WO2016038836A1 - Curable silicone composition, cured object obtained therefrom, and optical semiconductor device - Google Patents
Curable silicone composition, cured object obtained therefrom, and optical semiconductor device Download PDFInfo
- Publication number
- WO2016038836A1 WO2016038836A1 PCT/JP2015/004355 JP2015004355W WO2016038836A1 WO 2016038836 A1 WO2016038836 A1 WO 2016038836A1 JP 2015004355 W JP2015004355 W JP 2015004355W WO 2016038836 A1 WO2016038836 A1 WO 2016038836A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- mass
- formula
- composition
- curable silicone
- Prior art date
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 223
- 239000000203 mixture Substances 0.000 title claims abstract description 208
- 230000003287 optical effect Effects 0.000 title claims description 40
- 239000004065 semiconductor Substances 0.000 title claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 30
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 12
- -1 polysiloxane Polymers 0.000 claims description 236
- 125000003342 alkenyl group Chemical group 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000002252 acyl group Chemical group 0.000 claims description 14
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- 239000000758 substrate Substances 0.000 abstract description 40
- 150000001282 organosilanes Chemical class 0.000 abstract description 10
- 230000009974 thixotropic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 86
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 55
- 239000004205 dimethyl polysiloxane Substances 0.000 description 50
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 50
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 50
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 28
- 229910052697 platinum Inorganic materials 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 23
- 238000006482 condensation reaction Methods 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 20
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 18
- 239000011164 primary particle Substances 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 11
- 238000001723 curing Methods 0.000 description 11
- 229920001400 block copolymer Polymers 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 125000003710 aryl alkyl group Chemical group 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- 239000012463 white pigment Substances 0.000 description 6
- 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 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 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 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000006038 hexenyl group Chemical group 0.000 description 4
- 125000005386 organosiloxy group Chemical group 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000001579 optical reflectometry Methods 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 description 1
- GRGVQLWQXHFRHO-AATRIKPKSA-N (e)-3-methylpent-3-en-1-yne Chemical compound C\C=C(/C)C#C GRGVQLWQXHFRHO-AATRIKPKSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QWOVEJBDMKHZQK-UHFFFAOYSA-N 1,3,5-tris(3-trimethoxysilylpropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CO[Si](OC)(OC)CCCN1C(=O)N(CCC[Si](OC)(OC)OC)C(=O)N(CCC[Si](OC)(OC)OC)C1=O QWOVEJBDMKHZQK-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-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
- 229910052582 BN Inorganic materials 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KYTGWYJWMAKBPN-UHFFFAOYSA-N [dimethyl(prop-2-enyl)silyl]oxy-dimethyl-prop-2-enylsilane Chemical compound C=CC[Si](C)(C)O[Si](C)(C)CC=C KYTGWYJWMAKBPN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011067 equilibration 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
- KPWVUBSQUODFPP-UHFFFAOYSA-N ethenyl-(ethenyl-methyl-phenylsilyl)oxy-methyl-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C=C)O[Si](C)(C=C)C1=CC=CC=C1 KPWVUBSQUODFPP-UHFFFAOYSA-N 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- HOMYFVKFSFMSFF-UHFFFAOYSA-N ethenyl-[ethenyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=C)O[Si](C=C)(C=1C=CC=CC=1)C1=CC=CC=C1 HOMYFVKFSFMSFF-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000286 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 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
- 229920006163 vinyl copolymer Polymers 0.000 description 1
Images
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
- H01L2224/48237—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a die pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Definitions
- the present invention relates to a curable silicone composition, a cured product thereof, and an optical semiconductor device.
- the optical semiconductor device is provided with a light reflecting material in order to efficiently reflect light emitted from the optical semiconductor element.
- a light reflecting material examples include a hydrosilylation reactive silicone having a structure in which one of a vinyl group and an allyl group and a hydrogen atom are directly bonded to a silicon atom.
- a curable silicone composition comprising a resin, a platinum-based catalyst, and a white pigment (see Patent Document 1), a vinyl group-containing organopolysiloxane having a weight average molecular weight (Mw) of 30,000 or more, and a silicon atom bond in one molecule
- Curable silicone composition comprising organohydrogenpolysiloxane having at least two hydrogen atoms, white pigment, inorganic filler other than white pigment, platinum metal catalyst, and reaction control agent (see Patent Document 2), silicon atom bond Branched chain in which 30 to 80 mol% of all organic groups are phenyl groups and 5 to 20 mol% are alkenyl groups
- Organopolysiloxane in the form of a molecule, organopolysiloxane having 10 or less silicon atoms, in which 30 to 60 mol% of all silicon-bonded organic groups are alkenyl groups, and having at least two silicon-bonded hydrogen atoms in one molecule
- a curable silicone composition comprising an
- the present invention has thixotropy, good handling workability, cured, low thermal expansion coefficient, high concealment ratio, high mechanical strength, and good adhesion to various substrates. It is an object of the present invention to provide a curable silicone composition that forms a cured product, a cured product that has a low coefficient of thermal expansion, a high concealment rate, a high mechanical strength, and an optical semiconductor device that is excellent in reliability.
- the curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 ⁇ m and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 ⁇ m, and the content of the titanium oxide powder is A thermosetting silicone composition having a content of 50 to 90% by mass in the present composition and a content of the inorganic powder of 5 to 40% by mass in the present composition, wherein the titanium oxide powder and the inorganic powder But the general formula: R 1 (4-a) Si (OR 2 ) a Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3.
- R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group
- R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond
- R 5 is an oxygen atom or a divalent hydrocarbon group.
- a hydrogen group R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
- b is an integer of 1 to 3
- p is an integer of 1 or more.
- the cured product of the present invention is characterized by curing the above curable silicone composition.
- the optical semiconductor device of the present invention is characterized by having a light reflecting material made of a cured product of the curable silicone composition.
- the curable silicone composition of the present invention has thixotropy, good handling workability, is cured, has a low coefficient of thermal expansion, a high concealment rate, a high mechanical strength, and various substrates. It has the characteristic of forming a cured product with good adhesion to the substrate. Further, the cured product of the present invention is characterized by a low coefficient of thermal expansion, a high concealment rate, and a high mechanical strength. Furthermore, the optical semiconductor device of the present invention is characterized by excellent reliability.
- the curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 ⁇ m and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 ⁇ m, and the content of the titanium oxide powder is It is 50 to 90% by mass in the present composition, and the content of the inorganic powder is 5 to 40% by mass in the present composition.
- This titanium oxide powder is a white pigment for imparting light reflection performance to the cured product of the present composition.
- examples of such titanium oxide powder include anatase-type titanium oxide powder and rutile-type titanium oxide powder, and rutile-type titanium oxide powder is preferable because the light reflection performance and hiding power of the cured product are high.
- the average particle diameter of the titanium oxide is in the range of 0.05 to 10 ⁇ m, preferably in the range of 0.01 to 5 ⁇ m, or in the range of 0.01 to 3 ⁇ m.
- This titanium oxide may have a surface that has been surface-treated with a silane coupling agent, silica, alumina, zirconia or the like in advance.
- the content of the titanium oxide powder is in the range of 50 to 90% by mass in the present composition, preferably in the range of 50 to 85% by mass, in the range of 50 to 80% by mass, and 55 to 90% by mass. %, 55-85% by weight, or 55-80% by weight.
- the content of the titanium oxide powder is not less than the lower limit of the above range, the resulting curable silicone composition has good thixotropy, and the concealability and strength of the obtained cured product.
- operativity of the curable silicone composition obtained as it is below the upper limit of the said range is favorable.
- the content of titanium oxide powder is 10 to 30% by mass with respect to the curable silicone composition.
- the content of 50% by mass or more not only improves the concealability of the resulting cured product. Also, the mechanical strength can be improved. Moreover, in this composition, even if it does not mix
- the inorganic powder other than titanium oxide is a component for reducing the linear expansion coefficient of the cured product and improving the dimensional stability when used in combination with the above titanium oxide powder.
- examples of such inorganic powders include spherical silica, non-spherical silica, and glass fiber, and spherical silica is preferred because the viscosity increase of the resulting curable silicone composition is small.
- examples of the spherical silica include dry silica, wet silica, fused silica, and deflagration silica, but fused silica is preferred because the filling property of the present composition is good.
- the average particle size of the inorganic powder is in the range of 0.1 to 20 ⁇ m, and preferably 0.1 to 15 ⁇ m because of the ease of passing through the mesh and the ease of forming a thin film when using a coating process by screen printing.
- 0.1 to 10 ⁇ m within a range of 0.1 to 10 ⁇ m, within a range of 0.2 to 20 ⁇ m, within a range of 0.2 to 15 ⁇ m, or within a range of 0.2 to 10 ⁇ m.
- the content of the inorganic powder is in the range of 5 to 40% by mass in the present composition, preferably in the range of 5 to 35% by mass, or in the range of 5 to 30% by mass. This is because when the content of the inorganic powder is not less than the lower limit of the above range, the resulting cured product has a low coefficient of linear expansion and good dimensional stability, while it is not more than the upper limit of the above range. This is because the viscosity of the resulting curable silicone composition does not become too high and the handling workability is good.
- the titanium oxide powder and the inorganic powder have the general formula: R 1 (4-a) Si (OR 2 ) a
- R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms
- R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
- a is an integer of 1 to 3.
- R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group
- R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond
- R 5 is an oxygen atom or a divalent hydrocarbon group.
- a hydrogen group R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
- b is an integer of 1 to 3
- p is an integer of 1 or more.
- R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms. This is because when R 1 has less than 6 carbon atoms, the effect of lowering the viscosity of the resulting curable silicone composition is poor. On the other hand, when the number of carbon atoms exceeds 20, the compatibility with the organopolysiloxane component decreases. Because it does.
- R 1 monovalent hydrocarbon group includes hexyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups; benzyl group, phenylethyl group and other aralkyl groups; these alkyl groups and aralkyl groups. Examples thereof include groups in which part or all of the hydrogen atoms in the group are substituted with halogen atoms such as fluorine and chlorine, and alkyl groups having 6 to 20 carbon atoms are preferred.
- R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
- an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group;
- Illustrative examples include alkenyl groups such as isopropylene group and isobutenyl group; acyl groups such as acetoxy group, preferably an alkyl group, and particularly a methyl group and an ethyl group.
- a is an integer of 1 to 3, preferably 3.
- organosilanes include the following compounds. C 6 H 13 Si (OCH 3 ) 3 C 8 H 17 Si (OC 2 H 5 ) 3 C 10 H 21 Si (OCH 3 ) 3 C 12 H 25 Si (OCH 3 ) 3 C 14 H 29 Si (OC 2 H 5 ) 3 C 6 H 5 —CH 2 CH 2 Si (OCH 3 ) 3
- the amount of the organosilane blended is in the range of 0.1 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the present composition. In the range of 0.5 part by weight or in the range of 0.5 to 10 parts by weight. This is because the surface of titanium oxide and inorganic powder can be sufficiently treated when the compounding amount of organosilane is at least the lower limit of the above range, and on the other hand, when the amount is less than the upper limit of the above range, This is because the mechanical strength and adhesive strength can be improved.
- R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group, an aryl Group, aralkyl group and halogenated alkyl group.
- the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group.
- Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and 2-ethylhexyl group.
- Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.
- Examples of the alkenyl group include a vinyl group and an allyl group.
- Examples of the aryl group include a phenyl group and a tolyl group.
- Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group.
- halogenated alkyl group examples include a 3,3,3-trifluoropropyl group, a 2- (nonafluorobutyl) ethyl group, and a 2- (heptadecafluorooctyl) ethyl group.
- R 3 is preferably a methyl group or a vinyl group.
- R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aryl group, Examples include aralkyl groups and halogenated alkyl groups.
- Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group.
- Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and 2-ethylhexyl group.
- Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.
- Examples of the aryl group include a phenyl group and a tolyl group.
- Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group.
- Examples of the halogenated alkyl group include a 3,3,3-trifluoropropyl group, a 2- (nonafluorobutyl) ethyl group, and a 2- (heptadecafluorooctyl) ethyl group.
- R 4 is preferably a methyl group or a phenyl group.
- R 5 is an oxygen atom or a divalent hydrocarbon group.
- the divalent hydrocarbon group for R 5 include alkylene groups such as ethylene group, propylene group, and butylene group; and alkylenearylene alkylene groups such as ethylenephenyleneethylene group and ethylenephenylenepropylene group.
- R 6 represents an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
- an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group;
- Illustrative examples include alkenyl groups such as isopropylene group and isobutenyl group; acyl groups such as acetoxy group, preferably an alkyl group, and particularly a methyl group and an ethyl group.
- b is an integer of 1 to 3, preferably 3.
- p is an integer of 1 or more, preferably an integer in the range of 1 to 200, an integer in the range of 5 to 200, or
- Examples of such an organosiloxane include the following compounds.
- Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
- the amount of the organosiloxane blended is in the range of 0.1 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the composition. In the range of 0.5 part by weight or in the range of 0.5 to 10 parts by weight. This is because the surface of titanium oxide and inorganic powder can be sufficiently treated when the amount of the organosiloxane is not less than the lower limit of the above range, and on the other hand, if the amount is less than the upper limit of the above range, This is because a decrease in hardness can be suppressed, an increase in linear expansion coefficient can be suppressed, and mechanical strength and adhesive strength can be improved.
- the above organosilane or the above organosiloxane may be used alone or in combination. By using these together, it is possible to efficiently perform the surface treatment of the titanium oxide powder and the inorganic powder, and simultaneously impart high mechanical strength, low linear expansion coefficient, and high adhesive ability to the resulting cured product. it can.
- the mass ratio of the organosilane to the organosiloxane is preferably in the range of 3: 7 to 7: 3, particularly 1: 1.
- This composition is thermosetting, and its curing mechanism is not particularly limited. Examples thereof include hydrosilylation reactions, radical reactions with organic peroxides, and condensation reactions, and hydrosilylation reactions are preferred.
- Examples of the hydrosilylation reaction-curable silicone composition include: (A) an organopolysiloxane having at least two alkenyl groups in one molecule; (B) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule ⁇ the amount of silicon-bonded hydrogen atoms in this component is 0.1 to 0.1 mol per 1 mole of alkenyl groups in component (A) Amount to be 10 moles ⁇ , (C) Titanium oxide powder having an average particle size of 0.05 to 10 ⁇ m (in the present composition, an amount of 50 to 90% by mass), (D) Inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 ⁇ m (amount of 5 to 40% by mass in the present composition), (E) (E-1) General formula: R 1 (4-a)
- a hydrogen group R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, b is an integer of 1 to 3, and p is an integer of 1 or more.
- Hydrosilylation catalyst (amount for promoting the hydrosilylation reaction of the composition) represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the composition)
- a curable silicone composition comprising at least
- the organopolysiloxane of the component has at least two alkenyl groups in one molecule.
- alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group.
- the group bonded to the silicon atom other than the alkenyl group in the component (A) has 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like.
- alkyl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group; a part of hydrogen atoms of these groups Or the group which substituted all with halogen atoms, such as a fluorine atom and a chlorine atom, is illustrated.
- Component organopolysiloxane has at least two silicon-bonded hydrogen atoms in one molecule.
- the group bonded to the silicon atom other than the hydrogen atom in the component (B) has 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group.
- alkyl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group; a part of hydrogen atoms of these groups Or the group which substituted all with halogen atoms, such as a fluorine atom and a chlorine atom, is illustrated.
- the component (A) is represented by the formula (A-1): -(R 7 R 8 SiO 2/2 ) m-
- R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- alkyl group for R 7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group.
- R 8 is an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
- m is an integer in the range of 5 to 50, preferably an integer in the range of 5 to 30. This is because when m is not less than the lower limit of the above range, the thermal expansion coefficient of the obtained cured product is remarkably reduced, and when it is not more than the upper limit of the above range, the mechanical strength of the obtained cured product is improved. It is.
- the component (A-1) is a linear organopolysiloxane composed of only the above-mentioned linear siloxane block and having both molecular chain ends blocked.
- Examples of the group at the end of the molecular chain include hydroxyl groups; alkoxy groups such as methoxy group, ethoxy group, and propoxy group; and organosiloxy groups such as trimethylsiloxy group, dimethylvinylsiloxy group, dimethylphenylsiloxy group, and methylphenylvinylsiloxy group. Is done.
- the component (A-1) may be a block copolymer in which the linear siloxane block (X) and another siloxane block (Y) are linked.
- a block copolymer As such a block copolymer, an XY copolymer in which X and Y are connected one by one, an XYX copolymer in which X is connected to both ends of Y, and X and Y are alternately connected z times repeatedly ( XY) z copolymers are exemplified.
- the siloxane block (Y) has a general formula: -(R 7 c SiO (4-c) / 2 )- (Wherein R 7 is the same as above, and c is a number from 0.5 to 2). Or a polysiloxane composed of a repetition thereof.
- the group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
- the organopolysiloxane is generally prepared by polymerizing a cyclic diorganosiloxane by a re-equilibration reaction in the presence of a base catalyst or an acid catalyst. In such a method, the linear siloxane block is retained. It is difficult to prepare a block copolymer. Therefore, as a method for preparing the block copolymer as described above, the polysiloxane having the linear siloxane block (X) and the siloxane or polysiloxane having another siloxane block (Y) are subjected to a condensation reaction. A method is illustrated.
- the content of the component (A-1) is such that the content of the linear siloxane block is 20 to 60% by mass of the total of the organopolysiloxanes in the present composition, preferably 30 to 50% by mass. This is because when the content of the linear siloxane block is equal to or higher than the lower limit of the above range, the thermal expansion coefficient of the resulting cured product is remarkably lowered, whereas when the content is equal to or lower than the upper limit of the above range, the obtained curing is obtained. This is because the flexibility and mechanical strength of the object are improved.
- (A) in addition to the component (A-1), (A-2) a linear or branched organopolysiloxane having at least two alkenyl groups in one molecule May be used in combination.
- alkenyl group in the component (A-2) include alkenyl groups having 2 to 6 carbon atoms such as vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, and cyclohexenyl group.
- the group bonded to the silicon atom other than the alkenyl group in the component (A-2) includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a phenyl group, a tolyl group, and a xylyl group.
- Aryl groups having 6 to 12 carbon atoms such as benzyl groups, phenethyl groups and other aralkyl groups having 7 to 12 carbon atoms; halogenated alkyl groups such as 3-chloropropyl groups and 3,3,3-trifluoropropyl groups; Illustrated.
- molecular chain both ends dimethylvinylsiloxy group-capped dimethylpolysiloxane
- Examples include dimethylsiloxane / methylphenylsiloxane copolymers blocked with dimethylvinylsiloxy groups blocked at both molecular chains, and dimethylsiloxane / methylvinylsiloxane random copolymers blocked with trimethylsiloxy groups blocked at both molecular chains.
- the branched chain organopolysiloxane (A-2) includes a siloxane unit represented by the formula: SiO 4/2 and a siloxane unit represented by the general formula: R 7 2 R 8 SiO 1/2. And those composed of siloxane units represented by the general formula: R 7 3 SiO 1/2 .
- R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples thereof are the same groups as described above.
- R 8 is an alkenyl group having 2 to 10 carbon atoms, and examples thereof are the same groups as described above.
- the total of the siloxane units represented by 2 is preferably in the range of 0.5 to 1.5.
- the organopolysiloxane may have a very small amount of hydroxyl groups, alkoxy groups, etc. bonded to silicon atoms in the molecule.
- the content of the component (A-2) is not particularly limited, but the alkenyl group in this component is at most 10 mol% with respect to the total of the alkenyl group in component (A-1) and the alkenyl group in this component. It is preferable that the amount is as follows. This is because the thermal expansion coefficient of the resulting cured product is significantly reduced when the content of this component is not more than the upper limit of the above range.
- R 9 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples thereof include the same groups as R 7 .
- n is an integer in the range of 10 to 100, preferably an integer in the range of 20 to 80. This is because when n is not less than the lower limit of the above range, the coefficient of thermal expansion of the obtained cured product is remarkably reduced, while when it is not more than the upper limit of the above range, the mechanical strength of the obtained cured product is improved. It is.
- an organopolysiloxane composed only of the above-mentioned linear siloxane block and blocked at both ends of the molecular chain is exemplified.
- the group at the end of this molecular chain is a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group; an organosiloxy group such as a trimethylsiloxy group, a dimethylhydrogensiloxy group, a dimethylphenylsiloxy group, or a methylphenylhydrogensiloxy group Is exemplified.
- the component (B) may be a block copolymer in which the linear siloxane block (X ′) and another siloxane block (Y ′) are linked.
- a block copolymer an X′Y copolymer in which X ′ and Y are linked one by one, an X′YX ′ copolymer in which X ′ is linked to both ends of Y, and X ′ and Y are alternated And (X′Y) z copolymer linked repeatedly z times.
- Examples of the siloxane block (Y) are the same as those described above.
- the group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
- the content of component (B) is such that the silicon-bonded hydrogen atoms in this component are within the range of 0.1 to 10 mol per mol of alkenyl groups in component (A), preferably , An amount in the range of 0.5 to 10 mol, an amount in the range of 0.5 to 5 mol, or an amount in the range of 0.7 to 2 mol.
- the content of the component (B) is not less than the lower limit of the above range, the thermal expansion coefficient of the resulting cured product is remarkably reduced, whereas when it is not more than the upper limit of the above range, the resulting cured product is a machine. This is because the mechanical strength is improved.
- Tianium oxide powder of component (C) and inorganic powder of component (D) are as described above. Further, the organosilane and organosiloxane of the component (E) are as described above.
- the component (C) and the component (D) are mixed with part or all of the component (A), Next, a method of mixing the component (E) with this and heating as necessary, mixing the component (C) with a part of the component (A), and then mixing a part of the component (E) with this Then, the component (D) was mixed with part of the component (A) that was heated as necessary, and then part of the component (E) was mixed with this and heated as necessary.
- the method of mixing things is illustrated. Moreover, you may mix
- the component (F) is a hydrosilylation reaction catalyst for promoting the curing reaction of the composition.
- the component (F) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
- the component (F) is preferably a platinum-based catalyst because curing of the composition can be remarkably accelerated.
- the platinum catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex.
- alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like.
- the content of the component (F) is not particularly limited as long as it is an amount sufficient to promote the hydrosilylation reaction of the present composition.
- the metal atom in the present component is in mass units relative to the present composition. In an amount in the range of 0.01 to 500 ppm, an amount in the range of 0.01 to 100 ppm, or an amount in the range of 0.01 to 50 ppm.
- the content of the component (F) is not less than the lower limit of the above range, the resulting composition is cured well.
- the content is not more than the upper limit of the above range, the resulting cured product is colored. It is difficult.
- the composition may contain (G) a reaction inhibitor in order to appropriately control the curing rate of the composition.
- a reaction inhibitor in order to appropriately control the curing rate of the composition.
- Examples of such component (G) include 1-ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyne- Alkyne alcohols such as 2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole.
- the content of the component (G) is not limited, but is preferably in the range of 1 to 5,000 ppm by
- the composition may contain (H) an adhesion promoter in order to further improve the adhesion to the substrate that is in contact with the curing process.
- a trialkoxysiloxy group for example, trimethoxysiloxy group, triethoxysiloxy group
- a trialkoxysilylalkyl group for example, trimethoxysilylethyl group, triethoxysilylethyl group
- a hydrosilyl group or Organosilane having an alkenyl group for example, vinyl group, allyl group
- Organosilane having a roxyalkyl group for example, 3-methacryloxypropyl group
- the viscosity at 25 ° C. at a shear rate of 1 s ⁇ 1 is preferably 1000 Pa ⁇ s or less, and the viscosity at 25 ° C. at a shear rate of 10 s ⁇ 1 is preferably 100 Pa ⁇ s or less. This is because when the viscosity is as described above, it is easy to cope with various production processes when a cured product is formed. Further, since the liquid does not easily drip at the time of use, the value of the thixo index determined by the following formula is preferably 5.0 or more.
- the present composition may be mixed with a diluent such as an organic solvent or silicone oil to adjust the viscosity.
- a diluent such as an organic solvent or silicone oil to adjust the viscosity.
- This diluent preferably has a boiling point within the range of 150 to 250 ° C. because it is easily volatilized in the curing or post-cure process of the present composition and hardly remains in the cured product.
- examples of such diluents include isoparaffinic organic solvents such as IP solvent manufactured by Idemitsu Kosan Co., Ltd., glycol ether organic solvents such as diethylene glycol monomethyl ether, or OS-20 manufactured by Toray Dow Corning Co., Ltd. Silicone solvents are exemplified.
- the content of this diluent is not particularly limited, but it is easily volatilized in the curing or post-curing process of the present composition and hardly remains in the cured product. Therefore, 0.1 to 10 parts per 100 parts by mass of the present composition. It is preferably within the range of parts by mass.
- the cured product of the present invention is obtained by curing the above curable silicone composition.
- the linear expansion coefficient of the cured product of the present invention is not particularly limited, but the average linear expansion coefficient at 25 to 200 ° C. is preferably 100 ppm / ° C. or less, and more preferably 50 ppm / ° C. or less.
- JIS K 7375: 2008 “Plastic total light transmittance and total light reflectance calculation method” when it is a 100 ⁇ m film cured product
- the total light reflectance in is preferably 90% or more.
- the shape of the cured product of the present invention is not particularly limited, but may be a plate or film formed on the support. Since the thermal expansion coefficient of the cured product of the present invention is extremely low, it is suitable as a coating film or film for coating the support.
- a method for forming such a cured product of the present invention a method of forming a film-like or plate-like cured product on a support by a molding process of the above curable silicone composition, or the above curable silicone composition The method of forming a film-like or plate-like cured product on a support by an application step is mentioned.
- imide resin bismaleimide / triazine resin
- glass fiber-containing epoxy resin paper phenol resin, bakelite, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacrylonitrile resin, polycarbonate resin, fluororesin, polyimide resin, polyphenylene Sulfide resin, aramid resin, polyether ether resin, polyether imide resin, liquid crystal polymer, polyether sulfone resin, cycloolefin resin, silicone rubber, silicone resin and other resin supports; aluminum foil, copper foil, nickel foil, Or metal supports, such as aluminum nitride foil, are illustrated.
- Examples of methods for forming a cured product on the support include a molding process and a coating process.
- Examples of the molding process include press molding and compression molding using a mold.
- Examples of the coating process include screen printing and bar coater. , Roll coater, reverse coater, gravure coater, air knife coater, spray coater, curtain coater are exemplified, and in particular, when coating on a thin film, a known coating method such as a high-precision offset coater or a multi-stage roll coater is used. be able to.
- the cured product of the present invention is preferably formed on the support in the form of a plate or film by the method as described above. Since the hardened
- COB chip-on-board type
- the optical semiconductor device of the present invention has a light reflecting material made of a cured product of the above composition. Such an optical semiconductor device of the present invention will be described in detail with reference to FIGS.
- FIG. 1 shows a cross-sectional view of a chip-on-board (COB) type optical semiconductor device which is an example of the optical semiconductor device of the present invention.
- COB chip-on-board
- an optical semiconductor element 1 is mounted on a COB substrate 2 by die bonding, and the optical semiconductor element 1 and circuits 3 and 4 are electrically connected by a bonding wire 5.
- a light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 so as to efficiently reflect light emitted from the optical semiconductor element 1.
- FIG. 2 shows a sectional view of another chip-on-board (COB) type optical semiconductor device which is an example of the optical semiconductor device of the present invention.
- COB chip-on-board
- the optical semiconductor element 1 is electrically connected to the circuits 3 and 4 on the COB substrate 2 by bonding pads.
- a light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 so as to efficiently reflect light emitted from the optical semiconductor element 1.
- the substrate 2 may be a metal substrate such as aluminum or copper, and the circuits 3 and 4 are formed on the surface of the metal substrate via an insulating layer (not shown). Is formed.
- a non-metallic substrate is used as the substrate 2, it is not necessary to form an insulating layer.
- Such non-metallic substrates include glass epoxy substrates, polybutylene terephthalate (PBT) substrates, polyimide substrates, polyester substrates, aluminum nitride substrates, boron nitride substrates, silicon nitride substrates, alumina ceramic substrates, glass substrates, flexible glass substrates. Is illustrated.
- a hybrid substrate made of an aluminum substrate or a copper substrate having an insulating resin layer, a printed wiring silicon substrate, a silicon carbide substrate, or a sapphire substrate can be used as the substrate 2.
- the circuits 3 and 4 are made of at least one metal selected from the group consisting of silver, copper, and aluminum having high electrical conductivity, or an alloy containing at least one selected from the group consisting of silver, copper, and aluminum. Used. Further, it is preferable that a light reflecting material 6 is formed on the substrate 2 so as to expose a portion on which the optical semiconductor element 1 is mounted.
- the optical semiconductor element 1 and the light reflecting material 6 are sealed with the sealing material 7, but only the optical semiconductor element 1 may be sealed with the sealing material 7 in a dome shape.
- FIG. 1 and FIG. 2 only one optical semiconductor element 1 is shown on the substrate 2, but a plurality of optical semiconductor elements 1 may be mounted on the substrate 2.
- a viscosity is a value in each share rate in 25 degreeC.
- Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
- the hardness, bending strength, linear expansion coefficient, adhesion to metal, and total light reflectance of the cured product were measured as follows.
- the curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product.
- the hardness of the cured product was measured with a type D durometer specified in JIS K 7215-1986 “Method for testing the durometer hardness of plastics”.
- Total light reflectance of cured product The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product having a thickness of 100 ⁇ m. The total light reflectance of this cured product was measured by the method defined in JIS K 7375: 2008 “Plastic Total Light Transmittance and Total Light Reflectance Determination Method”.
- Example 1 formula: - (MeViSiO 2/2) 20 - 4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula: Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 ⁇ m (SX-3103 manufactured by Sakai Chemical Industry), and an average particle size of 15 ⁇ m 21.8 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure.
- a silicone base was prepared by
- a curable silicone composition (I) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the amount of platinum atoms with respect to the present composition is 3.5 ppm by mass). ) was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition.
- the curable silicone composition and the properties of the cured product are shown in Table 1.
- Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3 After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
- a silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
- Silicone composition (VII) was prepared.
- content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition.
- the curable silicone composition and the properties of the cured product are shown in Table 1.
- Example 8 formula: - (MeViSiO 2/2) 20 - 5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula: Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi 5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.24 ⁇ m (Taipaque R-630 manufactured by Ishihara Sangyo), an average particle size of 15 ⁇ m Of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 6 parts by mass, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa ⁇
- Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3 After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
- a curable silicone composition (XI) was prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (with respect to the present composition, an amount in which platinum atoms are 3.5 ppm by mass). ) was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
- a curable silicone composition (XV) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (amount in which platinum atoms are 3 ppm by mass with respect to the present composition). Prepared. In addition, content of said linear methylvinylsiloxane block is 34.7 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
- Example 10 to 12 Inside the support of either PET film, aluminum plate, or copper plate, a spacer with a thickness of 100 ⁇ m is installed so that a space of 5 cm ⁇ 5 cm can be taken, and the curability prepared above within the range surrounded by the spacer 0.8 g of the silicone composition was injected. Next, a release film is placed on the curable silicone composition and heated at 150 ° C. and a press pressure of 5 kg for 15 minutes to produce an integrally molded product of the light reflecting material comprising the cured product and the support. did. The appearance of the cured product was visually observed, and the results are shown in Table 3.
- Examples 13 to 15, Comparative Examples 13 to 15 Using a film coater (PI-1210) manufactured by Tester Sangyo Co., Ltd., the curable silicone composition prepared above was applied to any one of an aluminum plate, a copper plate, a PET film, and a glass plate with a gap size of 100 ⁇ m. And applied. The state of application was visually observed. Then, it heated in 150 degreeC oven for 1 hour, and produced the integral molded product of the light reflection material which consists of hardened
- PI-1210 manufactured by Tester Sangyo Co., Ltd.
- the adhesiveness to the support is good and the cured product does not have cracks or the like. I understood.
- the curable silicone composition of the present invention has thixotropy, dripping hardly occurs between the coating process and heat curing, and no change in shape was observed.
- the curable silicone composition of the present invention has a low coefficient of thermal expansion of a cured product obtained by curing, and has high light reflectivity in a thin film. Therefore, the curable silicone composition is suitable as a composite light reflecting material to be used integrally with other members. is there.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Led Device Packages (AREA)
Abstract
A heat-curable silicone composition which includes a titanium oxide powder having an average particle diameter of 0.05-10 μm and an inorganic powder that is not titanium oxide and has an average particle diameter of 0.1-20 μm, the content of the titanium oxide powder being 50-90 mass% relative to the composition and the content of the inorganic powder being 5-40 mass% relative to the composition, characterized in that the surfaces of the titanium oxide powder and of the inorganic powder have been treated with a specific organosilane and/or a specific organosiloxane. The curable silicone composition is thixotropic, has satisfactory handleability and applicability, and cures to form a cured object which has a low coefficient of thermal expansion, a high hiding power, a high mechanical strength, and satisfactory adhesion to various substrates.
Description
本発明は、硬化性シリコーン組成物、その硬化物、および光半導体装置に関する。
The present invention relates to a curable silicone composition, a cured product thereof, and an optical semiconductor device.
光半導体装置には、光半導体素子から出る光を効率よく反射するために光反射材が設けられている。この光反射材を形成するための硬化性シリコーン組成物としては、例えば、ビニル基およびアリル基のいずれか一方と、水素原子が、直接ケイ素原子に結合してなる構造を有するヒドロシリル化反応性シリコーン樹脂、白金系触媒、および白色顔料からなる硬化性シリコーン組成物（特許文献１参照）、重量平均分子量（Ｍｗ）が３０,０００以上であるビニル基含有オルガノポリシロキサン、一分子中にケイ素原子結合水素原子を少なくとも２個有するオルガノハイドロジェンポリシロキサン、白色顔料、白色顔料以外の無機充填剤、白金金属系触媒、および反応制御剤からなる硬化性シリコーン組成物（特許文献２参照）、ケイ素原子結合全有機基の３０～８０モル％がフェニル基であり、かつ５～２０モル％がアルケニル基である分岐鎖状のオルガノポリシロキサン、ケイ素原子結合全有機基の３０～６０モル％がアルケニル基である、ケイ素原子数が１０以下のオルガノポリシロキサン、一分子中に少なくとも２個のケイ素原子結合水素原子を有し、ケイ素原子結合全有機基の２０～７０モル％がフェニル基であるオルガノポリシロキサン、白色顔料、非球状シリカまたはガラスファイバー、球状シリカ、およびヒドロシリル化反応用触媒からなる硬化性シリコーン組成物（特許文献３参照）が挙げられる。
The optical semiconductor device is provided with a light reflecting material in order to efficiently reflect light emitted from the optical semiconductor element. Examples of the curable silicone composition for forming the light reflecting material include a hydrosilylation reactive silicone having a structure in which one of a vinyl group and an allyl group and a hydrogen atom are directly bonded to a silicon atom. A curable silicone composition comprising a resin, a platinum-based catalyst, and a white pigment (see Patent Document 1), a vinyl group-containing organopolysiloxane having a weight average molecular weight (Mw) of 30,000 or more, and a silicon atom bond in one molecule Curable silicone composition comprising organohydrogenpolysiloxane having at least two hydrogen atoms, white pigment, inorganic filler other than white pigment, platinum metal catalyst, and reaction control agent (see Patent Document 2), silicon atom bond Branched chain in which 30 to 80 mol% of all organic groups are phenyl groups and 5 to 20 mol% are alkenyl groups Organopolysiloxane in the form of a molecule, organopolysiloxane having 10 or less silicon atoms, in which 30 to 60 mol% of all silicon-bonded organic groups are alkenyl groups, and having at least two silicon-bonded hydrogen atoms in one molecule A curable silicone composition comprising an organopolysiloxane in which 20 to 70 mol% of all silicon-bonded organic groups are phenyl groups, a white pigment, non-spherical silica or glass fiber, spherical silica, and a catalyst for hydrosilylation reaction ( Patent Document 3).
近年、光半導体装置において、光反射材が基板上に薄膜で使用される場合には、光反射材と基板の熱膨張率の差によるクラックが発生しにくく、また、基板から剥離しにくいことが求められている。また、このような光反射材には、十分な光反射性能の他、薄膜でも光を透過させない十分な隠蔽性能も求められている。
In recent years, in an optical semiconductor device, when a light reflecting material is used as a thin film on a substrate, cracks due to the difference in thermal expansion coefficient between the light reflecting material and the substrate are less likely to occur, and it is difficult to peel off from the substrate. It has been demanded. Further, such a light reflecting material is required to have sufficient concealing performance that does not transmit light even in a thin film in addition to sufficient light reflecting performance.
しかし、光反射性能に優れ、薄膜における遮蔽性能を向上させるため、白色顔料を硬化性シリコーン組成物中に多量に配合すると、得られる組成物の取り扱い作業性が低下し、また、基板に対する接着性が低下するという課題がある。
However, in order to improve the light reflection performance and improve the shielding performance in the thin film, if a large amount of white pigment is blended in the curable silicone composition, the handling workability of the resulting composition is lowered, and the adhesion to the substrate is reduced. There is a problem that decreases.
本発明は、チキソ性を有し、取り扱い作業性が良好であり、硬化して、熱膨張率が低く、隠蔽率が高く、機械的強度が高く、さらには各種基材に対する接着性が良好な硬化物を形成する硬化性シリコーン組成物、熱膨張率が低く、隠蔽率が高く、機械的強度が高い硬化物、および信頼性に優れる光半導体装置を提供することを目的とする。
The present invention has thixotropy, good handling workability, cured, low thermal expansion coefficient, high concealment ratio, high mechanical strength, and good adhesion to various substrates. It is an object of the present invention to provide a curable silicone composition that forms a cured product, a cured product that has a low coefficient of thermal expansion, a high concealment rate, a high mechanical strength, and an optical semiconductor device that is excellent in reliability.
本発明の硬化性シリコーン組成物は、平均粒子径０.０５～１０μｍの酸化チタン粉末および平均粒子径０.１～２０μｍの酸化チタン以外の無機粉末を含有し、前記酸化チタン粉末の含有量が本組成物中の５０～９０質量％であり、前記無機粉末の含有量が本組成物中の５～４０質量％である熱硬化性シリコーン組成物であって、前記酸化チタン粉末および前記無機粉末が、一般式：
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシランおよび／または一般式：
（式中、Ｒ３は非置換またはハロゲン置換の一価炭化水素基、Ｒ４は同種または異種の脂肪族不飽和結合を有さない一価炭化水素基、Ｒ５は酸素原子または二価炭化水素基、Ｒ６はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ｂは１～３の整数、ｐは１以上の整数である。）
で表されるオルガノシロキサンにより表面処理されていることを特徴とする。 The curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 μm and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm, and the content of the titanium oxide powder is A thermosetting silicone composition having a content of 50 to 90% by mass in the present composition and a content of the inorganic powder of 5 to 40% by mass in the present composition, wherein the titanium oxide powder and the inorganic powder But the general formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
And / or a general formula:
(Wherein R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond, and R 5 is an oxygen atom or a divalent hydrocarbon group. A hydrogen group, R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, b is an integer of 1 to 3, and p is an integer of 1 or more.)
It is characterized by being surface-treated with an organosiloxane represented by the formula:
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシランおよび／または一般式：
で表されるオルガノシロキサンにより表面処理されていることを特徴とする。 The curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 μm and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm, and the content of the titanium oxide powder is A thermosetting silicone composition having a content of 50 to 90% by mass in the present composition and a content of the inorganic powder of 5 to 40% by mass in the present composition, wherein the titanium oxide powder and the inorganic powder But the general formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
And / or a general formula:
It is characterized by being surface-treated with an organosiloxane represented by the formula:
また、本発明の硬化物は、上記の硬化性シリコーン組成物を硬化してなることを特徴とする。
The cured product of the present invention is characterized by curing the above curable silicone composition.
さらに、本発明の光半導体装置は、上記の硬化性シリコーン組成物の硬化物からなる光反射材を有することを特徴とする。
Furthermore, the optical semiconductor device of the present invention is characterized by having a light reflecting material made of a cured product of the curable silicone composition.
本発明の硬化性シリコーン組成物は、チキソ性を有し、取り扱い作業性が良好であり、硬化して、熱膨張率が低く、隠蔽率が高く、機械的強度が高く、さらには各種基材に対する接着性が良好な硬化物を形成するという特徴がある。また、本発明の硬化物は、熱膨張率が低く、隠蔽率が高く、機械的強度が高いという特徴がある。さらに、本発明の光半導体装置は、信頼性が優れるという特徴がある。
The curable silicone composition of the present invention has thixotropy, good handling workability, is cured, has a low coefficient of thermal expansion, a high concealment rate, a high mechanical strength, and various substrates. It has the characteristic of forming a cured product with good adhesion to the substrate. Further, the cured product of the present invention is characterized by a low coefficient of thermal expansion, a high concealment rate, and a high mechanical strength. Furthermore, the optical semiconductor device of the present invention is characterized by excellent reliability.
はじめに、本発明の硬化性シリコーン組成物を説明する。
First, the curable silicone composition of the present invention will be described.
本発明の硬化性シリコーン組成物は、平均粒子径０.０５～１０μｍの酸化チタン粉末および平均粒子径０.１～２０μｍの酸化チタン以外の無機粉末を含有し、前記酸化チタン粉末の含有量が本組成物中の５０～９０質量％であり、前記無機粉末の含有量が本組成物中の５～４０質量％である。
The curable silicone composition of the present invention contains a titanium oxide powder having an average particle size of 0.05 to 10 μm and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm, and the content of the titanium oxide powder is It is 50 to 90% by mass in the present composition, and the content of the inorganic powder is 5 to 40% by mass in the present composition.
この酸化チタン粉末は本組成物の硬化物に光反射性能を付与するための白色顔料である。このような酸化チタン粉末としては、アナタース型酸化チタン粉末、ルチル型酸化チタン粉末が例示され、硬化物の光反射性能及び隠蔽力が高いことから、ルチル型酸化チタン粉末が好ましい。この酸化チタンの平均粒子径は０.０５～１０μｍの範囲内であり、好ましくは、０.０１～５μｍの範囲内、または０.０１～３μｍの範囲内である。この酸化チタンは、予めその表面をシランカップリング剤、シリカ、アルミナ、ジルコニア等で表面処理したものを使用してもよい。
This titanium oxide powder is a white pigment for imparting light reflection performance to the cured product of the present composition. Examples of such titanium oxide powder include anatase-type titanium oxide powder and rutile-type titanium oxide powder, and rutile-type titanium oxide powder is preferable because the light reflection performance and hiding power of the cured product are high. The average particle diameter of the titanium oxide is in the range of 0.05 to 10 μm, preferably in the range of 0.01 to 5 μm, or in the range of 0.01 to 3 μm. This titanium oxide may have a surface that has been surface-treated with a silane coupling agent, silica, alumina, zirconia or the like in advance.
この酸化チタン粉末の含有量は、本組成物中の５０～９０質量％の範囲内であり、好ましくは、５０～８５質量％の範囲内、５０～８０質量％の範囲内、５５～９０質量％の範囲内、５５～８５質量％の範囲内、または５５～８０質量％の範囲内である。これは、本組成物において、酸化チタン粉末の含有量が、上記範囲の下限以上であると、得られる硬化性シリコーン組成物のチキソ性が良好で、また、得られる硬化物の隠蔽性や強度が良好であり、一方、上記範囲の上限以下であると、得られる硬化性シリコーン組成物の取り扱い作業性が良好であるからである。一般に、酸化チタン粉末の含有量は硬化性シリコーン組成物に対して１０～３０質量％であるが、本発明では５０質量％以上含有することにより、得られる硬化物の隠蔽性を向上させるばかりか、機械的強度も向上することができる。また、本組成物では、煙霧状シリカ等のチキソ性付与成分を配合しなくても、本組成物に適度なチキソ性を付与することができる。
The content of the titanium oxide powder is in the range of 50 to 90% by mass in the present composition, preferably in the range of 50 to 85% by mass, in the range of 50 to 80% by mass, and 55 to 90% by mass. %, 55-85% by weight, or 55-80% by weight. In this composition, when the content of the titanium oxide powder is not less than the lower limit of the above range, the resulting curable silicone composition has good thixotropy, and the concealability and strength of the obtained cured product. On the other hand, it is because the workability | operativity of the curable silicone composition obtained as it is below the upper limit of the said range is favorable. In general, the content of titanium oxide powder is 10 to 30% by mass with respect to the curable silicone composition. In the present invention, the content of 50% by mass or more not only improves the concealability of the resulting cured product. Also, the mechanical strength can be improved. Moreover, in this composition, even if it does not mix | blend thixotropic provision components, such as fumed silica, moderate thixotropy can be provided to this composition.
酸化チタン以外の無機粉末は、上記の酸化チタン粉末と併用することで、硬化物の線膨張率を小さくし、寸法安定性を改善するための成分である。このような無機粉末としては、球状シリカ、非球状シリカ、もしくはガラスファイバーが例示されるが、得られる硬化性シリコーン組成物の粘度上昇が少ないことから、球状シリカが好ましい。球状シリカとしては、乾式シリカ、湿式シリカ、溶融シリカ、爆燃シリカが例示されるが、本組成物への充填性が良好であることから、溶融シリカが好ましい。この無機粉末の平均粒子径は０.１～２０μｍの範囲内であり、スクリーン印刷による塗布工程を用いたときのメッシュの通りやすさや薄膜の形成しやすさから、好ましくは、０.１～１５μｍの範囲内、０.１～１０μｍの範囲内、０.２～２０μｍの範囲内、０.２～１５μｍの範囲内、または０.２～１０μｍの範囲内である。
The inorganic powder other than titanium oxide is a component for reducing the linear expansion coefficient of the cured product and improving the dimensional stability when used in combination with the above titanium oxide powder. Examples of such inorganic powders include spherical silica, non-spherical silica, and glass fiber, and spherical silica is preferred because the viscosity increase of the resulting curable silicone composition is small. Examples of the spherical silica include dry silica, wet silica, fused silica, and deflagration silica, but fused silica is preferred because the filling property of the present composition is good. The average particle size of the inorganic powder is in the range of 0.1 to 20 μm, and preferably 0.1 to 15 μm because of the ease of passing through the mesh and the ease of forming a thin film when using a coating process by screen printing. Within a range of 0.1 to 10 μm, within a range of 0.2 to 20 μm, within a range of 0.2 to 15 μm, or within a range of 0.2 to 10 μm.
この無機粉末の含有量は、本組成物中の５～４０質量％の範囲内であり、好ましくは、５～３５質量％の範囲内、または５～３０質量％の範囲内である。これは、無機粉末の含有量が、上記範囲の下限以上であると、得られる硬化物の線膨張率が低く、寸法安定性が良好であり、一方、上記範囲の上限以下であると、得られる硬化性シリコーン組成物の粘度が高くなりすぎず、取り扱い作業性が良好であるからである。
The content of the inorganic powder is in the range of 5 to 40% by mass in the present composition, preferably in the range of 5 to 35% by mass, or in the range of 5 to 30% by mass. This is because when the content of the inorganic powder is not less than the lower limit of the above range, the resulting cured product has a low coefficient of linear expansion and good dimensional stability, while it is not more than the upper limit of the above range. This is because the viscosity of the resulting curable silicone composition does not become too high and the handling workability is good.
本組成物では、前記酸化チタン粉末および前記無機粉末が、一般式：
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシランおよび／または一般式：
（式中、Ｒ３は非置換またはハロゲン置換の一価炭化水素基、Ｒ４は同種または異種の脂肪族不飽和結合を有さない一価炭化水素基、Ｒ５は酸素原子または二価炭化水素基、Ｒ６はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ｂは１～３の整数、ｐは１以上の整数である。）
で表されるオルガノシロキサンにより表面処理されていることを特徴とする。 In the present composition, the titanium oxide powder and the inorganic powder have the general formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
And / or a general formula:
(Wherein R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond, and R 5 is an oxygen atom or a divalent hydrocarbon group. A hydrogen group, R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, b is an integer of 1 to 3, and p is an integer of 1 or more.)
It is characterized by being surface-treated with an organosiloxane represented by the formula:
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシランおよび／または一般式：
で表されるオルガノシロキサンにより表面処理されていることを特徴とする。 In the present composition, the titanium oxide powder and the inorganic powder have the general formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
And / or a general formula:
It is characterized by being surface-treated with an organosiloxane represented by the formula:
上記オルガノシランにおいて、式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基である。これは、Ｒ１の炭素数が６未満である場合、得られる硬化性シリコーン組成物の粘度を低下させる効果が乏しく、一方、炭素数が２０を超えるとオルガノポリシロキサン成分との相溶性が低下するからである。Ｒ１の一価炭化水素基としては、ヘキシル基、オクチル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等のアルキル基；ベンジル基、フェニルエチル基等のアラルキル基；これらのアルキル基またはアラルキル基中の水素原子の一部または全部をフッ素、塩素等のハロゲン原子で置換した基が例示され、好ましくは、炭素数６～２０のアルキル基である。
In the above organosilane, R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms. This is because when R 1 has less than 6 carbon atoms, the effect of lowering the viscosity of the resulting curable silicone composition is poor. On the other hand, when the number of carbon atoms exceeds 20, the compatibility with the organopolysiloxane component decreases. Because it does. R 1 monovalent hydrocarbon group includes hexyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups; benzyl group, phenylethyl group and other aralkyl groups; these alkyl groups and aralkyl groups. Examples thereof include groups in which part or all of the hydrogen atoms in the group are substituted with halogen atoms such as fluorine and chlorine, and alkyl groups having 6 to 20 carbon atoms are preferred.
また、式中、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基である。具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の炭素数１～６のアルキル基；メトキシメチル基、エトキシメチル基、メトキシエチル基等のアルコキシアルキル基；イソプロピレン基、イソブテニル基等のアルケニル基；アセトキシ基等のアシル基が例示され、好ましくは、アルキル基であり、特には、メチル基、エチル基である。また、式中、ａは１～３の整数であり、好ましくは、３である。
In the formula, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group. Specifically, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group; Illustrative examples include alkenyl groups such as isopropylene group and isobutenyl group; acyl groups such as acetoxy group, preferably an alkyl group, and particularly a methyl group and an ethyl group. In the formula, a is an integer of 1 to 3, preferably 3.
このようなオルガノシランとしては、次の化合物が例示される。
Ｃ６Ｈ１３Ｓi(ＯＣＨ３)３
Ｃ８Ｈ１７Ｓi(ＯＣ２Ｈ５)３
Ｃ１０Ｈ２１Ｓi(ＯＣＨ３)３
Ｃ１２Ｈ２５Ｓi(ＯＣＨ３)３
Ｃ１４Ｈ２９Ｓi(ＯＣ２Ｈ５)３
Ｃ６Ｈ５－ＣＨ２ＣＨ２Ｓi(ＯＣＨ３)３ Examples of such organosilanes include the following compounds.
C 6 H 13 Si (OCH 3 ) 3
C 8 H 17 Si (OC 2 H 5 ) 3
C 10 H 21 Si (OCH 3 ) 3
C 12 H 25 Si (OCH 3 ) 3
C 14 H 29 Si (OC 2 H 5 ) 3
C 6 H 5 —CH 2 CH 2 Si (OCH 3 ) 3
Ｃ６Ｈ１３Ｓi(ＯＣＨ３)３
Ｃ８Ｈ１７Ｓi(ＯＣ２Ｈ５)３
Ｃ１０Ｈ２１Ｓi(ＯＣＨ３)３
Ｃ１２Ｈ２５Ｓi(ＯＣＨ３)３
Ｃ１４Ｈ２９Ｓi(ＯＣ２Ｈ５)３
Ｃ６Ｈ５－ＣＨ２ＣＨ２Ｓi(ＯＣＨ３)３ Examples of such organosilanes include the following compounds.
C 6 H 13 Si (OCH 3 ) 3
C 8 H 17 Si (OC 2 H 5 ) 3
C 10 H 21 Si (OCH 3 ) 3
C 12 H 25 Si (OCH 3 ) 3
C 14 H 29 Si (OC 2 H 5 ) 3
C 6 H 5 —CH 2 CH 2 Si (OCH 3 ) 3
このオルガノシランの配合量は、本組成物１００質量部に対して０.１～１０質量部の範囲内であり、好ましくは、０.１～５質量部の範囲内、０.５～５質量部の範囲内、または０.５～１０質量部の範囲内である。これは、オルガノシランの配合量が上記範囲の下限以上であると、酸化チタンおよび無機粉末の表面を十分に処理できるからであり、一方、上記範囲の上限以下であると、得られる硬化物の機械的強度や接着力を向上できるからである。
The amount of the organosilane blended is in the range of 0.1 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the present composition. In the range of 0.5 part by weight or in the range of 0.5 to 10 parts by weight. This is because the surface of titanium oxide and inorganic powder can be sufficiently treated when the compounding amount of organosilane is at least the lower limit of the above range, and on the other hand, when the amount is less than the upper limit of the above range, This is because the mechanical strength and adhesive strength can be improved.
一方、上記のオルガノシロキサンにおいて、式中、Ｒ３は非置換またはハロゲン置換の一価炭化水素基であり、例えば、直鎖状アルキル基、分岐鎖状アルキル基、環状アルキル基、アルケニル基、アリール基、アラルキル基、ハロゲン化アルキル基が挙げられる。直鎖状アルキル基としては、メチル基、エチル基、プロピル基、ヘキシル基、オクチル基が例示される。分岐鎖状アルキル基としては、イソプロピル基、イソブチル基、tert－ブチル基、２－エチルヘキシル基が例示される。環状アルキル基としては、シクロペンチル基、シクロヘキシル基が例示される。アルケニル基としては、ビニル基、アリル基が例示される。アリール基としては、フェニル基、トリル基が例示される。アラルキル基としては、２－フェニルエチル基、２－メチル－２－フェニルエチル基が例示される。ハロゲン化アルキル基としては、例えば、３,３,３－トリフルオロプロピル基、２－(ノナフルオロブチル)エチル基、２－(ヘプタデカフルオロオクチル)エチル基が例示される。Ｒ３としては、メチル基、ビニル基が好ましい。
On the other hand, in the above organosiloxane, in the formula, R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group, an aryl Group, aralkyl group and halogenated alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group. Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and 2-ethylhexyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group. Examples of the halogenated alkyl group include a 3,3,3-trifluoropropyl group, a 2- (nonafluorobutyl) ethyl group, and a 2- (heptadecafluorooctyl) ethyl group. R 3 is preferably a methyl group or a vinyl group.
また、式中、Ｒ４は同種または異種の脂肪族不飽和結合を有さない一価炭化水素基であり、例えば、直鎖状アルキル基、分岐鎖状アルキル基、環状アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基が挙げられる。直鎖状アルキル基としては、メチル基、エチル基、プロピル基、ヘキシル基、オクチル基が例示される。分岐鎖状アルキル基としては、イソプロピル基、イソブチル基、ｔert－ブチル基、２－エチルヘキシル基が例示される。環状アルキル基としては、シクロペンチル基、シクロヘキシル基が例示される。アリール基としては、フェニル基、トリル基が例示される。アラルキル基としては、２－フェニルエチル基、２－メチル－２－フェニルエチル基が例示される。ハロゲン化アルキル基としては、３,３,３－トリフルオロプロピル基、２－(ノナフルオロブチル)エチル基、２－(ヘプタデカフルオロオクチル)エチル基が例示される。Ｒ４としては、メチル基、フェニル基が好ましい。
In the formula, R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aryl group, Examples include aralkyl groups and halogenated alkyl groups. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and an octyl group. Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, and 2-ethylhexyl group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group. Examples of the halogenated alkyl group include a 3,3,3-trifluoropropyl group, a 2- (nonafluorobutyl) ethyl group, and a 2- (heptadecafluorooctyl) ethyl group. R 4 is preferably a methyl group or a phenyl group.
また、式中、Ｒ５は酸素原子または二価炭化水素基である。Ｒ５の二価炭化水素基としては、エチレン基、プロピレン基、ブチレン基等のアルキレン基；エチレンフェニレンエチレン基、エチレンフェニレンプロピレン基等のアルキレンアリーレンアルキレン基が例示される。
In the formula, R 5 is an oxygen atom or a divalent hydrocarbon group. Examples of the divalent hydrocarbon group for R 5 include alkylene groups such as ethylene group, propylene group, and butylene group; and alkylenearylene alkylene groups such as ethylenephenyleneethylene group and ethylenephenylenepropylene group.
また、式中、Ｒ６はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基である。具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等の炭素数１～６のアルキル基；メトキシメチル基、エトキシメチル基、メトキシエチル基等のアルコキシアルキル基；イソプロピレン基、イソブテニル基等のアルケニル基；アセトキシ基等のアシル基が例示され、好ましくは、アルキル基であり、特には、メチル基、エチル基である。また、式中、ｂは１～３の整数であり、好ましくは、３である。また、式中、ｐは１以上の整数であり、好ましくは、１～２００の範囲内の整数、５～２００の範囲内の整数、または５～１５０の範囲内の整数である。
In the formula, R 6 represents an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group. Specifically, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkoxyalkyl group such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group; Illustrative examples include alkenyl groups such as isopropylene group and isobutenyl group; acyl groups such as acetoxy group, preferably an alkyl group, and particularly a methyl group and an ethyl group. In the formula, b is an integer of 1 to 3, preferably 3. In the formula, p is an integer of 1 or more, preferably an integer in the range of 1 to 200, an integer in the range of 5 to 200, or an integer in the range of 5 to 150.
このようなオルガノシロキサンとしては、次の化合物が例示される。なお、式中、Ｍe、Ｐh、Ｖiは、それぞれメチル基、フェニル基、ビニル基を表す。
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１５Ｓi(ＯＭe)３
Ｍe３ＳiＯ(Ｍe２ＳiＯ)２３Ｓi(ＯＭe)３
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
ＶiＭe２ＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
ＶiＭe２ＳiＯ(Ｍe２ＳiＯ)１０Ｓi(ＯＭe)３
ＶiＭe２ＳiＯ(Ｍe２ＳiＯ)５Ｓi(ＯＭe)３
Ｍe３ＳiＯ(ＭeＰhＳiＯ)１０Ｓi(ＯＭe)３ Examples of such an organosiloxane include the following compounds. In the formulae, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
Me 3 SiO (Me 2 SiO) 15 Si (OMe) 3
Me 3 SiO (Me 2 SiO) 23 Si (OMe) 3
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
ViMe 2 SiO (Me 2 SiO) 29 Si (OMe) 3
ViMe 2 SiO (Me 2 SiO) 10 Si (OMe) 3
ViMe 2 SiO (Me 2 SiO) 5 Si (OMe) 3
Me 3 SiO (MePhSiO) 10 Si (OMe) 3
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１５Ｓi(ＯＭe)３
Ｍe３ＳiＯ(Ｍe２ＳiＯ)２３Ｓi(ＯＭe)３
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
ＶiＭe２ＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
ＶiＭe２ＳiＯ(Ｍe２ＳiＯ)１０Ｓi(ＯＭe)３
ＶiＭe２ＳiＯ(Ｍe２ＳiＯ)５Ｓi(ＯＭe)３
Ｍe３ＳiＯ(ＭeＰhＳiＯ)１０Ｓi(ＯＭe)３ Examples of such an organosiloxane include the following compounds. In the formulae, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
Me 3 SiO (Me 2 SiO) 15 Si (OMe) 3
Me 3 SiO (Me 2 SiO) 23 Si (OMe) 3
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
ViMe 2 SiO (Me 2 SiO) 29 Si (OMe) 3
ViMe 2 SiO (Me 2 SiO) 10 Si (OMe) 3
ViMe 2 SiO (Me 2 SiO) 5 Si (OMe) 3
Me 3 SiO (MePhSiO) 10 Si (OMe) 3
このオルガノシロキサンの配合量は、本組成物１００質量部に対して０.１～１０質量部の範囲内であり、好ましくは、０.１～５質量部の範囲内、０.５～５質量部の範囲内、または０.５～１０質量部の範囲内である。これは、オルガノシロキサンの配合量が上記範囲の下限以上であると、酸化チタンおよび無機粉末の表面を十分に処理できるからであり、一方、上記範囲の上限以下であると、得られる硬化物の硬度の低下を抑制したり、線膨張係数の増加を抑制したり、機械的強度や接着力を向上できるからである。
The amount of the organosiloxane blended is in the range of 0.1 to 10 parts by weight, preferably in the range of 0.1 to 5 parts by weight, and 0.5 to 5 parts by weight with respect to 100 parts by weight of the composition. In the range of 0.5 part by weight or in the range of 0.5 to 10 parts by weight. This is because the surface of titanium oxide and inorganic powder can be sufficiently treated when the amount of the organosiloxane is not less than the lower limit of the above range, and on the other hand, if the amount is less than the upper limit of the above range, This is because a decrease in hardness can be suppressed, an increase in linear expansion coefficient can be suppressed, and mechanical strength and adhesive strength can be improved.
本組成物においては、上記オルガノシランまたは上記オルガノシロキサンを単独で使用してもよく、また、これらを併用してもよい。これらを併用することにより、上記酸化チタン粉末および無機粉末の表面処理を効率良く行うことができ、得られる硬化物に高い機械的強度、低い線膨張率、および高い接着能力を同時に付与することができる。上記オルガノシランと上記オルガノシロキサンの質量比は、好ましくは、３：７～７：３の範囲内であり、特には、１：１である。
In the present composition, the above organosilane or the above organosiloxane may be used alone or in combination. By using these together, it is possible to efficiently perform the surface treatment of the titanium oxide powder and the inorganic powder, and simultaneously impart high mechanical strength, low linear expansion coefficient, and high adhesive ability to the resulting cured product. it can. The mass ratio of the organosilane to the organosiloxane is preferably in the range of 3: 7 to 7: 3, particularly 1: 1.
本組成物は熱硬化性であって、その硬化機構は特に限定されず、例えば、ヒドロシリル化反応、有機過酸化物によるラジカル反応、縮合反応が例示され、好ましくは、ヒドロシリル化反応である。ヒドロシリル化反応硬化性シリコーン組成物としては、例えば、
（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、
（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルとなる量｝、
（Ｃ）平均粒子径０.０５～１０μｍの酸化チタン粉末（本組成物中、５０～９０質量％となる量）、
（Ｄ）平均粒子径０.１～２０μｍの酸化チタン以外の無機粉末（本組成物中、５～４０質量％となる量）、
（Ｅ）（Ｅ－１）一般式：
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシラン（本組成物１００質量部に対して０.１～１０質量部）および／または（Ｅ－２）一般式：
（式中、Ｒ３は非置換またはハロゲン置換の一価炭化水素基、Ｒ４は同種または異種の脂肪族不飽和結合を有さない一価炭化水素基、Ｒ５は酸素原子または二価炭化水素基、Ｒ６はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ｂは１～３の整数、ｐは１以上の整数である。）
で表されるオルガノシロキサン（本組成物１００質量部に対して０.１～１０質量部）、および
（Ｆ）ヒドロシリル化反応用触媒（本組成物のヒドロシリル化反応を促進する量）
から少なくともなる硬化性シリコーン組成物が好ましい。 This composition is thermosetting, and its curing mechanism is not particularly limited. Examples thereof include hydrosilylation reactions, radical reactions with organic peroxides, and condensation reactions, and hydrosilylation reactions are preferred. Examples of the hydrosilylation reaction-curable silicone composition include:
(A) an organopolysiloxane having at least two alkenyl groups in one molecule;
(B) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the amount of silicon-bonded hydrogen atoms in this component is 0.1 to 0.1 mol per 1 mole of alkenyl groups in component (A) Amount to be 10 moles},
(C) Titanium oxide powder having an average particle size of 0.05 to 10 μm (in the present composition, an amount of 50 to 90% by mass),
(D) Inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm (amount of 5 to 40% by mass in the present composition),
(E) (E-1) General formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
Represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the present composition) and / or (E-2) general formula:
(Wherein R 3 is an unsubstituted or halogen-substituted monovalent hydrocarbon group, R 4 is a monovalent hydrocarbon group having no same or different aliphatic unsaturated bond, and R 5 is an oxygen atom or a divalent hydrocarbon group. A hydrogen group, R 6 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, b is an integer of 1 to 3, and p is an integer of 1 or more.)
(F) Hydrosilylation catalyst (amount for promoting the hydrosilylation reaction of the composition) represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the composition)
A curable silicone composition comprising at least
（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、
（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルとなる量｝、
（Ｃ）平均粒子径０.０５～１０μｍの酸化チタン粉末（本組成物中、５０～９０質量％となる量）、
（Ｄ）平均粒子径０.１～２０μｍの酸化チタン以外の無機粉末（本組成物中、５～４０質量％となる量）、
（Ｅ）（Ｅ－１）一般式：
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシラン（本組成物１００質量部に対して０.１～１０質量部）および／または（Ｅ－２）一般式：
で表されるオルガノシロキサン（本組成物１００質量部に対して０.１～１０質量部）、および
（Ｆ）ヒドロシリル化反応用触媒（本組成物のヒドロシリル化反応を促進する量）
から少なくともなる硬化性シリコーン組成物が好ましい。 This composition is thermosetting, and its curing mechanism is not particularly limited. Examples thereof include hydrosilylation reactions, radical reactions with organic peroxides, and condensation reactions, and hydrosilylation reactions are preferred. Examples of the hydrosilylation reaction-curable silicone composition include:
(A) an organopolysiloxane having at least two alkenyl groups in one molecule;
(B) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the amount of silicon-bonded hydrogen atoms in this component is 0.1 to 0.1 mol per 1 mole of alkenyl groups in component (A) Amount to be 10 moles},
(C) Titanium oxide powder having an average particle size of 0.05 to 10 μm (in the present composition, an amount of 50 to 90% by mass),
(D) Inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm (amount of 5 to 40% by mass in the present composition),
(E) (E-1) General formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
Represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the present composition) and / or (E-2) general formula:
(F) Hydrosilylation catalyst (amount for promoting the hydrosilylation reaction of the composition) represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the composition)
A curable silicone composition comprising at least
（Ａ）成分のオルガノポリシロキサンは一分子中に少なくとも２個のアルケニル基を有する。このアルケニル基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等の炭素原子数２～１０のアルケニル基が例示される。（Ａ）成分中のアルケニル基以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基等の炭素原子数１～６のアルキル基；フェニル基、トリル基、キシリル基等の炭素原子数６～１２のアリール基；ベンジル基、フェネチル基等の炭素原子数７～１２のアラルキル基；これらの基の水素原子の一部または全部をフッ素原子、塩素原子等のハロゲン原子で置換した基が例示される。
(A) The organopolysiloxane of the component has at least two alkenyl groups in one molecule. Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group. The group bonded to the silicon atom other than the alkenyl group in the component (A) has 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. An alkyl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group; a part of hydrogen atoms of these groups Or the group which substituted all with halogen atoms, such as a fluorine atom and a chlorine atom, is illustrated.
（Ｂ）成分のオルガノポリシロキサンは一分子中に少なくとも２個のケイ素原子結合水素原子を有する。（Ｂ）成分中の水素原子以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基等の炭素原子数１～６のアルキル基；フェニル基、トリル基、キシリル基等の炭素原子数６～１２のアリール基；ベンジル基、フェネチル基等の炭素原子数７～１２のアラルキル基；これらの基の水素原子の一部または全部をフッ素原子、塩素原子等のハロゲン原子で置換した基が例示される。
(B) Component organopolysiloxane has at least two silicon-bonded hydrogen atoms in one molecule. The group bonded to the silicon atom other than the hydrogen atom in the component (B) has 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group. An alkyl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 12 carbon atoms such as a benzyl group or a phenethyl group; a part of hydrogen atoms of these groups Or the group which substituted all with halogen atoms, such as a fluorine atom and a chlorine atom, is illustrated.
本組成物では、得られる硬化物の熱膨張率を著しく低下できることから、（Ａ）成分は、（Ａ－１）一般式：
－(Ｒ７Ｒ８ＳiＯ２/２)ｍ－
で表される直鎖状シロキサンブロックを少なくとも有するオルガノポリシロキサンであり、（Ｂ）成分は、（Ｂ－１）一般式：
－(Ｒ９ＨＳiＯ２/２)ｎ－
で表される直鎖状シロキサンブロックを少なくとも有するオルガノポリシロキサンであることが好ましい。 In the present composition, since the coefficient of thermal expansion of the resulting cured product can be significantly reduced, the component (A) is represented by the formula (A-1):
-(R 7 R 8 SiO 2/2 ) m-
An organopolysiloxane having at least a linear siloxane block represented by the formula (B-1):
-(R 9 HSiO 2/2 ) n-
An organopolysiloxane having at least a linear siloxane block represented by
－(Ｒ７Ｒ８ＳiＯ２/２)ｍ－
で表される直鎖状シロキサンブロックを少なくとも有するオルガノポリシロキサンであり、（Ｂ）成分は、（Ｂ－１）一般式：
－(Ｒ９ＨＳiＯ２/２)ｎ－
で表される直鎖状シロキサンブロックを少なくとも有するオルガノポリシロキサンであることが好ましい。 In the present composition, since the coefficient of thermal expansion of the resulting cured product can be significantly reduced, the component (A) is represented by the formula (A-1):
-(R 7 R 8 SiO 2/2 ) m-
An organopolysiloxane having at least a linear siloxane block represented by the formula (B-1):
-(R 9 HSiO 2/2 ) n-
An organopolysiloxane having at least a linear siloxane block represented by
（Ａ－１）成分において、式中、Ｒ７は炭素原子数１～６のアルキル基またはフェニル基である。Ｒ７のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基が例示される。また、式中、Ｒ８は炭素原子数２～１０のアルケニル基であり、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基が例示される。
In the component (A-1), R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group. Examples of the alkyl group for R 7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, and a cyclohexyl group. In the formula, R 8 is an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
また、式中、ｍは５～５０の範囲内の整数であり、好ましくは、５～３０の範囲内の整数である。これは、ｍが上記範囲の下限以上であると、得られる硬化物の熱膨張率が著しく低下し、一方、上記範囲の上限以下であると、得られる硬化物の機械的強度が向上するからである。
In the formula, m is an integer in the range of 5 to 50, preferably an integer in the range of 5 to 30. This is because when m is not less than the lower limit of the above range, the thermal expansion coefficient of the obtained cured product is remarkably reduced, and when it is not more than the upper limit of the above range, the mechanical strength of the obtained cured product is improved. It is.
（Ａ－１）成分は、上記の直鎖状シロキサンブロックのみからなり、その分子鎖両末端が封鎖された鎖状のオルガノポリシロキサンが例示される。この分子鎖末端の基としては、水酸基；メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基；トリメチルシロキシ基、ジメチルビニルシロキシ基、ジメチルフェニルシロキシ基、メチルフェニルビニルシロキシ基等のオルガノシロキシ基が例示される。また、（Ａ－１）成分は、上記直鎖状シロキサンブロック（Ｘ）と他のシロキサンブロック（Ｙ）とが連結したブロック共重合体であってもよい。このようなブロック共重合体としては、Ｘ、Ｙが１個ずつ連結したＸＹ共重合体、Ｙの両端にＸを連結したＸＹＸ共重合体、Ｘ、Ｙが交互にｚ回繰り返して連結した（ＸＹ）ｚ共重合体が例示される。このシロキサンブロック（Ｙ）としては、一般式：
－(Ｒ７ ｃＳiＯ(４－ｃ)/２)－
（式中、Ｒ７は前記と同じであり、ｃは０.５～２の数である。）
で表されるシロキサンもしくはその繰り返しからなるポリシロキサンが例示される。なお、このブロック共重合体の分子鎖末端の基としては、水酸基、上記と同様のアルコキシ基、または上記と同様のオルガノシロキシ基が例示される。 The component (A-1) is a linear organopolysiloxane composed of only the above-mentioned linear siloxane block and having both molecular chain ends blocked. Examples of the group at the end of the molecular chain include hydroxyl groups; alkoxy groups such as methoxy group, ethoxy group, and propoxy group; and organosiloxy groups such as trimethylsiloxy group, dimethylvinylsiloxy group, dimethylphenylsiloxy group, and methylphenylvinylsiloxy group. Is done. The component (A-1) may be a block copolymer in which the linear siloxane block (X) and another siloxane block (Y) are linked. As such a block copolymer, an XY copolymer in which X and Y are connected one by one, an XYX copolymer in which X is connected to both ends of Y, and X and Y are alternately connected z times repeatedly ( XY) z copolymers are exemplified. The siloxane block (Y) has a general formula:
-(R 7 c SiO (4-c) / 2 )-
(Wherein R 7 is the same as above, and c is a number from 0.5 to 2).
Or a polysiloxane composed of a repetition thereof. The group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
－(Ｒ７ ｃＳiＯ(４－ｃ)/２)－
（式中、Ｒ７は前記と同じであり、ｃは０.５～２の数である。）
で表されるシロキサンもしくはその繰り返しからなるポリシロキサンが例示される。なお、このブロック共重合体の分子鎖末端の基としては、水酸基、上記と同様のアルコキシ基、または上記と同様のオルガノシロキシ基が例示される。 The component (A-1) is a linear organopolysiloxane composed of only the above-mentioned linear siloxane block and having both molecular chain ends blocked. Examples of the group at the end of the molecular chain include hydroxyl groups; alkoxy groups such as methoxy group, ethoxy group, and propoxy group; and organosiloxy groups such as trimethylsiloxy group, dimethylvinylsiloxy group, dimethylphenylsiloxy group, and methylphenylvinylsiloxy group. Is done. The component (A-1) may be a block copolymer in which the linear siloxane block (X) and another siloxane block (Y) are linked. As such a block copolymer, an XY copolymer in which X and Y are connected one by one, an XYX copolymer in which X is connected to both ends of Y, and X and Y are alternately connected z times repeatedly ( XY) z copolymers are exemplified. The siloxane block (Y) has a general formula:
-(R 7 c SiO (4-c) / 2 )-
(Wherein R 7 is the same as above, and c is a number from 0.5 to 2).
Or a polysiloxane composed of a repetition thereof. The group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
オルガノポリシロキサンは、一般には、環状ジオルガノシロキサンを、塩基触媒もしくは酸触媒の存在下、再平衡化反応により重合して調製するが、このような方法では、上記直鎖状シロキサンブロックを保持したブロック共重合体を調製することは難しい。このため、上記のようなブロック共重合体を調製する方法としては、上記直鎖状シロキサンブロック（Ｘ）を有するポリシロキサンと、他のシロキサンブロック（Ｙ）を有するシロキサンもしくはポリシロキサンを縮合反応する方法が例示される。
The organopolysiloxane is generally prepared by polymerizing a cyclic diorganosiloxane by a re-equilibration reaction in the presence of a base catalyst or an acid catalyst. In such a method, the linear siloxane block is retained. It is difficult to prepare a block copolymer. Therefore, as a method for preparing the block copolymer as described above, the polysiloxane having the linear siloxane block (X) and the siloxane or polysiloxane having another siloxane block (Y) are subjected to a condensation reaction. A method is illustrated.
本組成物において、（Ａ－１）成分の含有量は、上記直鎖状シロキサンブロックの含有量が本組成物中のオルガノポリシロキサンの合計の２０～６０質量％となる量であり、好ましくは、３０～５０質量％となる量である。これは、上記の直鎖状シロキサンブロックの含有量が上記範囲の下限以上であると、得られる硬化物の熱膨張率が著しく低下し、一方、上記範囲の上限以下であると、得られる硬化物の柔軟性と機械的強度が向上するからである。
In the present composition, the content of the component (A-1) is such that the content of the linear siloxane block is 20 to 60% by mass of the total of the organopolysiloxanes in the present composition, preferably 30 to 50% by mass. This is because when the content of the linear siloxane block is equal to or higher than the lower limit of the above range, the thermal expansion coefficient of the resulting cured product is remarkably lowered, whereas when the content is equal to or lower than the upper limit of the above range, the obtained curing is obtained. This is because the flexibility and mechanical strength of the object are improved.
本組成物には、（Ａ）成分として、上記（Ａ－１）成分以外に、（Ａ－２）一分子中に少なくとも２個のアルケニル基を有する直鎖状あるいは分岐鎖状のオルガノポリシロキサンを併用してもよい。（Ａ－２）成分中のアルケニル基としては、ビニル基、アリル基、イソプロペニル基、ブテニル基、ヘキセニル基、シクロヘキセニル基等の炭素数２～６のアルケニル基が例示される。また、（Ａ－２）成分中のアルケニル基以外のケイ素原子に結合する基としては、メチル基、エチル基、プロピル基等の炭素数１～６のアルキル基；フェニル基、トリル基、キシリル基等の炭素数６～１２のアリール基；ベンジル基、フェネチル基等の炭素数７～１２のアラルキル基；３－クロロプロピル基、３,３,３－トリフロロプロピル基等のハロゲン化アルキル基が例示される。
In this composition, as the component (A), in addition to the component (A-1), (A-2) a linear or branched organopolysiloxane having at least two alkenyl groups in one molecule May be used in combination. Examples of the alkenyl group in the component (A-2) include alkenyl groups having 2 to 6 carbon atoms such as vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, and cyclohexenyl group. In addition, the group bonded to the silicon atom other than the alkenyl group in the component (A-2) includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a phenyl group, a tolyl group, and a xylyl group. Aryl groups having 6 to 12 carbon atoms such as benzyl groups, phenethyl groups and other aralkyl groups having 7 to 12 carbon atoms; halogenated alkyl groups such as 3-chloropropyl groups and 3,3,3-trifluoropropyl groups; Illustrated.
（Ａ－２）成分の直鎖状のオルガノポリシロキサンとしては、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサンランダム共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサンランダム共重合体が例示される。
As the linear organopolysiloxane of component (A-2), molecular chain both ends dimethylvinylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane random copolymer, Examples include dimethylsiloxane / methylphenylsiloxane copolymers blocked with dimethylvinylsiloxy groups blocked at both molecular chains, and dimethylsiloxane / methylvinylsiloxane random copolymers blocked with trimethylsiloxy groups blocked at both molecular chains.
また、（Ａ－２）成分の分岐鎖状のオルガノポリシロキサンとしては、式：ＳiＯ４/２で表されるシロキサン単位、一般式：Ｒ７
２Ｒ８ＳiＯ１/２で表されるシロキサン単位、および一般式：Ｒ７
３ＳiＯ１/２で表されるシロキサン単位からなるものが挙げられる。式中、Ｒ７は炭素原子数１～６のアルキル基またはフェニル基であり、前記と同様の基が例示される。また、Ｒ８は炭素原子数２～１０のアルケニル基であり、前記と同様の基が例示される。このオルガノポリシロキサンにおいて、式：ＳiＯ４/２で表されるシロキサン単位１個に対する、一般式：Ｒ７
２Ｒ８ＳiＯ１/２で表されるシロキサン単位および一般式：Ｒ７
３ＳiＯ１/２で表されるシロキサン単位の合計は、０.５～１.５の範囲内であることが好ましい。また、このオルガノポリシロキサンには、分子中のケイ素原子にごく少量の水酸基、アルコキシ基等を結合していてもよい。
The branched chain organopolysiloxane (A-2) includes a siloxane unit represented by the formula: SiO 4/2 and a siloxane unit represented by the general formula: R 7 2 R 8 SiO 1/2. And those composed of siloxane units represented by the general formula: R 7 3 SiO 1/2 . In the formula, R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples thereof are the same groups as described above. R 8 is an alkenyl group having 2 to 10 carbon atoms, and examples thereof are the same groups as described above. In this organopolysiloxane, a siloxane unit represented by the general formula: R 7 2 R 8 SiO 1/2 and a general formula: R 7 3 SiO 1 / with respect to one siloxane unit represented by the formula: SiO 4/2 The total of the siloxane units represented by 2 is preferably in the range of 0.5 to 1.5. The organopolysiloxane may have a very small amount of hydroxyl groups, alkoxy groups, etc. bonded to silicon atoms in the molecule.
（Ａ－２）成分の含有量は特に限定されないが、（Ａ－１）成分中のアルケニル基と本成分中のアルケニル基の合計に対して、本成分中のアルケニル基が多くとも１０モル％となる量であることが好ましい。これは、本成分の含有量が上記範囲の上限以下であると、得られる硬化物の熱膨張率が著しく低下するからである。
The content of the component (A-2) is not particularly limited, but the alkenyl group in this component is at most 10 mol% with respect to the total of the alkenyl group in component (A-1) and the alkenyl group in this component. It is preferable that the amount is as follows. This is because the thermal expansion coefficient of the resulting cured product is significantly reduced when the content of this component is not more than the upper limit of the above range.
また、（Ｂ－１）成分において、式中、Ｒ９は炭素原子数１～６のアルキル基またはフェニル基であり、前記Ｒ７と同様の基が例示される。また、式中、ｎは１０～１００の範囲内の整数であり、好ましくは、２０～８０の範囲内の整数である。これは、ｎが上記範囲の下限以上であると、得られる硬化物の熱膨張率が著しく低下し、一方、上記範囲の上限以下であると、得られる硬化物の機械的強度が向上するからである。
In the component (B-1), R 9 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and examples thereof include the same groups as R 7 . In the formula, n is an integer in the range of 10 to 100, preferably an integer in the range of 20 to 80. This is because when n is not less than the lower limit of the above range, the coefficient of thermal expansion of the obtained cured product is remarkably reduced, while when it is not more than the upper limit of the above range, the mechanical strength of the obtained cured product is improved. It is.
（Ｂ－１）成分としては、上記直鎖状シロキサンブロックのみからなり、その分子鎖両末端が封鎖されたオルガノポリシロキサンが例示される。この分子鎖末端の基としては、水酸基；メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基；トリメチルシロキシ基、ジメチルハイドロジェンシロキシ基、ジメチルフェニルシロキシ基、メチルフェニルハイドロジェンシロキシ基等のオルガノシロキシ基が例示される。また、（Ｂ）成分は、上記直鎖状シロキサンブロック（Ｘ'）と他のシロキサンブロック（Ｙ'）とが連結したブロック共重合体であってもよい。このようなブロック共重合体としては、Ｘ'、Ｙが１個ずつ連結したＸ'Ｙ共重合体、Ｙの両端にＸ'を連結したＸ'ＹＸ'共重合体、Ｘ'、Ｙが交互にｚ回繰り返して連結した（Ｘ'Ｙ）ｚ共重合体が例示される。このシロキサンブロック（Ｙ）としては、前記と同様のものが例示される。なお、このブロック共重合体の分子鎖末端の基としては、水酸基、上記と同様のアルコキシ基、または上記と同様のオルガノシロキシ基が例示される。
As the component (B-1), an organopolysiloxane composed only of the above-mentioned linear siloxane block and blocked at both ends of the molecular chain is exemplified. The group at the end of this molecular chain is a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group; an organosiloxy group such as a trimethylsiloxy group, a dimethylhydrogensiloxy group, a dimethylphenylsiloxy group, or a methylphenylhydrogensiloxy group Is exemplified. The component (B) may be a block copolymer in which the linear siloxane block (X ′) and another siloxane block (Y ′) are linked. As such a block copolymer, an X′Y copolymer in which X ′ and Y are linked one by one, an X′YX ′ copolymer in which X ′ is linked to both ends of Y, and X ′ and Y are alternated And (X′Y) z copolymer linked repeatedly z times. Examples of the siloxane block (Y) are the same as those described above. The group at the end of the molecular chain of this block copolymer is exemplified by a hydroxyl group, an alkoxy group similar to the above, or an organosiloxy group similar to the above.
（Ｂ）成分の含有量は、（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルの範囲内となる量であり、好ましくは、０.５～１０モルの範囲内となる量、０.５～５モルの範囲内となる量、または、０.７～２モルの範囲内となる量である。これは、（Ｂ）成分の含有量が上記範囲の下限以上であると、得られる硬化物の熱膨張率が著しく低下し、一方、上記範囲の上限以下であると、得られる硬化物の機械的強度が向上するからである。
The content of component (B) is such that the silicon-bonded hydrogen atoms in this component are within the range of 0.1 to 10 mol per mol of alkenyl groups in component (A), preferably , An amount in the range of 0.5 to 10 mol, an amount in the range of 0.5 to 5 mol, or an amount in the range of 0.7 to 2 mol. When the content of the component (B) is not less than the lower limit of the above range, the thermal expansion coefficient of the resulting cured product is remarkably reduced, whereas when it is not more than the upper limit of the above range, the resulting cured product is a machine. This is because the mechanical strength is improved.
（Ｃ）成分の酸化チタン粉末および（Ｄ）成分の無機粉末については前記の通りである。また、（Ｅ）成分のオルガノシランおよびオルガノシロキサンについても前記の通りである。
(Titanium oxide powder of component (C) and inorganic powder of component (D) are as described above. Further, the organosilane and organosiloxane of the component (E) are as described above.
本組成物において、（Ｃ）成分および（Ｄ）成分の表面処理をin-situ処理する場合には、（Ａ）成分の一部または全部に（Ｃ）成分および（Ｄ）成分を混合し、次いで、これに（Ｅ）成分を混合して、必要に応じて加熱する方法、（Ａ）成分の一部に（Ｃ）成分を混合し、次いで、これに（Ｅ）成分の一部を混合して、必要に応じて加熱したものと、（Ａ）成分の一部に（Ｄ）成分を混合し、次いで、これに（Ｅ）成分の一部を混合して、必要に応じて加熱したものとを混合する方法が例示される。また、（Ｅ）成分を（Ｃ）成分および（Ｄ）成分と共に本組成物中に単に配合させてもよい。
In the present composition, when the surface treatment of the component (C) and the component (D) is performed in-situ, the component (C) and the component (D) are mixed with part or all of the component (A), Next, a method of mixing the component (E) with this and heating as necessary, mixing the component (C) with a part of the component (A), and then mixing a part of the component (E) with this Then, the component (D) was mixed with part of the component (A) that was heated as necessary, and then part of the component (E) was mixed with this and heated as necessary. The method of mixing things is illustrated. Moreover, you may mix | blend (E) component with this composition with (C) component and (D) component simply.
（Ｆ）成分は、本組成物の硬化反応を促進するためのヒドロシリル化反応用触媒である。（Ｆ）成分としては、白金系触媒、ロジウム系触媒、パラジウム系触媒が例示される。本組成物の硬化を著しく促進できることから、（Ｆ）成分は白金系触媒であることが好ましい。この白金系触媒としては、白金微粉末、塩化白金酸、塩化白金酸のアルコール溶液、白金－アルケニルシロキサン錯体、白金－オレフィン錯体、白金－カルボニル錯体が例示される。このアルケニルシロキサンとしては、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をエチル基、フェニル基等で置換したアルケニルシロキサン、これらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等で置換したアルケニルシロキサンが例示される。
The component (F) is a hydrosilylation reaction catalyst for promoting the curing reaction of the composition. Examples of the component (F) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. The component (F) is preferably a platinum-based catalyst because curing of the composition can be remarkably accelerated. Examples of the platinum catalyst include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like.
また、この白金－アルケニルシロキサン錯体の安定性を向上できることから、この錯体に１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン、１,３－ジアリル－１,１,３,３－テトラメチルジシロキサン、１,３－ジビニル－１,３－ジメチル－１,３－ジフェニルジシロキサン、１,３－ジビニル－１,１,３,３－テトラフェニルジシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン等のアルケニルシロキサンやジメチルシロキサンオリゴマー等のオルガノシロキサンオリゴマーを添加することが好ましい。
Further, since the stability of the platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3, 3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3, It is preferable to add an alkenyl siloxane such as 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as a dimethylsiloxane oligomer.
（Ｆ）成分の含有量は、本組成物のヒドロシリル化反応を促進するに十分な量であれば特に限定されないが、好ましくは、本組成物に対して、本成分中の金属原子が質量単位で０.０１～５００ｐｐｍの範囲内となる量、０.０１～１００ｐｐｍの範囲内となる量、または０.０１～５０ｐｐｍの範囲内となる量である。これは、（Ｆ）成分の含有量が上記範囲の下限以上であると、得られる組成物の硬化が良好であり、一方、上記範囲の上限以下であると、得られる硬化物に着色を生じ難くいからである。
The content of the component (F) is not particularly limited as long as it is an amount sufficient to promote the hydrosilylation reaction of the present composition. Preferably, the metal atom in the present component is in mass units relative to the present composition. In an amount in the range of 0.01 to 500 ppm, an amount in the range of 0.01 to 100 ppm, or an amount in the range of 0.01 to 50 ppm. When the content of the component (F) is not less than the lower limit of the above range, the resulting composition is cured well. On the other hand, when the content is not more than the upper limit of the above range, the resulting cured product is colored. It is difficult.
また、本組成物には、本組成物の硬化速度を適切に制御するために（Ｇ）反応抑制剤を含有してもよい。このような（Ｇ）成分としては、１－エチニルシクロヘキサノール、２－メチル－３－ブチン－２－オール、３,５－ジメチル－１－ヘキシン－３－オール、２－フェニル－３－ブチン－２－オール等のアルキンアルコール；３－メチル－３－ペンテン－１－イン、３,５－ジメチル－３－ヘキセン－１－イン等のエンイン化合物；１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラヘキセニルシクロテトラシロキサン、ベンゾトリアゾールが例示される。（Ｇ）成分の含有量は限定されないが、本組成物に対して、質量単位で１～５,０００ｐｐｍの範囲内であることが好ましい。
In addition, the composition may contain (G) a reaction inhibitor in order to appropriately control the curing rate of the composition. Examples of such component (G) include 1-ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyne- Alkyne alcohols such as 2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole. The content of the component (G) is not limited, but is preferably in the range of 1 to 5,000 ppm by mass with respect to the present composition.
また、本組成物には、硬化途上で接触している基材への接着性を更に向上させるために（Ｈ）接着促進剤を含有してもよい。（Ｈ）成分としては、トリアルコキシシロキシ基（例えば、トリメトキシシロキシ基、トリエトキシシロキシ基）もしくはトリアルコキシシリルアルキル基（例えば、トリメトキシシリルエチル基、トリエトキシシリルエチル基）と、ヒドロシリル基もしくはアルケニル基（例えば、ビニル基、アリル基）を有するオルガノシランまたはケイ素原子数４～２０程度の直鎖状、分岐鎖状または環状のオルガノシロキサンオリゴマー；トリアルコキシシロキシ基もしくはトリアルコキシシリルアルキル基とメタクリロキシアルキル基（例えば、３－メタクリロキシプロピル基）を有するオルガノシランまたはケイ素原子数４～２０程度の直鎖状、分岐鎖状または環状のオルガノシロキサンオリゴマー；トリアルコキシシロキシ基もしくはトリアルコキシシリルアルキル基とエポキシ基結合アルキル基（例えば、３－グリシドキシプロピル基、４－グリシドキシブチル基、２－(３,４－エポキシシクロヘキシル)エチル基、３－(３,４－エポキシシクロヘキシル)プロピル基）を有するオルガノシランまたはケイ素原子数４～２０程度の直鎖状、分岐鎖状または環状のオルガノシロキサンオリゴマー；アミノアルキルトリアルコキシシランとエポキシ基結合アルキルトリアルコキシシランの反応物、エポキシ基含有エチルポリシリケートが例示される。具体的には、ビニルトリメトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、ハイドロジェントリエトキシシラン、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トリエトキシシラン、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－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トリエトキシシラン、３－グリシドキシプロピルトリエトキシシランと３－アミノプロピルトリエトキシシランの反応物、分子鎖両末端水酸基封鎖メチルビニルシロキサンオリゴマーと３－グリシドキシプロピルトリメトキシシランの縮合反応物、分子鎖両末端水酸基封鎖メチルビニルシロキサンオリゴマーと３－メタクリロキシプロピルトリエトキシシランの縮合反応物、トリス（３－トリメトキシシリルプロピル）イソシアヌレートが例示される。（Ｈ）成分の含有量は限定されないが、（Ａ）成分１００質量部に対して、０.１～１０質量部の範囲内であることが好ましい。
In addition, the composition may contain (H) an adhesion promoter in order to further improve the adhesion to the substrate that is in contact with the curing process. As the component (H), a trialkoxysiloxy group (for example, trimethoxysiloxy group, triethoxysiloxy group) or a trialkoxysilylalkyl group (for example, trimethoxysilylethyl group, triethoxysilylethyl group), a hydrosilyl group or Organosilane having an alkenyl group (for example, vinyl group, allyl group) or linear, branched or cyclic organosiloxane oligomer having about 4 to 20 silicon atoms; trialkoxysiloxy group or trialkoxysilylalkyl group and methacrylate Organosilane having a roxyalkyl group (for example, 3-methacryloxypropyl group) or a linear, branched or cyclic organosiloxane oligomer having about 4 to 20 silicon atoms; trialkoxysiloxy group or trial Xylylalkyl group and epoxy group-bonded alkyl group (for example, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxy) (Cyclohexyl) propyl group) organosilane or linear, branched or cyclic organosiloxane oligomer having about 4 to 20 silicon atoms; reaction product of aminoalkyltrialkoxysilane and epoxy group-bonded alkyltrialkoxysilane, epoxy Group-containing ethyl polysilicate is exemplified. Specifically, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-aminopropyltriethoxysilane reactant, molecule Condensation reaction product of hydroxyl chain-blocked methyl vinyl siloxane oligomer and 3-glycidoxypropyltrimethoxysilane at both chain ends, molecular chain both end hydroxyl-blocked methyl vinyl siloxane oligomer and 3-methacryloxypropyl triethoxysilane Condensation reaction product, tris (3-trimethoxysilylpropyl) isocyanurate and the like. The content of component (H) is not limited, but is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of component (A).
本組成物は酸化チタンを高充填するため、他の無機充填剤を用いた時には見られないような高いチキソ性を示す。せん断速度１ｓ－１における２５℃の粘度は１０００Ｐａ・ｓ以下であることが好ましく、せん断速１０ｓ－１における２５℃の粘度は１００Ｐａ・ｓ以下であることが好ましい。これは、上記のような粘度であると、硬化物を形成する際に、様々な生産プロセスに対応しやすいためである。また、使用時に液だれしにくいことから、下記式により求められるチキソ指数の値が５.０以上であることが好ましい。
Since the present composition is highly filled with titanium oxide, it exhibits a high thixotropy that is not observed when other inorganic fillers are used. The viscosity at 25 ° C. at a shear rate of 1 s −1 is preferably 1000 Pa · s or less, and the viscosity at 25 ° C. at a shear rate of 10 s −1 is preferably 100 Pa · s or less. This is because when the viscosity is as described above, it is easy to cope with various production processes when a cured product is formed. Further, since the liquid does not easily drip at the time of use, the value of the thixo index determined by the following formula is preferably 5.0 or more.
また、本組成物には、その塗布作業性を向上させるために、有機溶剤やシリコーンオイル等の希釈剤を配合して、粘度を調整してもよい。この希釈剤は、本組成物の硬化あるいはポストキュア工程において揮発しやすく、硬化物に残存しにくいことから、沸点が１５０～２５０℃の範囲内であるものが好ましい。このような希釈剤としては、出光興産株式会社製のＩＰソルベント等のイソパラフィン系の有機溶剤、ジエチレングリコールモノメチルエーテル等のグリコールエーテル系の有機溶剤、あるいは東レ・ダウコーニング株式会社製のＯＳ－２０等のシリコーン系の溶剤が例示される。この希釈剤の含有量は特に限定されないが、本組成物の硬化あるいはポストキュア工程において揮発しやすく、硬化物に残存しにくいことから、本組成物１００質量部に対して、０.１～１０質量部の範囲内であることが好ましい。
In addition, in order to improve the coating workability, the present composition may be mixed with a diluent such as an organic solvent or silicone oil to adjust the viscosity. This diluent preferably has a boiling point within the range of 150 to 250 ° C. because it is easily volatilized in the curing or post-cure process of the present composition and hardly remains in the cured product. Examples of such diluents include isoparaffinic organic solvents such as IP solvent manufactured by Idemitsu Kosan Co., Ltd., glycol ether organic solvents such as diethylene glycol monomethyl ether, or OS-20 manufactured by Toray Dow Corning Co., Ltd. Silicone solvents are exemplified. The content of this diluent is not particularly limited, but it is easily volatilized in the curing or post-curing process of the present composition and hardly remains in the cured product. Therefore, 0.1 to 10 parts per 100 parts by mass of the present composition. It is preferably within the range of parts by mass.
次に、本発明の硬化物について詳細に説明する。
Next, the cured product of the present invention will be described in detail.
本発明の硬化物は、上記の硬化性シリコーン組成物を硬化してなることを特徴とする。本発明の硬化物の線膨張率は特に限定されないが、２５～２００℃における平均線膨張率が１００ｐｐｍ／℃以下であることが好ましく、さらには５０ｐｐｍ／℃以下であることが好ましい。また、本発明の硬化物は薄膜状でも隠蔽性能が優れることから、それを１００μｍのフィルム状硬化物とした場合のＪＩＳ Ｋ ７３７５：２００８「プラスチック 全光線透過率及び全光線反射率の求め方」における全光線反射率が９０％以上であることが好ましい。
The cured product of the present invention is obtained by curing the above curable silicone composition. The linear expansion coefficient of the cured product of the present invention is not particularly limited, but the average linear expansion coefficient at 25 to 200 ° C. is preferably 100 ppm / ° C. or less, and more preferably 50 ppm / ° C. or less. In addition, since the cured product of the present invention has excellent concealment performance even in a thin film form, JIS K 7375: 2008 “Plastic total light transmittance and total light reflectance calculation method” when it is a 100 μm film cured product The total light reflectance in is preferably 90% or more.
本発明の硬化物の形状は特に限定されないが、支持体上に板状または膜状に形成されたものであってもよい。本発明の硬化物は熱膨張率が極めて低いため、支持体を被覆する塗膜やフィルムとして好適である。
The shape of the cured product of the present invention is not particularly limited, but may be a plate or film formed on the support. Since the thermal expansion coefficient of the cured product of the present invention is extremely low, it is suitable as a coating film or film for coating the support.
このような本発明の硬化物の形成方法としては、上記の硬化性シリコーン組成物を成型工程により、支持体上に膜状又は板状の硬化物を形成する方法や、上記の硬化性シリコーン組成物を塗布工程により、支持体上に膜状又は板状の硬化物を形成する方法が挙げられる。
As a method for forming such a cured product of the present invention, a method of forming a film-like or plate-like cured product on a support by a molding process of the above curable silicone composition, or the above curable silicone composition The method of forming a film-like or plate-like cured product on a support by an application step is mentioned.
この支持体としては、イミド樹脂、ビスマレイミド・トリアジン樹脂、ガラス繊維含有エポキシ樹脂、紙フェノール樹脂、ベークライト、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリアクリロニトリル樹脂、ポリカーボネート樹脂、フッ素樹脂、ポリイミド樹脂、ポリフェニレンサルファイド樹脂、アラミド樹脂、ポリエーテルエーテル樹脂、ポリエーテルイミド樹脂、液晶ポリマー、ポリエーテルサルフォン樹脂、シクロオレフィン樹脂、シリコーンゴム、シリコーン樹脂等の樹脂製支持体；アルミニウム箔、銅箔、ニッケル箔、又は窒化アルミニウム箔等の金属製支持体が例示される。
As this support, imide resin, bismaleimide / triazine resin, glass fiber-containing epoxy resin, paper phenol resin, bakelite, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacrylonitrile resin, polycarbonate resin, fluororesin, polyimide resin, polyphenylene Sulfide resin, aramid resin, polyether ether resin, polyether imide resin, liquid crystal polymer, polyether sulfone resin, cycloolefin resin, silicone rubber, silicone resin and other resin supports; aluminum foil, copper foil, nickel foil, Or metal supports, such as aluminum nitride foil, are illustrated.
支持体上に硬化物を形成する方法としては、成型工程、塗布工程が例示され、成型工程としては金型を用いたプレス成型や圧縮成型が例示され、塗布工程としては、スクリーン印刷、バーコーター、ロールコーター、リバースコーター、グラビアコーター、エアナイフコーター、スプレーコーター、カーテンコーターが例示され、特に、薄膜に塗工する場合には、高精度のオフセットコーター、多段ロールコーター等の公知の塗布方法を用いることができる。
Examples of methods for forming a cured product on the support include a molding process and a coating process. Examples of the molding process include press molding and compression molding using a mold. Examples of the coating process include screen printing and bar coater. , Roll coater, reverse coater, gravure coater, air knife coater, spray coater, curtain coater are exemplified, and in particular, when coating on a thin film, a known coating method such as a high-precision offset coater or a multi-stage roll coater is used. be able to.
本発明の硬化物は前記の様な方法により支持体上に板状又は膜状で形成されることが好ましい。本発明の硬化物は高い光反射性を示すため、光半導体装置に用いられる光反射材として利用できる。特に、本発明の材料を光半導体装置に用いる場合、チップオンボードタイプ（ＣＯＢ）の光半導体装置に使用するのが好適である。
The cured product of the present invention is preferably formed on the support in the form of a plate or film by the method as described above. Since the hardened | cured material of this invention shows high light reflectivity, it can utilize as a light reflection material used for an optical semiconductor device. In particular, when the material of the present invention is used for an optical semiconductor device, it is preferably used for a chip-on-board type (COB) optical semiconductor device.
次に、本発明の光半導体装置について詳細に説明する。
Next, the optical semiconductor device of the present invention will be described in detail.
本発明の光半導体装置は、上記組成物の硬化物からなる光反射材を有することを特徴とする。このような本発明の光半導体装置を図１および図２を用いて詳細に説明する。
The optical semiconductor device of the present invention has a light reflecting material made of a cured product of the above composition. Such an optical semiconductor device of the present invention will be described in detail with reference to FIGS.
図１は、本発明の光半導体装置の一例であるチップオンボード（ＣＯＢ）型の光半導体装置の断面図を示す。図１のＣＯＢ型光半導体装置では、光半導体素子１がＣＯＢ用の基板２にダイボンドにより搭載され、この光半導体素子１と回路３、４とをボンディングワイヤ５により電気的に接続している。また、基板２上の光半導体素子１周囲には、光半導体素子１から出る光を効率よく反射するように光反射材６が形成されている。
FIG. 1 shows a cross-sectional view of a chip-on-board (COB) type optical semiconductor device which is an example of the optical semiconductor device of the present invention. In the COB type optical semiconductor device of FIG. 1, an optical semiconductor element 1 is mounted on a COB substrate 2 by die bonding, and the optical semiconductor element 1 and circuits 3 and 4 are electrically connected by a bonding wire 5. A light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 so as to efficiently reflect light emitted from the optical semiconductor element 1.
図２は、本発明の光半導体装置の一例である他のチップオンボード（ＣＯＢ）型の光半導体装置の断面図を示す。図２のＣＯＢ型光半導体装置では、光半導体素子１がＣＯＢ用の基板２上の回路３、４とボンディングパッドにより電気的に接続されている。また、基板２上の光半導体素子１周囲には、光半導体素子１から出る光を効率よく反射するように光反射材６が形成されている。
FIG. 2 shows a sectional view of another chip-on-board (COB) type optical semiconductor device which is an example of the optical semiconductor device of the present invention. In the COB type optical semiconductor device of FIG. 2, the optical semiconductor element 1 is electrically connected to the circuits 3 and 4 on the COB substrate 2 by bonding pads. A light reflecting material 6 is formed around the optical semiconductor element 1 on the substrate 2 so as to efficiently reflect light emitted from the optical semiconductor element 1.
図１および図２の光半導体装置において、基板２はアルミニウムや銅等の金属製基板であってもよい、その金属製基板の表面に絶縁層（図示せず）を介して回路３、４が形成されている。また、基板２として非金属製基板を用いる場合には、絶縁層を形成する必要はない。このような非金属製基板としては、ガラスエポキシ基板、ポリブチレンテレフタレート（ＰＢＴ）基板、ポリイミド基板、ポリエステル基板、窒化アルミニウム基板、窒化ホウ素基板、窒化ケイ素基板、アルミナセラミックス基板、ガラス基板、フレキシブルガラス基板が例示され。さらには、この基板２として、絶縁樹脂層を有するアルミニウム製基板または銅製基板からなるハイブリッド基板や、プリント配線したシリコン基板、炭化ケイ素基板、サファイア基板を用いることもできる。
In the optical semiconductor device of FIGS. 1 and 2, the substrate 2 may be a metal substrate such as aluminum or copper, and the circuits 3 and 4 are formed on the surface of the metal substrate via an insulating layer (not shown). Is formed. Further, when a non-metallic substrate is used as the substrate 2, it is not necessary to form an insulating layer. Such non-metallic substrates include glass epoxy substrates, polybutylene terephthalate (PBT) substrates, polyimide substrates, polyester substrates, aluminum nitride substrates, boron nitride substrates, silicon nitride substrates, alumina ceramic substrates, glass substrates, flexible glass substrates. Is illustrated. Furthermore, as the substrate 2, a hybrid substrate made of an aluminum substrate or a copper substrate having an insulating resin layer, a printed wiring silicon substrate, a silicon carbide substrate, or a sapphire substrate can be used.
この回路３、４は、電気伝導性の高い、銀、銅、およびアルミニウムからなる群から選ばれる少なくとも一種の金属、または、銀、銅、およびアルミニウムからなる群から選ばれる少なくとも一種を含む合金が用いられる。さらに、この基板２には、光半導体素子１を搭載する部分を露出するように光反射材６が形成されていることが好ましい。
The circuits 3 and 4 are made of at least one metal selected from the group consisting of silver, copper, and aluminum having high electrical conductivity, or an alloy containing at least one selected from the group consisting of silver, copper, and aluminum. Used. Further, it is preferable that a light reflecting material 6 is formed on the substrate 2 so as to expose a portion on which the optical semiconductor element 1 is mounted.
図１および図２では、光半導体素子１および光反射材６が封止材７により封止されているが、光半導体素子１のみを封止材７でドーム状に封止してもよい。なお、図１および図２では、光半導体素子１が基板２上に１個のみ図示されているが、この光半導体素子１を基板２上に複数搭載してもよい。
1 and 2, the optical semiconductor element 1 and the light reflecting material 6 are sealed with the sealing material 7, but only the optical semiconductor element 1 may be sealed with the sealing material 7 in a dome shape. In FIG. 1 and FIG. 2, only one optical semiconductor element 1 is shown on the substrate 2, but a plurality of optical semiconductor elements 1 may be mounted on the substrate 2.
本発明の硬化性シリコーン組成物、硬化物、および光半導体装置を実施例により詳細に説明する。なお、実施例中、粘度は２５℃における各シェアレートでの値である。また、式中、Ｍe、Ｐh、およびＶiは、それぞれメチル基、フェニル基、およびビニル基を表す。
Examples The curable silicone composition, cured product, and optical semiconductor device of the present invention will be described in detail with reference to examples. In addition, in an Example, a viscosity is a value in each share rate in 25 degreeC. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
また、硬化物の硬さ、曲げ強さ、線膨張率、金属に対する接着力、および全光線反射率を次のようにして測定した。
Also, the hardness, bending strength, linear expansion coefficient, adhesion to metal, and total light reflectance of the cured product were measured as follows.
［硬化物の硬さ］
硬化性シリコーン組成物を１５０℃で２時間加熱して硬化物を作製した。この硬化物の硬さを、ＪＩＳ Ｋ ７２１５-1986「プラスチックのデュロメータ硬さ試験方法」に規定のタイプＤデュロメータにより測定した。 [Hardness of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The hardness of the cured product was measured with a type D durometer specified in JIS K 7215-1986 “Method for testing the durometer hardness of plastics”.
硬化性シリコーン組成物を１５０℃で２時間加熱して硬化物を作製した。この硬化物の硬さを、ＪＩＳ Ｋ ７２１５-1986「プラスチックのデュロメータ硬さ試験方法」に規定のタイプＤデュロメータにより測定した。 [Hardness of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The hardness of the cured product was measured with a type D durometer specified in JIS K 7215-1986 “Method for testing the durometer hardness of plastics”.
［硬化物の曲げ強度］
硬化性シリコーン組成物を１５０℃で２時間加熱して硬化物を作製した。この硬化物の曲げ強度を、ＪＩＳ Ｋ ６９１１-1995「熱硬化性プラスチック一般試験方法」に規定の方法により測定した。 [Bending strength of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The bending strength of the cured product was measured by the method specified in JIS K 6911-1995 “General Test Method for Thermosetting Plastics”.
硬化性シリコーン組成物を１５０℃で２時間加熱して硬化物を作製した。この硬化物の曲げ強度を、ＪＩＳ Ｋ ６９１１-1995「熱硬化性プラスチック一般試験方法」に規定の方法により測定した。 [Bending strength of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The bending strength of the cured product was measured by the method specified in JIS K 6911-1995 “General Test Method for Thermosetting Plastics”.
［硬化物の線膨張率］
硬化性シリコーン組成物を１５０℃で２時間加熱して硬化物を作製した。この硬化物の線膨張率を、ＪＩＳ Ｋ ７１９７-1991「プラスチックの熱機械分析による線膨張率の試験方法」に規定の方法により測定した。 [Linear expansion coefficient of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The linear expansion coefficient of the cured product was measured by a method specified in JIS K 7197-1991 “Test method for linear expansion coefficient by thermomechanical analysis of plastics”.
硬化性シリコーン組成物を１５０℃で２時間加熱して硬化物を作製した。この硬化物の線膨張率を、ＪＩＳ Ｋ ７１９７-1991「プラスチックの熱機械分析による線膨張率の試験方法」に規定の方法により測定した。 [Linear expansion coefficient of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The linear expansion coefficient of the cured product was measured by a method specified in JIS K 7197-1991 “Test method for linear expansion coefficient by thermomechanical analysis of plastics”.
［硬化物の全光線反射率］
硬化性シリコーン組成物を１５０℃で２時間加熱して、厚さ１００μｍの硬化物を作製した。この硬化物の全光線反射率を、ＪＩＳ Ｋ ７３７５：２００８「プラスチック 全光線透過率及び全光線反射率の求め方」に規定の方法により測定した。 [Total light reflectance of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product having a thickness of 100 μm. The total light reflectance of this cured product was measured by the method defined in JIS K 7375: 2008 “Plastic Total Light Transmittance and Total Light Reflectance Determination Method”.
硬化性シリコーン組成物を１５０℃で２時間加熱して、厚さ１００μｍの硬化物を作製した。この硬化物の全光線反射率を、ＪＩＳ Ｋ ７３７５：２００８「プラスチック 全光線透過率及び全光線反射率の求め方」に規定の方法により測定した。 [Total light reflectance of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product having a thickness of 100 μm. The total light reflectance of this cured product was measured by the method defined in JIS K 7375: 2008 “Plastic Total Light Transmittance and Total Light Reflectance Determination Method”.
［硬化物の金属に対する接着力］
２５ｍｍ×７５ｍｍのアルミニウム板上に、硬化性シリコーン組成物をディスペンサーにより約１００ｍｇづつを５ヶ所に塗布した。次に、この組成物に厚さ１ｍｍの６ｍｍ角のアルミニウム製チップを被せ、１ｋｇの板により圧着した状態で、１５０℃で２時間加熱して硬化させた。その後、室温に冷却し、シェア強度測定装置（西進商事株式会社製のボンドテスターＳＳ－１００ＫＰ）によりダイシェア強度を測定した。また、上記と同様にして、銅板に対する銅板製チップのダイシェア強度についても測定した。 [Adhesive strength of cured product to metal]
About 100 mg of the curable silicone composition was applied to five locations on a 25 mm × 75 mm aluminum plate by a dispenser. Next, the composition was covered with a 6 mm square aluminum chip having a thickness of 1 mm, and cured by heating at 150 ° C. for 2 hours in a state where the chip was pressed by a 1 kg plate. Thereafter, the product was cooled to room temperature, and the die shear strength was measured with a shear strength measuring device (Bond Tester SS-100KP manufactured by Nishishin Shoji Co., Ltd.). In addition, the die shear strength of the copper plate chip relative to the copper plate was also measured in the same manner as described above.
２５ｍｍ×７５ｍｍのアルミニウム板上に、硬化性シリコーン組成物をディスペンサーにより約１００ｍｇづつを５ヶ所に塗布した。次に、この組成物に厚さ１ｍｍの６ｍｍ角のアルミニウム製チップを被せ、１ｋｇの板により圧着した状態で、１５０℃で２時間加熱して硬化させた。その後、室温に冷却し、シェア強度測定装置（西進商事株式会社製のボンドテスターＳＳ－１００ＫＰ）によりダイシェア強度を測定した。また、上記と同様にして、銅板に対する銅板製チップのダイシェア強度についても測定した。 [Adhesive strength of cured product to metal]
About 100 mg of the curable silicone composition was applied to five locations on a 25 mm × 75 mm aluminum plate by a dispenser. Next, the composition was covered with a 6 mm square aluminum chip having a thickness of 1 mm, and cured by heating at 150 ° C. for 2 hours in a state where the chip was pressed by a 1 kg plate. Thereafter, the product was cooled to room temperature, and the die shear strength was measured with a shear strength measuring device (Bond Tester SS-100KP manufactured by Nishishin Shoji Co., Ltd.). In addition, the die shear strength of the copper plate chip relative to the copper plate was also measured in the same manner as described above.
［実施例１］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ２１.８質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 1]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), and an average particle size of 15 μm 21.8 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure. A silicone base was prepared by kneading while heating.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ２１.８質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 1]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), and an average particle size of 15 μm 21.8 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure. A silicone base was prepared by kneading while heating.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（Ｉ）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 moles per 1 mole of vinyl groups in the polysiloxane), and the viscosity is 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A curable silicone composition (I) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the amount of platinum atoms with respect to the present composition is 3.5 ppm by mass). ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（Ｉ）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 moles per 1 mole of vinyl groups in the polysiloxane), and the viscosity is 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A curable silicone composition (I) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the amount of platinum atoms with respect to the present composition is 3.5 ppm by mass). ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
［実施例２］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ５１.８質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ３０質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 2]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
4 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by 51.8 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, average particle A spherical silica having a diameter of 15 μm (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.), 30 parts by mass, and a viscosity of 24 mPa · s, a formula:
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ５１.８質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ３０質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 2]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
4 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by 51.8 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, average particle A spherical silica having a diameter of 15 μm (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.), 30 parts by mass, and a viscosity of 24 mPa · s, a formula:
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（II）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), andplatinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Curable silicone composition (II) was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（II）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and
［実施例３］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ６質量部、ｎ－デシルトリメトキシシラン １質量部、および粘度１２５ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 3]
formula:
- (MeViSiO 2/2) 20 -
5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), an average particle size of 15 μm Of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 6 parts by mass, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa · s.
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ６質量部、ｎ－デシルトリメトキシシラン １質量部、および粘度１２５ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 3]
formula:
- (MeViSiO 2/2) 20 -
5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), an average particle size of 15 μm Of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 6 parts by mass, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa · s.
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（III）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.9 parts by mass of a methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by formula (II) and having both ends of the molecular chain blocked with trimethyl siloxy groups (methyl vinyl polysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa ·s 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and platinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Curable silicone composition (III) was prepared. In addition, content of said linear methylvinylsiloxane block is 34.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（III）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.9 parts by mass of a methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by formula (II) and having both ends of the molecular chain blocked with trimethyl siloxy groups (methyl vinyl polysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa ·
［実施例４］
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.０質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １０質量部、ｎ－オクチルトリエトキシシラン ３質量部、および粘度２２ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)２３Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン １質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 4]
formula:
-(MeViSiO 2/2 ) 6-
4.2 parts by mass of a methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 4.0 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry) 72 parts by mass, average particle size: 15 μm 10 parts by mass of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 3 parts by mass of n-octyltriethoxysilane, and a viscosity of 22 mPa · s, the formula:
Me 3 SiO (Me 2 SiO) 23 Si (OMe) 3
1 part by weight of dimethylpolysiloxane in which one end of a molecular chain represented by the formula is blocked with a trimethylsiloxy group and the other end of a molecular chain is blocked with a trimethoxysiloxy group, is mixed at room temperature, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.０質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １０質量部、ｎ－オクチルトリエトキシシラン ３質量部、および粘度２２ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)２３Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン １質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 4]
formula:
-(MeViSiO 2/2 ) 6-
4.2 parts by mass of a methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 4.0 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry) 72 parts by mass, average particle size: 15 μm 10 parts by mass of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 3 parts by mass of n-octyltriethoxysilane, and a viscosity of 22 mPa · s, the formula:
Me 3 SiO (Me 2 SiO) 23 Si (OMe) 3
1 part by weight of dimethylpolysiloxane in which one end of a molecular chain represented by the formula is blocked with a trimethylsiloxy group and the other end of a molecular chain is blocked with a trimethoxysiloxy group, is mixed at room temperature, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
次に、室温下、このシリコーンベースに、式：
－(ＭｅＨＳiＯ２/２)２０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン ４.５質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.３モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.５質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で３００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（IV）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.５質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 20 -
4.5 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and molecular chain in silicone base) Both ends of dimethylvinylsiloxy group-blocked dimethylpolysiloxane in a total amount of 1 mol of vinyl groups, the amount of silicon atom-bonded hydrogen atoms in this component is 1.3 mol), both ends of the molecular chain with a viscosity of 20 mPa · s 1.5 parts by mass of a 1: 2 mass condensation reaction product of a hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) 1,3-divinyl of platinum after mixing with the product in an amount of 300 ppm by mass) 1,1,3,3-tetramethyldisiloxane in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (with respect to this composition, platinum atoms are 5 ppm by mass) Curable silicone composition (IV) was prepared. In addition, content of said linear methylvinylsiloxane block is 34.5 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭｅＨＳiＯ２/２)２０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン ４.５質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.３モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.５質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で３００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（IV）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.５質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 20 -
4.5 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and molecular chain in silicone base) Both ends of dimethylvinylsiloxy group-blocked dimethylpolysiloxane in a total amount of 1 mol of vinyl groups, the amount of silicon atom-bonded hydrogen atoms in this component is 1.3 mol), both ends of the molecular chain with a viscosity of 20 mPa · s 1.5 parts by mass of a 1: 2 mass condensation reaction product of a hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) 1,3-divinyl of platinum after mixing with the product in an amount of 300 ppm by mass) 1,1,3,3-tetramethyldisiloxane in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (with respect to this composition, platinum atoms are 5 ppm by mass) Curable silicone composition (IV) was prepared. In addition, content of said linear methylvinylsiloxane block is 34.5 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
［実施例５］
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)４６ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １７質量部、ｎ－オクチルトリエトキシシラン ２質量部、および粘度１２５ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 5]
formula:
-(MeViSiO 2/2 ) 6-
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 46 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by 4.1 parts by weight, titanium oxide having an average primary particle diameter of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), 65 parts by weight, and an average particle diameter of 15 μm Spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 17 parts by mass, n-octyltriethoxysilane 2 parts by mass, and viscosity 125 mPa · s, formula:
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
2 parts by weight of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the formula, and blocked with a trimethoxysiloxy group at the other end of the molecular chain, and mixed at room temperature, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)４６ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １７質量部、ｎ－オクチルトリエトキシシラン ２質量部、および粘度１２５ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 5]
formula:
-(MeViSiO 2/2 ) 6-
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 46 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by 4.1 parts by weight, titanium oxide having an average primary particle diameter of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), 65 parts by weight, and an average particle diameter of 15 μm Spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 17 parts by mass, n-
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
2 parts by weight of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the formula, and blocked with a trimethoxysiloxy group at the other end of the molecular chain, and mixed at room temperature, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（Ｖ）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.７質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), andplatinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (amount of platinum atoms in mass units of 3 ppm with respect to the composition) Were mixed to prepare a curable silicone composition (V). In addition, content of said linear methylvinylsiloxane block is 34.7 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（Ｖ）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.７質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and
［実施例６］
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロック５個と式：
－(ＭeＰhＳiＯ)６－
で表される直鎖状メチルフェニルシロキサンブロック５個が交互に連結し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルシロキサン・メチルフェニルシロキサンブロック共重合体 ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ８質量部、ｎ－デシルトリメトキシシラン ２質量部、および粘度２２ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)２３Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 6]
formula:
-(MeViSiO 2/2 ) 6-
5 linear methylvinylsiloxane blocks represented by the formula:
-(MePhSiO) 6-
5.8 parts by mass of a methylvinylsiloxane / methylphenylsiloxane block copolymer in which five linear methylphenylsiloxane blocks represented by the formula are alternately linked and both ends of the molecular chain are blocked with trimethylsiloxy groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain represented by the formula: 70 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), 15 μm in average particle size Spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 8 parts by mass, n-decyltrimethoxysilane 2 parts by mass, and a viscosity of 22 mPa · s.
Me 3 SiO (Me 2 SiO) 23 Si (OMe) 3
2 parts by weight of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the formula, and blocked with a trimethoxysiloxy group at the other end of the molecular chain, and mixed at room temperature, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロック５個と式：
－(ＭeＰhＳiＯ)６－
で表される直鎖状メチルフェニルシロキサンブロック５個が交互に連結し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルビニルシロキサン・メチルフェニルシロキサンブロック共重合体 ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ８質量部、ｎ－デシルトリメトキシシラン ２質量部、および粘度２２ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)２３Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 6]
formula:
-(MeViSiO 2/2 ) 6-
5 linear methylvinylsiloxane blocks represented by the formula:
-(MePhSiO) 6-
5.8 parts by mass of a methylvinylsiloxane / methylphenylsiloxane block copolymer in which five linear methylphenylsiloxane blocks represented by the formula are alternately linked and both ends of the molecular chain are blocked with trimethylsiloxy groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain represented by the formula: 70 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), 15 μm in average particle size Spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 8 parts by mass, n-
Me 3 SiO (Me 2 SiO) 23 Si (OMe) 3
2 parts by weight of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the formula, and blocked with a trimethoxysiloxy group at the other end of the molecular chain, and mixed at room temperature, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
次に、室温下、このシリコーンベースに、式：
－(ＭｅＨＳiＯ２/２)２０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルシロキサン・メチルフェニルシロキサンブロック共重合体と分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（VI）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 20 -
5.9 parts by mass of methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by the formula and having both molecular chain ends blocked with trimethylsiloxy groups (methyl vinyl siloxane / methyl phenyl siloxane in silicone base) Viscosity: 20 mPa) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 mol with respect to a total of 1 mol of vinyl groups in the block copolymer and both ends of the molecular chain dimethylvinylsiloxy-blocked dimethylpolysiloxane. 1 part by weight of a condensation reaction of 1: 2 in a mass ratio of s dimethylsiloxane with both ends hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1- Cyclohexanol (in an amount of 200 ppm by mass with respect to the composition) After mixing, a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum in a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (in this composition) On the other hand, a curable silicone composition (VI) was prepared by mixing platinum atoms in an amount of 3 ppm by mass). In addition, content of said linear methylvinylsiloxane block is 34.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭｅＨＳiＯ２/２)２０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルシロキサン・メチルフェニルシロキサンブロック共重合体と分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（VI）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 20 -
5.9 parts by mass of methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by the formula and having both molecular chain ends blocked with trimethylsiloxy groups (methyl vinyl siloxane / methyl phenyl siloxane in silicone base) Viscosity: 20 mPa) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 mol with respect to a total of 1 mol of vinyl groups in the block copolymer and both ends of the molecular chain dimethylvinylsiloxy-blocked dimethylpolysiloxane. 1 part by weight of a condensation reaction of 1: 2 in a mass ratio of s dimethylsiloxane with both ends hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1- Cyclohexanol (in an amount of 200 ppm by mass with respect to the composition) After mixing, a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution of platinum in a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (in this composition) On the other hand, a curable silicone composition (VI) was prepared by mixing platinum atoms in an amount of 3 ppm by mass). In addition, content of said linear methylvinylsiloxane block is 34.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
［実施例７］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ２１.８質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 7]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), and an average particle size of 15 μm 21.8 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure. A silicone base was prepared by kneading while heating.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ２１.８質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 7]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), and an average particle size of 15 μm 21.8 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure. A silicone base was prepared by kneading while heating.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合し、最後に、イソパラフィン系溶剤（出光興産社製のＩＰソルベント１６２０、沸点＝１６２～２０２℃）を本組成物の固形分量が９５質量％となるように混合して、硬化性シリコーン組成物（VII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), andplatinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Finally, an isoparaffinic solvent (IP Solvent 1620 manufactured by Idemitsu Kosan Co., Ltd., boiling point = 162 to 202 ° C.) is mixed so that the solid content of the composition is 95% by mass, and then cured. Silicone composition (VII) was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合し、最後に、イソパラフィン系溶剤（出光興産社製のＩＰソルベント１６２０、沸点＝１６２～２０２℃）を本組成物の固形分量が９５質量％となるように混合して、硬化性シリコーン組成物（VII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and
［実施例８］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ６質量部、ｎ－デシルトリメトキシシラン １質量部、および粘度１２５ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 8]
formula:
- (MeViSiO 2/2) 20 -
5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), an average particle size of 15 μm Of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 6 parts by mass, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa · s.
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ６質量部、ｎ－デシルトリメトキシシラン １質量部、および粘度１２５ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 8]
formula:
- (MeViSiO 2/2) 20 -
5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), an average particle size of 15 μm Of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron), 6 parts by mass, 1 part by mass of n-decyltrimethoxysilane, and a viscosity of 125 mPa · s.
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
After putting 3 parts by mass of dimethylpolysiloxane blocked with a trimethylsiloxy group at one end of the molecular chain represented by the following formula, and mixing at room temperature with 3 parts by mass of dimethylpolysiloxane blocked with a trimethoxysiloxy group at the other end, A silicone base was prepared by kneading while heating to 150 ° C. under reduced pressure.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合し、最後に、シリコーン系溶剤（東レ・ダウコーング社製のＯＳ－２０、沸点＝１５２℃）を本組成物の固形分量が９５質量％となるように混合して、硬化性シリコーン組成物（VIII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.9 parts by mass of a methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by formula (II) and having both ends of the molecular chain blocked with trimethyl siloxy groups (methyl vinyl polysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa ·s 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and platinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Finally, a silicone-based solvent (OS-20 manufactured by Toray Dow Corning Co., Ltd., boiling point = 152 ° C.) was mixed so that the solid content of the composition was 95% by mass, and curable silicone Composition (VIII) was prepared. In addition, content of said linear methylvinylsiloxane block is 34.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合し、最後に、シリコーン系溶剤（東レ・ダウコーング社製のＯＳ－２０、沸点＝１５２℃）を本組成物の固形分量が９５質量％となるように混合して、硬化性シリコーン組成物（VIII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.9 parts by mass of a methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by formula (II) and having both ends of the molecular chain blocked with trimethyl siloxy groups (methyl vinyl polysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa ·
［実施例９］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ７.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン １６.６質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ５５.０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ７質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 9]
formula:
- (MeViSiO 2/2) 20 -
7.2 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
16.6 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 55.0 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm,average particle 7 parts by mass of spherical silica with a diameter of 15 μm (HS-202 manufactured by Nippon Steel Materials Micron), and a viscosity of 24 mPa · s, the formula:
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ７.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン １６.６質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ５５.０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ７質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Example 9]
formula:
- (MeViSiO 2/2) 20 -
7.2 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
16.6 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 55.0 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm,
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ８.２質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 ２質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（IX）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の２３.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
8.2 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and molecule in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 2 parts by mass of a condensation reaction product having a mass ratio of 1: 2 between a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), andplatinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Curable silicone composition (IX) was prepared. In addition, content of said linear methylvinylsiloxane block is 23.4 mass% of the sum total of the organopolysiloxane in this composition. The curable silicone composition and the properties of the cured product are shown in Table 1.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ８.２質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 ２質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（IX）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の２３.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表１に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
8.2 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and molecule in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 2 parts by mass of a condensation reaction product having a mass ratio of 1: 2 between a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and
［比較例１］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ２５質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ５６.３質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 1]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), 25 parts by mass, and an average particle size of 15 μm 56.3 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then reduced to 150 ° C. under reduced pressure. A silicone base was prepared by kneading while heating.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ２５質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ５６.３質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 1]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), 25 parts by mass, and an average particle size of 15 μm 56.3 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then reduced to 150 ° C. under reduced pressure. A silicone base was prepared by kneading while heating.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（Ｘ）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 moles per mole of vinyl groups in the polysiloxane), and the molecular chain both ends hydroxyl-blocked dimethylsiloxane and methylvinylsiloxane with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (in which the amount of platinum atoms is 3.5 ppm in terms of mass unit) is mixed with the curable silicone composition (X ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（Ｘ）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 moles per mole of vinyl groups in the polysiloxane), and the molecular chain both ends hydroxyl-blocked dimethylsiloxane and methylvinylsiloxane with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (in which the amount of platinum atoms is 3.5 ppm in terms of mass unit) is mixed with the curable silicone composition (X ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
［比較例２］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.４４μｍのアルミナ（住友化学製のＡＥＳ－１２） ６０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ２１.８質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 2]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, alumina having an average primary particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.) 21.8 parts by weight of silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure. While kneading, a silicone base was prepared.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.４４μｍのアルミナ（住友化学製のＡＥＳ－１２） ６０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ２１.８質量部、およびｎ－オクチルトリエトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 2]
formula:
- (MeViSiO 2/2) 20 -
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 4.1 parts by mass, alumina having an average primary particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.) 21.8 parts by weight of silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by weight of n-octyltriethoxysilane were put into a loss mixer, mixed at room temperature, and then heated to 150 ° C. under reduced pressure. While kneading, a silicone base was prepared.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XI）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 moles per mole of vinyl groups in the polysiloxane), and the molecular chain both ends hydroxyl-blocked dimethylsiloxane and methylvinylsiloxane with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A curable silicone composition (XI) was prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (with respect to the present composition, an amount in which platinum atoms are 3.5 ppm by mass). ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XI）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３２.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.5 moles per mole of vinyl groups in the polysiloxane), and the molecular chain both ends hydroxyl-blocked dimethylsiloxane and methylvinylsiloxane with a viscosity of 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A curable silicone composition (XI) was prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (with respect to the present composition, an amount in which platinum atoms are 3.5 ppm by mass). ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 32.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
［比較例３］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７８質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 3]
formula:
- (MeViSiO 2/2) 20 -
5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 78 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), and a viscosity of 24 mPa · s is the formula:
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ５.８質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２４μｍの酸化チタン（石原産業製のタイペークＲ－６３０） ７８質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 3]
formula:
- (MeViSiO 2/2) 20 -
5.8 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by: 78 parts by mass of titanium oxide having an average primary particle size of 0.24 μm (Taipaque R-630 manufactured by Ishihara Sangyo), and a viscosity of 24 mPa · s is the formula:
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.9 parts by mass of a methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by formula (II) and having both ends of the molecular chain blocked with trimethyl siloxy groups (methyl vinyl polysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa ·s 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and platinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Curable silicone composition (XII) was prepared. In addition, content of said linear methylvinylsiloxane block is 34.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.９質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.9 parts by mass of a methyl hydrogen polysiloxane having a linear methyl hydrogen siloxane block represented by formula (II) and having both ends of the molecular chain blocked with trimethyl siloxy groups (methyl vinyl polysiloxane and molecules in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa ·
［比較例４］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ７.６質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ７.７質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ５６質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ４質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ５.２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 4]
formula:
- (MeViSiO 2/2) 20 -
7.6 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
7.7 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain represented by the formula: 56 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, average particle size of 15μm 4 parts by weight of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron) and a viscosity of 24 mPa · s, the formula:
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
5.2 parts by mass of dimethylpolysiloxane in which one end of the molecular chain represented by the formula is blocked with a trimethylsiloxy group and the other end of the molecular chain is blocked with a trimethoxysiloxy group was put into a loss mixer and mixed at room temperature. Thereafter, the mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ７.６質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ７.７質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ５６質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ４質量部、および粘度２４ｍＰａ・ｓである、式：
Ｍe３ＳiＯ(Ｍe２ＳiＯ)１１０Ｓi(ＯＭe)３
で表される分子鎖片末端がトリメチルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ５.２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 4]
formula:
- (MeViSiO 2/2) 20 -
7.6 parts by mass of a methylvinylpolysiloxane having a linear methylvinylsiloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
7.7 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain represented by the formula: 56 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, average particle size of 15
Me 3 SiO (Me 2 SiO) 110 Si (OMe) 3
5.2 parts by mass of dimethylpolysiloxane in which one end of the molecular chain represented by the formula is blocked with a trimethylsiloxy group and the other end of the molecular chain is blocked with a trimethoxysiloxy group was put into a loss mixer and mixed at room temperature. Thereafter, the mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ７.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.３質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XIII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
7.7 parts by mass of a methyl hydrogen polysiloxane having both ends of a molecular chain blocked with a trimethyl siloxy group (methyl vinyl polysiloxane and molecules in a silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa · s 1.3 parts by mass of a condensation reaction product having a mass ratio of 1: 2 between a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol 1,3-divinyl in platinum after mixing with the composition in an amount of 200 ppm by mass) 1,1,3,3-tetramethyldisiloxane in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the platinum atom is 3.5 ppm by mass relative to the composition) ) Was mixed to prepare a curable silicone composition (XIII). In addition, content of said linear methylvinylsiloxane block is 34.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ７.７質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.４モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.３質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XIII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
7.7 parts by mass of a methyl hydrogen polysiloxane having both ends of a molecular chain blocked with a trimethyl siloxy group (methyl vinyl polysiloxane and molecules in a silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.4 mol of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mol of vinyl groups), both molecular chains with a viscosity of 20 mPa · s 1.3 parts by mass of a condensation reaction product having a mass ratio of 1: 2 between a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-
［比較例５］
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １０質量部、およびメチルトリメトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 5]
formula:
-(MeViSiO 2/2 ) 6-
4.2 parts by mass of a methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
4 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), spherical with an average particle size of 15 μm 10 parts by mass of silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by mass of methyltrimethoxysilane were put into a loss mixer, mixed at room temperature, and then kneaded while heating to 150 ° C. under reduced pressure. A silicone base was prepared.
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ７２質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １０質量部、およびメチルトリメトキシシラン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 5]
formula:
-(MeViSiO 2/2 ) 6-
4.2 parts by mass of a methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
4 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 72 parts by mass of titanium oxide having an average primary particle size of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), spherical with an average particle size of 15 μm 10 parts by mass of silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) and 4 parts by mass of methyltrimethoxysilane were put into a loss mixer, mixed at room temperature, and then kneaded while heating to 150 ° C. under reduced pressure. A silicone base was prepared.
次に、室温下、このシリコーンベースに、式：
－(ＭｅＨＳiＯ２/２)２０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン ４.５質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.３モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.５質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で３００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XIV）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.５質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 20 -
And 4.5 parts by mass of methylhydrogenpolysiloxane having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and dimethylpolysiloxane in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.3 moles per 1 mole of vinyl groups in the siloxane), and the molecular chain both-ends hydroxyl-blocked dimethylsiloxane and methylvinylsiloxane have a viscosity of 20 mPa · s. 1.5 parts by mass of a 1: 2 mass condensation reaction product of polymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (300 ppm by mass with respect to the composition) Of theplatinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane A 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (in which the platinum atom is 5 ppm by mass) is mixed with the composition to obtain a curable silicone composition (XIV ) Was prepared. In addition, content of said linear methylvinylsiloxane block is 34.5 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭｅＨＳiＯ２/２)２０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンポリシロキサン ４.５質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.３モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.５質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で３００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XIV）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.５質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 20 -
And 4.5 parts by mass of methylhydrogenpolysiloxane having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and dimethylpolysiloxane in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.3 moles per 1 mole of vinyl groups in the siloxane), and the molecular chain both-ends hydroxyl-blocked dimethylsiloxane and methylvinylsiloxane have a viscosity of 20 mPa · s. 1.5 parts by mass of a 1: 2 mass condensation reaction product of polymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (300 ppm by mass with respect to the composition) Of the
［比較例６］
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)４６ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １７質量部、メチルトリメトキシシラン ２質量部、およびフェニルトリメトキシシラン ２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 6]
formula:
-(MeViSiO 2/2 ) 6-
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 46 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by 4.1 parts by weight, titanium oxide having an average primary particle diameter of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), 65 parts by weight, and an average particle diameter of 15 μm 17 parts by mass of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.), 17 parts by mass, 2 parts by mass of methyltrimethoxysilane, and 2 parts by mass of phenyltrimethoxysilane were placed in a Ross mixer and mixed at room temperature. The mixture was kneaded while being heated to 150 ° C. to prepare a silicone base.
式：
－(ＭeＶiＳiＯ２/２)６－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ４.４質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)４６ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ４.１質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １７質量部、メチルトリメトキシシラン ２質量部、およびフェニルトリメトキシシラン ２質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 6]
formula:
-(MeViSiO 2/2 ) 6-
4.4 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 46 SiMe 2 Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by 4.1 parts by weight, titanium oxide having an average primary particle diameter of 0.2 μm (SX-3103 manufactured by Sakai Chemical Industry), 65 parts by weight, and an average particle diameter of 15 μm 17 parts by mass of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.), 17 parts by mass, 2 parts by mass of methyltrimethoxysilane, and 2 parts by mass of phenyltrimethoxysilane were placed in a Ross mixer and mixed at room temperature. The mixture was kneaded while being heated to 150 ° C. to prepare a silicone base.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.２モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XV）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.７質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.2 moles per 1 mole of vinyl groups in the polysiloxane), and the viscosity is 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A curable silicone composition (XV) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (amount in which platinum atoms are 3 ppm by mass with respect to the present composition). Prepared. In addition, content of said linear methylvinylsiloxane block is 34.7 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ４.７質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.２モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XV）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の３４.７質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
4.7 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula (II) and having both ends of the molecular chain blocked with trimethylsiloxane groups (methylvinylpolysiloxane and dimethyl in silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.2 moles per 1 mole of vinyl groups in the polysiloxane), and the viscosity is 20 mPa · s. 1 part by weight of a condensation reaction product having a mass ratio of 1: 2 of copolymerized oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (200 ppm by mass with respect to the composition) 1) of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane of platinum. A curable silicone composition (XV) is prepared by mixing a 3-divinyl-1,1,3,3-tetramethyldisiloxane solution (amount in which platinum atoms are 3 ppm by mass with respect to the present composition). Prepared. In addition, content of said linear methylvinylsiloxane block is 34.7 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
［比較例７］
式：
－(ＭeＶiＳiＯ２/２)－
で表されるメチルビニルシロキサン３個と式：
－(Ｍe２ＳiＯ２/２)－
で表されるジメチルシロキサン６個がランダムに連結し、分子鎖両末端が水酸基で封鎖されたジメチルシロキサン・メチルビニルシロキサンランダム共重合体 ８.５質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、および平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １６.３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 7]
formula:
-(MeViSiO 2/2 )-
Three methylvinylsiloxanes represented by the formula:
-(Me 2 SiO 2/2 )-
A dimethylsiloxane / methylvinylsiloxane random copolymer in which six dimethylsiloxanes represented by the formula are randomly linked and both ends of the molecular chain are blocked with hydroxyl groups, 8.5 parts by mass, a formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 65 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, and an average particle size 15 μm spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 16.3 parts by mass was put into a loss mixer, mixed at room temperature, and then kneaded while heating to 150 ° C. under reduced pressure to obtain a silicone base. Prepared.
式：
－(ＭeＶiＳiＯ２/２)－
で表されるメチルビニルシロキサン３個と式：
－(Ｍe２ＳiＯ２/２)－
で表されるジメチルシロキサン６個がランダムに連結し、分子鎖両末端が水酸基で封鎖されたジメチルシロキサン・メチルビニルシロキサンランダム共重合体 ８.５質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、および平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １６.３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 7]
formula:
-(MeViSiO 2/2 )-
Three methylvinylsiloxanes represented by the formula:
-(Me 2 SiO 2/2 )-
A dimethylsiloxane / methylvinylsiloxane random copolymer in which six dimethylsiloxanes represented by the formula are randomly linked and both ends of the molecular chain are blocked with hydroxyl groups, 8.5 parts by mass, a formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 65 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, and an average particle size 15 μm spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 16.3 parts by mass was put into a loss mixer, mixed at room temperature, and then kneaded while heating to 150 ° C. under reduced pressure to obtain a silicone base. Prepared.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.７質量部（シリコーンベース中のジメチルシロキサン・メチルビニルシロキサンランダム共重合体とジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が２.６モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.１質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XVI）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の１５.１質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.7 parts by mass of a methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both molecular chain ends blocked with a trimethylsiloxane group (dimethylsiloxane / methylvinylsiloxane in a silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 2.6 moles per 1 mole of vinyl copolymer in the random copolymer and dimethylpolysiloxane), and the molecular chain is blocked at both ends by 20 mPa · s. 1.1 parts by mass of a 1: 2 mass condensation product of dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (in this composition) The amount of 200 ppm in mass unit) is mixed, and thenplatinum 1,3-divinyl-1,1, , 3-Tetramethyldisiloxane in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (the amount of platinum atoms in this unit is 3.5 ppm by mass) Thus, a curable silicone composition (XVI) was prepared. In addition, content of said linear methylvinylsiloxane block is 15.1 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ５.７質量部（シリコーンベース中のジメチルシロキサン・メチルビニルシロキサンランダム共重合体とジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が２.６モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.１質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XVI）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の１５.１質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
5.7 parts by mass of a methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both molecular chain ends blocked with a trimethylsiloxane group (dimethylsiloxane / methylvinylsiloxane in a silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 2.6 moles per 1 mole of vinyl copolymer in the random copolymer and dimethylpolysiloxane), and the molecular chain is blocked at both ends by 20 mPa · s. 1.1 parts by mass of a 1: 2 mass condensation product of dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (in this composition) The amount of 200 ppm in mass unit) is mixed, and then
［比較例８］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ３.７質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、および平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １６.３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 8]
formula:
- (MeViSiO 2/2) 20 -
3.7 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 65 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, and an average particle size 15 μm spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 16.3 parts by mass was put into a loss mixer, mixed at room temperature, and then kneaded while heating to 150 ° C. under reduced pressure to obtain a silicone base. Prepared.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ３.７質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン ５.９質量部、平均一次粒子径０.２μｍの酸化チタン（堺化学工業製のＳＸ－３１０３） ６５質量部、および平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） １６.３質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 8]
formula:
- (MeViSiO 2/2) 20 -
3.7 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
5.9 parts by mass of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula: 65 parts by mass of titanium oxide (SX-3103 manufactured by Sakai Chemical Industry) with an average primary particle size of 0.2 μm, and an average particle size 15 μm spherical silica (HS-202 manufactured by Nippon Steel Materials Micron Co., Ltd.) 16.3 parts by mass was put into a loss mixer, mixed at room temperature, and then kneaded while heating to 150 ° C. under reduced pressure to obtain a silicone base. Prepared.
次に、室温下、このシリコーンベースに、式：
－(Ｍe２ＳiＯ２/２)－
で表されるジメチルシロキサン３個と式：
－(ＭeＨＳiＯ２/２)－
で表されるメチルハイドロジェンシロキサン７個とがランダムに連結し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンシロキサン・ジメチルシロキサンランダム共重合体 ８.１質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.７モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.１質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XVII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の２０.６質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
-(Me 2 SiO 2/2 )-
Three dimethylsiloxanes represented by the formula:
-(MeHSIO 2/2 )-
8.1 parts by mass of a methyl hydrogen siloxane / dimethyl siloxane random copolymer in which 7 molecular hydrogen siloxanes represented by the above formula are randomly linked and both ends of the molecular chain are blocked with trimethylsiloxy groups (in the silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.7 moles per 1 mole of total vinyl groups in methylvinylpolysiloxane and dimethylpolysiloxane), and both ends of the molecular chain are blocked with a viscosity of 20 mPa · s. 1.1 parts by mass of a 1: 2 mass condensation product of dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (in this composition) The amount of 200 ppm in mass unit) is mixed, and thenplatinum 1,3-divinyl-1 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Amount) was mixed to prepare a curable silicone composition (XVII). In addition, content of said linear methylvinylsiloxane block is 20.6 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(Ｍe２ＳiＯ２/２)－
で表されるジメチルシロキサン３個と式：
－(ＭeＨＳiＯ２/２)－
で表されるメチルハイドロジェンシロキサン７個とがランダムに連結し、分子鎖両末端がトリメチルシロキシ基で封鎖されたメチルハイドロジェンシロキサン・ジメチルシロキサンランダム共重合体 ８.１質量部（シリコーンベース中のメチルビニルポリシロキサンとジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.７モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 １.１質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XVII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の２０.６質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
-(Me 2 SiO 2/2 )-
Three dimethylsiloxanes represented by the formula:
-(MeHSIO 2/2 )-
8.1 parts by mass of a methyl hydrogen siloxane / dimethyl siloxane random copolymer in which 7 molecular hydrogen siloxanes represented by the above formula are randomly linked and both ends of the molecular chain are blocked with trimethylsiloxy groups (in the silicone base) The amount of silicon atom-bonded hydrogen atoms in this component is 1.7 moles per 1 mole of total vinyl groups in methylvinylpolysiloxane and dimethylpolysiloxane), and both ends of the molecular chain are blocked with a viscosity of 20 mPa · s. 1.1 parts by mass of a 1: 2 mass condensation product of dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (in this composition) The amount of 200 ppm in mass unit) is mixed, and then
［比較例９］
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ７.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン １６.６質量部、平均一次粒子径０.４４μｍのアルミナ（住友化学製のＡＥＳ－１２） ５５.０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ７質量部、および粘度２４ｍＰa・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 9]
formula:
- (MeViSiO 2/2) 20 -
7.2 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
16.6 parts by mass of dimethylpolysiloxane blocked with a dimethylvinylsiloxy group at both ends of the molecular chain represented by the following formula: 55.0 parts by mass of alumina having an average primary particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.), 15 μm inaverage particle size 7 parts by mass of spherical silica (HS-202 manufactured by Nippon Steel Materials Micron) and a viscosity of 24 mPa · s, the formula:
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
式：
－(ＭeＶiＳiＯ２/２)２０－
で表される直鎖状メチルビニルシロキサンブロックを有し、分子鎖両末端が水酸基で封鎖されたメチルビニルポリシロキサン ７.２質量部、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)１６０ＳiＭe２Ｖi
で表される分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン １６.６質量部、平均一次粒子径０.４４μｍのアルミナ（住友化学製のＡＥＳ－１２） ５５.０質量部、平均粒子径１５μｍの球状シリカ（新日鉄マテリアルズ マイクロン社製のＨＳ－２０２） ７質量部、および粘度２４ｍＰa・ｓである、式：
Ｍe２ＶiＳiＯ(Ｍe２ＳiＯ)２９Ｓi(ＯＭe)３
で表される分子鎖片末端がジメチルビニルシロキシ基で封鎖され、他の分子鎖片末端がトリメトキシシロキシ基で封鎖されたジメチルポリシロキサン ４質量部をロスミキサーに投入し、室温で混合した後、減圧下、１５０℃に加熱しながら混練して、シリコーンベースを調製した。 [Comparative Example 9]
formula:
- (MeViSiO 2/2) 20 -
7.2 parts by mass of methyl vinyl polysiloxane having a linear methyl vinyl siloxane block represented by the formula and having both ends of the molecular chain blocked with hydroxyl groups, the formula:
Me 2 ViSiO (Me 2 SiO) 160 SiMe 2 Vi
16.6 parts by mass of dimethylpolysiloxane blocked with a dimethylvinylsiloxy group at both ends of the molecular chain represented by the following formula: 55.0 parts by mass of alumina having an average primary particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.), 15 μm in
Me 2 ViSiO (Me 2 SiO) 29 Si (OMe) 3
4 parts by weight of dimethylpolysiloxane in which the molecular chain end represented by is blocked with a dimethylvinylsiloxy group and the other molecular chain end is blocked with a trimethoxysiloxy group is added to a Ross mixer and mixed at room temperature The mixture was kneaded while heating at 150 ° C. under reduced pressure to prepare a silicone base.
次に、室温下、このシリコーンベースに、式：
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ８.２質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 ２質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XVIII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の２３.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
8.2 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and molecule in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 2 parts by mass of a condensation reaction product having a mass ratio of 1: 2 between a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), andplatinum 1,3-divinyl- 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane solution of 1,3,3-tetramethyldisiloxane (the platinum atom is 3.5 ppm in terms of mass relative to the composition) Curable silicone composition (XVIII) was prepared. In addition, content of said linear methylvinylsiloxane block is 23.4 mass% of the sum total of the organopolysiloxane in this composition. Table 2 shows the properties of the curable silicone composition and the cured product.
－(ＭeＨＳiＯ２/２)５０－
で表される直鎖状メチルハイドロジェンシロキサンブロックを有し、分子鎖両末端がトリメチルシロシキ基で封鎖されたメチルハイドロジェンポリシロキサン ８.２質量部（シリコーンベース中のメチルビニルポリシロキサンと分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン中のビニル基の合計１モルに対して、本成分中のケイ素原子結合水素原子が１.５モルとなる量）、粘度２０ｍＰa・ｓの分子鎖両末端水酸基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーと３－グリシドキシプロピルトリメトキシシランとの質量比１：２の縮合反応物 ２質量部、および１－エチニル－１－シクロヘキサノール（本組成物に対して、質量単位で２００ｐｐｍとなる量）を混合した後、白金の１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンの１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン溶液（本組成物に対して、白金原子が質量単位で３.５ｐｐｍとなる量）を混合して、硬化性シリコーン組成物（XVIII）を調製した。なお、上記の直鎖状メチルビニルシロキサンブロックの含有量は本組成物中のオルガノポリシロキサンの合計の２３.４質量％である。この硬化性シリコーン組成物、およびその硬化物の特性を表２に示した。 Then, at room temperature, on this silicone base, the formula:
- (MeHSiO 2/2) 50 -
8.2 parts by mass of methylhydrogenpolysiloxane having a linear methylhydrogensiloxane block represented by the formula and having both ends of the molecular chain blocked with trimethylsiloxy groups (methylvinylpolysiloxane and molecule in silicone base) Both ends of the chain are dimethylvinylsiloxy group-blocked dimethylpolysiloxane in an amount of 1.5 moles of silicon-bonded hydrogen atoms in this component with respect to a total of 1 mole of vinyl groups in the dimethylpolysiloxane, and both molecular chains with a viscosity of 20 mPa · s. 2 parts by mass of a condensation reaction product having a mass ratio of 1: 2 between a terminal hydroxyl-blocked dimethylsiloxane / methylvinylsiloxane copolymer oligomer and 3-glycidoxypropyltrimethoxysilane, and 1-ethynyl-1-cyclohexanol (this composition) Is mixed with an amount of 200 ppm in mass unit), and
表１および表２の結果から、酸化チタンの含有量が多いと、硬化性シリコーン組成物のチキソ性が高くなり、また、硬化物の強度が高くなることが分かった。また、特定のオルガノポリシロキサン成分を用いることで、硬化物の線膨張係数を低下させることができ、さらに、特定のフィラー処理剤を用いることで、硬化性シリコーン組成物の粘度を効果的に低下させ、硬化物の強度、線膨張係数、金属への接着力の全ての物性を改善できることが分かった。
From the results of Tables 1 and 2, it was found that when the content of titanium oxide is large, the thixotropy of the curable silicone composition is increased and the strength of the cured product is increased. In addition, the linear expansion coefficient of the cured product can be reduced by using a specific organopolysiloxane component, and the viscosity of the curable silicone composition can be effectively reduced by using a specific filler treatment agent. It was found that all the physical properties of the strength, linear expansion coefficient, and adhesion to metal can be improved.
［実施例１０～１２、比較例１０～１２］
ＰＥＴフィルム、アルミニウム板、または銅板のいずれかの支持体の内側に、厚みが１００μｍのスペーサーを５ｃｍ×５ｃｍの空間が取れるように設置し、スペーサーで囲まれた範囲内に上記で調製した硬化性シリコーン組成物０.８ｇを注入した。次に、硬化性シリコーン組成物の上に離型フィルムを被せ、１５０℃、プレス圧５Ｋｇにて、１５分間加熱して、硬化物からなる光反射材と前記支持体との一体成形物を作製した。硬化物の外観を目視により観察し、その結果を表３に示した。 [Examples 10 to 12, Comparative Examples 10 to 12]
Inside the support of either PET film, aluminum plate, or copper plate, a spacer with a thickness of 100 μm is installed so that a space of 5 cm × 5 cm can be taken, and the curability prepared above within the range surrounded by the spacer 0.8 g of the silicone composition was injected. Next, a release film is placed on the curable silicone composition and heated at 150 ° C. and a press pressure of 5 kg for 15 minutes to produce an integrally molded product of the light reflecting material comprising the cured product and the support. did. The appearance of the cured product was visually observed, and the results are shown in Table 3.
ＰＥＴフィルム、アルミニウム板、または銅板のいずれかの支持体の内側に、厚みが１００μｍのスペーサーを５ｃｍ×５ｃｍの空間が取れるように設置し、スペーサーで囲まれた範囲内に上記で調製した硬化性シリコーン組成物０.８ｇを注入した。次に、硬化性シリコーン組成物の上に離型フィルムを被せ、１５０℃、プレス圧５Ｋｇにて、１５分間加熱して、硬化物からなる光反射材と前記支持体との一体成形物を作製した。硬化物の外観を目視により観察し、その結果を表３に示した。 [Examples 10 to 12, Comparative Examples 10 to 12]
Inside the support of either PET film, aluminum plate, or copper plate, a spacer with a thickness of 100 μm is installed so that a space of 5 cm × 5 cm can be taken, and the curability prepared above within the range surrounded by the spacer 0.8 g of the silicone composition was injected. Next, a release film is placed on the curable silicone composition and heated at 150 ° C. and a press pressure of 5 kg for 15 minutes to produce an integrally molded product of the light reflecting material comprising the cured product and the support. did. The appearance of the cured product was visually observed, and the results are shown in Table 3.
［実施例１３～１５、比較例１３～１５］
テスター産業社製のフィルムコーター（ＰＩ－１２１０）を用いて、アルミニウム板、銅板、ＰＥＴフィルム、またはガラス板のいずれかの支持体上に、上記で調製した硬化性シリコーン組成物をギャップサイズ１００μｍにて塗布した。塗布の状態を目視により観察した。その後、１５０℃のオーブンで１時間加熱して、硬化物からなる光反射材と前記支持体との一体成形物を作製した。硬化物の外観を目視により観察し、その結果を表４に示した。 [Examples 13 to 15, Comparative Examples 13 to 15]
Using a film coater (PI-1210) manufactured by Tester Sangyo Co., Ltd., the curable silicone composition prepared above was applied to any one of an aluminum plate, a copper plate, a PET film, and a glass plate with a gap size of 100 μm. And applied. The state of application was visually observed. Then, it heated in 150 degreeC oven for 1 hour, and produced the integral molded product of the light reflection material which consists of hardened | cured material, and the said support body. The appearance of the cured product was visually observed, and the results are shown in Table 4.
テスター産業社製のフィルムコーター（ＰＩ－１２１０）を用いて、アルミニウム板、銅板、ＰＥＴフィルム、またはガラス板のいずれかの支持体上に、上記で調製した硬化性シリコーン組成物をギャップサイズ１００μｍにて塗布した。塗布の状態を目視により観察した。その後、１５０℃のオーブンで１時間加熱して、硬化物からなる光反射材と前記支持体との一体成形物を作製した。硬化物の外観を目視により観察し、その結果を表４に示した。 [Examples 13 to 15, Comparative Examples 13 to 15]
Using a film coater (PI-1210) manufactured by Tester Sangyo Co., Ltd., the curable silicone composition prepared above was applied to any one of an aluminum plate, a copper plate, a PET film, and a glass plate with a gap size of 100 μm. And applied. The state of application was visually observed. Then, it heated in 150 degreeC oven for 1 hour, and produced the integral molded product of the light reflection material which consists of hardened | cured material, and the said support body. The appearance of the cured product was visually observed, and the results are shown in Table 4.
［実施例１６～１８、比較例１６～１８］
ニューロング精密工業社製の自動スクリーン印刷機（ＤＰ－３２０）を用いて、ＰＥＴフィルムを支持体として、上記で調製した硬化性シリコーン組成物をスクリーン印刷した。スクリーン板としてＳＵＳ製のメッシュサイズ＃１００、線径が４０μｍのものを用いた。スクリーン印刷の状態を目視により観察した。その後、１５０℃のオーブンで１時間加熱して、硬化物からなる光反射材と前記支持体との一体成形物を作製した。硬化物の外観を目視により観察し、その結果を表５に示した。 [Examples 16 to 18, Comparative Examples 16 to 18]
Using an automatic screen printer (DP-320) manufactured by New Long Seimitsu Kogyo Co., Ltd., the curable silicone composition prepared above was screen-printed using a PET film as a support. A screen plate having a mesh size of # 100 and a wire diameter of 40 μm was used. The state of screen printing was observed visually. Then, it heated in 150 degreeC oven for 1 hour, and produced the integral molded product of the light reflection material which consists of hardened | cured material, and the said support body. The appearance of the cured product was visually observed, and the results are shown in Table 5.
ニューロング精密工業社製の自動スクリーン印刷機（ＤＰ－３２０）を用いて、ＰＥＴフィルムを支持体として、上記で調製した硬化性シリコーン組成物をスクリーン印刷した。スクリーン板としてＳＵＳ製のメッシュサイズ＃１００、線径が４０μｍのものを用いた。スクリーン印刷の状態を目視により観察した。その後、１５０℃のオーブンで１時間加熱して、硬化物からなる光反射材と前記支持体との一体成形物を作製した。硬化物の外観を目視により観察し、その結果を表５に示した。 [Examples 16 to 18, Comparative Examples 16 to 18]
Using an automatic screen printer (DP-320) manufactured by New Long Seimitsu Kogyo Co., Ltd., the curable silicone composition prepared above was screen-printed using a PET film as a support. A screen plate having a mesh size of # 100 and a wire diameter of 40 μm was used. The state of screen printing was observed visually. Then, it heated in 150 degreeC oven for 1 hour, and produced the integral molded product of the light reflection material which consists of hardened | cured material, and the said support body. The appearance of the cured product was visually observed, and the results are shown in Table 5.
プレス成型、フィルムコーター、スクリーン印刷のいずれの方法を用いても、本発明の硬化性シリコーン組成物を用いると、支持体との接着性が良好で、硬化物にクラック等の発生がないことが分かった。また、本発明の硬化性シリコーン組成物はチキソ性を有するので、塗布工程から熱硬化までの間に液だれを起こしにくく、形状の変化は観察されなかった。
Regardless of the method of press molding, film coater, or screen printing, when the curable silicone composition of the present invention is used, the adhesiveness to the support is good and the cured product does not have cracks or the like. I understood. In addition, since the curable silicone composition of the present invention has thixotropy, dripping hardly occurs between the coating process and heat curing, and no change in shape was observed.
本発明の硬化性シリコーン組成物は、硬化して得られる硬化物の熱膨張率が小さく、薄膜での光反射性が高いので、他部材と一体化して使用する複合用光反射材料として好適である。
The curable silicone composition of the present invention has a low coefficient of thermal expansion of a cured product obtained by curing, and has high light reflectivity in a thin film. Therefore, the curable silicone composition is suitable as a composite light reflecting material to be used integrally with other members. is there.
１ 光半導体素子
２ 基板
３ 回路
４ 回路
５ ボンディングワイヤ
６ 光反射材
７ 封止材 DESCRIPTION OFSYMBOLS 1 Optical semiconductor element 2 Board | substrate 3 Circuit 4 Circuit 5 Bonding wire 6 Light reflecting material 7 Sealing material
２ 基板
３ 回路
４ 回路
５ ボンディングワイヤ
６ 光反射材
７ 封止材 DESCRIPTION OF
Claims (11)
- 平均粒子径０.０５～１０μｍの酸化チタン粉末および平均粒子径０.１～２０μｍの酸化チタン以外の無機粉末を含有し、前記酸化チタン粉末の含有量が本組成物中の５０～９０質量％であり、前記無機粉末の含有量が本組成物中の５～４０質量％である熱硬化性シリコーン組成物であって、前記酸化チタン粉末および前記無機粉末が、一般式：
Ｒ１ ａＳi(ＯＲ２)(４－ａ)
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシランおよび／または一般式：
で表されるオルガノシロキサンにより表面処理されていることを特徴とする硬化性シリコーン組成物。 It contains a titanium oxide powder having an average particle size of 0.05 to 10 μm and an inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm, and the content of the titanium oxide powder is 50 to 90% by mass in the composition. And the content of the inorganic powder is 5 to 40% by mass in the present composition, wherein the titanium oxide powder and the inorganic powder have the general formula:
R 1 a Si (OR 2 ) (4-a)
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
And / or a general formula:
A curable silicone composition which is surface-treated with an organosiloxane represented by the formula: - 硬化性シリコーン組成物が、
（Ａ）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、
（Ｂ）一分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン｛（Ａ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０.１～１０モルとなる量｝、
（Ｃ）平均粒子径０.０５～１０μｍの酸化チタン粉末（本組成物中、５０～９０質量％となる量）、
（Ｄ）平均粒子径０.１～２０μｍの酸化チタン以外の無機粉末（本組成物中、５～４０質量％となる量）、
（Ｅ）（Ｅ－１）一般式：
Ｒ１ (４－ａ)Ｓi(ＯＲ２)ａ
（式中、Ｒ１は炭素数６～２０の非置換またはハロゲン置換の一価炭化水素基、Ｒ２はアルキル基、アルコキシアルキル基、アルケニル基、またはアシル基、ａは１～３の整数である。）
で表されるオルガノシラン（本組成物１００質量部に対して０.１～１０質量部）および／または（Ｅ－２）一般式：
で表されるオルガノシロキサン（本組成物１００質量部に対して０.１～１０質量部）、および
（Ｆ）ヒドロシリル化反応用触媒（本組成物のヒドロシリル化反応を促進する量）
から少なくともなるヒドロリル化反応硬化性シリコーン組成物である、請求項１に記載の硬化性シリコーン組成物。 The curable silicone composition is
(A) an organopolysiloxane having at least two alkenyl groups in one molecule;
(B) Organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {the amount of silicon-bonded hydrogen atoms in this component is 0.1 to 0.1 mol per 1 mole of alkenyl groups in component (A) Amount to be 10 moles},
(C) Titanium oxide powder having an average particle size of 0.05 to 10 μm (in the present composition, an amount of 50 to 90% by mass),
(D) Inorganic powder other than titanium oxide having an average particle size of 0.1 to 20 μm (amount of 5 to 40% by mass in the present composition),
(E) (E-1) General formula:
R 1 (4-a) Si (OR 2 ) a
Wherein R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 6 to 20 carbon atoms, R 2 is an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group, and a is an integer of 1 to 3. is there.)
Represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the present composition) and / or (E-2) general formula:
(F) Hydrosilylation catalyst (amount for promoting the hydrosilylation reaction of the composition) represented by the formula (0.1 to 10 parts by mass with respect to 100 parts by mass of the composition)
The curable silicone composition according to claim 1, which is a hydrolyzed reaction-curable silicone composition comprising at least - （Ａ）成分が、（Ａ－１）一般式：
－(Ｒ７Ｒ８ＳiＯ２/２)ｍ－
（式中、Ｒ７は炭素原子数１～６のアルキル基またはフェニル基、Ｒ８は炭素原子数２～１０のアルケニル基、ｍは５～５０の整数である。）
で表される直鎖状ポリシロキサンブロックを少なくとも有するオルガノポリシロキサン｛ただし、上記直鎖状ポリシロキサンブロックの含有量が本組成物中のオルガノポリシロキサンの合計の２０～６０質量％｝であり、（Ｂ）成分が、（Ｂ－１）一般式：
－(Ｒ９ＨＳiＯ２/２)ｎ－
（式中、Ｒ９は炭素原子数１～６のアルキル基またはフェニル基、ｎは１０～１００の整数である。）
で表される直鎖状ポリシロキサンブロックを少なくとも有するオルガノポリシロキサンである、請求項２に記載の硬化性シリコーン組成物。 (A) component is (A-1) general formula:
-(R 7 R 8 SiO 2/2 ) m-
(Wherein R 7 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, R 8 is an alkenyl group having 2 to 10 carbon atoms, and m is an integer of 5 to 50.)
An organopolysiloxane having at least a linear polysiloxane block represented by the formula (wherein the content of the linear polysiloxane block is 20 to 60% by mass of the total of the organopolysiloxane in the composition), (B) component is (B-1) general formula:
-(R 9 HSiO 2/2 ) n-
(Wherein R 9 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and n is an integer of 10 to 100.)
The curable silicone composition of Claim 2 which is an organopolysiloxane which has at least the linear polysiloxane block represented by these. - さらに、（Ａ）成分として（Ａ－２）一分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン｛ただし、（Ａ－１）成分を除く｝を、（Ａ－１）成分中のアルケニル基と本成分中のアルケニル基の合計に対して、本成分中のアルケニル基が多くとも１０モル％となる量を含有する、請求項３に記載の硬化性シリコーン組成物。 Further, (A) component (A-2) organopolysiloxane having at least two alkenyl groups in one molecule {however, excluding component (A-1)} is replaced with alkenyl in component (A-1) The curable silicone composition according to claim 3, which contains an amount of alkenyl groups in this component at most 10 mol% based on the total of the groups and alkenyl groups in this component.
- 下記式により求められるチキソ指数の値が５.０以上である、請求項１乃至４のいずれか１項に記載の硬化性シリコーン組成物。
- 請求項１乃至５のいずれか１項に記載の硬化性シリコーン組成物を硬化してなる硬化物。 Hardened | cured material formed by hardening | curing the curable silicone composition of any one of Claims 1 thru | or 5.
- ２５～２００℃における平均線膨張率が１００ｐｐｍ／℃以下である、請求項６に記載の硬化物。 The cured product according to claim 6, wherein the average linear expansion coefficient at 25 to 200 ° C is 100 ppm / ° C or less.
- １００μｍのフィルム状硬化物における全光線反射率が９０％以上である、請求項６に記載の硬化物。 The cured product according to claim 6, wherein the total light reflectance in a 100 μm film-shaped cured product is 90% or more.
- 請求項１乃至５のいずれか１項に記載の硬化性シリコーン組成物を成型工程により、支持体上に膜状又は板状の硬化物を形成する方法。 A method of forming a film-like or plate-like cured product on a support by a molding process of the curable silicone composition according to any one of claims 1 to 5.
- 請求項１乃至５のいずれか１項に記載の硬化性シリコーン組成物を塗布工程により、支持体上に膜状又は板状の硬化物を形成する方法。 A method for forming a film-like or plate-like cured product on a support by applying the curable silicone composition according to any one of claims 1 to 5.
- 請求項６乃至８のいずれか１項に記載の硬化物からなる光反射材を有する光半導体装置。 An optical semiconductor device having a light reflecting material made of the cured product according to any one of claims 6 to 8.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020177009581A KR20170052649A (en) | 2014-09-10 | 2015-08-28 | Curable silicone composition, cured object obtained therefrom, and optical semiconductor device |
| CN201580047531.9A CN106661329B (en) | 2014-09-10 | 2015-08-28 | Curable silicone composition, cured product thereof, and optical semiconductor device |
| JP2016547680A JP6590445B2 (en) | 2014-09-10 | 2015-08-28 | Curable silicone composition, cured product thereof, and optical semiconductor device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014183912 | 2014-09-10 | ||
| JP2014-183912 | 2014-09-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016038836A1 true WO2016038836A1 (en) | 2016-03-17 |
Family
ID=55458610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2015/004355 WO2016038836A1 (en) | 2014-09-10 | 2015-08-28 | Curable silicone composition, cured object obtained therefrom, and optical semiconductor device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6590445B2 (en) |
| KR (1) | KR20170052649A (en) |
| CN (1) | CN106661329B (en) |
| TW (1) | TWI690553B (en) |
| WO (1) | WO2016038836A1 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018030287A1 (en) | 2016-08-08 | 2018-02-15 | 東レ・ダウコーニング株式会社 | Curable particulate silicone composition, semiconductor member comprising curable particulate silicone composition, and molding method for semiconductor member comprising curable particulate silicone composition |
| WO2018043270A1 (en) * | 2016-09-01 | 2018-03-08 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition, and protection agent or adhesive composition for electrical/electronic components |
| KR20190039962A (en) | 2016-08-08 | 2019-04-16 | 다우 코닝 도레이 캄파니 리미티드 | Curable particulate silicone composition, light reflector comprising the same, and process for producing the same |
| WO2019181713A1 (en) * | 2018-03-23 | 2019-09-26 | 信越化学工業株式会社 | Silicone composition |
| JP2020132824A (en) * | 2019-02-25 | 2020-08-31 | 信越化学工業株式会社 | Addition-curable silicone composition, silicone cured product for light reflection material, light reflection material and optical semiconductor element |
| EP3684078A4 (en) * | 2017-09-11 | 2020-11-04 | FUJIFILM Corporation | Acoustic wave probe composition, acoustic wave probe silicone resin, acoustic wave probe, ultrasonic probe, acoustic wave measuring apparatus, ultrasonic diagnostic apparatus, photoacoustic wave measuring apparatus, and ultrasonic endoscope |
| WO2020241368A1 (en) * | 2019-05-31 | 2020-12-03 | ダウ・東レ株式会社 | Curable organopolysiloxane composition, and optical member formed from cured product of same |
| KR20210108990A (en) | 2018-12-27 | 2021-09-03 | 다우 도레이 캄파니 리미티드 | Curable silicone composition, cured product thereof, and manufacturing method thereof |
| CN113396188A (en) * | 2018-12-27 | 2021-09-14 | 陶氏东丽株式会社 | Curable silicone composition for transfer molding, cured product thereof, and method for producing same |
| WO2022038888A1 (en) * | 2020-08-21 | 2022-02-24 | ダウ・東レ株式会社 | Curable organopolysiloxane composition, thermally conductive member and heat dissipation structure |
| US11555119B2 (en) | 2017-06-19 | 2023-01-17 | Dow Toray Co., Ltd. | Curable granular silicone composition, semiconductor member comprising same, and forming method thereof |
| WO2023164019A1 (en) * | 2022-02-24 | 2023-08-31 | Dow Silicones Corporation | Curable silicone composition |
| WO2023164018A1 (en) * | 2022-02-24 | 2023-08-31 | Dow Silicones Corporation | Curable silicone composition and cured product thereof |
| US11845869B2 (en) | 2019-06-21 | 2023-12-19 | Dow Silicones Corporation | Method for producing thixotropic curable silicone composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021160962A (en) * | 2020-03-31 | 2021-10-11 | 住友化学株式会社 | Particle, powder composition, solid composition, liquid composition, and molded body |
| JP2023044473A (en) | 2021-09-17 | 2023-03-30 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | Thermally conductive silicone composition |
| JP2023062628A (en) | 2021-10-21 | 2023-05-08 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | Heat conductive silicone composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012021137A (en) * | 2010-06-18 | 2012-02-02 | Kaneka Corp | Curable resin composition tablet and semiconductor package using the same |
| JP2013076050A (en) * | 2011-09-16 | 2013-04-25 | Dow Corning Toray Co Ltd | Curable silicone composition, cured product thereof, and optical semiconductor device |
| JP2013159671A (en) * | 2012-02-02 | 2013-08-19 | Dow Corning Toray Co Ltd | Curable silicone composition, cured product thereof, and optical semiconductor device |
| JP2013159670A (en) * | 2012-02-02 | 2013-08-19 | Dow Corning Toray Co Ltd | Curable silicone composition, its cured product, and optical semiconductor device |
| JP2013175762A (en) * | 2013-04-17 | 2013-09-05 | Kaneka Corp | Curable resin composition for semiconductor package and semiconductor |
| JP2014009322A (en) * | 2012-06-29 | 2014-01-20 | Dow Corning Toray Co Ltd | Reactive silicone composition, reactive thermoplastic body, cured product and optical semiconductor device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4788897B2 (en) * | 2006-03-02 | 2011-10-05 | 信越化学工業株式会社 | Room temperature curable polyorganosiloxane composition |
| KR20120123242A (en) * | 2009-06-26 | 2012-11-08 | 가부시키가이샤 아사히 러버 | White color reflecting material and process for production thereof |
| WO2011118108A1 (en) * | 2010-03-23 | 2011-09-29 | 株式会社朝日ラバー | Silicone resin reflective substrate, manufacturing method for same, and base material composition used in reflective substrate |
| CN102844383B (en) * | 2010-04-02 | 2016-01-20 | 株式会社钟化 | Curable resin composition, curable resin composition sheet, formed body, semiconductor sealing material, semiconductor device and photodiode |
| WO2013047898A1 (en) * | 2011-09-29 | 2013-04-04 | Dow Corning Toray Co., Ltd. | Curable silicone composition and cured product thereof |
-
2015
- 2015-08-28 JP JP2016547680A patent/JP6590445B2/en active Active
- 2015-08-28 CN CN201580047531.9A patent/CN106661329B/en active Active
- 2015-08-28 WO PCT/JP2015/004355 patent/WO2016038836A1/en active Application Filing
- 2015-08-28 KR KR1020177009581A patent/KR20170052649A/en active IP Right Grant
- 2015-09-08 TW TW104129693A patent/TWI690553B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012021137A (en) * | 2010-06-18 | 2012-02-02 | Kaneka Corp | Curable resin composition tablet and semiconductor package using the same |
| JP2013076050A (en) * | 2011-09-16 | 2013-04-25 | Dow Corning Toray Co Ltd | Curable silicone composition, cured product thereof, and optical semiconductor device |
| JP2013159671A (en) * | 2012-02-02 | 2013-08-19 | Dow Corning Toray Co Ltd | Curable silicone composition, cured product thereof, and optical semiconductor device |
| JP2013159670A (en) * | 2012-02-02 | 2013-08-19 | Dow Corning Toray Co Ltd | Curable silicone composition, its cured product, and optical semiconductor device |
| JP2014009322A (en) * | 2012-06-29 | 2014-01-20 | Dow Corning Toray Co Ltd | Reactive silicone composition, reactive thermoplastic body, cured product and optical semiconductor device |
| JP2013175762A (en) * | 2013-04-17 | 2013-09-05 | Kaneka Corp | Curable resin composition for semiconductor package and semiconductor |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11136437B2 (en) | 2016-08-08 | 2021-10-05 | Dow Toray Co., Ltd. | Curable particulate silicone composition, semiconductor member comprising curable particulate silicone composition, and method for molding semiconductor member |
| WO2018030287A1 (en) | 2016-08-08 | 2018-02-15 | 東レ・ダウコーニング株式会社 | Curable particulate silicone composition, semiconductor member comprising curable particulate silicone composition, and molding method for semiconductor member comprising curable particulate silicone composition |
| KR20190039162A (en) | 2016-08-08 | 2019-04-10 | 다우 코닝 도레이 캄파니 리미티드 | Curable granular silicone composition, member for semiconductor comprising same, and molding method thereof |
| KR20190039962A (en) | 2016-08-08 | 2019-04-16 | 다우 코닝 도레이 캄파니 리미티드 | Curable particulate silicone composition, light reflector comprising the same, and process for producing the same |
| US11555118B2 (en) | 2016-09-01 | 2023-01-17 | Dow Toray Co., Ltd. | Curable organopolysiloxane composition and a protectant or adhesive composition of electric/electronic parts |
| KR20190075047A (en) * | 2016-09-01 | 2019-06-28 | 다우 도레이 캄파니 리미티드 | Curable organopolysiloxane compositions and protective or adhesive compositions for electrical and electronic components |
| CN110088206A (en) * | 2016-09-01 | 2019-08-02 | 陶氏东丽株式会社 | The protective agent or adhesive composition of curable organopolysiloxane composition and electric and electronic components |
| WO2018043270A1 (en) * | 2016-09-01 | 2018-03-08 | 東レ・ダウコーニング株式会社 | Curable organopolysiloxane composition, and protection agent or adhesive composition for electrical/electronic components |
| KR102208498B1 (en) | 2016-09-01 | 2021-01-27 | 다우 도레이 캄파니 리미티드 | Curable organopolysiloxane composition and protective agent or adhesive composition for electric and electronic parts |
| CN110088206B (en) * | 2016-09-01 | 2021-08-20 | 陶氏东丽株式会社 | Curable organopolysiloxane composition and protective agent or adhesive composition for electrical and electronic components |
| JPWO2018043270A1 (en) * | 2016-09-01 | 2019-07-11 | ダウ・東レ株式会社 | Curable organopolysiloxane composition and protecting agent or adhesive composition for electric and electronic parts |
| US11555119B2 (en) | 2017-06-19 | 2023-01-17 | Dow Toray Co., Ltd. | Curable granular silicone composition, semiconductor member comprising same, and forming method thereof |
| EP3684078A4 (en) * | 2017-09-11 | 2020-11-04 | FUJIFILM Corporation | Acoustic wave probe composition, acoustic wave probe silicone resin, acoustic wave probe, ultrasonic probe, acoustic wave measuring apparatus, ultrasonic diagnostic apparatus, photoacoustic wave measuring apparatus, and ultrasonic endoscope |
| WO2019181713A1 (en) * | 2018-03-23 | 2019-09-26 | 信越化学工業株式会社 | Silicone composition |
| US11773264B2 (en) | 2018-03-23 | 2023-10-03 | Shin-Etsu Chemical Co., Ltd. | Silicone composition |
| JPWO2019181713A1 (en) * | 2018-03-23 | 2021-02-25 | 信越化学工業株式会社 | Silicone composition |
| KR20210108990A (en) | 2018-12-27 | 2021-09-03 | 다우 도레이 캄파니 리미티드 | Curable silicone composition, cured product thereof, and manufacturing method thereof |
| CN113396188A (en) * | 2018-12-27 | 2021-09-14 | 陶氏东丽株式会社 | Curable silicone composition for transfer molding, cured product thereof, and method for producing same |
| CN113396188B (en) * | 2018-12-27 | 2023-01-17 | 陶氏东丽株式会社 | Curable silicone composition for transfer molding, cured product thereof, and method for producing same |
| CN111607231B (en) * | 2019-02-25 | 2022-04-22 | 信越化学工业株式会社 | Addition curing type silicone composition, silicone cured product for light reflecting material, and optical semiconductor device |
| JP7103974B2 (en) | 2019-02-25 | 2022-07-20 | 信越化学工業株式会社 | Additive-curable silicone composition, cured silicone for light-reflecting material, light-reflecting material and optical semiconductor device |
| CN111607231A (en) * | 2019-02-25 | 2020-09-01 | 信越化学工业株式会社 | Addition curing type silicone composition, silicone cured product for light reflecting material, and optical semiconductor device |
| JP2020132824A (en) * | 2019-02-25 | 2020-08-31 | 信越化学工業株式会社 | Addition-curable silicone composition, silicone cured product for light reflection material, light reflection material and optical semiconductor element |
| WO2020241368A1 (en) * | 2019-05-31 | 2020-12-03 | ダウ・東レ株式会社 | Curable organopolysiloxane composition, and optical member formed from cured product of same |
| US11845869B2 (en) | 2019-06-21 | 2023-12-19 | Dow Silicones Corporation | Method for producing thixotropic curable silicone composition |
| WO2022038888A1 (en) * | 2020-08-21 | 2022-02-24 | ダウ・東レ株式会社 | Curable organopolysiloxane composition, thermally conductive member and heat dissipation structure |
| WO2023164019A1 (en) * | 2022-02-24 | 2023-08-31 | Dow Silicones Corporation | Curable silicone composition |
| WO2023164018A1 (en) * | 2022-02-24 | 2023-08-31 | Dow Silicones Corporation | Curable silicone composition and cured product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6590445B2 (en) | 2019-10-16 |
| JPWO2016038836A1 (en) | 2017-06-22 |
| KR20170052649A (en) | 2017-05-12 |
| CN106661329A (en) | 2017-05-10 |
| TWI690553B (en) | 2020-04-11 |
| TW201615714A (en) | 2016-05-01 |
| CN106661329B (en) | 2020-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6590445B2 (en) | Curable silicone composition, cured product thereof, and optical semiconductor device | |
| JP5769622B2 (en) | Curable organopolysiloxane composition, optical semiconductor element sealant, and optical semiconductor device | |
| JP5534977B2 (en) | Curable organopolysiloxane composition and optical semiconductor device | |
| JP6652917B2 (en) | Hot melt silicone and curable hot melt composition | |
| US9068049B2 (en) | Curable silicone composition and cured product thereof | |
| JP5972511B2 (en) | Curable organopolysiloxane composition and cured product thereof | |
| EP2721108B1 (en) | Cross-linkable silicone composition and cross-linked product thereof | |
| JP5922463B2 (en) | Curable silicone composition, cured product thereof, and optical semiconductor device | |
| TW201817815A (en) | Curable granulated silicone composition, semiconductor article thereof, and molding process thereof | |
| KR20110053470A (en) | Curable organopolysiloxane composition, optical semiconductor element sealant, and optical semiconductor device | |
| JP2018119167A (en) | Curable silicone composition | |
| KR20120105528A (en) | Silicone elastomer composition | |
| JP2012082300A (en) | Addition-curable silicone composition, and semiconductor device in which semiconductor element is covered with cured product of the composition | |
| TWI765925B (en) | Reactive hot-melt silicone-filled cartridge and method of producing reactive hot-melt silicone | |
| CN110382625B (en) | Curable organopolysiloxane composition and semiconductor device | |
| JP6707369B2 (en) | Silicone material, curable silicone composition, and optical device | |
| CN114196375A (en) | Heat-curable silicone composition | |
| WO2015093329A1 (en) | Silicone adhesive film and semiconductor device | |
| CN114106770A (en) | Curable silicone composition, sealing material, and optical semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15840887 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2016547680 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 20177009581 Country of ref document: KR Kind code of ref document: A |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 15840887 Country of ref document: EP Kind code of ref document: A1 |