JP3573472B2 - Photoreactive polyfunctional vinyl ether, method for producing the same, and photocurable composition containing the vinyl ether - Google Patents
Photoreactive polyfunctional vinyl ether, method for producing the same, and photocurable composition containing the vinyl ether Download PDFInfo
- Publication number
- JP3573472B2 JP3573472B2 JP19880693A JP19880693A JP3573472B2 JP 3573472 B2 JP3573472 B2 JP 3573472B2 JP 19880693 A JP19880693 A JP 19880693A JP 19880693 A JP19880693 A JP 19880693A JP 3573472 B2 JP3573472 B2 JP 3573472B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl ether
- group
- cationic polymerization
- reaction
- polyfunctional vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 22
- 239000003505 polymerization initiator Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910017008 AsF 6 Inorganic materials 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims 1
- 229960000834 vinyl ether Drugs 0.000 description 25
- 239000000047 product Substances 0.000 description 18
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000003776 cleavage reaction Methods 0.000 description 12
- 125000003700 epoxy group Chemical group 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 8
- -1 vinyl ether compound Chemical class 0.000 description 8
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012663 cationic photopolymerization Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RQJCIXUNHZZFMB-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxypropoxy)propane Chemical compound C=COCC(C)OCC(C)OC=C RQJCIXUNHZZFMB-UHFFFAOYSA-N 0.000 description 1
- ZOJIBRUWYLWNRB-UHFFFAOYSA-N 2-(2-ethenoxyethoxymethyl)oxirane Chemical compound C=COCCOCC1CO1 ZOJIBRUWYLWNRB-UHFFFAOYSA-N 0.000 description 1
- WVXLLHWEQSZBLW-UHFFFAOYSA-N 2-(4-acetyl-2-methoxyphenoxy)acetic acid Chemical compound COC1=CC(C(C)=O)=CC=C1OCC(O)=O WVXLLHWEQSZBLW-UHFFFAOYSA-N 0.000 description 1
- IOQHHUMFFSCULW-UHFFFAOYSA-N 2-[1-(1-ethenoxypropan-2-yloxy)propan-2-yloxymethyl]oxirane Chemical compound C=COCC(C)OCC(C)OCC1CO1 IOQHHUMFFSCULW-UHFFFAOYSA-N 0.000 description 1
- UKHXPHLUQGMQOF-UHFFFAOYSA-N 2-carboxyethyl(dimethyl)sulfanium;bromide Chemical compound [Br-].C[S+](C)CCC(O)=O UKHXPHLUQGMQOF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- MPZMVUQGXAOJIK-UHFFFAOYSA-N 4-bromopyridine;hydron;chloride Chemical compound Cl.BrC1=CC=NC=C1 MPZMVUQGXAOJIK-UHFFFAOYSA-N 0.000 description 1
- YYTFQDRGDZTBEV-UHFFFAOYSA-N 4-ethenoxy-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(OC=C)CCC2OC21 YYTFQDRGDZTBEV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- QLRKASHXFNIPLZ-UHFFFAOYSA-M benzyl-dimethyl-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 QLRKASHXFNIPLZ-UHFFFAOYSA-M 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical class OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- QNUPENXMUJPLDQ-UHFFFAOYSA-M cyclopenta-1,3-diene;cyclopenta-1,3-dien-1-ylmethyl(trimethyl)azanium;iron(2+);bromide Chemical compound [Fe+2].[Br-].C=1C=C[CH-]C=1.C[N+](C)(C)CC1=CC=C[CH-]1 QNUPENXMUJPLDQ-UHFFFAOYSA-M 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- JMJGNDIWCVQJJZ-UHFFFAOYSA-M diphenyliodanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C=1C=CC=CC=1[I+]C1=CC=CC=C1 JMJGNDIWCVQJJZ-UHFFFAOYSA-M 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- VVDUZZGYBOWDSQ-UHFFFAOYSA-M eschenmoser's salt Chemical compound [I-].C[N+](C)=C VVDUZZGYBOWDSQ-UHFFFAOYSA-M 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- GMRIOAVKKGNMMV-UHFFFAOYSA-N tetrabutylazanium;azide Chemical compound [N-]=[N+]=[N-].CCCC[N+](CCCC)(CCCC)CCCC GMRIOAVKKGNMMV-UHFFFAOYSA-N 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WMSWXWGJYOIACA-UHFFFAOYSA-M triethyl(phenyl)azanium;iodide Chemical compound [I-].CC[N+](CC)(CC)C1=CC=CC=C1 WMSWXWGJYOIACA-UHFFFAOYSA-M 0.000 description 1
- FWYKRJUVEOBFGH-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FWYKRJUVEOBFGH-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Sealing Material Composition (AREA)
- Polymerization Catalysts (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、新規な光反応性多官能ビニルエーテル及びその製造方法並びに該光反応性多官能ビニルエーテルを含有する光硬化性組成物に関する。
【０００２】
【従来の技術】
ビニルエーテル化合物はカチオン重合開始剤により重合して対応するポリビニルエーテルを生成するので、塗料、接着剤、シーリング剤、レジスト剤などとして広範な用途を有する。
従来、側鎖又は末端にビニルエーテル基を有するポリビニルエーテルとしては、例えば、特開平４−１７０４８６号公報にアクリル系重合体やフルオロオレフィン系重合体にエポキシ基及び／又はビニルエーテル基を導入して得られるビニル系重合体が記載され、さらに、これにカチオン重合を開始させる触媒を併用することによって加熱又は活性エネルギー線の照射によって硬化する硬化性樹脂組成物が開示されている。また、上記特開平４−１７０４８６号公報には、ビニルエーテル基を導入する反応として、カルボキシル基を含有する重合体に、グリシジルビニルエーテルなどのエポキシ基とビニルエーテル基の両方を有する化合物を反応させる方法も教示されている。
同様に、グリシジルビニルエーテルと無水フタル酸を反応させて側鎖にビニルエーテル基を有するポリマーを合成できることが、高分子論文集、Ｖｏｌ．４８、Ｎｏ．８（１９９１年８月）第４７８頁に記載されている。しかしながら、これらの合成反応はカルボキシル基とエポキシ基との反応であるため、収率が低いという問題がある。
【０００３】
【発明が解決しようとする課題】
従って、本発明の主たる目的は、ビニルエーテル基を有する光反応性多官能ビニルエーテルを収率よく製造し、もって生産性よくかつ比較的に低コストで光反応性多官能ビニルエーテルを提供することにある。
本発明の他の目的は、光反応性多官能ビニルエーテルを含有し、広範な用途に適用可能な光硬化性組成物を提供することにある。
【０００４】
【課題を解決するための手段】
前記目的を達成するために、本発明によれば、グリシジルビニルエーテルと分子中に２つ以上のカルボン酸クロリド基（−ＣＯＣｌ）を有する化合物（以下、多価カルボン酸クロリドと略称する。）との反応物であって、分子内に多官能性のビニルエーテル基を有し、下記化５の一般式（１）、（２）、又は（３）で表わされることを特徴とする光反応性多官能ビニルエーテルが提供される。
【化５】
【０００５】
【化６】
また本発明によれば、上記光反応性多官能ビニルエーテルの製造方法も提供され、その方法は、グリシジルビニルエーテルと多価カルボン酸クロリドを、有機溶媒中あるいは無溶媒下で、触媒の存在下に反応させることを特徴とするものである。好適な態様においては、反応は５０〜１５０℃、３〜４８時間、好ましくは７０〜１２０℃、８〜２４時間の条件で行われ、上記多価カルボン酸クロリドとして、下記化７の（１′）〜（１８′）の化合物からなる群より選ばれた多価カルボン酸クロリドが用いられる。
【化７】
さらに本発明によれば、前記光反応性多官能ビニルエーテルと活性エネルギー線によりカチオン重合を開始させるカチオン重合開始剤とを含有することを特徴とする光硬化性組成物も提供される。好適には、カチオン重合開始剤として、下記化８の（Ａ）〜（Ｇ）の塩からなる群より選ばれたカチオン重合開始剤が用いられる。
【化８】
【０００８】
【発明の作用及び態様】
本発明者らは、グリシジルビニルエーテルと多価カルボン酸クロリドを、有機溶媒中、触媒の存在下に反応させることによって、多官能ビニルエーテル基を有する光反応性多官能ビニルエーテルを収率よく製造でき、また、該多官能ビニルエーテルを活性エネルギー線によりカチオン重合を開始させるカチオン重合開始剤と共存させることにより良好な光硬化性を示すことを見い出し、本発明を完成するに至ったものである。
【０００９】
グリシジルビニルエーテルと多価カルボン酸クロリド、例えばジカルボン酸クロリドを有機溶媒中、触媒の存在下に反応させると、下記化９で示される反応式（Ｉ）のように反応し、主としてグリシジルビニルエーテルのエポキシ基のβ開裂が生じて、クロロメチル基（−ＣＨ２ Ｃｌ）が側基として主鎖に結合している主生成物（一般式（１′）で示される多官能ビニルエーテル）を生成する。
【化９】
【００１０】
グリシジルビニルエーテルと反応させる多価カルボン酸クロリドとしては、−ＣＯＣｌ基を２個以上有するカルボン酸クロリドであれば全て使用可能であるが、それらの中でも前記（１′）〜（１８′）の脂肪族炭化水素系（炭素数１〜８）、ベンゼン系、ベンゾフェノン系、ビスフェノール系、ビフェニル系、テトラヒドロフタル酸系、シクロヘキサン系、マレイン酸系、ナフタレン系、フルオレン系等の多価カルボン酸クロリドが好ましい。
グリシジルビニルエーテルと多価カルボン酸クロリドは、有機溶媒中、相間移動触媒の存在下に反応させる。反応条件としては、反応温度は、後述する実施例から明らかなように、約８０％以上の反応収率を得るためには５０〜１５０℃の範囲が適当であり、より好ましくは７０〜１２０℃である。また、反応時間は３〜４８時間、好ましくは８〜２４時間が適当である。反応時間が３時間未満では目的物の生成が不充分で反応収率が満足し得るものではなく、一方、高い反応温度では２４時間を超えると反応収率がほぼ飽和に達しており、生産性、経済性の点で好ましくない。
【００１１】
反応は無溶媒下でもよく進行するが、生成物の洗浄や反応系のコントロールの観点からは、反応溶媒の使用が適当である。有機溶媒としては、アルコール、アセトン等の親水性の溶媒以外の疎水性の有機溶媒であれば全て使用できるが、それらの中でもトルエン、ジメチルホルムアミド、ジメチルアセテート、Ｎ−メチルピロリドン、ジエチレングリコールジメチルエーテル（商品名：ジグライム）、アニソール、ジクロロベンゼン、スルホラン等が好ましく、特に最も好ましいのはトルエンである。反応系に水が混入すると収率が低下するので好ましくない。さらに本反応の反応溶媒としては、（メタ）アクリル酸エステルや多官能性（メタ）アクリル酸エステル等の光ラジカル重合性化合物を使用することも可能であり、この反応生成物はそのまま多機能型の光硬化性オリゴマーとしての活用も可能となる。
【００１２】
触媒としては、テトラ−ｎ−ブチルアンモニウムクロリド、テトラ−ｎ−ブチルアンモニウムブロミド、テトラ−ｎ−ブチルアンモニウムヨージド、テトラ−ｎ−ブチルアンモニウムフルオリド、テトラ−ｎ−ブチルアンモニウムヒドロキシド、テトラ−ｎ−ブチルアンモニウムアジド、テトラ−ｎ−ブチルアンモニウムホスフェート、ジメチルベンジルフェニルアンモニウムクロリド、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、トリメチルベンジルアンモニウムクロリド、トリオクチルメチルアンモニウムクロリド、ベンジルトリ−ｎ−ブチルアンモニウムブロミド、セチルジメチルエチルアンモニウムブロミド、ジラウリルジメチルアンモニウムブロミド、（フェロセニルメチル）トリメチルアンモニウムブロミド、Ｎ，Ｎ−ジメチルメチレンアンモニウムヨージド、フェニルトリエチルアンモニウムヨージド、テトラエチルアンモニウムヒドロキシド、ジメチルアミノピリジン、４−ブロモピリジンヒドロクロリド、Ｎ−ｎ−ブチルピリジニウムクロリド、トリブチルアミン、テトラ−ｎ−ブチルホスホニウムブロミド、アリルトリフェニルホスホニウムブロミド、ジフェニルヨードニウムパークロレート、（２−カルボキシエチル）ジメチルスルホニウムブロミド等、従来公知の種々の第四オニウム塩や第三アミン、第三ホスフィン、クラウンエーテル錯体などの触媒が挙げられる。
【００１３】
本発明によればさらに、前記のようにして得られた光反応性の多官能ビニルエーテルに活性エネルギー線によりカチオン重合を開始させるカチオン重合開始剤を混合することにより、光硬化性組成物が得られる。活性エネルギー線カチオン重合開始剤としては、ジアリールヨードニウム塩類、トリアリールスルホニウム塩類、チオビストリアリールスルホニウム塩類、セレノニウム塩類、ホスホニウム塩類など従来公知の種々のカチオン重合開始剤を用いることができるが、特に前記した（Ａ）〜（Ｅ）の塩類が好ましい。これらのカチオン重合開始剤は、単独で用いてもよく、あるいは２種以上を併用してもよい。光硬化性組成物中におけるカチオン重合開始剤の配合割合は、多官能ビニルエーテルのビニル基に対して０．０５モル％以上、好ましくは０．１モル％以上が適当であり、最も好ましくは０．５〜１０モル％である。後述する実施例から明らかなように、カチオン重合開始剤の配合割合が０．０５モル％未満であると充分な光硬化性が得られ難いので好ましくない。
【００１４】
本発明に係る光硬化性組成物には、さらに、その光硬化性を損なわない範囲で、一分子中に少なくとも１個のエポキシ基及び／又はビニルエーテル基を有する重合体、例えばエポキシ樹脂類、又はエポキシ基もしくはビニルエーテル基を導入したポリエーテル樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン樹脂あるいはシリコーン樹脂などを、硬化物の特性を改善するために混合することができる。エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、Ｎ−グリシジル型エポキシ樹脂または脂環式エポキシ樹脂などがあり、あるいはさらにこれに反応促進のためのアミン化合物類、イミダゾール化合物類、カルボン酸類、フェノール類、第四級アンモニウム塩類またはメチロール基含有化合物類などの公知のエポキシ硬化促進剤を少量併用することができ、これら熱硬化性成分の添加により、塗膜を加熱することにより熱硬化させることが可能になると共に、硬度、耐薬品性、耐熱性等の諸特性を改善することもできる。
【００１５】
また、本発明の光硬化性組成物には、一分子中に少なくとも１個のエポキシ基及び／又はビニルエーテル基を有する化合物、例えば３，４−エポキシシクロヘキシルビニルエーテル、エチレングリコールモノグリシジルモノビニルエーテル、トリエチレングリコールモノグリシジルモノビニルエーテル、ジプロピレングリコールモノグリシジルモノビニルエーテル、シクロヘキシルビニルエーテル、ベンジルビニルエーテル、２−エチルヘキシルビニルエーテル、トリエチレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、１，４−ビスジビニルオキシメチルシクロヘキサン、イソホロンジイソシアネートと４−ヒドロキシブチルビニルエーテルのモル比１：２付加物または水添キシリレンジイソシアネートと４−ヒドロキシブチルビニルエーテルのモル比１：２付加物などを混合することもできる。
【００１６】
本発明の光硬化性組成物には、さらに必要に応じて硫酸バリウム、酸化珪素、タルク、クレー、炭酸カルシウムなどの公知慣用の充填剤、フタロシアニン・ブルー、フタロシアニン・グリーン、酸化チタン、カーボンブラックなどの公知慣用の着色用顔料、消泡剤、密着性付与剤またはレベリング剤などの各種添加剤類を加えてもよい。
【００１７】
本発明の光硬化性組成物を光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプなどが適当である。また、レーザー光線なども露光用活性光線として利用できる。その他、電子線、α線、β線、γ線、Ｘ線、中性子線なども利用可能である。
【００１８】
【実施例】
以下、実施例を示して本発明についてさらに具体的に説明するが、本発明が下記実施例に限定されるものでないことはもとよりである。
【００１９】
実施例１
グリシジルビニルエーテル（セイケミカル（株）製、商品名ＧＶＥ）を１０ミリモル、テレフタル酸ジクロリド（ＴＰＣ）を５ミリモル、及びテトラ−ｎ−ブチルアンモニウムブロミド（ＴＢＡＢ）をＧＶＥに対して５モル％の割合でトルエン５ミリリットル中に溶解し、オイルバス中で９０℃で２４時間攪拌下に反応させた。２４時間後、氷冷して反応を停止させた。反応物を水洗してＴＢＡＢを除き、次いで有機相中の水分をＭｇＳＯ４ で除いた。その後、減圧乾燥してトルエンを除き、テレフタル酸ジクロリドから誘導したクロロメチル基を有する液状の多官能ビニルエーテル（以下、ＴＣＶＥと略記する）を収率９０％で得た。
【００２０】
得られた生成物（ＴＣＶＥ）の １Ｈ−ＮＭＲスペクトル（２００ＭＨｚ、ＣＤＣｌ３ 、内部標準ＴＭＳ（テトラメチルシラン））のデータをまとめると以下のとおりである。なお、各符号Ａ，ａ〜ｆは下記化１０に示すＴＣＶＥの炭素に結合している各水素に対応している。
【化１０】
グリシジルビニルエーテルのエポキシ基が全てβ開裂を生じてＴＣＶＥが生じたと仮定して計算した−ＣＨ２ Ｃｌ基の水素によるピークの積分比に比べて、実際の積分比は若干小さくなっていた。これは、エポキシ基のα開裂が生じた結果であると考えられる。この積分比の差異に基づき、主生成物と副生成物の割合を計算すると、前記一般式（１）で表わされるような主生成物のＴＣＶＥは９３％、前記一般式（２）又は（３）で表わされるような副生成物のＴＣＶＥは７％であった。
また、得られた生成物のＩＲスペクトルによれば、ＴＣＶＥのカルボニル基（−Ｃ＝Ｏ）の伸縮運動によるピークが波数１７２４ｃｍ−１のところに、ビニル基（−ＣＨ＝ＣＨ２ ）によるそれが波数１６１９及び１２００ｃｍ−１のところに現われていた。
ＩＲ（ＫＢｒ、ｃｍ−１）：１７２４（νｃ＝０ ）、１６１９（νＣ＝Ｃ ビニル）、１２００（νＣ＝Ｃ ビニル）
以上の結果より、前記反応式（Ｉ）において一般式（１′）のＲがベンゼン環であるＴＣＶＥ（一般式（２′）及び（３′）のＲがベンゼン環の副生成物が約７％混在）が得られたことが確認された。
【００２１】
実施例２
実施例１において、テレフタル酸ジクロリド（ＴＰＣ）に代えてイソフタル酸ジクロリド（ＩＰＣ）を用いる以外は実施例１と同様にして、イソフタル酸ジクロリドから誘導したクロロメチル基を有する液状の多官能ビニルエーテル（以下、ＩＣＶＥと略記する）を収率８２％で得た。
得られたＩＣＶＥの １Ｈ−ＮＭＲスペクトル及びＩＲスペクトルのデータは下記のとおりである。なお、ＩＣＶＥのベンゼン環に結合している水素の符号を下記化１１に示す。
【化１１】
実施例３
実施例１において、テレフタル酸ジクロリドに代えてＣｌＯＣ（ＣＨ２ ）４ＣＯＣｌを用いる以外は実施例１と同様にして、クロロメチル基を有する液状の多官能ビニルエーテル（以下、ＡＰＶＥと略記する）を収率７８％で得た。
得られたＡＰＶＥの １Ｈ−ＮＭＲスペクトル及びＩＲスペクトルのデータは下記のとおりである。なお、ＡＰＶＥのアルキレン基に結合している水素の符号を下記化１２に示す。
【化１２】
実施例４
実施例１において、テレフタル酸ジクロリドに代えてＣｌＯＣ（ＣＨ２ ）８ＣＯＣｌを用いる以外は実施例１と同様にして、クロロメチル基を有する液状の多官能ビニルエーテル（以下、ＳＣＶＥと略記する）を収率８４％で得た。
得られたＳＣＶＥの １Ｈ−ＮＭＲスペクトル及びＩＲスペクトルのデータは下記のとおりである。なお、ＳＣＶＥのアルキレン基に結合している水素の符号を下記化１３に示す。
【化１３】
応用実施例１
前記実施例１で得られたＴＣＶＥに、このビニル基に対して０．０５〜１モル％の割合のビス［４−ジフェニルスルホニオ）−フェニル］サルフィド−ビスヘキサフルオロホスフェート（ドイツ、デグサＡＧ社製、商品名８５Ｂ、前記式（Ｃ）で示される化合物）を光カチオン重合開始剤として加え、ＫＢｒ板に塗布し、高圧水銀灯（２５０Ｗ）によりＵＶ光を全波長照射した。なお、照度は５×１０−４Ｗ／ｃｍ２ （３１０ｎｍ）であった。得られた硬化膜についてフーリエ変換赤外分光光度計ＦＴ−ＩＲ（吸光度ＡＢＳ、１６１９ｃｍ−１）を用いて反応率を調べた。
約２分の照射時間で光重合反応がほぼ飽和状態に達し、また、特に、８５Ｂが０．５モル％以上でより短い照射時間でより高い反応率が得られた。
なお、比較のために、上記ＴＣＶＥに代えて、商品化されている二官能ビニルエーテル（１，４−シクロヘキサンジメタノールジビニルエーテル及びトリエチレングリコールジビニルエーテル）を用いて同様に反応率を調べたが、光カチオン重合開始剤８５Ｂとうまく混合できず、反応できなかった。
【００２５】
実施例５
グリシジルビニルエーテル（セイケミカル（株）製、商品名ＧＶＥ）を１５ミリモル、多価カルボン酸クロリドとして三官能のトリメソイルクロリドを５ミリモル用いる以外は実施例１と同様にして、下記化１４で示される化学構造を有する白色粉末状の多官能ビニルエーテルを収率９４％で得た。
なお、グリシジルビニルエーテルのβ開裂とα開裂による主生成物（化１４で示される化合物）と副生成物の割合は、主生成物（β開裂）：副生成物（α開裂）＝９３：７であった。
【化１４】
実施例６
グリシジルビニルエーテル（セイケミカル（株）製、商品名ＧＶＥ）を１０ミリモル、多価カルボン酸クロリドとしてビスＡＦ型の２，２−ビス（４−ベンゾイルクロリド）ヘキサフロロプロパンを５ミリモル用いる以外は実施例１と同様にして、下記化１５で示される化学構造を有する高粘度液状の多官能ビニルエーテルを収率７１％で得た。
なお、グリシジルビニルエーテルのβ開裂とα開裂による主生成物（化１５で示される化合物）と副生成物の割合は、主生成物（β開裂）：副生成物（α開裂）＝９３：７であった。
【化１５】
【発明の効果】
以上のように、本発明の方法によれば、グリシジルビニルエーテルと多価カルボン酸クロリドとの反応により高収率で光反応性多官能ビニルエーテルを製造できる。また、若干の副生成物を生成するが、主生成物及び副生成物も共に末端にビニルエーテル基を有する光反応性の多官能ビニルエーテルであるため、副生成物の分離・精製が不要である。従って、生産性よくかつ比較的低コストで光反応性多官能ビニルエーテルを製造できるという利点が得られる。
また、本発明の光硬化性組成物は、上記光反応性に富む多官能ビニルエーテルと活性エネルギー線によりカチオン重合を開始させるカチオン重合開始剤を基本成分として含むものであるため、比較的に短時間の活性エネルギー線の照射により速やかに反応して硬化物を生成するので、各種保護膜、塗料、接着剤、シーリング剤等広範な用途に有利に用いることができる。[0001]
[Industrial applications]
The present invention relates to a novel photoreactive polyfunctional vinyl ether, a method for producing the same, and a photocurable composition containing the photoreactive polyfunctional vinyl ether.
[0002]
[Prior art]
A vinyl ether compound is polymerized by a cationic polymerization initiator to form a corresponding polyvinyl ether, and thus has a wide range of uses as a paint, an adhesive, a sealing agent, a resist agent, and the like.
Conventionally, a polyvinyl ether having a vinyl ether group at a side chain or a terminal is obtained by, for example, introducing an epoxy group and / or a vinyl ether group into an acrylic polymer or a fluoroolefin polymer in JP-A-4-170486. A vinyl-based polymer is described, and a curable resin composition which is cured by heating or irradiation with active energy rays by using a catalyst for initiating cationic polymerization is disclosed. JP-A-4-170486 also teaches, as a reaction for introducing a vinyl ether group, a method of reacting a compound having both an epoxy group and a vinyl ether group such as glycidyl vinyl ether with a polymer containing a carboxyl group. Have been.
Similarly, it is reported that a polymer having a vinyl ether group in a side chain can be synthesized by reacting glycidyl vinyl ether with phthalic anhydride. 48, no. 8 (August 1991) p. 478. However, since these synthetic reactions are reactions between carboxyl groups and epoxy groups, there is a problem that the yield is low.
[0003]
[Problems to be solved by the invention]
Accordingly, a main object of the present invention is to produce a photoreactive polyfunctional vinyl ether having a vinyl ether group in good yield and to provide a photoreactive polyfunctional vinyl ether with good productivity and at relatively low cost.
Another object of the present invention is to provide a photocurable composition containing a photoreactive polyfunctional vinyl ether and applicable to a wide range of uses.
[0004]
[Means for Solving the Problems]
In order to achieve the above object, according to the present invention, glycidyl vinyl ether and a compound having two or more carboxylic acid chloride groups (—COCl) in a molecule (hereinafter, abbreviated as polyvalent carboxylic acid chloride ). a reaction product, have a multi-functional vinyl ether group in the molecule, the general formula of 5 (1), (2), or photoreactive polyfunctional, characterized in that represented by (3) vinyl ether Ru is provided.
Embedded image
[0005]
Embedded image
According to the present invention, there is also provided a method for producing the photoreactive polyfunctional vinyl ether, the method comprising reacting glycidyl vinyl ether with a polycarboxylic acid chloride in an organic solvent or in the absence of a solvent in the presence of a catalyst. It is characterized by the following. In a preferred embodiment, the reaction is carried out at 50 to 150 ° C. for 3 to 48 hours, preferably at 70 to 120 ° C. for 8 to 24 hours, and the above polyvalent carboxylic acid chloride is represented by the following formula (1 ′) ) To (18 ') are used.
Embedded image
Further, according to the present invention, there is also provided a photocurable composition comprising the photoreactive polyfunctional vinyl ether and a cationic polymerization initiator for initiating cationic polymerization with an active energy ray. Preferably, a cationic polymerization initiator selected from the group consisting of salts of (A) to (G) in Chemical Formula 8 below is used as the cationic polymerization initiator.
Embedded image
[0008]
Operation and Mode of the Invention
The present inventors can produce a photoreactive polyfunctional vinyl ether having a polyfunctional vinyl ether group in good yield by reacting glycidyl vinyl ether and polycarboxylic acid chloride in an organic solvent in the presence of a catalyst, and The present inventors have found that when the polyfunctional vinyl ether is coexisted with a cationic polymerization initiator for initiating cationic polymerization by active energy rays, good photocurability is exhibited, and the present invention has been completed.
[0009]
When glycidyl vinyl ether is reacted with a polycarboxylic acid chloride, for example, dicarboxylic acid chloride in an organic solvent in the presence of a catalyst, the reaction proceeds as shown in the following reaction formula (I), and the epoxy group of glycidyl vinyl ether is mainly reacted. Is generated to produce a main product (polyfunctional vinyl ether represented by the general formula (1 ′)) in which a chloromethyl group (—CH 2 Cl) is bonded to a main chain as a side group.
Embedded image
[0010]
As the polyvalent carboxylic acid chloride to be reacted with glycidyl vinyl ether, any carboxylic acid chloride having two or more —COCl groups can be used, and among them, the aliphatic (1 ′) to (18 ′) Preferred are polyvalent carboxylic acid chlorides such as hydrocarbons (having 1 to 8 carbon atoms), benzenes, benzophenones, bisphenols, biphenyls, tetrahydrophthalic acids, cyclohexanes, maleic acids, naphthalenes, and fluorenes.
Glycidyl vinyl ether and polycarboxylic acid chloride are reacted in an organic solvent in the presence of a phase transfer catalyst. As is clear from the examples described below, the reaction temperature is suitably in the range of 50 to 150 ° C., and more preferably 70 to 120 ° C., in order to obtain a reaction yield of about 80% or more. It is. The reaction time is 3 to 48 hours, preferably 8 to 24 hours. If the reaction time is less than 3 hours, the production of the desired product is insufficient and the reaction yield is not satisfactory. On the other hand, if the reaction time is longer than 24 hours, the reaction yield is almost saturated, and the productivity is high. However, it is not preferable in terms of economy.
[0011]
Although the reaction proceeds well without solvent, use of a reaction solvent is appropriate from the viewpoint of washing the product and controlling the reaction system. As the organic solvent, any hydrophobic organic solvent other than a hydrophilic solvent such as alcohol and acetone can be used. Among them, toluene, dimethylformamide, dimethyl acetate, N-methylpyrrolidone, diethylene glycol dimethyl ether (trade name) : Diglyme), anisole, dichlorobenzene, sulfolane and the like are preferable, and toluene is particularly preferable. If water is mixed into the reaction system, the yield is undesirably reduced. Further, as a reaction solvent of this reaction, a photo-radical polymerizable compound such as a (meth) acrylate or a polyfunctional (meth) acrylate may be used. Can also be used as a photocurable oligomer.
[0012]
As the catalyst, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium fluoride, tetra-n-butylammonium hydroxide, tetra-n -Butylammonium azide, tetra-n-butylammonium phosphate, dimethylbenzylphenylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride, trioctylmethylammonium chloride, benzyltri-n-butylammonium bromide, cetyldimethylethyl Ammonium bromide, dilauryldimethylammonium bromide, (ferrocenylmethyl) trimethylammonium Bromide, N, N-dimethylmethyleneammonium iodide, phenyltriethylammonium iodide, tetraethylammonium hydroxide, dimethylaminopyridine, 4-bromopyridinehydrochloride, Nn-butylpyridinium chloride, tributylamine, tetra-n-butyl Various known quaternary onium salts such as phosphonium bromide, allyltriphenylphosphonium bromide, diphenyliodonium perchlorate, (2-carboxyethyl) dimethylsulfonium bromide, and other catalysts such as tertiary amines, tertiary phosphines, and crown ether complexes can be used. No.
[0013]
According to the present invention, further, a photocurable composition is obtained by mixing the photoreactive polyfunctional vinyl ether obtained as described above with a cationic polymerization initiator that initiates cationic polymerization with active energy rays. . As the active energy ray cationic polymerization initiator, conventionally known various cationic polymerization initiators such as diaryliodonium salts, triarylsulfonium salts, thiobistriarylsulfonium salts, selenonium salts, and phosphonium salts can be used. The salts (A) to (E) are preferred. These cationic polymerization initiators may be used alone or in combination of two or more. The compounding ratio of the cationic polymerization initiator in the photocurable composition is appropriately 0.05 mol% or more, preferably 0.1 mol% or more, and most preferably 0.1 mol% or more, based on the vinyl group of the polyfunctional vinyl ether. 5 to 10 mol%. As will be apparent from the examples described later, if the blending ratio of the cationic polymerization initiator is less than 0.05 mol%, it is difficult to obtain sufficient photocurability, which is not preferable.
[0014]
The photocurable composition according to the present invention further includes a polymer having at least one epoxy group and / or vinyl ether group in one molecule, for example, epoxy resins, or the like, as long as the photocurability is not impaired. A polyether resin, a polyester resin, an alkyd resin, a urethane resin or a silicone resin having an epoxy group or a vinyl ether group introduced therein can be mixed to improve the properties of the cured product. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin and alicyclic epoxy resin. Alternatively, a small amount of a known epoxy curing accelerator such as an amine compound, an imidazole compound, a carboxylic acid, a phenol, a quaternary ammonium salt or a methylol group-containing compound for accelerating the reaction can be used. By adding these thermosetting components, the coating film can be cured by heating by heating, and various properties such as hardness, chemical resistance and heat resistance can be improved.
[0015]
Further, the photocurable composition of the present invention includes a compound having at least one epoxy group and / or vinyl ether group in one molecule, such as 3,4-epoxycyclohexyl vinyl ether, ethylene glycol monoglycidyl monovinyl ether, and triethylene. Glycol monoglycidyl monovinyl ether, dipropylene glycol monoglycidyl monovinyl ether, cyclohexyl vinyl ether, benzyl vinyl ether, 2-ethylhexyl vinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, 1,4-bisdivinyloxymethylcyclohexane, isophorone diisocyanate and 4-hydroxybutyl vinyl ether in a molar ratio of 1: 2 adduct or hydrogenated xylylene diisocyanate and 4 The molar ratio of hydroxybutyl vinyl ether 1: can be mixed like 2 adduct.
[0016]
The photocurable composition of the present invention further includes, if necessary, known and customary fillers such as barium sulfate, silicon oxide, talc, clay, and calcium carbonate, phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black. Various additives such as known coloring pigments, antifoaming agents, adhesion-imparting agents or leveling agents may be added.
[0017]
As the irradiation light source for photocuring the photocurable composition of the present invention, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is suitable. Further, a laser beam or the like can also be used as an active light beam for exposure. In addition, electron beams, α-rays, β-rays, γ-rays, X-rays, neutron rays, and the like can also be used.
[0018]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, it goes without saying that the present invention is not limited to the following examples.
[0019]
Example 1
Glycidyl vinyl ether (manufactured by Seika Chemical Co., Ltd., trade name: GVE) was 10 mmol, terephthalic acid dichloride (TPC) was 5 mmol, and tetra-n-butylammonium bromide (TBAB) was 5 mol% based on GVE. It was dissolved in 5 ml of toluene and reacted under stirring at 90 ° C. for 24 hours in an oil bath. After 24 hours, the reaction was stopped by cooling with ice. Except TBAB The reaction was washed with water, then remove water in the organic phase over MgSO 4. Thereafter, the residue was dried under reduced pressure to remove toluene, and a liquid polyfunctional vinyl ether having a chloromethyl group derived from terephthalic acid dichloride (hereinafter abbreviated as TCVE) was obtained at a yield of 90%.
[0020]
The data of the 1 H-NMR spectrum (200 MHz, CDCl 3 , internal standard TMS (tetramethylsilane)) of the obtained product (TCVE) are summarized as follows. In addition, each code | symbol A, af respond | corresponds to each hydrogen couple | bonded with the carbon of TCVE shown in following formula 10.
Embedded image
Compared to the integral ratio of the peak due to hydrogen -CH 2 Cl group which epoxy groups of glycidyl vinyl ether was calculated assuming TCVE occurs all β cleavage occurs, the actual integration ratio was slightly reduced. This is believed to be the result of the α-cleavage of the epoxy group. When the ratio of the main product and the by-product is calculated based on the difference of the integration ratio, the TCVE of the main product represented by the general formula (1) is 93%, and the TCVE of the main product is represented by the general formula (2) or (3). ) Was 7%.
In addition, according to the IR spectrum of the obtained product, the peak due to the stretching movement of the carbonyl group (—C ＝ O) of TCVE was at a wave number of 1,724 cm −1 , and the peak due to the vinyl group (—CH ＝ CH 2 ) was It appeared at wave numbers of 1619 and 1200 cm -1 .
IR (KBr, cm −1 ): 1724 (ν c = 0 ), 1619 (ν C = C vinyl), 1200 (ν C = C vinyl)
From the above results, in the above reaction formula (I), TCVE in which R in the general formula (1 ′) is a benzene ring (R in the general formulas (2 ′) and (3 ′) is about 7% by-product of the benzene ring) % Mixed) was obtained.
[0021]
Example 2
A liquid polyfunctional vinyl ether having a chloromethyl group derived from isophthalic acid dichloride (hereinafter referred to as "Example 1") except that isophthalic acid dichloride (IPC) is used instead of terephthalic acid dichloride (TPC). , ICVE) in a yield of 82%.
The data of 1 H-NMR spectrum and IR spectrum of the obtained ICVE are as follows. The sign of hydrogen bonded to the benzene ring of ICVE is shown in the following formula (11).
Embedded image
Example 3
A liquid polyfunctional vinyl ether having a chloromethyl group (hereinafter abbreviated as APVE) was collected in the same manner as in Example 1 except that ClOC (CH 2 ) 4 COCl was used instead of terephthalic acid dichloride. Obtained at a rate of 78%.
The data of 1 H-NMR spectrum and IR spectrum of the obtained APVE are as follows. The sign of hydrogen bonded to the alkylene group of APVE is shown in the following formula (12).
Embedded image
Example 4
A liquid polyfunctional vinyl ether having a chloromethyl group (hereinafter abbreviated as SCVE) was collected in the same manner as in Example 1 except that ClOC (CH 2 ) 8 COCl was used instead of terephthalic acid dichloride. Obtained at a rate of 84%.
The data of 1 H-NMR spectrum and IR spectrum of the obtained SCVE are as follows. In addition, the sign of the hydrogen bonded to the alkylene group of SCVE is shown in the following Chemical Formula 13.
Embedded image
Application Example 1
The TCVE obtained in Example 1 was added to bis [4-diphenylsulfonio) -phenyl] sulfide-bishexafluorophosphate (Degussa AG, Germany) in a ratio of 0.05 to 1 mol% based on the vinyl group. Was added as a cationic photopolymerization initiator, applied to a KBr plate, and irradiated with UV light by a high-pressure mercury lamp (250 W) at all wavelengths. The illuminance was 5 × 10 −4 W / cm 2 (310 nm). The reaction rate of the obtained cured film was examined using a Fourier transform infrared spectrophotometer FT-IR (absorbance ABS, 1619 cm -1 ).
With the irradiation time of about 2 minutes, the photopolymerization reaction almost reached a saturated state, and in particular, when 85B was 0.5 mol% or more, a higher reaction rate was obtained with a shorter irradiation time.
For the sake of comparison, the reaction rate was similarly examined using commercially available bifunctional vinyl ethers (1,4-cyclohexane dimethanol divinyl ether and triethylene glycol divinyl ether) instead of TCVE. It could not be mixed well with the cationic photopolymerization initiator 85B and could not react.
[ 0025 ]
Example 5
In the same manner as in Example 1 except that 15 mmol of glycidyl vinyl ether (trade name: GVE, manufactured by Seika Chemical Co., Ltd.) and 5 mmol of trifunctional trimesoyl chloride as the polyvalent carboxylic acid chloride are represented by the following formula (14). A white powdery polyfunctional vinyl ether having a chemical structure was obtained in a yield of 94%.
The ratio of the main product (compound represented by Chemical formula 14) and the by-product by β-cleavage and α-cleavage of glycidyl vinyl ether is as follows: main product (β-cleavage): by-product (α-cleavage) = 93: 7. there were.
Embedded image
Example 6
Example 1 except that 10 mmol of glycidyl vinyl ether (trade name: GVE, manufactured by Seika Chemical Co., Ltd.) and 5 mmol of 2,2-bis (4-benzoyl chloride) hexafluoropropane of bis AF type as polyvalent carboxylic acid chloride were used. In the same manner as in Example 1, a highly viscous liquid polyfunctional vinyl ether having a chemical structure represented by the following chemical formula 15 was obtained in a yield of 71%.
The ratio of the main product (compound represented by Chemical Formula 15) and the by-product by β-cleavage and α-cleavage of glycidyl vinyl ether is as follows: main product (β-cleavage): by-product (α-cleavage) = 93: 7. there were.
Embedded image
【The invention's effect】
As described above, according to the method of the present invention, a photoreactive polyfunctional vinyl ether can be produced at a high yield by reacting glycidyl vinyl ether with a polycarboxylic acid chloride. Although some by-products are produced, both the main product and the by-product are photoreactive polyfunctional vinyl ethers having a vinyl ether group at a terminal, so that there is no need to separate and purify the by-products. Therefore, there is an advantage that the photoreactive polyfunctional vinyl ether can be produced with good productivity and at relatively low cost.
Further, since the photocurable composition of the present invention contains, as basic components, the above-mentioned photoreactive polyfunctional vinyl ether and a cationic polymerization initiator that initiates cationic polymerization by active energy rays, the activity of the photocurable composition for a relatively short time is reduced. Since it reacts promptly by irradiation with energy rays to produce a cured product, it can be advantageously used in a wide range of applications such as various protective films, paints, adhesives and sealing agents.
Claims (6)
の（Ａ）〜（Ｇ）の塩からなる群より選ばれたカチオン重合開始剤である請求項５に記載の光硬化性組成物。The cationic polymerization initiator is represented by the following formula 4.
The photocurable composition according to claim 5 , which is a cationic polymerization initiator selected from the group consisting of salts of (A) to (G).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19880693A JP3573472B2 (en) | 1993-07-19 | 1993-07-19 | Photoreactive polyfunctional vinyl ether, method for producing the same, and photocurable composition containing the vinyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19880693A JP3573472B2 (en) | 1993-07-19 | 1993-07-19 | Photoreactive polyfunctional vinyl ether, method for producing the same, and photocurable composition containing the vinyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0733711A JPH0733711A (en) | 1995-02-03 |
| JP3573472B2 true JP3573472B2 (en) | 2004-10-06 |
Family
ID=16397224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19880693A Expired - Lifetime JP3573472B2 (en) | 1993-07-19 | 1993-07-19 | Photoreactive polyfunctional vinyl ether, method for producing the same, and photocurable composition containing the vinyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3573472B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4443161B2 (en) | 2002-10-25 | 2010-03-31 | ダイセル化学工業株式会社 | Aromatic vinyl ether compounds |
-
1993
- 1993-07-19 JP JP19880693A patent/JP3573472B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0733711A (en) | 1995-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW524810B (en) | Process of preparing curable compositions and compositions therefrom | |
| JP4973868B2 (en) | Curable resin composition and curing method | |
| US20060030636A1 (en) | Unsaturated carboxylic ester compound, process for producing the same, and composition curable with actinic energy ray | |
| JP2008540710A (en) | Radiation curable methacrylate polyester | |
| JP2008243600A (en) | Transparent conductive material and film, manufacturing method of transparent conductive film, and display element | |
| JP4762659B2 (en) | Epoxy resin and epoxy resin composition | |
| JP3573472B2 (en) | Photoreactive polyfunctional vinyl ether, method for producing the same, and photocurable composition containing the vinyl ether | |
| JP5719831B2 (en) | Epoxy acrylate, acrylic composition, cured product and method for producing the same | |
| JP2007153853A (en) | Method for producing ester compound | |
| WO1995024387A1 (en) | Sulfonium salt compound and polymerization initiator | |
| JP4469072B2 (en) | Alkali-developable photocurable / thermosetting composition | |
| JP6541585B2 (en) | (Meth) acrylic epoxy isocyanurate compounds, synthesis method thereof and use of the isocyanurate compounds | |
| JP4563053B2 (en) | Poly (meth) acrylate resin, method for producing the same, and curable resin composition | |
| JP2827567B2 (en) | New sulfonium salt and polymerization initiator | |
| JP3158619B2 (en) | Photocurable resin composition | |
| JPH04327574A (en) | Novel pyridinium salt compound and polymerization initiator | |
| JP2004331768A (en) | Epoxy group-containing highly branched compound, curable composition containing the same and printed wiring board using the curable composition | |
| JPH06844B2 (en) | Process for producing halogen-containing unsaturated polyester | |
| JP5758923B2 (en) | Epoxy acrylate, acrylic curable composition, cured product and method for producing the same | |
| JPH101540A (en) | Polyfunctional vinyl ether, polymerizable composition and cured product thereof | |
| JPH10182634A (en) | Photopolymerization initiator, energy ray-curable composition and cured product | |
| CN114746392A (en) | Alicyclic acrylate compound, alicyclic epoxy acrylate compound, curable composition, and cured product | |
| JPH0548764B2 (en) | ||
| JPS5956422A (en) | Modified epoxy(meth)acrylate resin | |
| JPH10147626A (en) | Production of polyurethane resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040309 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040510 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040608 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040629 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080709 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080709 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090709 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090709 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100709 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100709 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110709 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120709 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130709 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130709 Year of fee payment: 9 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130709 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term | ||
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |