JP7481011B2 - Thermally cationic polymerizable resin composition - Google Patents
Thermally cationic polymerizable resin composition Download PDFInfo
- Publication number
- JP7481011B2 JP7481011B2 JP2021000194A JP2021000194A JP7481011B2 JP 7481011 B2 JP7481011 B2 JP 7481011B2 JP 2021000194 A JP2021000194 A JP 2021000194A JP 2021000194 A JP2021000194 A JP 2021000194A JP 7481011 B2 JP7481011 B2 JP 7481011B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- group
- resin composition
- manufactured
- 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.)
- Active
Links
- 125000002091 cationic group Chemical group 0.000 title claims description 31
- 239000011342 resin composition Substances 0.000 title claims description 28
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 12
- 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 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000001451 organic peroxides Chemical class 0.000 claims description 11
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 9
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- -1 vinyl ether compound Chemical class 0.000 description 28
- 238000010943 off-gassing Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 8
- 239000003504 photosensitizing agent Substances 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000012766 organic filler Substances 0.000 description 6
- 150000004756 silanes Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 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 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- 239000013008 thixotropic agent Substances 0.000 description 5
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 4
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 4
- 239000004844 aliphatic epoxy resin Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- 229960000834 vinyl ether Drugs 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 2
- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- POZBDDCHVAOFSL-UHFFFAOYSA-N S(=O)(OC)[O-].OC1=CC=C(C=C1)[S+](C)C Chemical compound S(=O)(OC)[O-].OC1=CC=C(C=C1)[S+](C)C POZBDDCHVAOFSL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 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
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 125000006839 xylylene group Chemical group 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- QKAIFCSOWIMRJG-UHFFFAOYSA-N (4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 QKAIFCSOWIMRJG-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-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
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LJWZDTGRJUXOCE-UHFFFAOYSA-N 2-(2-ethylhexyl)oxetane Chemical compound CCCCC(CC)CC1CCO1 LJWZDTGRJUXOCE-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- NUIZZJWNNGJSGL-UHFFFAOYSA-N 2-phenylpropan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)c1ccccc1 NUIZZJWNNGJSGL-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- FRBAZRWGNOJHRO-UHFFFAOYSA-N 6-tert-butylperoxycarbonyloxyhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CC(C)(C)OOC(=O)OCCCCCCOC(=O)OOC(C)(C)C FRBAZRWGNOJHRO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QKQFIIOUCQZCFT-UHFFFAOYSA-O benzyl-(4-hydroxyphenyl)-methylsulfanium Chemical compound C=1C=C(O)C=CC=1[S+](C)CC1=CC=CC=C1 QKQFIIOUCQZCFT-UHFFFAOYSA-O 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical class OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
- Epoxy Resins (AREA)
Description
本発明は熱カチオン重合性樹脂組成物に関する。 The present invention relates to a thermally cationic polymerizable resin composition.
カチオン硬化性樹脂は、その硬化物が機械的強度、耐薬品性、電気絶縁性、接着性などの特性に優れていることから、塗料、電気・電子、土木・建築、接着剤分野などで幅広く利用されている。 Cationically curable resins are widely used in fields such as paints, electrical and electronics, civil engineering and construction, and adhesives because the cured products have excellent properties such as mechanical strength, chemical resistance, electrical insulation, and adhesive properties.
一般に、ラジカルレッドクス機構(ヨードニウム塩系の光カチオン重合開始剤と有機過酸化物(熱ラジカル重合開始剤)との組み合わせ)を利用した熱硬化性の樹脂組成物は、低温で硬化可能で、且つ熱硬化のみの場合でも、紫外線硬化及び熱硬化の両方を行った場合と同等の物性を発現することが可能である。このような組成物として、特許文献1~3には、前記したラジカルレッドクス機構及びカチオン硬化性樹脂を含む熱カチオン重合性の組成物が開示されている。 In general, thermosetting resin compositions that utilize the radical redox mechanism (a combination of an iodonium salt-based photocationic polymerization initiator and an organic peroxide (thermal radical polymerization initiator)) can be cured at low temperatures, and even when only thermal curing is performed, they can exhibit physical properties equivalent to those when both UV curing and thermal curing are performed. As such compositions, Patent Documents 1 to 3 disclose thermal cationic polymerizable compositions that contain the above-mentioned radical redox mechanism and a cationic curable resin.
しかしながら、特許文献1~3に記載された熱カチオン重合性の組成物は、ラジカル発生の機構を利用しているため、酸素阻害を受け易く、表面の硬化性が不十分になることがあった。これにより、硬化が不十分な成分が耐熱試験等でアウトガスとして揮発し、周辺部材を汚染する等の不具合が懸念されていた。 However, the thermally cationic polymerizable compositions described in Patent Documents 1 to 3 utilize a mechanism of radical generation, and are therefore susceptible to oxygen inhibition, which can result in insufficient curing of the surface. This has raised concerns that insufficiently cured components may volatilize as outgassing during heat resistance tests, contaminating surrounding components, and other problems.
よって、本発明は、表面硬化性に優れ、かつ、アウトガス量が低減された、熱カチオン重合性樹脂組成物を提供することを課題とする。 Therefore, the objective of the present invention is to provide a thermally cationic polymerizable resin composition that has excellent surface curing properties and reduced outgassing.
本発明者等は、上記課題を鑑み鋭意検討を重ねた結果、ラジカルレドックス機構を利用した配合に、熱カチオン開始剤を新たに添加することで、樹脂表面の硬化性を改善することができると共に、アウトガス量を低減することができることを見出した。また、熱カチオン開始剤の添加量を調整することで、ガラス転移温度を高温で維持したまま、表面硬化性を改善することができ、その結果、アウトガス量を低減することができることを見出した。 The inventors of the present invention have conducted extensive research in light of the above problems and have found that adding a thermal cationic initiator to a formulation that utilizes a radical redox mechanism can improve the curing properties of the resin surface and reduce the amount of outgassing. They have also found that adjusting the amount of thermal cationic initiator added can improve the surface curing properties while maintaining the glass transition temperature at a high temperature, thereby reducing the amount of outgassing.
本発明は、以下の[1]~[4]に関する。
[1](A)カチオン硬化性樹脂、
(B)式:Ar1-I+-Ar2・X-(式中、Ar1及びAr2は、独立して、置換又は非置換のアリール基であり、X-は、アニオンである)で示されるヨードニウム塩、
(C)有機過酸化物、及び
(D)熱カチオン重合開始剤
を含み、(A)成分の100重量部に対して、(D)成分の含有量が0.03重量部以上1.50重量部以下である、熱カチオン重合性樹脂組成物。
[2](D)成分が、スルフォニウム塩である、[1]の熱カチオン重合性樹脂組成物。
[3](D)成分のアニオンが、SbF6
-、B(C6F5)4
-、又は[P(RF)nF6-n]-(式中、RFは、独立して、炭素原子数1~6の部分又は全フッ素化アルキル基であり、nは0~5の整数である)である、[1]又は[2]の熱カチオン重合性樹脂組成物。
[4](A)成分が、エポキシ樹脂及びオキセタン樹脂からなる群より選択される少なくとも一種である、[1]~[3]のいずれかの熱カチオン重合性樹脂組成物。
The present invention relates to the following [1] to [4].
[1] (A) a cationically curable resin,
(B) iodonium salts of the formula Ar 1 -I + -Ar 2 ·X - , where Ar 1 and Ar 2 are independently substituted or unsubstituted aryl groups, and X - is an anion;
1. A thermal cationic polymerization resin composition comprising: (C) an organic peroxide; and (D) a thermal cationic polymerization initiator, wherein the content of the (D) component is 0.03 parts by weight or more and 1.50 parts by weight or less per 100 parts by weight of the (A) component.
[2] The thermally cationically polymerizable resin composition according to [1], wherein the component (D) is a sulfonium salt.
[3] The thermally cationically polymerizable resin composition according to [1] or [2 ], in which the anion of component (D) is SbF 6 - , B(C 6 F 5 ) 4 - , or [P(R F ) n F 6-n ] - (wherein R F is independently a partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 5).
[4] The thermally cationically polymerizable resin composition according to any one of [1] to [3], wherein the component (A) is at least one selected from the group consisting of an epoxy resin and an oxetane resin.
本発明により、表面硬化性に優れ、かつ、アウトガス量が低減された、熱カチオン重合性樹脂組成物が提供される。 The present invention provides a thermally cationic polymerizable resin composition that has excellent surface curing properties and reduced outgassing.
以下、本発明の実施の形態について詳細に説明する。 The following describes in detail the embodiments of the present invention.
[熱カチオン重合性樹脂組成物]
熱カチオン重合性樹脂組成物は、(A)カチオン硬化性樹脂、(B)式:Ar1-I+-Ar2・X-(式中、Ar1及びAr2は、独立して、置換又は非置換のアリール基であり、X-は、アニオンである)で示されるヨードニウム塩、(C)有機過酸化物、及び(D)熱カチオン重合開始剤を含み、(A)成分の100重量部に対して、(D)成分の含有量が0.03重量部以上1.50重量部以下である。
[Thermal cationically polymerizable resin composition]
The thermal cationic polymerizable resin composition comprises (A) a cationic curable resin, (B) an iodonium salt represented by the formula: Ar 1 -I + -Ar 2.X - (wherein Ar 1 and Ar 2 are independently a substituted or unsubstituted aryl group, and X - is an anion), (C) an organic peroxide, and (D) a thermal cationic polymerization initiator, and the content of the component (D) is 0.03 parts by weight or more and 1.50 parts by weight or less per 100 parts by weight of the component (A).
熱カチオン重合性樹脂組成物は、(D)成分の含有量が0.03重量部以上1.50重量部以下であることから、ガラス転移温度(Tg)を高温で維持できる。 The thermally cationic polymerizable resin composition has a content of component (D) of 0.03 parts by weight or more and 1.50 parts by weight or less, so that the glass transition temperature (Tg) can be maintained at a high temperature.
<(A)カチオン硬化性樹脂>
カチオン硬化性樹脂としては、分子内に1以上のカチオン重合性基を有する樹脂であれば、特に限定されない。カチオン重合性基としては、エポキシ基、オキセタニル基、ビニルエーテル基等が挙げられる。カチオン硬化性樹脂の具体例としては、エポキシ樹脂、オキセタン樹脂、ポリスチレン系化合物、及びビニルエーテル化合物等が挙げられる。
<(A) Cationic curable resin>
The cationic curable resin is not particularly limited as long as it has one or more cationic polymerizable groups in the molecule. Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Specific examples of the cationic curable resin include an epoxy resin, an oxetane resin, a polystyrene compound, and a vinyl ether compound.
≪エポキシ樹脂≫
エポキシ樹脂としては、芳香族、脂肪族及び脂環式エポキシ樹脂を挙げることができる。
<Epoxy resin>
Epoxy resins can include aromatic, aliphatic and cycloaliphatic epoxy resins.
芳香族エポキシ化合物としては、ビスフェノールA型エポキシ樹脂(DIC社製のEPICLON850、850-S、EXA-850CRP、EXA-8067等)、ビスフェノールF型エポキシ樹脂(DIC社製のEPICLON830-S、EXA-830LVP等)、ビスフェノールAD型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ナフタレン型エポキシ樹脂(DIC社製のEPICLONのHP-4032D、HP-7200H等)、フェノールノボラック型エポキシ樹脂(DIC社製のEPICLON N-740、N-770等)、クレゾールノボラック型エポキシ樹脂(DIC社製のEPICLON N-660、N-670、N-655-EXP-S等)、多官能型エポキシ樹脂等が挙げられる。多官能型エポキシ化合物としては、テトラ(ヒドロキシフェニル)アルカンのグリシジルエーテル、テトラヒドロキシベンゾフェノンのグリシジルエーテル、エポキシ化ポリビニルフェノール等が挙げられる。 Examples of aromatic epoxy compounds include bisphenol A type epoxy resins (DIC's EPICLON 850, 850-S, EXA-850CRP, EXA-8067, etc.), bisphenol F type epoxy resins (DIC's EPICLON 830-S, EXA-830LVP, etc.), bisphenol AD type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins (DIC's EPICLON HP-4032D, HP-7200H, etc.), phenol novolac type epoxy resins (DIC's EPICLON N-740, N-770, etc.), cresol novolac type epoxy resins (DIC's EPICLON N-660, N-670, N-655-EXP-S, etc.), and multifunctional epoxy resins. Examples of polyfunctional epoxy compounds include glycidyl ethers of tetra(hydroxyphenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenones, and epoxidized polyvinylphenols.
脂肪族エポキシ樹脂としては、多価アルコール又はそのアルキレンオキシド付加物のポリグリシジルエーテルが挙げられる。脂肪族エポキシ化合物の具体例としては、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル(共栄社化学社製のエポライト100MF)、ポリエチレングリコールジグリシジルエーテル、2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物(ダイセル社製のEHPE3150)等が挙げられる。 Examples of aliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts. Specific examples of aliphatic epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol diglycidyl ether, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation).
脂肪族エポキシ樹脂は、脂環構造を形成する2つの炭素原子と酸素原子とで、エポキシ基が形成された構造を有する樹脂であり、脂環構造を形成する1つの炭素原子に、エポキシ基が結合する脂肪族エポキシ樹脂は含まれない。脂環式エポキシ化合物としては、シクロヘキサン系、シクロヘキシルメチルエステル系、シクロヘキシルメチルエーテル系、スピロ系及びトリシクロデカン系エポキシ化合物が挙げられる。脂環式エポキシ化合物の具体例としては、(3,3’,4,4’-ジエポキシ)ビシクロヘキシル(ダイセル社製のセロキサイド8010等)、3’,4’-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート(ダイセル社製のセロキサイド2021P等)、1,2:8,9-ジエポキシリモネン、1,2-エポキシ-4-ビニルシクロヘキサン等が挙げられる。 Aliphatic epoxy resins are resins having a structure in which an epoxy group is formed by two carbon atoms and an oxygen atom that form an alicyclic structure, and do not include aliphatic epoxy resins in which an epoxy group is bonded to one carbon atom that forms an alicyclic structure. Examples of alicyclic epoxy compounds include cyclohexane-based, cyclohexyl methyl ester-based, cyclohexyl methyl ether-based, spiro-based, and tricyclodecane-based epoxy compounds. Specific examples of alicyclic epoxy compounds include (3,3',4,4'-diepoxy)bicyclohexyl (Celloxide 8010 manufactured by Daicel Corporation, etc.), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Celloxide 2021P manufactured by Daicel Corporation, etc.), 1,2:8,9-diepoxylimonene, and 1,2-epoxy-4-vinylcyclohexane.
≪オキセタン樹脂≫
オキセタン樹脂の具体例としては、3-エチル-3-ヒドロキシメチルオキセタン(オキセタンアルコール)(東亞合成社製のOXT-101等)、2-エチルヘキシルオキセタン(東亞合成社製のOXT-212等)、キシリレンビスオキセタン(XDO。東亞合成社製のOXT-121等)、3-エチル-3{[(3-エチルオキセタン-3-イル)メトキシ]メチル}オキセタン(東亞合成社製のOXT-221等)、オキセタニルシルセスキオキセタン(東亞合成社製OXT-191等)、フェノールノボラックオキセタン(東亞合成社製PHOX等)及び3-エチル-3-フェノキシメチルオキセタン(POX。東亞合成社製OXT-211等)が挙げられる。
<Oxetane resin>
Specific examples of oxetane resins include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (OXT-101 manufactured by Toagosei Co., Ltd., etc.), 2-ethylhexyloxetane (OXT-212 manufactured by Toagosei Co., Ltd., etc.), xylylene bisoxetane (XDO, OXT-121 manufactured by Toagosei Co., Ltd., etc.), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221 manufactured by Toagosei Co., Ltd., etc.), oxetanyl silsesquioxetane (OXT-191 manufactured by Toagosei Co., Ltd., etc.), phenol novolak oxetane (PHOX manufactured by Toagosei Co., Ltd., etc.), and 3-ethyl-3-phenoxymethyloxetane (POX, OXT-211 manufactured by Toagosei Co., Ltd., etc.).
≪ビニルエーテル化合物≫
ビニルエーテル化合物の具体例としては、ヒドロキシブチルビニルエーテル(ISP社製のHBVE等)、1,4-シクロヘキサンジメタノールのビニルエーテル(ISP社製のCHVE等)、トリエチレングリコールジビニルエーテル(ISP社製のDVE-3等)、ドデシルビニルエーテル(ISP社製のDDVE等)、及びシクロヘキシルビニルエーテル(ISP社製CVE等)が挙げられる。
<Vinyl ether compounds>
Specific examples of the vinyl ether compound include hydroxybutyl vinyl ether (such as HBVE manufactured by ISP), vinyl ether of 1,4-cyclohexanedimethanol (such as CHVE manufactured by ISP), triethylene glycol divinyl ether (such as DVE-3 manufactured by ISP), dodecyl vinyl ether (such as DDVE manufactured by ISP), and cyclohexyl vinyl ether (such as CVE manufactured by ISP).
≪好ましいカチオン硬化性樹脂≫
(A)成分は、エポキシ樹脂及びオキセタン樹脂からなる群より選択される少なくとも一種であることが好ましい。
(A)成分は、1種又は2種以上の組み合わせであってよい。
<Preferred cationic curable resin>
The component (A) is preferably at least one selected from the group consisting of epoxy resins and oxetane resins.
The component (A) may be one type or a combination of two or more types.
<(B)式:Ar1-I+-Ar2・X-で示されるヨードニウム塩>
(B)成分は、式:Ar1-I+-Ar2・X-(式中、Ar1及びAr2は、独立して、置換又は非置換のアリール基であり、X-は、アニオンである)で示されるヨードニウム塩(以下、単に「ヨードニウム塩」ともいう。)である。ここで「アリール基」とは、炭素原子数6~18の芳香族炭化水素基、好ましくは、フェニル基又はナフチル基を意味する。アリール基は、非置換であっても、1つ以上の任意の置換基で置換されていてもよく、そのような置換基として、炭素原子数1~18の直鎖又は分岐鎖状のアルキル基、炭素原子数1~18の直鎖又は分岐鎖状のアルコキシ基、炭素原子数2~18の直鎖又は分岐鎖状のアルコキシカルボニル基、炭素原子数2~18の直鎖又は分岐鎖状のアシルオキシ基、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基等を挙げることができる。「アニオン」は、一価のカウンターアニオンであればよいが、非アンチモン系のアニオンであることが好ましく、BF4
-、AsF6
-、又はB(C6F5)4
-、あるいは[P(RF)nF6-n]-、[C(RFSO2)3]-、又は[N(RFSO2)2]-(式中、RFは、独立して、炭素原子数1~6の部分又は全フッ素化アルキル基であり、nは0~5の整数である)であることが特に好ましい。
<(B) Iodonium Salt Represented by Formula: Ar 1 -I + -Ar 2 ·X - >
The component (B) is an iodonium salt (hereinafter, also simply referred to as "iodonium salt") represented by the formula: Ar 1 -I + -Ar 2.X - (wherein Ar 1 and Ar 2 are independently substituted or unsubstituted aryl groups, and X - is an anion). Here, the "aryl group" refers to an aromatic hydrocarbon group having 6 to 18 carbon atoms, preferably a phenyl group or a naphthyl group. The aryl group may be unsubstituted or substituted with one or more optional substituents, and such substituents may include a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a linear or branched alkoxycarbonyl group having 2 to 18 carbon atoms, a linear or branched acyloxy group having 2 to 18 carbon atoms, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and the like. The "anion" may be any monovalent counter anion, but is preferably a non-antimony anion, and particularly preferably BF 4 - , AsF 6 - , or B(C 6 F 5 ) 4 - , or [P(R F ) n F 6-n ] - , [C(R F SO 2 ) 3 ] - , or [N(R F SO 2 ) 2 ] - (wherein R F is independently a partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 5).
(B)成分の具体例としては、ジフェニルヨードニウム・ヘキサフルオロアルセネート、ジ(4-クロロフェニル)ヨードニウム・ヘキサフルオロアルセネート、ジ(4-ブロムフェニル)ヨードニウム・ヘキサフルオロアルセネート、フェニル(4-メトキシフェニル)ヨードニウム・ヘキサフルオロアルセネート、4-メチルフェニル-4-(1-メチルエチル)フェニルヨードニウム・ヘキサフルオロホスフェート、4-メチルフェニル-4-(1-メチルエチル)フェニルヨードニウム・トリ(ペンタフルオロエチル)トリフルオロホスフェート(例えば、サンアプロ社製のIK-1)、4-メチルフェニル-4-(1-メチルエチル)フェニルヨードニウム・テトラキス(ペンタフルオロフェニル)ボレート(例えば、ローディア社製のPI-2074)、4-メチルフェニル-4-(2-メチルプロピル)フェニルヨードニウム・ヘキサフルオロホスフェート(例えば、BASF社製のIRGACURE(登録商標)250)、ビス(C10~14-アルキルフェニル)ヨードニウム・ヘキサフルオロホスフェート(例えば、和光純薬工業社製のWPI-113)、4-メチルフェニル-4-(1-メチルエチル)フェニルヨードニウム・ヘキサフルオロアンチモネート(例えば、和光純薬工業製のWPI-116等)等を挙げることができる。このようなヨードニウム塩は、例えばカチオン開始剤として、試薬供給業者から市販されており、容易に入手することができる。 Specific examples of the component (B) include diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Co., Ltd.), 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate (e.g., PI-2074 manufactured by Rhodia Co., Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE (registered trademark) 250 manufactured by BASF Co., Ltd.), bis(C Examples of iodonium salts include 10-14 -alkylphenyl)iodonium hexafluorophosphate (e.g., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd.), 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate (e.g., WPI-116 manufactured by Wako Pure Chemical Industries, Ltd.), etc. Such iodonium salts are commercially available from reagent suppliers as, for example, cationic initiators, and can be easily obtained.
(B)成分は、1種又は2種以上の組み合わせであってよい。 Component (B) may be one type or a combination of two or more types.
<(C)有機過酸化物>
(C)有機過酸化物は、パーオキシ基(-O-O-)を含む化合物である。有機過酸化物は、ラジカル源である。有機過酸化物から発生したラジカルが、(B)成分のヨードニウム塩を還元的に分解し、光によらず酸を発生させることにより、カチオン重合を促進させる。有機過酸化物としては、ジアシルパーオキシド類、ヒドロパーオキシド類、ジアルキルパーオキシド類、パーオキシケタール類、パーオキシエステル類、パーオキシカーボネート類等が挙げられる。
<(C) Organic Peroxide>
The organic peroxide (C) is a compound containing a peroxy group (-O-O-). The organic peroxide is a radical source. The radicals generated from the organic peroxide reductively decompose the iodonium salt of the component (B) to generate an acid without the use of light, thereby promoting cationic polymerization. Examples of the organic peroxide include diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxycarbonates.
(C)成分の具体例としては、ジラウロイルパーオキシド、ジベンゾイルパーオキシド、ビス-3,5,5-トリメチルヘキサノイルパーオキシドのようなジアシルパーオキシド類;1,1,3,3-テトラメチルブチルヒドロパーオキシド、クメンヒドロパーオキシド(例えば、化薬アグゾ社製のカヤクメンH)、t-ブチルヒドロパーオキシドのようなヒドロパーオキシド類;ジクミルパーオキシド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン、1,3-ビス(t-ブチルパーオキシソプロピル)ベンゼン、t-ブチルクミルパーオキシド、ジ-t-ブチルパーオキシド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン-3のようなジアルキルパーオキシド類;2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン、1,1-ジ-t-ブチルパーオキシシクロヘキサン、2,2-ジ-t-ブチルペルオキブタンのようなパーオキシケタール類;1,1,3,3-テトラメチルブチルパーオキシネオデカノエート、α-クミルパーオキシネオデカノエート、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシネオヘプタノエート、t-ブチルパーオキシピバレート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、t-アミルパーオキシ2-エチルヘキサノエート、t-ブチルパーオキシ2-エチルヘキサノエート、ジ-t-ブチルパーオキシヘキサヒドロテレフタレート、t-アミルパーオキシ3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシアセテート、t-ブチルパーオキシベンゾエート、t-ヘキシルパーオキシベンゾエート、t-アミルパーオキシベンゾエートのようなパーオキシエステル類;ジ-2-エチルヘキシルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、t-ブチルパーオキシソプロピルカーボネート、t-ブチルパーオキシ2-エチルヘキシルカーボネート、1,6-ビス(t-ブチルパーオキシカルボニルオキシ)ヘキサンのようなパーオキシカーボネート類等を挙げることができる。このような有機過酸化物は、試薬供給業者から市販されており、容易に入手することができる。 Specific examples of component (C) include diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, and bis-3,5,5-trimethylhexanoyl peroxide; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide (e.g., Kayacumene H manufactured by Kayaku Aguzo Co., Ltd.), and t-butyl hydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t dialkyl peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxypropyl)benzene, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; peroxyketals such as 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di-t-butylperoxycyclohexane, and 2,2-di-t-butylperoxybutane; 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-amyl peroxy 2-ethylhexanoate, t-butyl peroxy 2-ethylhexanoate, di-t-butyl peroxy hexahydroterephthalate, t-amyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxy Examples of organic peroxides include peroxyesters such as acetate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-amyl peroxybenzoate; and peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, t-butylperoxy 2-ethylhexyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane. These organic peroxides are commercially available from reagent suppliers and can be easily obtained.
(C)成分は、1種又は2種以上の組み合わせであってよい。 Component (C) may be one type or a combination of two or more types.
<(D)熱カチオン重合開始剤>
(D)熱カチオン重合開始剤は、加熱によりカチオン重合させる際のカチオン発生源となる成分である。熱カチオン重合開始剤としては、カチオン部分が、芳香族スルフォニウム、芳香族ジアゾニウム、芳香族アンモニウム、チアンスレニウム、チオキサントニウム、又は、(2,4-シクロペンタジエン-1-イル)[(1-メチルエチルベンゼン]-Feカチオンであり、アニオン部分が、SbF6
-、BF4
-、PF6
-、B(C6F5)4
-、[P(RF)nF6-n]-(式中、RFは、独立して、炭素原子数1~6の部分又は全フッ素化アルキル基であり、nは0~5の整数である)、又は、[BX4]-(式中、Xは少なくとも2つ以上のフッ素原子又はトリフルオロメチル基で置換されたフェニル基である)である、カチオン部分及びアニオン部分で構成されるオニウム塩が挙げられる。熱カチオン重合開始剤は、スルフォニウム塩であることが好ましい。熱カチオン重合開始剤のアニオンが、SbF6
-、B(C6F5)4
-、又は[P(RF)nF6-n]-(式中、RFは、独立して、炭素原子数1~6の部分又は全フッ素化アルキル基であり、nは0~5の整数である)であることが好ましい。
<(D) Thermal Cationic Polymerization Initiator>
The thermal cationic polymerization initiator (D) is a component that serves as a cation generating source when cationic polymerization is carried out by heating. The thermal cationic polymerization initiator may be an onium salt composed of a cationic portion and an anionic portion, the cationic portion being an aromatic sulfonium, aromatic diazonium, aromatic ammonium, thianthrhenium, thioxanthonium, or (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe cation, and the anionic portion being SbF 6 - , BF 4 - , PF 6 - , B(C 6 F 5 ) 4 - , [P(R F ) n F 6-n ] - (wherein R F is independently a moiety or a fully fluorinated alkyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 5), or [BX 4 ] - (wherein X is a phenyl group substituted with at least two or more fluorine atoms or trifluoromethyl groups). The thermal cationic polymerization initiator is preferably a sulfonium salt. The anion of the thermal cationic polymerization initiator may be SbF 6 - , B(C 6 F 5 ) 4 − , or [P(R F ) n F 6-n ] − (wherein R F is independently a partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and n is an integer from 0 to 5).
(D)成分の市販品としては、サンアプロ社製のTA-60、TA-60B、TA-100、TA-120;ADEKA社製のアデカオプトンCP-77、アデカオプトンCP-66;日本曹達社製のCI-2639、CI-2624;キングインダストリーズ社製のCXC-1612、CXC-1738;三新化学工業社製のサンエイドSI-45、サンエイドSI-60、サンエイドSI-80、サンエイドSI-100、サンエイドSI-110、サンエイドSI-B3、サンエイドSI-B3A、サンエイドSI-B4等が挙げられる。 Commercially available products of component (D) include TA-60, TA-60B, TA-100, and TA-120 manufactured by San-Apro Co., Ltd.; Adeka Opton CP-77 and Adeka Opton CP-66 manufactured by ADEKA Corporation; CI-2639 and CI-2624 manufactured by Nippon Soda Co., Ltd.; CXC-1612 and CXC-1738 manufactured by King Industries Co., Ltd.; and San-Aid SI-45, San-Aid SI-60, San-Aid SI-80, San-Aid SI-100, San-Aid SI-110, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4 manufactured by Sanshin Chemical Industry Co., Ltd.
(D)成分は、1種又は2種以上の組み合わせであってよい。 Component (D) may be one type or a combination of two or more types.
<(E)その他の成分>
熱カチオン重合性樹脂組成物は、本発明の効果を損なわない範囲内であれば、その目的に応じて、その他の成分を含むことができる。その他の成分として、光増感剤、充填剤、カップリング剤(特に、シランカップリング剤)、ポットライフ安定剤、重合禁止剤、溶剤、強化材、着色剤、安定剤、増量剤、粘度調節剤、粘着付与剤、難燃剤、紫外線吸収剤、酸化防止剤、変色防止剤、抗菌剤、防黴剤、老化防止剤、帯電防止剤、可塑剤、滑剤、平滑化剤、発泡剤、離型剤等が挙げられる。
<(E) Other Components>
The thermal cationic polymerizable resin composition may contain other components according to the purpose, as long as the effects of the present invention are not impaired. Examples of other components include photosensitizers, fillers, coupling agents (particularly silane coupling agents), pot life stabilizers, polymerization inhibitors, solvents, reinforcing agents, colorants, stabilizers, extenders, viscosity regulators, tackifiers, flame retardants, UV absorbers, antioxidants, discoloration inhibitors, antibacterial agents, antifungal agents, antiaging agents, antistatic agents, plasticizers, lubricants, smoothing agents, foaming agents, and release agents.
≪光増感剤≫
光増感剤は、光への感度を高めるための成分である。光増感剤としては、チオキサントン誘導体、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ及びジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられ、チオキサントン誘導体が好ましい。チオキサントン誘導体の具体例としては、イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、チオキサントンアンモニウム塩等が挙げられ、2,4-ジエチルチオキサントンが好ましい。
光増感剤は、1種又は2種以上の組み合わせであってよい。
<Photosensitizer>
The photosensitizer is a component for increasing sensitivity to light. Examples of the photosensitizer include thioxanthone derivatives, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, and the like, with thioxanthone derivatives being preferred. Specific examples of the thioxanthone derivatives include isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthone ammonium salt, and the like, with 2,4-diethylthioxanthone being preferred.
The photosensitizer may be one type or a combination of two or more types.
≪充填剤≫
充填剤は、特に限定されず、公知の無機充填剤及び有機充填剤が挙げられる。
<Filling agent>
The filler is not particularly limited, and examples thereof include known inorganic fillers and organic fillers.
無機充填剤としては、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸マグネシウム、珪酸アルミニウム、酸化チタン、アルミナ、酸化亜鉛、二酸化ケイ素(沈降性シリカ、フュームドシリカ(煙霧質シリカ)等)、カオリン、タルク、ガラスビーズ、セリサイト活性白土、水酸化アルミニウム、石綿粉、酸化銅、水酸化銅、酸化鉄、酸化鉛、酸化マグネシウム、酸化スズ、カーボン、マイカ、スメクタイト、カーボンブラック、ベントナイト、窒化アルミニウム、及び窒化ケイ素が挙げられる。密着性の観点から、無機充填剤は、二酸化ケイ素、ガラスビーズ及びタルクであることが好ましく、タルクが特に好ましい。 Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide (precipitated silica, fumed silica, etc.), kaolin, talc, glass beads, sericite activated clay, aluminum hydroxide, asbestos powder, copper oxide, copper hydroxide, iron oxide, lead oxide, magnesium oxide, tin oxide, carbon, mica, smectite, carbon black, bentonite, aluminum nitride, and silicon nitride. From the viewpoint of adhesion, the inorganic fillers are preferably silicon dioxide, glass beads, and talc, and talc is particularly preferred.
有機充填剤としては、アクリル粒子、ポリメタクリル酸メチル、ポリスチレン(ポリスチレンビーズ)、これらを構成するモノマー(即ち、メタクリル酸メチル又はスチレン)と他のモノマーとを共重合させて得られる共重合体、ポリエチレン粒子、ポリシロキサン樹脂粒子、ポリアミド粒子、ポリエステル微粒子、ポリウレタン微粒子、及びゴム微粒子(アクリルゴム粒子、イソプレンゴム粒子)が挙げられる。有機充填剤は、コアシェル構造を有していてもよい。密着性の観点から、有機充填剤は、ゴム微粒子であることが好ましく、コアシェル構造を有するゴム微粒子であることが特に好ましい。 Organic fillers include acrylic particles, polymethyl methacrylate, polystyrene (polystyrene beads), copolymers obtained by copolymerizing the monomers constituting these (i.e., methyl methacrylate or styrene) with other monomers, polyethylene particles, polysiloxane resin particles, polyamide particles, polyester microparticles, polyurethane microparticles, and rubber microparticles (acrylic rubber particles, isoprene rubber particles). The organic filler may have a core-shell structure. From the viewpoint of adhesion, the organic filler is preferably rubber microparticles, and particularly preferably rubber microparticles having a core-shell structure.
充填剤が、有機充填剤である場合、有機充填剤の重量平均分子量は、特に限定されないが、5万~400万であることが好ましく、30万~300万であることが特に好ましい。 When the filler is an organic filler, the weight average molecular weight of the organic filler is not particularly limited, but is preferably 50,000 to 4,000,000, and particularly preferably 300,000 to 3,000,000.
充填剤の平均粒子径は、特に限定されないが、0.01μm以上10μm未満であることが好ましく、1μm~5μmであることが特に好ましい。充填剤の平均粒子径は、レーザー回折式粒度分布測定装置で測定することができる。 The average particle size of the filler is not particularly limited, but is preferably 0.01 μm or more and less than 10 μm, and particularly preferably 1 μm to 5 μm. The average particle size of the filler can be measured using a laser diffraction particle size distribution measuring device.
なお、充填剤は、チキソ付与剤として機能する成分であってもよい。チキソ付与剤は、第一の封止用組成物に、塗工性改善等を付与する成分である。チキソ付与剤として機能する充填剤としては、ヒュームドシリカが挙げられる。ヒュームドシリカは、表面処理されていてもよい。無機系のチキソ付与剤の表面処理剤としては、モノアルキルトリアルコキシシラン、ジメチルジクロロシラン、ポリジメチルシロキサン、ヘキサメチルジシラザン等が挙げられる。表面処理された又は未処理のヒュームドシリカは、市販品を用いることができる。
充填剤は、1種単独又は2種以上の組み合わせであってよい。
The filler may be a component that functions as a thixotropic agent. The thixotropic agent is a component that imparts coating properties and the like to the first sealing composition. An example of a filler that functions as a thixotropic agent is fumed silica. The fumed silica may be surface-treated. Examples of surface treatment agents for inorganic thixotropic agents include monoalkyltrialkoxysilane, dimethyldichlorosilane, polydimethylsiloxane, and hexamethyldisilazane. Surface-treated or untreated fumed silica may be a commercially available product.
The fillers may be used alone or in combination of two or more.
≪シランカップリング剤≫
シランカップリング剤としては、エポキシ基、アルケニル基(例えば、ビニル基)、(メタ)アクリル基、第1級又は第2級アミノ基、メルカプト基、イソシアナト基、ウレイド基及びハロゲン原子からなる群より選択される1種以上の反応性官能基又は前記基で置換されたアルキル基と、1以上のアルコキシ基とを有し、非置換のアルキル基を有していてもよいシラン化合物が挙げられる。なお、前記反応性官能基は、前記反応性官能基で置換されたアルキル基として、シラン化合物のケイ素原子に結合していてもよい。
<Silane coupling agent>
Examples of the silane coupling agent include a silane compound having one or more reactive functional groups selected from the group consisting of epoxy group, alkenyl group (e.g., vinyl group), (meth)acrylic group, primary or secondary amino group, mercapto group, isocyanato group, ureido group and halogen atom, or an alkyl group substituted with said group, and one or more alkoxy groups, and may have an unsubstituted alkyl group.The reactive functional group may be bonded to the silicon atom of the silane compound as the alkyl group substituted with said reactive functional group.
シランカップリング剤の具体例としては、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン等のエポキシ基とアルコキシ基とを有し、アルキル基を有していてもよいシラン化合物;ビニルトリメトキシシラン、p-スチリルトリメトキシシラン等のアルケニル基とアルコキシ基とを有し、アルキル基を有していてもよいシラン化合物;3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン等の(メタ)アクリル基とアルコキシ基とを有し、アルキル基を有していてもよいシラン化合物;N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン等の第1級又は第2級アミノ基とアルコキシ基とを有し、アルキル基を有していてもよいシラン化合物;3-ウレイドプロピルトリエトキシシラン、3-クロロプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアナトプロピルトリエトキシシラン等のメルカプト基、イソシアナト基、ウレイド基及びハロゲン原子からなる群より選択される1種以上の基と、1以上のアルコキシ基とを有し、アルキル基を有していてもよいシラン化合物等が挙げられる。
シランカップリング剤は、1種又は2種以上の組み合わせでもよい。
Specific examples of the silane coupling agent include silane compounds having an epoxy group and an alkoxy group, and which may have an alkyl group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; silane compounds having an alkenyl group and an alkoxy group, and which may have an alkyl group, such as vinyltrimethoxysilane and p-styryltrimethoxysilane; silane compounds having a (meth)acrylic group and an alkoxy group, and which may have an alkyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(a [0043] Examples of such silane compounds include silane compounds having a primary or secondary amino group and an alkoxy group, and optionally having an alkyl group, such as N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; and silane compounds having one or more groups selected from the group consisting of a mercapto group, an isocyanato group, a ureido group, and a halogen atom, and one or more alkoxy groups, and optionally having an alkyl group, such as 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane.
The silane coupling agent may be used alone or in combination of two or more kinds.
≪その他の(E)成分≫
重合禁止剤としては、ヒドロキノン、パラメトキシフェノール、ジブチルヒドロキシトルエン等が挙げられる。
ポットライフ安定剤としては、SI助剤(4-ヒドロキシフェニルジメチルスルホニウムメチルサルファイト)、ヒンダードフェノール系酸化防止剤が挙げられる。
上記した成分以外は、公知の成分から適宜選択できる。
<Other components (E)>
The polymerization inhibitor includes hydroquinone, paramethoxyphenol, dibutylhydroxytoluene, and the like.
Examples of the pot life stabilizer include an SI auxiliary (4-hydroxyphenyldimethylsulfonium methylsulfite) and a hindered phenol-based antioxidant.
Components other than those mentioned above can be appropriately selected from known components.
(E)成分は、それぞれ、1種又は2種以上の組み合わせであってよい。例えば、(E)成分は、1種以上の無機充填剤と、1種以上の光増感剤との組み合わせであってもよい。 The (E) component may be one or a combination of two or more. For example, the (E) component may be a combination of one or more inorganic fillers and one or more photosensitizers.
<組成物の調製方法>
熱カチオン重合性樹脂組成物は、各成分を混合することで製造することができる。なお、(B)成分~(E)成分が固体である場合は、各成分(特に、(A)成分)との相溶性の向上のために、溶剤に溶解させて、カチオン重合性樹脂組成物の製造に供されてもよい。
<Method of preparing the composition>
The thermally cationically polymerizable resin composition can be produced by mixing the components. When the components (B) to (E) are solids, they may be dissolved in a solvent to improve compatibility with the components (particularly the component (A)) and then used to produce the cationically polymerizable resin composition.
〔硬化方法〕
熱カチオン重合性樹脂組成物は、熱を加えることにより硬化させることができる。また、熱カチオン重合性樹脂組成物は、紫外線等のエネルギー線を照射することにより仮硬化(仮固定)させた後に、熱を加えることによって本硬化(本固定)させてもよい。熱カチオン重合性樹脂組成物を、エネルギー線を照射することにより仮硬化させる場合は、熱カチオン重合性樹脂組成物は、光増感剤を含んでいてもよい。
[Curing method]
The thermally cationic polymerizable resin composition can be cured by applying heat. The thermally cationic polymerizable resin composition may be temporarily cured (temporarily fixed) by irradiating with energy rays such as ultraviolet rays, and then permanently cured (mainly fixed) by applying heat. When the thermally cationic polymerizable resin composition is temporarily cured by irradiating with energy rays, the thermally cationic polymerizable resin composition may contain a photosensitizer.
<成分の含有量>
熱カチオン重合性樹脂組成物における、各成分の含有量は以下の通りであることが好ましい。
(A)成分中のエポキシ樹脂及びオキセタン樹脂の合計の含有量は、(A)成分の100重量部に対して、60~100重量部であることが好ましく、80~100重量部であることが特に好ましい。
(A)成分中のオキセタン樹脂の合計の含有量は、エポキシ樹脂の100重量部に対して、5~50重量部であることが好ましく、10~40重量部であることが特に好ましい。
(A)成分中の脂環式エポキシ樹脂及び芳香族エポキシ樹脂の合計の含有量は、(A)成分中のエポキシ樹脂の100重量部に対して、60~100重量部であることが好ましく、80~100重量部であることが特に好ましい。
(B)成分の含有量は、熱硬化速度の観点から、(A)成分の100重量部に対して、0.1~10.0重量部であることが好ましく、0.5~5.0重量部であることが特に好ましい。
(C)成分の含有量は、熱硬化速度の観点から、(A)成分の100重量部に対して、1.0~10.0重量部であることが好ましく、1.5~5.0重量部であることが特に好ましい。
(D)成分の含有量は、(A)成分の100重量部に対して、0.03重量部以上1.50重量部以下である。(D)成分の含有量が、(A)成分の100重量部に対して、0.03重量部未満である場合、表面硬化性が劣り、かつ、アウトガス量が増加する傾向があり、1.50重量部超である場合、ガラス転移温度が低温になり、かつ、アウトガス量が増加する傾向がある。
(A)成分~(D)成分の合計は、熱カチオン重合性樹脂組成物の総量に対して、20~100重量部であることが好ましく、30~100重量部であることが好ましく、40~100重量部であることが特に好ましい。残余は、(E)成分である。
<Content of ingredients>
The content of each component in the thermally cationic polymerizable resin composition is preferably as follows.
The total content of the epoxy resin and oxetane resin in component (A) is preferably 60 to 100 parts by weight, and particularly preferably 80 to 100 parts by weight, per 100 parts by weight of component (A).
The total content of the oxetane resins in the component (A) is preferably 5 to 50 parts by weight, and particularly preferably 10 to 40 parts by weight, per 100 parts by weight of the epoxy resin.
The total content of the alicyclic epoxy resin and aromatic epoxy resin in component (A) is preferably 60 to 100 parts by weight, and particularly preferably 80 to 100 parts by weight, per 100 parts by weight of the epoxy resins in component (A).
From the viewpoint of thermal curing speed, the content of the component (B) is preferably 0.1 to 10.0 parts by weight, and particularly preferably 0.5 to 5.0 parts by weight, per 100 parts by weight of the component (A).
From the viewpoint of thermal curing speed, the content of the component (C) is preferably 1.0 to 10.0 parts by weight, and particularly preferably 1.5 to 5.0 parts by weight, per 100 parts by weight of the component (A).
The content of the (D) component is 0.03 to 1.50 parts by weight per 100 parts by weight of the (A) component. If the content of the (D) component is less than 0.03 parts by weight per 100 parts by weight of the (A) component, the surface curing property tends to be poor and the amount of outgassing tends to increase, whereas if the content of the (D) component is more than 1.50 parts by weight, the glass transition temperature tends to be low and the amount of outgassing tends to increase.
The total amount of components (A) to (D) is preferably 20 to 100 parts by weight, more preferably 30 to 100 parts by weight, and particularly preferably 40 to 100 parts by weight, based on the total amount of the thermally cationic polymerizable resin composition. The remainder is component (E).
[用途]
熱カチオン重合性樹脂組成物は、光学部品固定(例えばディスプレイ装置バックライトユニット組立、光ピックアップ組立)、カメラモジュール組立、レンズモジュール組立、光通信用モジュール組立、ハードディスク組立、及び電子部品の保護(例えば、モールド)に用いることができる。
[Application]
The thermally cationic polymerizable resin composition can be used for fixing optical components (e.g., backlight unit assembly of a display device, optical pickup assembly), camera module assembly, lens module assembly, optical communication module assembly, hard disk assembly, and protection of electronic components (e.g., molding).
以下に本発明の具体的な実施様態を明らかにするために実施例を示すが、本発明はここに示す実施例のみに限定されるわけではない。 The following examples are presented to clarify specific embodiments of the present invention, but the present invention is not limited to the examples shown here.
実施例及び比較例の各組成物を以下の原材料を使用して製造した。
1.(A)成分:カチオン硬化性樹脂
(1)エポキシ樹脂
クレゾールノボラック型エポキシ樹脂(DIC社製、EPICLON N-655-EXP-S)
ビスフェノールA型エポキシ樹脂(DIC社製、EPICLON EXA-850CRP)
ビスフェノールF型エポキシ樹脂(DIC社製、EPICLON EXA-830LVP)
脂環式エポキシ樹脂;(3,3’,4,4’-ジエポキシ)ビシクロヘキシル(ダイセル社製、セロキサイド8010)
脂環式エポキシ樹脂;3’,4’-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート(ダイセル社製、セロキサイド2021P)
(2)オキセタン樹脂
3-エチル-3-フェノキシメチルオキセタン(東亞合成社製、OXT-211(POX))
キシリレンビスオキセタン(東亞合成社製、OXT-121(XDO))
オキセタニルシルセスキオキセタン(東亞合成社製、OXT-191)
Each composition of the examples and comparative examples was produced using the following raw materials.
1. Component (A): Cationic curable resin (1) Epoxy resin Cresol novolac type epoxy resin (EPICLON N-655-EXP-S, manufactured by DIC Corporation)
Bisphenol A type epoxy resin (DIC Corporation, EPICLON EXA-850CRP)
Bisphenol F type epoxy resin (DIC Corporation, EPICLON EXA-830LVP)
Alicyclic epoxy resin: (3,3',4,4'-diepoxy)bicyclohexyl (manufactured by Daicel Corporation, Celloxide 8010)
Alicyclic epoxy resin: 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, Celloxide 2021P)
(2) Oxetane resin 3-ethyl-3-phenoxymethyloxetane (manufactured by Toagosei Co., Ltd., OXT-211 (POX))
Xylylene bisoxetane (manufactured by Toagosei Co., Ltd., OXT-121 (XDO))
Oxetanylsilsesquioxetane (manufactured by Toagosei Co., Ltd., OXT-191)
2.(B)成分:ヨードニウム塩
4-メチルフェニル-4-(1-メチルエチル)フェニルヨードニウム・テトラキス(ペンタフルオロフェニル)ボレート(ソルベイ(ローディア)社製、PI-2074)。
2. Component (B): Iodonium salt 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate (manufactured by Solvay (Rhodia) Co., Ltd., PI-2074).
3.(C)成分:有機過酸化物
1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート(日本油脂社製、パーオクタO)。
3. Component (C): organic peroxide 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, manufactured by NOF Corporation).
4.(D)成分:熱カチオン重合開始剤
4-ヒドロキシフェニル-メチル-ベンジルスルホニウムトリス(ペンタフルオロエチル)トリフルオロホスフェート(サンアプロ社製、TA-100)。
4. Component (D): Thermal cationic polymerization initiator 4-hydroxyphenyl-methyl-benzylsulfonium tris(pentafluoroethyl)trifluorophosphate (TA-100, manufactured by San-Apro Co., Ltd.).
5.(E)成分:その他の成分
光増感剤:2,4-ジエチルチオキサントン(日本化薬社製、DETX-s)
充填剤(フィラー):シリカ(AGC エスアイテック社製、NP-100)
充填剤(チキソ付与剤):ヒュームドシリカ(日本アエロジル社製、NKC130)
溶剤:4-ブチロラクトン(関東化学社製)
ポットライフ安定剤:4-ヒドロキシフェニルジメチルスルホニウムメチルサルファイト(三新化学社製、SI助剤)
重合禁止剤):ジブチルヒドロキシトルエン(関東化学社製、BHT)
カップリング剤:3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製、KBM403)
なお、一部の固体の増感剤、開始剤、添加剤などは樹脂に溶解しにくいものがあるため、予め4-ブチロラクトンに溶解してから樹脂と混合した。
5. (E) Component: Other components Photosensitizer: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., DETX-s)
Filler: Silica (AGC Si-Tech, NP-100)
Filler (thixotropic agent): Fumed silica (manufactured by Nippon Aerosil Co., Ltd., NKC130)
Solvent: 4-butyrolactone (Kanto Chemical)
Pot life stabilizer: 4-hydroxyphenyldimethylsulfonium methylsulfite (manufactured by Sanshin Chemical Industry Co., Ltd., SI auxiliary)
Polymerization inhibitor): dibutylhydroxytoluene (Kanto Chemical Co., Ltd., BHT)
Coupling agent: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)
Some solid sensitizers, initiators, additives, etc., are difficult to dissolve in the resin, so they were dissolved in 4-butyrolactone beforehand and then mixed with the resin.
実施例1~13、比較例1~7
〔調製条件〕
熱カチオン重合性樹脂組成物を、表1に記載の配合に基づき、各成分を混合し、室温(25±3℃。以下同じ。)環境の下、撹拌機で透明になるまで撹拌し、調製した。
Examples 1 to 13, Comparative Examples 1 to 7
[Preparation conditions]
A thermally cationically polymerizable resin composition was prepared by mixing the components based on the formulation shown in Table 1 and stirring the mixture with a stirrer at room temperature (25±3° C.; the same applies below) until the mixture became transparent.
〔評価条件〕
・表面硬化性
スライドガラス上に樹脂を50μm厚で塗布し、100℃に加熱したホットプレート上で60分間熱硬化を行った。室温で10分間冷却後、指触にて表面硬化性を確認した。
○:硬化、×:表面未硬化(べたつき、タックあり)
[Evaluation conditions]
Surface curability The resin was applied to a slide glass in a thickness of 50 μm and thermally cured for 60 minutes on a hot plate heated to 100° C. After cooling at room temperature for 10 minutes, the surface curability was confirmed by touching with a finger.
○: Cured, ×: Surface uncured (sticky, tacky)
・アウトガス量
100μlのアルミパンに樹脂を15±2mg塗布し、100℃に加熱したホットプレート上で60分間熱硬化を行った。室温で10分間冷却後、精密天秤(メトラー・トレド社製、XP2U)で秤量した(初期重量)。その後、150℃の熱風オーブン(エスペック社製、LC113)で15時間加熱した。室温で60分間冷却後、精密天秤で秤量した(加熱後重量)。以下の計算式から重量変化率(%)を求め、アウトガス量とした。
Amount of outgassing 15±2 mg of resin was applied to a 100 μl aluminum pan and thermally cured for 60 minutes on a hot plate heated to 100° C. After cooling at room temperature for 10 minutes, the resin was weighed (initial weight) using a precision balance (Mettler Toledo, XP2U). The resin was then heated for 15 hours in a hot air oven (Espec, LC113) at 150° C. After cooling at room temperature for 60 minutes, the resin was weighed (weight after heating) using a precision balance. The weight change rate (%) was calculated using the following formula and used as the amount of outgassing.
・ガラス転移温度(Tg)及び貯蔵弾性率
長さ50mm、幅10mm、厚さ0.5mmの型に注型し、100℃の熱風オーブン(エスペック社製、LC113)で60分間熱硬化を行い、硬化物試験片を作製した。得られた硬化物試験片を動的粘弾性測定装置(DMA、セイコーインスツル社製、DMS6100)にて、周波数1.0Hzで昇温させながら測定を行った。得られた結果の損失正接tanδにおけるピークトップ温度をTgとした。
Tgと同様の条件で硬化物試験片の作製及び動的粘弾性測定装置(DMA、セイコーインスツル社製、DMS6100)による測定を行った。得られた結果において25℃での貯蔵弾性率の値を抽出した。
Glass transition temperature (Tg) and storage modulus The resin was cast into a mold having a length of 50 mm, a width of 10 mm, and a thickness of 0.5 mm, and heat cured for 60 minutes in a hot air oven (LC113, manufactured by Espec Corp.) at 100°C to prepare a cured product test piece. The obtained cured product test piece was measured with a dynamic viscoelasticity measuring device (DMA, DMS6100, manufactured by Seiko Instruments Inc.) while increasing the temperature at a frequency of 1.0 Hz. The peak top temperature in the loss tangent tan δ of the obtained result was taken as Tg.
A test piece of the cured product was prepared under the same conditions as for Tg, and measurements were performed using a dynamic viscoelasticity measuring device (DMA, manufactured by Seiko Instruments Inc., DMS6100). From the results obtained, the value of the storage modulus at 25° C. was extracted.
結果を以下の表にまとめた。 The results are summarized in the table below.
実施例1~13の熱カチオン重合性樹脂組成物は、表面硬化性が優れており、かつ、アウトガス量が低減されていた。
特に、実施例1~5の比較により、(A)成分の100重量部に対して、(D)成分の含有量が好ましい範囲であると、アウトガス量がより低減されていた。実施例7~11の比較によっても、同様のことがいえる。
また、実施例1~5と実施例7~11、及び、実施例6と実施例12との比較により、熱カチオン重合性樹脂組成物が、更に(E)成分を含む場合であっても、表面硬化性が優れており、かつ、アウトガス量が低減されていた。
比較例1~6は、(D)成分を含まないか、(A)成分の100重量部に対して、(D)成分の含有量が0.03重量部未満であるため、表面硬化性が劣っていた。特に、比較例4~6は、アウトガス量が多かった。比較例7は、(A)成分の100重量部に対して、(D)成分の含有量が1.50重量部超であるため、アウトガス量が多かった。そして、実施例1~5と比較例1~3との比較により、(D)成分以外の組成がほぼ同じであるとき、(A)成分の100重量部に対して、(D)成分の含有量を所定の範囲とすることで、表面硬化性が優れており、かつ、アウトガス量が低減されていた。実施例7~11と比較例4~6との比較によっても、同様のことがいえる。
The thermally cationically polymerizable resin compositions of Examples 1 to 13 were excellent in surface curing properties and had reduced outgassing amounts.
In particular, a comparison of Examples 1 to 5 shows that the amount of outgassing was further reduced when the content of component (D) was within the preferred range relative to 100 parts by weight of component (A). The same can be said when comparing Examples 7 to 11.
Furthermore, comparison of Examples 1 to 5 with Examples 7 to 11, and Example 6 with Example 12 revealed that even when the thermally cationically polymerizable resin composition further contained the component (E), the surface curing property was excellent and the amount of outgassing was reduced.
Comparative Examples 1 to 6 did not contain the (D) component or contained less than 0.03 parts by weight of the (D) component relative to 100 parts by weight of the (A) component, and therefore had poor surface curability. In particular, Comparative Examples 4 to 6 had a large amount of outgassing. Comparative Example 7 had a large amount of outgassing because the content of the (D) component was more than 1.50 parts by weight relative to 100 parts by weight of the (A) component. Furthermore, a comparison between Examples 1 to 5 and Comparative Examples 1 to 3 showed that, when the composition other than the (D) component was almost the same, the content of the (D) component was within a predetermined range relative to 100 parts by weight of the (A) component, and thus the surface curability was excellent and the amount of outgassing was reduced. The same can be said by comparing Examples 7 to 11 with Comparative Examples 4 to 6.
Claims (3)
(B)式:Ar1-I+-Ar2・X-(式中、Ar1及びAr2は、独立して、置換又は非置換のアリール基であり、X-は、アニオンである)で示されるヨードニウム塩、
(C)有機過酸化物、及び
(D)熱カチオン重合開始剤
を含み、(A)成分の100重量部に対して、(D)成分の含有量が0.05重量部以上0.40重量部以下であり、(D)成分が、スルフォニウム塩である、熱カチオン重合性樹脂組成物。 (A) a cationically curable resin,
(B) iodonium salts of the formula Ar 1 -I + -Ar 2 ·X - , where Ar 1 and Ar 2 are independently substituted or unsubstituted aryl groups, and X - is an anion;
1. A thermal cationically polymerizable resin composition comprising: (C) an organic peroxide; and (D) a thermal cationic polymerization initiator, wherein the content of the component (D) is 0.05 part by weight or more and 0.40 part by weight or less per 100 parts by weight of the component (A), and the component (D) is a sulfonium salt .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021000194A JP7481011B2 (en) | 2021-01-04 | 2021-01-04 | Thermally cationic polymerizable resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021000194A JP7481011B2 (en) | 2021-01-04 | 2021-01-04 | Thermally cationic polymerizable resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2022105415A JP2022105415A (en) | 2022-07-14 |
JP7481011B2 true JP7481011B2 (en) | 2024-05-10 |
Family
ID=82362617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2021000194A Active JP7481011B2 (en) | 2021-01-04 | 2021-01-04 | Thermally cationic polymerizable resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP7481011B2 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002284966A (en) | 2001-03-27 | 2002-10-03 | Mitsubishi Gas Chem Co Inc | Flame-retardant cationic polymerizable resin composition |
JP2014129473A (en) | 2012-12-28 | 2014-07-10 | Kyoritsu Kagaku Sangyo Kk | Thermal cationic polymerizable composition |
JP2016172813A (en) | 2015-03-17 | 2016-09-29 | デクセリアルズ株式会社 | Compound, thermosetting resin composition, and thermosetting sheet |
-
2021
- 2021-01-04 JP JP2021000194A patent/JP7481011B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002284966A (en) | 2001-03-27 | 2002-10-03 | Mitsubishi Gas Chem Co Inc | Flame-retardant cationic polymerizable resin composition |
JP2014129473A (en) | 2012-12-28 | 2014-07-10 | Kyoritsu Kagaku Sangyo Kk | Thermal cationic polymerizable composition |
JP2016172813A (en) | 2015-03-17 | 2016-09-29 | デクセリアルズ株式会社 | Compound, thermosetting resin composition, and thermosetting sheet |
Also Published As
Publication number | Publication date |
---|---|
JP2022105415A (en) | 2022-07-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5812993B2 (en) | Low moisture-permeable resin composition and cured product thereof | |
JP5490726B2 (en) | Sealant for liquid crystal dropping method | |
JP2010018797A (en) | Curable composition for optical parts, adhesive agent for optical parts, and sealing agent for organic electroluminescence element | |
JP7007592B2 (en) | Cationic Curable Adhesive Compositions for Camera Modules, Cured Products and Bonds | |
JPWO2008153076A1 (en) | Optical adhesive for substrate bonding, and cured optical adhesive for substrate bonding | |
JP5973685B2 (en) | Cationic curable resin composition for assembling hard disk devices | |
JP6213717B2 (en) | Photocurable resin composition | |
JP6353306B2 (en) | RESIN COMPOSITION FOR OPTICAL SHEET-TYPE ADHESIVE CONTAINING POLYMER EPOXY RESIN, ADHESIVE FOR OPTICAL SHEET COMPRISING THE COMPOSITION, AND CURED PRODUCT THEREOF, AND METHOD FOR PRODUCING POLYMER EPOXY RESIN USED FOR THE COMPOSITION | |
US7714037B1 (en) | Photoinitiated cationic epoxy compositions and articles exhibiting low color | |
JP7063684B2 (en) | Adhesives for optical imaging devices and their cured products | |
TW201934645A (en) | Resin composition and cured material of same, adhesive, semiconductor device, and electronic component | |
JP7481011B2 (en) | Thermally cationic polymerizable resin composition | |
JP6293051B2 (en) | Curable composition for hard disk device | |
JP5310690B2 (en) | Epoxy resin composition and cured epoxy resin | |
US8030401B1 (en) | Photoinitiated cationic epoxy compositions | |
JP7530349B2 (en) | Two-part cyanoacrylate curable adhesive system | |
WO2024142447A1 (en) | Curable resin composition, adhesive, sealing material, cured product, semiconductor apparatus, and electronic device | |
WO2024142448A1 (en) | Curable resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic device | |
JP2018529791A (en) | Curable composition for one drop fill sealant applications | |
TW202426550A (en) | Curable resin composition, adhesive, sealing material, cured product, semiconductor device and electronic device | |
JP7455381B2 (en) | Cationic polymerizable resin composition | |
TW202426551A (en) | Curable resin composition, adhesive, sealing material, cured product, semiconductor device and electronic device | |
JP5931716B2 (en) | Thermally cationic polymerizable composition | |
WO2024142446A1 (en) | Curable resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic device | |
JP2012082272A (en) | Electron beam curable resin composition and cured product thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230315 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20231220 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240109 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240126 |
|
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: 20240409 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240418 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7481011 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |