TW202043315A - Heat-curable silicone composition and cured product thereof - Google Patents
Heat-curable silicone composition and cured product thereof Download PDFInfo
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- TW202043315A TW202043315A TW109104941A TW109104941A TW202043315A TW 202043315 A TW202043315 A TW 202043315A TW 109104941 A TW109104941 A TW 109104941A TW 109104941 A TW109104941 A TW 109104941A TW 202043315 A TW202043315 A TW 202043315A
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- acrylate compound
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- -1 methacryloyl group Chemical group 0.000 claims abstract description 49
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 8
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 239000003566 sealing material Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000035699 permeability Effects 0.000 abstract description 10
- 238000002845 discoloration Methods 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- XTMHZQHIQLSLMK-UHFFFAOYSA-N 3-[dimethylsilyloxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound C[SiH](C)O[Si](C)(C)CCCOC(=O)C(C)=C XTMHZQHIQLSLMK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-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
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-UHFFFAOYSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-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
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DGQFNPWGWSSTMN-UHFFFAOYSA-N 2-tert-butyl-4-[4-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1CCCCC1=CC(C(C)(C)C)=C(O)C=C1C DGQFNPWGWSSTMN-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- OIRWCSXDSJUCJN-UHFFFAOYSA-N 4-ethyl-1-(2-hydroxyethoxy)octan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCC(CC)CC(O)COCCO OIRWCSXDSJUCJN-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001444 catalytic combustion detection Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 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
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical class O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- DCVWZWOEQMSMLR-UHFFFAOYSA-N silylperoxysilane Chemical compound [SiH3]OO[SiH3] DCVWZWOEQMSMLR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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Abstract
Description
本發明有關熱硬化性矽氧組成物及其硬化物，更詳言之，係有關適宜作為光學元件密封材之熱硬化性矽氧組成物及其硬化物。The present invention relates to a thermosetting silica composition and a cured product thereof, and more specifically, relates to a thermosetting silica composition and a cured product thereof suitable as sealing materials for optical elements.
矽氧橡膠過去被使用作為光學元件密封材料。 於該用途中使用之矽氧橡膠被要求高透明、高折射率，為了滿足該等特性，已提案有於主骨架使用二甲基矽氧烷・二苯基矽氧烷共聚物或聚甲基苯基矽氧烷之材料(參考專利文獻1~5)。 然而，該等專利文獻1~5所揭示之矽氧橡膠由於主骨架為矽氧烷，故有氣體透過性高，無法保護光學元件周邊之構件免於受腐蝕性氣體影響之問題。 [先前技術文獻] [專利文獻]Silicone rubber was used as a sealing material for optical components in the past. The silicone rubber used in this application is required to have high transparency and high refractive index. In order to meet these characteristics, it has been proposed to use dimethylsiloxane/diphenylsiloxane copolymer or polymethyl as the main skeleton. Phenylsiloxane material (refer to Patent Documents 1 to 5). However, the silicone rubbers disclosed in these Patent Documents 1 to 5 have the problem of high gas permeability because the main skeleton is silicone, and cannot protect the components around the optical element from corrosive gases. [Prior Technical Literature] [Patent Literature]
[專利文獻1] 日本特開2004-143361號公報 [專利文獻2] 日本特開2005-076003號公報 [專利文獻3] 日本特開2005-105217號公報 [專利文獻4] 日本特開2005-307015號公報 [專利文獻5] 日本特開2010-132795號公報[Patent Document 1] JP 2004-143361 A [Patent Document 2] JP 2005-076003 A [Patent Document 3] JP 2005-105217 A [Patent Document 4] Japanese Patent Application Publication No. 2005-307015 [Patent Document 5] JP 2010-132795 A
[發明欲解決之課題][The problem to be solved by the invention]
本發明係鑑於上述情況而完成者，其目的在於提供可賦與具有耐熱變色性、高折射率、高透明、低氣體透過性的硬化物之熱硬化性矽氧組成物及其硬化物。 [用以解決課題之手段]The present invention was completed in view of the above circumstances, and its object is to provide a thermosetting silicone composition and a cured product thereof that can be imparted with a cured product having heat-resistant discoloration, high refractive index, high transparency, and low gas permeability. [Means to solve the problem]
本發明人等為達成上述目的而進行積極檢討之結果，發現藉由使用包含於末端具有(甲基)丙烯醯基之有機聚矽氧烷、不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物、酚系抗氧化劑及過氧化物之熱硬化性矽氧組成物，可獲得兼具低氣體透過性及耐熱變色性之硬化物，因而完成本發明。The inventors of the present invention conducted an active review to achieve the above-mentioned object and found that by using an organopolysiloxane having a (meth)acryloyl group at the end, a monofunctional (methyl) structure that does not contain a silicone structure is used. The thermosetting silicone composition of an acrylate compound, a phenolic antioxidant, and a peroxide can obtain a cured product having both low gas permeability and heat discoloration resistance, thus completing the present invention.
亦即本發明提供
1. 一種熱硬化性矽氧組成物，其包含
(A)以下述式(1)表示之有機聚矽氧烷：40~95質量份，
本發明之熱硬化性矽氧組成物可賦與具有耐熱變色性、高折射率、高透明、低氣體透過性之特性的硬化物。 具有此等特性之本發明之硬化物可適合使用作為光學元件密封材。The thermosetting silicone composition of the present invention can be endowed with a cured product having the characteristics of heat-resistant discoloration, high refractive index, high transparency, and low gas permeability. The cured product of the present invention having these characteristics can be suitably used as an optical element sealing material.
以下針對本發明具體加以說明。 本發明之熱硬化性矽氧組成物之特徵係含有 (A)以下述式(1)表示之有機聚矽氧烷：40~95質量份， (B)不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物、或不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物與不含矽氧烷構造之多官能(甲基)丙烯酸酯化合物兩者：5~60質量份(但，(A)成分與(B)成分之合計為100質量份)， (C)有機過氧化物：0.01~10質量份，及 (D)酚系抗氧化劑：50~5,000ppm。The following specifically describes the present invention. The thermosetting silica composition of the present invention is characterized by containing (A) Organopolysiloxane represented by the following formula (1): 40 to 95 parts by mass, (B) Monofunctional (meth)acrylate compounds without silicone structure, or monofunctional (meth)acrylate compounds without silicone structure, and polyfunctional (meth)acrylate compounds without silicone structure ) Both acrylate compounds: 5-60 parts by mass (however, the total of (A) component and (B) component is 100 parts by mass), (C) Organic peroxide: 0.01-10 parts by mass, and (D) Phenolic antioxidant: 50~5,000ppm.
(A)成分 本發明之熱硬化性矽氧組成物中，(A)成分之有機聚矽氧烷係對該組成物之硬化物賦與耐熱變色性及柔軟性之成分，係以下述式(1)表示。(A) Ingredient In the thermosetting silicone composition of the present invention, the organopolysiloxane of the component (A) is a component that imparts heat-resistant discoloration and flexibility to the cured product of the composition, and is represented by the following formula (1).
式(1)中，n表示滿足1≦n≦100之數，較佳為1≦n≦50，更佳為1≦n≦20。n小於1時容易揮發，n大於100時組成物之黏度變高，處理性較差。In formula (1), n represents a number satisfying 1≦n≦100, preferably 1≦n≦50, and more preferably 1≦n≦20. When n is less than 1, it is easy to volatilize, and when n is greater than 100, the viscosity of the composition becomes higher and the handling is poor.
Ar各獨立表示芳香族基，其碳原子數並未特別限定，但較佳為6~20。 作為芳香族之具體例舉例為苯基、聯苯基、萘基等之芳香族烴基；呋喃基等之包含雜原子(O、S、N)之芳香族基，該等芳香族基可具有鹵原子(例如氯原子、溴原子、氟原子)等之取代基。 該等中，作為Ar較佳為非取代之芳香族烴基，更佳為苯基。Each of Ar independently represents an aromatic group, and the number of carbon atoms is not particularly limited, but is preferably 6-20. Specific examples of aromatics include aromatic hydrocarbon groups such as phenyl, biphenyl, naphthyl, and the like; furyl and other aromatic groups containing heteroatoms (O, S, N), and these aromatic groups may have halogens. Substituents such as chlorine atoms, bromine atoms, and fluorine atoms. Among them, Ar is preferably an unsubstituted aromatic hydrocarbon group, and more preferably a phenyl group.
F1 各獨立表示下述式(2)或(3)表示之基，但式(3)表示之末端基之數相對於以F1 表示之全部末端基之合計數之比例為20%以上。F 1 each independently represents a group represented by the following formula (2) or (3), but the ratio of the number of terminal groups represented by formula (3) to the total number of all terminal groups represented by F 1 is 20% or more.
式(2)及(3)中，R1 各獨立表示碳原子數1~20，較佳1~10之一價烴基。 R1 之一價有機基可為直鏈、分支、環狀之任一者，作為其具體例可舉例為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正己基、環己基、正辛基、正癸基、正十二烷基等之烷基；乙烯基、烯丙基、1-丁烯基、1-己烯基等之烯基；苯基、甲苯基、二甲苯基、萘基等之芳基；苄基、2-苯基乙基、2-苯基丙基等之芳烷基；該等烴基之氫原子之一部分或全部經氯、氟、溴等之鹵原子取代之氟甲基、溴乙基、氯甲基、3,3,3-三氟丙基等之經鹵取代之一價烴基等。 作為上述烯基，基於合成容易性或成本面而言較佳為乙烯基。 尤其，基於合成容易性或成本面而言，較佳R1 全數之90%以上為甲基或苯基。In formulas (2) and (3), R 1 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10. The R 1 monovalent organic group may be any of linear, branched, cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Alkyl groups such as tertiary butyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, etc.; vinyl, allyl, 1-butenyl, 1-hexenyl, etc. Group; aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; aralkyl groups such as benzyl, 2-phenylethyl, 2-phenylpropyl, etc.; part of the hydrogen atoms of these hydrocarbon groups or Halogen-substituted monovalent hydrocarbon groups such as fluoromethyl, bromoethyl, chloromethyl, 3,3,3-trifluoropropyl, etc., all substituted by halogen atoms such as chlorine, fluorine, and bromine. The alkenyl group is preferably a vinyl group in terms of ease of synthesis and cost. In particular, in terms of ease of synthesis or cost, it is preferable that more than 90% of all R 1 are methyl groups or phenyl groups.
式(3)中，R2 表示氧原子或伸烷基，該伸烷基可為直鏈、分支、環狀之任一者。 作為其具體例可舉例為亞甲基、伸乙基、伸丙基、三亞甲基、四亞甲基、伸異丁基、五亞甲基、六亞甲基、七亞甲基、八亞甲基、九亞甲基、伸癸基等之碳原子數1~10之伸烷基等，其中，基於合成容易性或成本面而言，較佳為碳原子數1~5之伸烷基，更佳為伸乙基、三亞甲基，又更佳為伸乙基。 R3 表示丙烯醯基、甲基丙烯醯基、丙烯醯氧基烷基或甲基丙烯醯氧基烷基。該等丙烯醯氧基烷基及甲基丙烯醯氧基烷基中之烷基(伸烷基)之碳數並未特別限定，但較佳為1~10，更佳為1~5，作為其具體例可舉例為4-丙烯醯氧基丁基、3-丙烯醯氧基丙基、4-甲基丙烯醯氧基丁基、3-甲基丙烯醯氧基丙基等，其中若考慮合成容易性，則較佳為4-甲基丙烯醯氧基丁基、3-甲基丙烯醯氧基丙基。In the formula (3), R 2 represents an oxygen atom or an alkylene group, and the alkylene group may be any of linear, branched, and cyclic. As its specific examples can be exemplified methylene, ethylene, propylene, trimethylene, tetramethylene, isobutyl, pentamethylene, hexamethylene, heptamethylene, octaethylene Alkylene groups with 1 to 10 carbon atoms, such as methyl, nonamethylene, and decylene groups. Among them, an alkylene group with 1 to 5 carbon atoms is preferred in terms of ease of synthesis or cost. , More preferably ethylene and trimethylene, and even more preferably ethylene. R 3 represents an acryloyl group, a methacryloyl group, an acryloyloxyalkyl group or a methacryloyloxyalkyl group. The carbon number of the alkyl group (alkylene group) in the acryloxyalkyl group and methacryloxyalkyl group is not particularly limited, but it is preferably 1-10, more preferably 1-5, as Specific examples thereof can be exemplified by 4-propenoxybutyl, 3-propenyloxypropyl, 4-methacryloxybutyl, 3-methacryloxypropyl, etc. For ease of synthesis, 4-methacryloxybutyl and 3-methacryloxypropyl are preferred.
式(3)中，m表示滿足0≦m≦10之數，較佳為滿足1≦m≦8之數，更佳為滿足1≦m≦5之數。In the formula (3), m represents a number that satisfies 0≦m≦10, preferably a number that satisfies 1≦m≦8, and more preferably a number that satisfies 1≦m≦5.
作為(A)成分之有機聚矽氧烷之具體例可舉例為下述化合物，但不限定於該等。(A) Specific examples of the organopolysiloxane as the component include the following compounds, but are not limited to these.
又，上述(A)成分之有機聚矽氧烷可單獨使用亦可組合2種以上使用，但如上述，上述式(3)表示之具有反應基之末端基之數相對於上述式(1)表示之有機聚矽氧烷中以F1 表示之全部末端基之合計數之比例為20%以上，較佳為30%以上。若未達20%，則交聯反應不充分。In addition, the organopolysiloxane of the above component (A) may be used alone or in combination of two or more types. However, as described above, the number of terminal groups having reactive groups represented by the above formula (3) is relative to the above formula (1) The ratio of the total number of all terminal groups represented by F 1 in the organopolysiloxane is 20% or more, preferably 30% or more. If it is less than 20%, the crosslinking reaction is insufficient.
(A)成分之有機聚矽氧例如可使下述式(8)表示之有機聚矽氧烷與下述式(9)表示之有機聚矽氧烷在鉑觸媒存在下進行氫矽烷化反應而獲得。 此時，相對於1莫耳之有機聚矽氧烷(8)，有機聚矽氧烷(9)之莫耳數於0.4~2之範圍調整，可控制上述式(3)表示之具有反應基之末端基之數相對於以F1 表示之全部末端基之合計數之比例。The organopolysiloxane of component (A), for example, can make the organopolysiloxane represented by the following formula (8) and the organopolysiloxane represented by the following formula (9) undergo a hydrosilylation reaction in the presence of a platinum catalyst And get. At this time, relative to 1 mol of organopolysiloxane (8), the mol number of organopolysiloxane (9) is adjusted in the range of 0.4~2, which can control the reactive group represented by the above formula (3) the number of terminal groups of the ratio of the total number of all terminal groups of the indicated with an F 1.
(B)成分 (B)成分係不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物、或不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物及不含矽氧烷構造之多官能(甲基)丙烯酸酯化合物兩者，係用以使本發明之組成物的硬化物之氣體透過性降低之成分。(B) Ingredient (B) The component is a monofunctional (meth)acrylate compound without a silicone structure, or a monofunctional (meth)acrylate compound without a silicone structure, and a polyfunctional (meth)acrylate compound without a silicone structure ( Both meth)acrylate compounds are components for reducing the gas permeability of the cured product of the composition of the present invention.
作為不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物之具體例可舉例為丙烯酸異戊酯、丙烯酸月桂酯、丙烯酸硬脂酯、乙氧基-二乙二醇丙烯酸酯、甲氧基-三乙二醇丙烯酸酯、2-乙基己基-二乙二醇丙烯酸酯、苯氧基乙基丙烯酸酯、苯氧基二乙二醇丙烯酸酯、丙烯酸四氫糠酯、丙烯酸異冰片酯等，該等可單獨使用1種，亦可組合2種以上使用。該等中，特佳為丙烯酸異冰片酯。Specific examples of monofunctional (meth)acrylate compounds without a silicone structure can be exemplified by isoamyl acrylate, lauryl acrylate, stearyl acrylate, ethoxy-diethylene glycol acrylate, and methoxy Ethyl-triethylene glycol acrylate, 2-ethylhexyl-diethylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate Etc., these can be used alone or in combination of two or more. Among these, isobornyl acrylate is particularly preferred.
又，上述不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物之一部分可置換為不含矽氧烷構造之多官能(甲基)丙烯酸酯化合物。 作為不含矽氧烷構造之多官能(甲基)丙烯酸酯化合物之具體例可舉例為三乙二醇二丙烯酸酯、聚四亞甲二醇二丙烯酸酯、新戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二羥甲基-三環癸烷二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯等，該等可單獨使用1種，亦可組合2種以上使用。該等中，特佳為二羥甲基-三環癸烷二丙烯酸酯。 併用不含矽氧烷構造之單官能(甲基)丙烯酸酯化合物與不含矽氧烷構造之多官能(甲基)丙烯酸酯化合物之情況，其使用比例並未特別限定，以質量比計，較佳單官能(甲基)丙烯酸酯化合物:多官能(甲基)丙烯酸酯化合物=9:1~1:9，更佳為3:1~1:1。In addition, a part of the above-mentioned monofunctional (meth)acrylate compound without a silicone structure can be replaced with a polyfunctional (meth)acrylate compound without a silicone structure. As specific examples of the polyfunctional (meth)acrylate compound without a silicone structure, triethylene glycol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, 1 ,6-Hexanediol diacrylate, dimethylol-tricyclodecane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc., these can be used alone or in combination with 2 More than one kind of use. Among these, particularly preferred is dimethylol-tricyclodecane diacrylate. When a monofunctional (meth)acrylate compound without a silicone structure and a polyfunctional (meth)acrylate compound without a silicone structure are used together, the ratio of use is not particularly limited, and is based on mass ratio. Preferably monofunctional (meth)acrylate compound: multifunctional (meth)acrylate compound=9:1 to 1:9, more preferably 3:1 to 1:1.
(B)成分之使用量，相對於(A)成分40~95質量份，係成為與(A)成分之合計為100質量份之量。 (B)成分含量較少時，所得硬化物之氣體透過性變高，較多時耐熱變色性惡化。作為(B)成分之含量，較佳為5~50質量份，更佳為10~40質量份，又更佳為10~30質量份。The usage amount of (B) component is 40 to 95 parts by mass of (A) component, and the total amount with (A) component is 100 parts by mass. (B) When the content of the component is small, the gas permeability of the obtained cured product becomes high, and when it is large, the heat discoloration resistance deteriorates. The content of the component (B) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 10 to 30 parts by mass.
(C)成分 (C)成分之有機過氧化物係於本發明之組成物成型為期望形狀後，用以藉由加熱處理使上述(A)成分及(B)成分藉由交聯反應硬化而調配者。 亦即，藉由有機過氧化物之熱分解產生之游離自由基主要可使上述(A)及(B)成分中之(甲基)丙烯醯基彼此進行聚合反應而成為交聯硬化物。(C) Ingredients The organic peroxide of the component (C) is formulated after the composition of the present invention is molded into a desired shape and used to harden the above-mentioned (A) component and (B) component by crosslinking reaction by heat treatment. That is, the free radicals generated by the thermal decomposition of the organic peroxide can mainly cause the (meth)acrylic groups in the above-mentioned (A) and (B) components to undergo polymerization reaction with each other to form a crosslinked hardened product.
本發明所用之有機過氧化物，基於兼具高反應性與長的使用時間之觀點，較佳半衰期10小時之溫度為40℃以上，半衰期1分鐘之溫度為180℃以下，更佳半衰期10小時之溫度為60℃以上，半衰期1分鐘之溫度為170℃以下。The organic peroxide used in the present invention is based on the viewpoint of high reactivity and long use time. Preferably, the temperature with a half-life of 10 hours is 40°C or more, the temperature with a half-life of 1 minute is below 180°C, and the half-life is 10 hours. The temperature is above 60℃, and the temperature with a half-life of 1 minute is below 170℃.
有機過氧化物可使用自自由基聚合反應等所用之習知者適當選擇，可舉例為例如二醯基過氧化物、二烷基過氧化物、過氧二碳酸酯、過氧酯、過氧縮醛、過氧化氫、矽烷基過氧化物等。 作為其具體例，可舉例為月桂醯過氧化物、琥珀醯過氧化物、苯甲醯過氧化物、二異丙苯基過氧化物、二-第三丁基過氧化物、二-正丙基過氧二碳酸酯、二異丙基過氧二碳酸酯、第三丁基過氧苯甲酸酯、第三己基過氧異丙基單碳酸酯、1,1-雙(第三丁基過氧基)環己烷、2,2-雙(第三丁基過氧基)丁烷等，該等可單獨使用1種，亦可組合2種以上使用。該等中，較佳為1,1-雙(第三丁基過氧基)環己烷、2,2-雙(第三丁基過氧基)丁烷等之過氧縮醛。Organic peroxides can be appropriately selected using those known in radical polymerization reactions, etc., for example, diacyl peroxide, dialkyl peroxide, peroxydicarbonate, peroxyester, peroxy Acetal, hydrogen peroxide, silyl peroxide, etc. As specific examples thereof, laurel peroxide, succinyl peroxide, benzyl peroxide, dicumyl peroxide, di-tertiary butyl peroxide, di-n-propyl Peroxy dicarbonate, diisopropyl peroxy dicarbonate, tertiary butyl peroxy benzoate, tertiary hexyl peroxy isopropyl monocarbonate, 1,1-bis(tertiary butyl Peroxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, etc., can be used alone or in combination of two or more. Among these, peroxyacetals such as 1,1-bis(tert-butylperoxy)cyclohexane and 2,2-bis(tert-butylperoxy)butane are preferred.
(C)成分之調配量，相對於(A)及(B)成分之合計量100質量份，為0.01~10質量份，較佳為0.05~5質量份，更佳為0.1~1質量份。調配量未達0.01質量份時，有反應未充分進行之虞，超過10質量份時，有無法獲得硬化後之期望物性之虞。The compounding amount of (C) component is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 1 part by mass relative to 100 parts by mass of the total amount of (A) and (B) components. When the blending amount is less than 0.01 parts by mass, the reaction may not proceed sufficiently, and when it exceeds 10 parts by mass, the desired physical properties after curing may not be obtained.
(D)成分 (D)成分之酚系抗氧化劑係用於於本發明之組成物硬化後，防止暴露於高溫環境下之變色而調配。 作為酚系抗氧化劑可自以往習知者適當選擇使用，作為其具體例，可舉例2,6-二-第三丁基-4-甲基酚、2,5-二-第三戊基對苯二酚、2,5-二-第三丁基對苯二酚、4,4’-亞丁基雙(3-甲基-6-第三丁基酚)、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、IRGANOX1010、IRGANOX 3114、IRGANOX1098(商品名BASF公司製)、ADEKASTAB AO-20、ADEKASTAB AO-30、ADEKASTAB AO-40(商品名ADEKA公司製)等。該等可單獨使用1種，亦可組合2種以上使用。(D) Ingredients The phenolic antioxidant of component (D) is used to prevent discoloration when exposed to high temperature environment after the composition of the present invention is cured. The phenolic antioxidant can be appropriately selected and used from the conventionally known. As specific examples thereof, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-pentyl pair Hydroquinone, 2,5-di-tert-butylhydroquinone, 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,2'-methylene Bis (4-methyl-6-tertiary butyl phenol), IRGANOX 1010, IRGANOX 3114, IRGANOX 1098 (trade name made by BASF), ADEKASTAB AO-20, ADEKASTAB AO-30, ADEKASTAB AO-40 (trade name made by ADEKA) )Wait. These may be used individually by 1 type, and may be used in combination of 2 or more types.
(D)成分之調配量為50~5,000ppm，較佳為100~2,000ppm，更佳為300~1,000ppm。若為該範圍之調配量，則充分發揮抗氧化性能，可獲得不發生著色、白濁、氧化劣化等之光學特性優異之硬化物。(D) The blending amount of the component is 50 to 5,000 ppm, preferably 100 to 2,000 ppm, more preferably 300 to 1,000 ppm. If it is the compounding amount in this range, the antioxidant performance will be fully exhibited, and a cured product with excellent optical properties without coloration, white turbidity, and oxidative deterioration can be obtained.
又，本發明之組成物中，除上述(A)~(D)成分以外，只要不損及本發明目的，亦可調配以下例示之其他成分。 作為其他成分之具體例可舉例為結晶性氧化矽等之光散射劑或補強材；螢光體；石油溶劑；碳官能基矽烷等之接著性提升劑；酚系抗氧化劑以外之抗氧化劑等。該等其他成分可單獨使用1種，亦可組合2種以上使用。Moreover, in the composition of the present invention, in addition to the above-mentioned (A) to (D) components, other components exemplified below may be blended as long as they do not impair the purpose of the present invention. Specific examples of other components include light scattering agents or reinforcing materials such as crystalline silica; phosphors; petroleum solvents; adhesion promoters such as carbon-functional silanes; antioxidants other than phenolic antioxidants. These other components may be used individually by 1 type, and may be used in combination of 2 or more types.
本發明之熱硬化性矽氧組成物可藉由以任意順序混合、攪拌上述(A)~(D)成分及根據需要之其他成分而獲得。攪拌等之操作所用之裝置並未特別限定，但可使用擂潰機、3輥磨機、球磨機、行星式混合機等。又該等裝置亦可適當組合。 又，本發明之熱硬化性矽氧組成物可於習知硬化條件下藉由習知硬化方法而硬化。 具體而言通常於80~200℃，較佳100~160℃加熱本發明之組成物而硬化。 加熱時間通常為0.5分鐘~5小時左右，較佳為1分鐘~3小時左右，但於要求LED密封用等精度之情況，較佳拉長硬化時間。The thermosetting silicone composition of the present invention can be obtained by mixing and stirring the above-mentioned (A) to (D) components and other components as necessary in any order. The device used for the operation of stirring and the like is not particularly limited, but a crusher, a three-roll mill, a ball mill, a planetary mixer, etc. can be used. These devices can also be combined appropriately. In addition, the thermosetting silica composition of the present invention can be cured by a conventional curing method under conventional curing conditions. Specifically, the composition of the present invention is hardened by heating it at 80-200°C, preferably 100-160°C. The heating time is usually about 0.5 minutes to 5 hours, preferably about 1 minute to 3 hours. However, when precision is required for LED sealing, it is better to extend the curing time.
本發明之熱硬化性矽氧組成物之硬化物由於與通常之加成硬化性矽氧組成物之硬化物同樣係耐熱性、耐寒性、電性絕緣性優異，故適合使用作為光學元件之密封材。 作為光學元件可舉例為例如LED、半導體雷射、光電二極體、光電晶體管、太陽能電池、CCD等。 本發明之硬化物使用作為密封材之情況，只要對光學元件塗佈本發明之熱硬化性矽氧組成物，以上述習知方法及條件硬化即可。 該情況下，塗佈方法只要自例如旋轉塗佈、缺角輪塗佈、唇模塗佈、輥塗佈、模嘴塗佈、刮刀塗佈、刮板塗佈、桿塗佈、接觸塗佈、凹版塗佈、網版塗佈、浸漬塗佈、澆鑄塗佈等之習知方法適當選擇即可。 [實施例]Since the cured product of the thermosetting silicone composition of the present invention has excellent heat resistance, cold resistance, and electrical insulation similar to the cured product of the usual addition-curing silicone composition, it is suitable for use as a seal for optical components material. Examples of optical elements include LEDs, semiconductor lasers, photodiodes, phototransistors, solar cells, CCDs, and the like. When the cured product of the present invention is used as a sealing material, it is only necessary to apply the thermosetting silicone composition of the present invention to an optical element and cure it under the above-mentioned conventional methods and conditions. In this case, the coating method can be selected from, for example, spin coating, chipping wheel coating, lip die coating, roll coating, die nozzle coating, knife coating, blade coating, rod coating, and contact coating. , Gravure coating, screen coating, dip coating, casting coating and other conventional methods can be appropriately selected. [Example]
以下列舉合成例、實施例及比較例更具體說明本發明，但本發明並非限定於該等實施例。 又，以下中，各物性係藉由下述方法測定。 [1]折射率 針對硬化前之組成物，使用ATAGO製數位折射計RX-9000α於25℃測定589nm之折射率。 [2]硬度 使用橡膠硬度計A型硬度計於25℃測定。 [3]光透過率 2mm厚之薄片狀硬化物於25℃使用分光光度計U3310型(日立製作所(股)製)測定400nm之平行光線透過率。 [4]氧透過率 1mm厚之薄片狀硬化物於23℃使用氧透過率測定裝置8001(依利諾依公司製)進行測定。 [5]高溫暴露後之光透過率 2mm厚之薄片狀硬化物於180℃之環境暴露100小時後，於25℃使用分光光度計U3310型(日立製作所(股)製)測定400nm之平行光線透過率。The synthesis examples, examples, and comparative examples are listed below to more specifically illustrate the present invention, but the present invention is not limited to these examples. In addition, in the following, each physical property is measured by the following method. [1] Refractive index For the composition before curing, the refractive index at 589nm was measured at 25°C using a digital refractometer RX-9000α manufactured by ATAGO. [2] Hardness Measured at 25°C using a rubber durometer type A durometer. [3] Light transmittance The 2mm thick flaky hardened material was measured at a parallel light transmittance of 400nm using a spectrophotometer U3310 model (manufactured by Hitachi, Ltd.) at 25°C. [4] Oxygen transmission rate The 1 mm thick flaky cured product was measured at 23°C using an oxygen permeability measuring device 8001 (manufactured by Illinois). [5] Light transmittance after high temperature exposure After the 2mm thick flaky hardened material was exposed to an environment of 180°C for 100 hours, the parallel light transmittance of 400nm was measured using a spectrophotometer U3310 (manufactured by Hitachi, Ltd.) at 25°C.
(1)(A)成分之合成 [合成例1] 於3升燒瓶中，放入1-(3-甲基丙烯醯氧基丙基)-1,1,3,3-四甲基二矽氧烷520.96g及下述式(10)表示之有機聚矽氧烷905.42g，加溫至100℃，於其中添加Karstedt觸媒(氯化鉑酸與sym-二乙烯基四甲基二矽氧烷之錯合物) 0.30g，進而於100℃加熱3小時。冷卻至室溫，獲得有機聚矽氧烷(A-1)。 利用29 Si-NMR測定之末端甲基丙烯醯基之比例為90%，於25℃之黏度為700mPa・s。(1) Synthesis of component (A) [Synthesis example 1] Put 1-(3-methacryloxypropyl)-1,1,3,3-tetramethyldisilica in a 3-liter flask 520.96g of oxane and 905.42g of organopolysiloxane represented by the following formula (10), heated to 100°C, and added Karstedt catalyst (chloroplatinic acid and sym-divinyltetramethyldisiloxy Alkane complex) 0.30g, and then heated at 100°C for 3 hours. After cooling to room temperature, organopolysiloxane (A-1) was obtained. The proportion of terminal methacrylic groups determined by 29 Si-NMR is 90%, and the viscosity at 25°C is 700 mPa·s.
[合成例2] 除了將1-(3-甲基丙烯醯氧基丙基)-1,1,3,3-四甲基二矽氧烷之添加量設為260.48g以外，藉由與合成例1同樣方法，獲得有機聚矽氧烷(A-2)。 利用29 Si-NMR測定之末端甲基丙烯醯基之比例為50%，於25℃之黏度為900mPa・s。[Synthesis Example 2] Except that the addition amount of 1-(3-methacryloxypropyl)-1,1,3,3-tetramethyldisiloxane was set to 260.48g, the synthesis In the same manner as in Example 1, organopolysiloxane (A-2) was obtained. The proportion of terminal methacrylic acid groups determined by 29 Si-NMR is 50%, and the viscosity at 25°C is 900 mPa·s.
[合成例3] 除了將1-(3-甲基丙烯醯氧基丙基)-1,1,3,3-四甲基二矽氧烷之添加量設為52.01g以外，藉由與合成例1同樣方法，獲得有機聚矽氧烷(A-3)。 利用29 Si-NMR測定之末端甲基丙烯醯基之比例為10%，於25℃之黏度為1,800mPa・s。[Synthesis Example 3] Except that the addition amount of 1-(3-methacryloxypropyl)-1,1,3,3-tetramethyldisiloxane was set to 52.01g, the synthesis In the same manner as in Example 1, organopolysiloxane (A-3) was obtained. The proportion of terminal methacrylic acid groups measured by 29 Si-NMR is 10%, and the viscosity at 25°C is 1,800 mPa·s.
[實施例1~3、比較例1~5] 以表1所示組成均一混合各成分獲得熱硬化性矽氧組成物。 各實施例及比較例所得之組成物以成為厚度1mm或2mm之薄片狀之方式流入模框中，於150℃加熱1小時獲得硬化物。以上述方法測定各物性。該等結果示於表1。又，所使用之各成分如以下。[Examples 1 to 3, Comparative Examples 1 to 5] Each component was uniformly mixed with the composition shown in Table 1 to obtain a thermosetting silica composition. The composition obtained in each of the Examples and Comparative Examples was poured into the mold frame in a sheet shape with a thickness of 1 mm or 2 mm, and heated at 150° C. for 1 hour to obtain a hardened product. The physical properties were measured by the above methods. These results are shown in Table 1. In addition, the components used are as follows.
(A)成分 (A-1)合成例1所得之有機聚矽氧烷 (A-2)合成例2所得之有機聚矽氧烷 (A-3)合成例3所得之有機聚矽氧烷 (A-4)下述式(11)表示之有機聚矽氧烷(A) Ingredient (A-1) Organopolysiloxane obtained in Synthesis Example 1 (A-2) Organopolysiloxane obtained in Synthesis Example 2 (A-3) Organopolysiloxane obtained in Synthesis Example 3 (A-4) Organopolysiloxane represented by the following formula (11)
(B)成分 (B-1)丙烯酸異冰片酯(共榮社化學(股)製，LIGHT ACRYLATE IB-XA) (B-2)二羥甲基-三環癸烷二丙烯酸酯(共榮社化學(股)製，LIGHT ACRYLATE DCP-A)(B) Ingredient (B-1) Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ACRYLATE IB-XA) (B-2) Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ACRYLATE DCP-A)
(C)成分 1,1-雙(第三丁基過氧基)環己烷(純度70%，液體鏈烷稀釋，日本油脂(股)製，PERHEXA C(C))(C) Ingredients 1,1-Bis(tert-butylperoxy)cyclohexane (purity 70%, diluted with liquid alkane, manufactured by Japan Oil & Fat Co., Ltd., PERHEXA C(C))
(D)成分 三(3,5-二-第三丁基-4-羥基苄基)異氰脲酸酯(BASF製，IRGANOX3114)(D) Ingredients Tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (made by BASF, IRGANOX3114)
如表1所示可知，本發明之硬化性矽氧組成物係高折射率且具有耐熱變色性，可賦與高透明、低氣體透過性的硬化物。 相對於此，可知不含(B)成分之比較例1之硬化物，氧透過率較大，不含(D)成分之比較例2之硬化物及(B)成分比例較多之比較例5之硬化物，高溫暴露後之光透過率低。 將(A)成分之二芳基矽氧烷部位變更為二甲基矽氧烷之比較例4之組成物，可知為低折射率，且其硬化物之氧透過率高，高溫暴露後之光透過率低。 作為(A)成分使用末端甲基丙烯醯基未達20%之(A-3)的比較例3，藉由加熱並未引起硬化。As shown in Table 1, it can be seen that the curable silicone composition of the present invention has a high refractive index and heat discoloration resistance, and can provide a cured product with high transparency and low gas permeability. In contrast, it can be seen that the cured product of Comparative Example 1 that does not contain the (B) component has a higher oxygen permeability, and the cured product of Comparative Example 2 that does not contain the (D) component and Comparative Example 5 that has a large proportion of the (B) component The hardened material has low light transmittance after high temperature exposure. The composition of Comparative Example 4 in which the diarylsiloxane part of the component (A) is changed to dimethylsiloxane, it can be seen that it has a low refractive index, and the cured product has a high oxygen transmission rate. The transmittance is low. In Comparative Example 3 in which (A-3) with less than 20% of the terminal methacrylic groups was used as the component (A), heating did not cause curing.
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| JP2013181077A (en) * | 2012-02-29 | 2013-09-12 | Idemitsu Kosan Co Ltd | (meth)acrylate-based composition, resin, and molded article |
| JP2015028619A (en) * | 2013-07-30 | 2015-02-12 | 東友ファインケム株式会社 | Photosensitive resin composition for forming front light-shielding layer of display device |
| JP6481647B2 (en) * | 2016-03-22 | 2019-03-13 | 信越化学工業株式会社 | Ultraviolet curable silicone composition, cured product thereof, optical element sealing material comprising the composition, and optical element sealed with the optical element sealing material |
| CN110088159A (en) * | 2016-12-14 | 2019-08-02 | 电化株式会社 | Composition |
| JP7152854B2 (en) * | 2016-12-28 | 2022-10-13 | 東京応化工業株式会社 | Silicon-containing resin composition, silicon-containing resin film, silica film, light-emitting display element panel, and light-emitting display device |
| US11046907B2 (en) * | 2017-02-22 | 2021-06-29 | Eneos Corporation | Defoaming agent and lubricating oil composition |
| JP6754318B2 (en) * | 2017-05-10 | 2020-09-09 | 信越化学工業株式会社 | Silicone resin composition for die bonding, die bonding material and optical semiconductor device |
| KR102542235B1 (en) * | 2017-06-06 | 2023-06-12 | 신에쓰 가가꾸 고교 가부시끼가이샤 | UV-curable silicone pressure-sensitive adhesive composition and cured product thereof |
-
2019
- 2019-02-18 JP JP2019026278A patent/JP7099355B2/en active Active
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2020
- 2020-02-13 KR KR1020200017313A patent/KR20200100547A/en not_active Application Discontinuation
- 2020-02-17 CN CN202010094812.2A patent/CN111574664B/en active Active
- 2020-02-17 TW TW109104941A patent/TWI829863B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111574664A (en) | 2020-08-25 |
| JP7099355B2 (en) | 2022-07-12 |
| KR20200100547A (en) | 2020-08-26 |
| JP2020132727A (en) | 2020-08-31 |
| TWI829863B (en) | 2024-01-21 |
| CN111574664B (en) | 2024-08-09 |
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