on the photosensitive lithographic printing plate thus obtained.
5) (a gray scale in which the transmission density changes discontinuously) was placed in close contact with the film, a filter film that cuts light of 380 nm or less was placed on top of the film, and the film was exposed to light from above. The light source was a 100 W high-pressure mercury lamp, and the light intensity at the plate surface after passing through the filter was 0.01 mW/cm'. As for the sensitivity, the exposure amount when the sixth level of the gray scale remained after the plate was developed was expressed as the practical sensitivity.
現像は、下記の現像液に２５℃、１分間浸漬して行った
。Development was performed by immersing the film in the following developer at 25° C. for 1 minute.
０００ｇ
光重合開始剤の組み合せを変えたときの感度の結果を表
１に示す。Table 1 shows the sensitivity results when the combination of photopolymerization initiators was changed.
表２のごとく３種の光重合開始剤を組み合せることによ
って高感度になることが判明した。It has been found that high sensitivity can be achieved by combining three types of photopolymerization initiators as shown in Table 2.
本発明の光重合性組成物は極めて高感度である。 The photopolymerizable composition of the present invention has extremely high sensitivity.
Claims (1)
ン性不飽和基をもつ単量体と光重合開始剤と、必要とす
るならば線状有機高分子重合体とを含む光重合性組成物
において、光重合開始剤として （ａ）少なくとも１種の下記一般式（ I ）：▲数式、
化学式、表等があります▼ （Ｘはハロゲン原子を表わす。Ｙは−ＣＸ＿３、−ＮＨ
＿２、−ＮＨＲ′、−ＮＲ＿２′又は−ＯＲ′を表わす
。ここでＲ′はアルキル基又はアリール基を表わす。ま
たＲはアルキル基、アリール基、−ＣＸ＿３基又は▲数
式、化学式、表等があります▼Ｒ″を表わす。ここでＲ
″はアリール基又は複素環基を、ｎは１〜３の整数を表
わす。） （ｂ）少なくとも１種の下記一般式（II）：▲数式、化
学式、表等があります▼ （Ｒ＾１、Ｒ＾２、Ｒ＾３およびＲ＾４は同じでも異っ
ていてもよく、アルキル基、アリール基、アラルキル基
、アルカリール基、アルケニル基、アリサイクリック基
、アリル基又は複素環基を表わし、Ｒ＾１、Ｒ＾２、Ｒ
＾３およびＲ＾４はその２個以上の基が結合している環
状構造であってもよい。ただしＲ＾１、Ｒ＾２、Ｒ＾３
およびＲ＾４のうち少なくとも１つは、アルキル基であ
る。Ｘ＾■はアルカリ金属又は▲数式、化学式、表等が
あります▼で示される第四アンモニウムを表わ す。ここでＲ＾５、Ｒ＾６、Ｒ＾７およびＲ＾８は同じ
であっても異っていてもよく水素、アルキル基、アリー
ル基、アラルキル基、アルカリール基、アルケニル基、
アルキニル基、アリサイクリック基又はアリル基を表わ
す。）、および （ｃ）少なくとも１種のビス（ジアルキルアミノ）ベン
ゾフェノン又は下記一般式（III）： ▲数式、化学式、表等があります▼（III） （Ｚは窒素を含む５員環の複素環核を形成するのに必要
な非金属原子群を表わし、該複素環はＳ、Ｓｅ又はＯの
いずれかを異項原子として含有し、かつ縮合環となって
いる。Ｒ＾９はアルキル基を表わす。Ｒ＾１＾０はアル
キル基、アリール基またはチェニル基を表わす。Ｒ＾１
＾１は水素又は▲数式、化学式、表等があります▼を表
わす。）の組み合せを用いることを特徴とする光重合性
組成物。[Claims] Contains a monomer having at least one ethylenically unsaturated group that can be photopolymerized by actinic rays, a photopolymerization initiator, and, if necessary, a linear organic polymer. In the photopolymerizable composition, as a photopolymerization initiator (a) at least one of the following general formula (I): ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (X represents a halogen atom. Y is -CX_3, -NH
_2, -NHR', -NR_2' or -OR'. R' here represents an alkyl group or an aryl group. In addition, R represents an alkyl group, an aryl group, a -CX_3 group, or ▲a numerical formula, a chemical formula, a table, etc.▼R''.Here, R
'' represents an aryl group or a heterocyclic group, and n represents an integer of 1 to 3.) (b) At least one type of the following general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1, R^2, R^3 and R^4 may be the same or different and represent an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alicyclic group, an allyl group or a heterocyclic group; , R^1, R^2, R
^3 and R^4 may be a cyclic structure in which two or more groups thereof are bonded. However, R^1, R^2, R^3
and R^4, at least one of which is an alkyl group. X^■ represents an alkali metal or quaternary ammonium shown by ▲Formula, chemical formula, table, etc. are available. Here, R^5, R^6, R^7 and R^8 may be the same or different and represent hydrogen, an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group,
Represents an alkynyl group, an alicyclic group or an allyl group. ), and (c) at least one type of bis(dialkylamino)benzophenone or the following general formula (III): ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (Z is a 5-membered heterocyclic nucleus containing nitrogen represents a group of nonmetallic atoms necessary to form a heterocyclic ring containing S, Se, or O as a foreign atom, and is a condensed ring. R^9 represents an alkyl group. .R^1^0 represents an alkyl group, an aryl group or a chenyl group.R^1
^1 represents hydrogen or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) A photopolymerizable composition characterized by using a combination of the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63205903A JPH087437B2 (en) | 1988-08-19 | 1988-08-19 | Photopolymerizable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63205903A JPH087437B2 (en) | 1988-08-19 | 1988-08-19 | Photopolymerizable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0254268A true JPH0254268A (en) | 1990-02-23 |
| JPH087437B2 JPH087437B2 (en) | 1996-01-29 |
Family
ID=16514658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63205903A Expired - Lifetime JPH087437B2 (en) | 1988-08-19 | 1988-08-19 | Photopolymerizable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH087437B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04271352A (en) * | 1990-08-27 | 1992-09-28 | E I Du Pont De Nemours & Co | Borate co-initiator for optical polymerizing composition |
| JPH0545876A (en) * | 1991-03-15 | 1993-02-26 | Fuji Photo Film Co Ltd | Photosensitive bistrihalomethyl-s-triazine compound and photopolymerizable composition containing that |
| US7709519B2 (en) | 2004-06-04 | 2010-05-04 | Astellas Pharma Inc. | Benzimidazolylidene propane-1,3 dione derivative or salt thereof |
| US7960562B2 (en) | 2005-03-31 | 2011-06-14 | Astellas Pharma Inc. | Propane-1,3-dione derivative or salt thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414489A (en) * | 1977-07-05 | 1979-02-02 | Toray Ind Inc | Photosensitizer |
| JPS6076507A (en) * | 1983-09-01 | 1985-05-01 | Agency Of Ind Science & Technol | Photo-insolubilizable resin composition |
| JPS6076740A (en) * | 1983-10-04 | 1985-05-01 | Agency Of Ind Science & Technol | Resin composition sensitive to visible light |
| JPS6281403A (en) * | 1985-10-04 | 1987-04-14 | Nippon Oil & Fats Co Ltd | Photopolymerization initiator composition |
| JPS62143044A (en) * | 1985-11-20 | 1987-06-26 | サイカラー・インコーポレーテッド | Photosetting composition containing dye borate complex and photosensitive material using the same |
| JPS62150242A (en) * | 1985-11-20 | 1987-07-04 | サイカラー・インコーポレーテッド | Photosensitive material containing ion dye compound as initiator |
| JPS6413142A (en) * | 1987-07-06 | 1989-01-18 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| JPS6435548A (en) * | 1987-07-31 | 1989-02-06 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
-
1988
- 1988-08-19 JP JP63205903A patent/JPH087437B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414489A (en) * | 1977-07-05 | 1979-02-02 | Toray Ind Inc | Photosensitizer |
| JPS6076507A (en) * | 1983-09-01 | 1985-05-01 | Agency Of Ind Science & Technol | Photo-insolubilizable resin composition |
| JPS6076740A (en) * | 1983-10-04 | 1985-05-01 | Agency Of Ind Science & Technol | Resin composition sensitive to visible light |
| JPS6281403A (en) * | 1985-10-04 | 1987-04-14 | Nippon Oil & Fats Co Ltd | Photopolymerization initiator composition |
| JPS62143044A (en) * | 1985-11-20 | 1987-06-26 | サイカラー・インコーポレーテッド | Photosetting composition containing dye borate complex and photosensitive material using the same |
| JPS62150242A (en) * | 1985-11-20 | 1987-07-04 | サイカラー・インコーポレーテッド | Photosensitive material containing ion dye compound as initiator |
| JPS6413142A (en) * | 1987-07-06 | 1989-01-18 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| JPS6435548A (en) * | 1987-07-31 | 1989-02-06 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04271352A (en) * | 1990-08-27 | 1992-09-28 | E I Du Pont De Nemours & Co | Borate co-initiator for optical polymerizing composition |
| JPH0545876A (en) * | 1991-03-15 | 1993-02-26 | Fuji Photo Film Co Ltd | Photosensitive bistrihalomethyl-s-triazine compound and photopolymerizable composition containing that |
| US7709519B2 (en) | 2004-06-04 | 2010-05-04 | Astellas Pharma Inc. | Benzimidazolylidene propane-1,3 dione derivative or salt thereof |
| US8076367B2 (en) | 2004-06-04 | 2011-12-13 | Astellas Pharma Inc. | Benzimidazolylidene propane-1,3-dione derivative or salt thereof |
| US7960562B2 (en) | 2005-03-31 | 2011-06-14 | Astellas Pharma Inc. | Propane-1,3-dione derivative or salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH087437B2 (en) | 1996-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4950581A (en) | Photopolymerizable composition | |
| JP2764769B2 (en) | Photopolymerizable composition | |
| US4937161A (en) | Photopolymerizable composition | |
| JPS62212401A (en) | Photopolymerizable composition | |
| US5168032A (en) | Photopolymerizable composition initiated by a combination of boron compound, dye, and heterocyclic compound | |
| JPS5928328B2 (en) | Photopolymerizable composition | |
| JPH05281728A (en) | Photopolymerizable composition | |
| JPH09236913A (en) | Photopolymerizable composition | |
| JPH05142772A (en) | Photopolymerizable composition | |
| JPH02179643A (en) | Photopolymerizable composition | |
| JPH0820732B2 (en) | Photopolymerizable composition | |
| JPS63178105A (en) | Photopolymerizable composition | |
| US4774163A (en) | Photopolymerizable composition including an unsaturated monomer, a photopolymerization initator and a carbozole compound | |
| JP2547613B2 (en) | Photopolymerizable composition | |
| JPS6368831A (en) | Photosensitive composition | |
| US5250385A (en) | Photopolymerizable composition | |
| JPH0254268A (en) | Photopolymerizable composition | |
| US5346805A (en) | Photopolymerizable composition | |
| JPS6332541A (en) | Photopolymerizable composition | |
| JPH0774906B2 (en) | Photopolymerizable composition | |
| JPH08101498A (en) | Photosensitive planographic printing plate | |
| JPS63168403A (en) | Photopolymerizable composition | |
| JPS6261045A (en) | Photopolymerization composition | |
| JPH02113002A (en) | Photopolymerizable composition | |
| JPH0766186B2 (en) | Photosensitive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080129 Year of fee payment: 12 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090129 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090129 Year of fee payment: 13 |