JP2021178936A - Thermosetting silicone composition, sheet, and cured silicone product - Google Patents
Thermosetting silicone composition, sheet, and cured silicone product Download PDFInfo
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- JP2021178936A JP2021178936A JP2020085761A JP2020085761A JP2021178936A JP 2021178936 A JP2021178936 A JP 2021178936A JP 2020085761 A JP2020085761 A JP 2020085761A JP 2020085761 A JP2020085761 A JP 2020085761A JP 2021178936 A JP2021178936 A JP 2021178936A
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 48
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- -1 3-chloropropyl group Chemical group 0.000 description 22
- 239000000126 substance Substances 0.000 description 20
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 239000000470 constituent Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052712 strontium Inorganic materials 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 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 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- DCVWZWOEQMSMLR-UHFFFAOYSA-N silylperoxysilane Chemical compound [SiH3]OO[SiH3] DCVWZWOEQMSMLR-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- TUGAMVVIFZLKTI-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)peroxycarbonyl (3-methoxy-3-methylbutyl)peroxy carbonate Chemical compound COC(C)(C)CCOOOC(=O)OC(=O)OOOCCC(C)(C)OC TUGAMVVIFZLKTI-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- GKENVXBVOLNPDO-UHFFFAOYSA-N 1-[2,5-dimethyl-5-(3-methylphenyl)peroxyhexan-2-yl]peroxy-3-methylbenzene Chemical compound CC1=CC=CC(OOC(C)(C)CCC(C)(C)OOC=2C=C(C)C=CC=2)=C1 GKENVXBVOLNPDO-UHFFFAOYSA-N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- NRVDNSHWNQZNDC-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)decane Chemical compound CCCCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C NRVDNSHWNQZNDC-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- PJABOTZVAHGVAF-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-yl)-7,7-dimethyloctaneperoxoic acid Chemical compound CC(C)(C)CCCCC(C(=O)OO)C(C)(C)C1CCCCC1 PJABOTZVAHGVAF-UHFFFAOYSA-N 0.000 description 1
- CHKCPIUYSMYEEW-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-ylperoxy)-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C1CCCCC1 CHKCPIUYSMYEEW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- MNOVHWSHIUHSAZ-UHFFFAOYSA-N 2-ethylhexoxyperoxycarbonyl 2-ethylhexylperoxy carbonate Chemical compound CCCCC(CC)COOOC(=O)OC(=O)OOOCC(CC)CCCC MNOVHWSHIUHSAZ-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 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
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- FRBAZRWGNOJHRO-UHFFFAOYSA-N 6-tert-butylperoxycarbonyloxyhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CC(C)(C)OOC(=O)OCCCCCCOC(=O)OOC(C)(C)C FRBAZRWGNOJHRO-UHFFFAOYSA-N 0.000 description 1
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FVSKBQVTQRMJAJ-UHFFFAOYSA-N C(C)(C)(C)C=C[Si](C=C)(C=C)OO[Si](C=C)(C=C)C=CC(C)(C)C Chemical compound C(C)(C)(C)C=C[Si](C=C)(C=C)OO[Si](C=C)(C=C)C=CC(C)(C)C FVSKBQVTQRMJAJ-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- FNZSVEHJZREFPF-ZETCQYMHSA-N Nonate Chemical compound CCCCC[C@H](C(O)=O)CC(O)=O FNZSVEHJZREFPF-ZETCQYMHSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- UHAQRCJYQAKQEE-UHFFFAOYSA-M [O-2].[OH-].O.[Al+3].P Chemical compound [O-2].[OH-].O.[Al+3].P UHAQRCJYQAKQEE-UHFFFAOYSA-M 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 description 1
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- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JAHGTMJOPOCQIY-UHFFFAOYSA-N benzyl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOCC1=CC=CC=C1 JAHGTMJOPOCQIY-UHFFFAOYSA-N 0.000 description 1
- SJSFVIPHYCSGFS-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy] cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1CCC(C(=O)OOOC(C)(C)C)CC1 SJSFVIPHYCSGFS-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- UPDZRIPMRHNKPZ-UHFFFAOYSA-N carboxyoxy 4,4-dimethoxybutyl carbonate Chemical compound COC(OC)CCCOC(=O)OOC(O)=O UPDZRIPMRHNKPZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- LRIKRVKBBZQMPA-UHFFFAOYSA-N ethenylperoxysilane Chemical compound [SiH3]OOC=C LRIKRVKBBZQMPA-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- ZKJVECLVWFUBHN-UHFFFAOYSA-N platinum trimethyl(methylsilyloxy)silane Chemical compound [Pt].C[SiH2]O[Si](C)(C)C ZKJVECLVWFUBHN-UHFFFAOYSA-N 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- XTXFUQOLBKQKJU-UHFFFAOYSA-N tert-butylperoxy(trimethyl)silane Chemical compound CC(C)(C)OO[Si](C)(C)C XTXFUQOLBKQKJU-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- 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
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B32B2250/24—All layers being polymeric
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Abstract
Description
本発明は、有機過酸化物により硬化する熱硬化性シリコーン組成物に関する。 The present invention relates to a thermosetting silicone composition that is cured by an organic peroxide.
発光ダイオード（ＬＥＤ）は、その発光効率の目覚ましい向上を背景とし、低い消費電力、高寿命、意匠性などを特長として液晶ディスプレイ（ＬＣＤ）のバックライト向けや、車のヘッドライト等の車載分野ばかりではなく一般照明向けでも急激に市場を拡大しつつある。 Light emitting diodes (LEDs) are characterized by their low power consumption, long life, and designability against the background of remarkable improvement in luminous efficiency. The market is expanding rapidly even for general lighting.
ＬＥＤの発光スペクトルは、ＬＥＤチップを形成する半導体材料に依存するためその発光色は限られている。そのため、ＬＥＤを用いてＬＣＤバックライトや一般照明向けの白色光を得るためにはＬＥＤチップ上にそれぞれのチップに適合した蛍光体を配置し、発光波長を変換する必要がある。具体的には、青色発光するＬＥＤチップ上に黄色蛍光体を設置する方法、青色発光するＬＥＤチップ上に赤および緑の蛍光体を設置する方法、紫外線を発するＬＥＤチップ上に赤、緑、青の蛍光体を設置する方法などが提案されている。これらの中で、ＬＥＤチップの発光効率やコストの面から青色ＬＥＤ上に黄色蛍光体を設置する方法、および青色ＬＥＤ上に赤および緑の蛍光体を設置する方法が現在最も広く採用されている。 Since the emission spectrum of an LED depends on the semiconductor material forming the LED chip, its emission color is limited. Therefore, in order to obtain white light for LCD backlights and general lighting using LEDs, it is necessary to arrange a phosphor suitable for each chip on the LED chip and convert the emission wavelength. Specifically, a method of installing a yellow phosphor on an LED chip that emits blue light, a method of installing red and green phosphors on an LED chip that emits blue light, and a method of installing red, green, and blue on an LED chip that emits ultraviolet light. A method of installing the fluorescent substance of the above has been proposed. Among these, the method of installing the yellow phosphor on the blue LED and the method of installing the red and green phosphors on the blue LED are currently the most widely adopted in terms of the luminous efficiency and cost of the LED chip. ..
ＬＥＤチップ上に蛍光体を設置する具体的な方法の１つとして、ＬＥＤチップ上に、ハイドロジェンオルガノポリシロキサンとアルケニル基含有オルガノポリシロキサンを反応させる付加硬化型シリコーン組成物中に蛍光体を分散させたシートを貼りつける方法が提案されている。しかし、この方法では蛍光体シートを作製する際に付加反応が進んでしまわないようにシートを低温で保管しなければならず、また、組成中に付加反応制御剤を多量に添加する必要があった（特許文献１〜５）。 As one of the specific methods for placing the fluorescent substance on the LED chip, the fluorescent substance is dispersed in an addition-curable silicone composition in which a hydrogen organopolysiloxane and an alkenyl group-containing organopolysiloxane are reacted on the LED chip. A method of pasting the sheet is proposed. However, in this method, the sheet must be stored at a low temperature so that the addition reaction does not proceed when the phosphor sheet is prepared, and it is necessary to add a large amount of the addition reaction control agent to the composition. (Patent Documents 1 to 5).
本発明は上記事情に鑑みなされたもので、反応制御剤を添加せずとも未硬化状態における安定性に優れ、高硬度の硬化物を与える熱硬化性シリコーン組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermosetting silicone composition which is excellent in stability in an uncured state without adding a reaction control agent and gives a cured product having a high hardness. ..
上記課題を達成するために、本発明では、
（Ａ）下記平均単位式（１）で表されるオルガノポリシロキサン、
（ＳｉＯ２）ａ１（Ｒ１ ３ＳｉＯ１／２）ｂ１（Ｘ１Ｏ１／２）ｃ１ （１）
（式中、Ｒ１は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ１の全数のうち５０〜９９．９％はメチル基であり、かつ、０．１〜５０％はアルケニル基であり、Ｘ１は水素原子又はアルキル基である。ａ１は０．２〜０．８、ｂ１は０．２〜０．８、ｃ１は０〜０．１であり、ａ１＋ｂ１＋ｃ１＝１である。）
（Ｂ）下記平均単位式（２）で表されるオルガノポリシロキサン、
（ＳｉＯ２）ａ２（Ｒ２ ３ＳｉＯ１／２）ｂ２（Ｘ１Ｏ１／２）ｃ２ （２）
（式中、Ｒ２は同一又は異なっていても良い、置換又は非置換のアルケニル基を含まない一価炭化水素基であり、Ｘ１は水素原子又はアルキル基である。ａ２は０．２〜０．８、ｂ２は０．２〜０．８、ｃ２は０〜０．１であり、ａ２＋ｂ２＋ｃ２＝１である。）
（Ｃ）下記平均単位式（３）で表されるオルガノポリシロキサン、
（Ｒ３ ２ＳｉＯ）ａ３（Ｒ３ ３ＳｉＯ１／２）ｂ３ （３）
（式中、Ｒ３は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ３の全数のうち２０％以上がメチル基であり、かつ、０.０００１〜２５％はアルケニル基であり、ａ３は０．９９８０〜０．９９９９、ｂ３は０．０００１〜０．００２であり、ａ３＋ｂ３＝１である。）
（Ｄ）有機過酸化物
（Ｅ）溶剤
を含むものである熱硬化性シリコーン組成物を提供する。
In order to achieve the above problems, in the present invention,
(A) Organopolysiloxane represented by the following average unit formula (1),
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 50 to 99.9% of the total number of R 1 is a methyl group, and 0. 1 to 50% are alkenyl groups, X 1 is a hydrogen atom or an alkyl group. A1 is 0.2 to 0.8, b1 is 0.2 to 0.8, and c1 is 0 to 0.1. , A1 + b1 + c1 = 1)
(B) Organopolysiloxane represented by the following average unit formula (2),
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
(In the formula, R 2 is a monovalent hydrocarbon group containing no substituted or unsubstituted alkenyl group, which may be the same or different, and X 1 is a hydrogen atom or an alkyl group. A2 is 0.2 to 0.2. 0.8 and b2 are 0.2 to 0.8, c2 is 0 to 0.1, and a2 + b2 + c2 = 1).
(C) Organopolysiloxane represented by the following average unit formula (3),
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 20% or more of the total number of R 3 is a methyl group, and 0.001 to 25. % Is an alkenyl group, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3 + b3 = 1).
(D) A thermosetting silicone composition containing an organic peroxide (E) solvent is provided.
本発明の熱硬化性シリコーン組成物であれば、反応制御剤を添加しなくとも未硬化状態における安定性に優れ、高硬度の硬化物を与えることが可能である。 With the thermosetting silicone composition of the present invention, it is possible to provide a cured product having excellent stability in an uncured state and having a high hardness without adding a reaction control agent.
また、前記（Ｂ）成分の添加量が、前記（Ａ）成分１００質量部に対して１〜１００質量部であることが好ましい。 Further, the amount of the component (B) added is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the component (A).
また、前記（Ｃ）成分の添加量が、前記（Ａ）成分１００質量部に対して５〜１００質量部であることが好ましい。 Further, it is preferable that the amount of the component (C) added is 5 to 100 parts by mass with respect to 100 parts by mass of the component (A).
このようなものであれば、より機械特性に優れる硬化物を与えるものとなる。 If it is such a thing, a cured product having more excellent mechanical properties can be given.
また、前記（Ａ）〜（Ｅ）成分の合計１００質量部に対して（Ｆ）蛍光体２０〜５００質量部を含むものであることが好ましい。 Further, it is preferable that the component (F) contains 20 to 500 parts by mass with respect to 100 parts by mass in total of the components (A) to (E).
このようなものであれば、光半導体素子から発せられた光を効率的に目的の波長の光に波長変換することが可能となる。 With such a case, it is possible to efficiently convert the light emitted from the optical semiconductor element into light having a target wavelength.
また本発明では、上記の熱硬化型シリコーン組成物から形成されたものであるシートを提供する。 The present invention also provides a sheet formed from the above thermosetting silicone composition.
このようなシートであれば、未硬化状態における安定性に優れるため、広範な用途への応用が可能であり、ＬＥＤ素子等の光半導体装置の表面被覆用途に特に有用なものとなる。 Since such a sheet has excellent stability in an uncured state, it can be applied to a wide range of applications, and is particularly useful for surface coating applications of optical semiconductor devices such as LED elements.
さらに本発明では、上記の熱硬化性シリコーン組成物の硬化物であるシリコーン硬化物を提供する。 Further, the present invention provides a silicone cured product which is a cured product of the above thermosetting silicone composition.
このようなシリコーン硬化物であれば、機械特性に優れるものとなる。また、未硬化状態における安定性に優れる熱硬化性シリコーン組成物の硬化物であるため、広範な用途への応用が可能であり、ＬＥＤ素子等の光半導体装置の表面被覆用途に特に有用なものとなる。 Such a cured silicone product has excellent mechanical properties. Further, since it is a cured product of a thermosetting silicone composition having excellent stability in an uncured state, it can be applied to a wide range of applications, and is particularly useful for surface coating applications of optical semiconductor devices such as LED devices. It becomes.
本発明の熱硬化性シリコーン組成物は、必ずしも反応制御剤を添加しなくても未硬化状態における安定性に優れ、高硬度の硬化物を与えるため、広範な用途への応用が可能であり、蛍光体シート及びＬＥＤの表面被覆用途に有用である。 The thermosetting silicone composition of the present invention has excellent stability in an uncured state without necessarily adding a reaction control agent, and gives a cured product having high hardness, so that it can be applied to a wide range of applications. It is useful for surface coating applications of phosphor sheets and LEDs.
上述のように、多量の反応制御剤を添加しなくても未硬化状態における安定性に優れ、高硬度の硬化物を与える熱硬化性シリコーン組成物の開発が求められていた。 As described above, there has been a demand for the development of a thermosetting silicone composition which is excellent in stability in an uncured state and gives a cured product having high hardness without adding a large amount of reaction control agent.
本発明者らは、上記課題について鋭意検討を重ねた結果、有機過酸化物を含む特定の熱硬化性シリコーン組成物であれば、上記課題を解決できることを見出し、本発明を完成させた。 As a result of diligent studies on the above problems, the present inventors have found that a specific thermosetting silicone composition containing an organic peroxide can solve the above problems, and have completed the present invention.
即ち、本発明は、
（Ａ）下記平均単位式（１）で表されるオルガノポリシロキサン、
（ＳｉＯ２）ａ１（Ｒ１ ３ＳｉＯ１／２）ｂ１（Ｘ１Ｏ１／２）ｃ１ （１）
（式中、Ｒ１は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ１の全数のうち５０〜９９．９％はメチル基であり、かつ、０．１〜５０％はアルケニル基であり、Ｘ１は水素原子又はアルキル基である。ａ１は０．２〜０．８、ｂ１は０．２〜０．８、ｃ１は０〜０．１であり、ａ１＋ｂ１＋ｃ１＝１である。）
（Ｂ）下記平均単位式（２）で表されるオルガノポリシロキサン、
（ＳｉＯ２）ａ２（Ｒ２ ３ＳｉＯ１／２）ｂ２（Ｘ１Ｏ１／２）ｃ２ （２）
（式中、Ｒ２は同一又は異なっていても良い、置換又は非置換のアルケニル基を含まない一価炭化水素基であり、Ｘ１は水素原子又はアルキル基である。ａ２は０．２〜０．８、ｂ２は０．２〜０．８、ｃ２は０〜０．１であり、ａ２＋ｂ２＋ｃ２＝１である。）
（Ｃ）下記平均単位式（３）で表されるオルガノポリシロキサン、
（Ｒ３ ２ＳｉＯ）ａ３（Ｒ３ ３ＳｉＯ１／２）ｂ３ （３）
（式中、Ｒ３は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ３の全数のうち２０％以上がメチル基であり、かつ、０.０００１〜２５％はアルケニル基であり、ａ３は０．９９８０〜０．９９９９、ｂ３は０．０００１〜０．００２であり、ａ３＋ｂ３＝１である。）
（Ｄ）有機過酸化物
（Ｅ）溶剤
を含むものである熱硬化性シリコーン組成物である。
That is, the present invention
(A) Organopolysiloxane represented by the following average unit formula (1),
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 50 to 99.9% of the total number of R 1 is a methyl group, and 0. 1 to 50% are alkenyl groups, X 1 is a hydrogen atom or an alkyl group. A1 is 0.2 to 0.8, b1 is 0.2 to 0.8, and c1 is 0 to 0.1. , A1 + b1 + c1 = 1)
(B) Organopolysiloxane represented by the following average unit formula (2),
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
(In the formula, R 2 is a monovalent hydrocarbon group containing no substituted or unsubstituted alkenyl group, which may be the same or different, and X 1 is a hydrogen atom or an alkyl group. A2 is 0.2 to 0.2. 0.8 and b2 are 0.2 to 0.8, c2 is 0 to 0.1, and a2 + b2 + c2 = 1).
(C) Organopolysiloxane represented by the following average unit formula (3),
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 20% or more of the total number of R 3 is a methyl group, and 0.001 to 25. % Is an alkenyl group, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3 + b3 = 1).
(D) A thermosetting silicone composition containing an organic peroxide (E) solvent.
以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
［熱硬化性シリコーン組成物］
本発明の熱硬化性シリコーン組成物は、後述する（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）成分、及び必要に応じて（Ｆ）成分を含有するものである。
[Thermosetting silicone composition]
The thermosetting silicone composition of the present invention contains components (A), (B), (C), (D), (E), and if necessary, component (F), which will be described later.
＜（Ａ）成分＞
（Ａ）成分は、下記平均単位式（１）で表されるオルガノポリシロキサンである。
（ＳｉＯ２）ａ１（Ｒ１ ３ＳｉＯ１／２）ｂ１（Ｘ１Ｏ１／２）ｃ１ （１）
（式中、Ｒ１は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ１の全数のうち５０〜９９．９％はメチル基であり、かつ、０．１〜５０％はアルケニル基であり、Ｘ１は水素原子又はアルキル基である。ａ１は０．２〜０．８、ｂ１は０．２〜０．８、ｃ１は０〜０．１であり、ａ１＋ｂ１＋ｃ１＝１である。）
<Ingredient (A)>
The component (A) is an organopolysiloxane represented by the following average unit formula (1).
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 50 to 99.9% of the total number of R 1 is a methyl group, and 0. 1 to 50% are alkenyl groups, X 1 is a hydrogen atom or an alkyl group. A1 is 0.2 to 0.8, b1 is 0.2 to 0.8, and c1 is 0 to 0.1. , A1 + b1 + c1 = 1)
Ｒ１は置換又は非置換の一価炭化水素基であり、Ｒ１中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、ヘキセニル基が例示され、特に、ビニル基であることが好ましい。 R 1 is a substituted or unsubstituted monovalent hydrocarbon group, and examples of the alkenyl group in R 1 include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and in particular, it is a vinyl group. Is preferable.
Ｒ１の全数のうちアルケニル基が占める数の割合は、０．１〜５０％、好ましくは０．１〜３０％、特に好ましくは０．３〜２０％である。０．１％未満では、組成物の硬化性が不十分となり、５０％を超えると硬化物が脆くなる。 Ratio of the number occupied by the alkenyl group of the total number of R 1 is 0.1 to 50%, preferably from 0.1 to 30%, especially preferably from 0.3 to 20%. If it is less than 0.1%, the curability of the composition becomes insufficient, and if it exceeds 50%, the cured product becomes brittle.
また、Ｒ１中のアルケニル基以外のケイ素原子結合有機基としては、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、ヘプチル基等のアルキル基；フェニル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロメチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基等のハロゲン化アルキル置換又は非置換の一価炭化水素基が例示され、好ましくは炭素数が１〜３のアルキル基であり、耐熱性の面からメチル基が最も好ましい。 Examples of the silicon atom-bonded organic group other than the alkenyl group in R 1 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; phenyl group, naphthyl group and the like. Alaryl groups such as benzyl group and phenethyl group; alkyl halide-substituted or unsubstituted monovalent hydrocarbon groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group are exemplified. It is preferably an alkyl group having 1 to 3 carbon atoms, and a methyl group is most preferable from the viewpoint of heat resistance.
Ｒ１の全数のうちメチル基が占める数の割合は、５０〜９９．９％、好ましくは６０〜９７％である。５０モル％未満の場合は得られる硬化物の耐熱性が不十分となる。 Ratio of the number occupied by the methyl groups out of the total number of R 1 is 50 to 99.9%, preferably 60 to 97%. If it is less than 50 mol%, the heat resistance of the obtained cured product will be insufficient.
Ｘ１は水素原子又はアルキル基であり、このアルキル基としては、Ｒ１として例示したものと同様の有機基が挙げられ、特に、メチル基、エチル基であることが好ましい。 X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include organic groups similar to those exemplified as R 1 , and a methyl group and an ethyl group are particularly preferable.
ａ１は０．２〜０．８であり、ｂ１は０．２〜０．８であり、ｃ１は０〜０．１であり、ａ１＋ｂ１＋ｃ１＝１である。ａ１、ｂ１及びｃ１が上記範囲外であると、得られる硬化物の硬さ及び／又は強度が不十分となる。 a1 is 0.2 to 0.8, b1 is 0.2 to 0.8, c1 is 0 to 0.1, and a1 + b1 + c1 = 1. If a1, b1 and c1 are out of the above range, the hardness and / or strength of the obtained cured product will be insufficient.
ａ１は好ましくは０．３〜０．７、特に好ましくは０．４〜０．６であり、ｂ１は好ましくは０．３〜０．７、特に好ましくは０．４〜０．６であり、ｃ１は好ましくは０〜０．０５である。 a1 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, and b1 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6. c1 is preferably 0 to 0.05.
（Ａ）成分の分子量は限定されないが、トルエン溶媒を用いたＧＰＣ測定（標準ポリスチレン換算）による重量平均分子量（Ｍｗ）が５００〜２０，０００であることが好ましく、より好ましくは７００〜１５，０００、特に好ましくは、１，０００〜１０，０００である。 The molecular weight of the component (A) is not limited, but the weight average molecular weight (Mw) measured by GPC using a toluene solvent (standard polystyrene equivalent) is preferably 500 to 20,000, more preferably 700 to 15,000. , Particularly preferably 1,000 to 10,000.
（Ａ）成分は、一種単独で用いても二種以上を併用してもよい。 The component (A) may be used alone or in combination of two or more.
＜（Ｂ）成分＞
（Ｂ）成分は下記平均単位式（２）で表されるオルガノポリシロキサンである。
（ＳｉＯ２）ａ２（Ｒ２ ３ＳｉＯ１／２）ｂ２（Ｘ１Ｏ１／２）ｃ２ （２）
（式中、Ｒ２は同一又は異なっていても良い、置換又は非置換のアルケニル基を含まない一価炭化水素基であり、Ｘ１は水素原子又はアルキル基である。ａ２は０．２〜０．８、ｂ２は０．２〜０．８、ｃ２は０〜０．１であり、ａ２＋ｂ２＋ｃ２＝１である。）
<Ingredient (B)>
The component (B) is an organopolysiloxane represented by the following average unit formula (2).
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
(In the formula, R 2 is a monovalent hydrocarbon group containing no substituted or unsubstituted alkenyl group, which may be the same or different, and X 1 is a hydrogen atom or an alkyl group. A2 is 0.2 to 0.2. 0.8 and b2 are 0.2 to 0.8, c2 is 0 to 0.1, and a2 + b2 + c2 = 1).
Ｒ２中のアルケニル基を含まない一価炭化水素基としては、（Ａ）成分におけるＲ１中のアルケニル基以外のケイ素原子結合有機基と同様のものが挙げられ、中でも耐熱性の面からメチル基が最も好ましい。 Examples of the monovalent hydrocarbon group containing no alkenyl group in R 2 include those similar to the silicon atom-bonded organic group other than the alkenyl group in R 1 in the component (A), and among them, methyl from the viewpoint of heat resistance. Groups are most preferred.
Ｘ１は水素原子又はアルキル基であり、このアルキル基としては、（Ａ）成分においてＲ１として例示したものと同様の有機基が挙げられ、特に、メチル基、エチル基であることが好ましい。 X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include organic groups similar to those exemplified as R 1 in the component (A), and a methyl group and an ethyl group are particularly preferable.
ａ２は０．２〜０．８であり、ｂ２は０．２〜０．８であり、ｃ２は０〜０．１であり、ａ２＋ｂ２＋ｃ２＝１である。ａ２、ｂ２及びｃ２が上記範囲外であると、得られる硬化物の硬さ及び／又は強度が不十分となる。 a2 is 0.2 to 0.8, b2 is 0.2 to 0.8, c2 is 0 to 0.1, and a2 + b2 + c2 = 1. If a2, b2 and c2 are out of the above range, the hardness and / or strength of the obtained cured product will be insufficient.
ａ２は好ましくは０．３〜０．７、特に好ましくは０．４〜０．６であり、ｂ２は好ましくは０．３〜０．７、特に好ましくは０．４〜０．６であり、ｃ２は０．０１〜０．１とすることができるが、好ましくは０〜０．０５である。 a2 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6, and b2 is preferably 0.3 to 0.7, particularly preferably 0.4 to 0.6. c2 can be 0.01 to 0.1, but is preferably 0 to 0.05.
（Ｂ）成分の分子量は限定されないが、トルエン溶媒を用いたＧＰＣ測定（標準ポリスチレン換算）による重量平均分子量（Ｍｗ）が５００〜２０，０００であることが好ましく、より好ましくは７００〜１５，０００、特に好ましくは、１，０００〜１０，０００である。 The molecular weight of the component (B) is not limited, but the weight average molecular weight (Mw) measured by GPC using a toluene solvent (standard polystyrene equivalent) is preferably 500 to 20,000, more preferably 700 to 15,000. , Particularly preferably 1,000 to 10,000.
（Ｂ）成分は、一種単独で用いても二種以上を併用してもよい。 The component (B) may be used alone or in combination of two or more.
（Ｂ）成分の配合量は、硬化物の硬度の点から、（Ａ）成分１００質量部に対して好ましくは１〜１００質量部、より好ましくは５〜７０質量部、更に好ましくは７〜５０質量部である。 The blending amount of the component (B) is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts by mass, and further preferably 7 to 50 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the hardness of the cured product. It is a mass part.
＜（Ｃ）成分＞
（Ｃ）成分は下記平均単位式（３）で表されるオルガノポリシロキサンである。
（Ｒ３ ２ＳｉＯ）ａ３（Ｒ３ ３ＳｉＯ１／２）ｂ３ （３）
（式中、Ｒ３は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ３の全数のうち２０％以上がメチル基であり、かつ、０.０００１〜２５％はアルケニル基であり、ａ３は０．９９８０〜０．９９９９、ｂ３は０．０００１〜０．００２であり、ａ３＋ｂ３＝１である。）
<Ingredient (C)>
The component (C) is an organopolysiloxane represented by the following average unit formula (3).
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 20% or more of the total number of R 3 is a methyl group, and 0.001 to 25. % Is an alkenyl group, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3 + b3 = 1).
Ｒ３は、（Ａ）成分におけるＲ１と同様のものが挙げられ、Ｒ３中のアルケニル基として、好ましくは、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基が例示され、ビニル基であることが特に好ましい。 R 3 is the same groups as those of R 1 in component (A), the alkenyl group in R 3, preferably, a vinyl group, an allyl group, butenyl group, pentenyl group, hexenyl group and the like, vinyl group Is particularly preferable.
Ｒ３の全数のうちアルケニル基が占める数の割合は、０．０００１〜２５％、好ましくは０．１〜２０％、特に好ましくは０．３〜２０％である。０．０００１％未満では、組成物の硬化性が不十分となり、２５％を超えると硬化物が脆くなる。 Ratio of the number occupied by the alkenyl group of the total number of R 3 is from 0.0001 to 25%, preferably from 0.1% to 20%, particularly preferably 0.3 to 20%. If it is less than 0.0001%, the curability of the composition becomes insufficient, and if it exceeds 25%, the cured product becomes brittle.
また、Ｒ３中のアルケニル基以外のケイ素原子結合有機基としては、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、ヘプチル基等のアルキル基；フェニル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロメチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基等のハロゲン化アルキル置換又は非置換の一価炭化水素基が例示され、中でも耐熱性の面からメチル基が最も好ましい。全Ｒ３のうち、これらの一価炭化水素基の含有率が２０モル％以上であれば、安定した耐熱性を付与できるため好ましく、より好ましくは４０モル％以上である。 As the silicon-bonded organic groups other than alkenyl groups in R 3, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or similar alkyl groups; phenyl group, a naphthyl group Alaryl groups such as benzyl group and phenethyl group; alkyl halide-substituted or unsubstituted monovalent hydrocarbon groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group are exemplified. Of these, the methyl group is most preferable from the viewpoint of heat resistance. Of the total R 3, if the content of these monovalent hydrocarbon groups are 20 mol% or more, preferably because it can impart a stable heat resistance, more preferably 40 mol% or more.
Ｒ３の全数のうちメチル基が占める数の割合は、２０〜９９．９９９９％、好ましくは４０〜９９．９％である。２０モル％未満の場合は得られる硬化物の耐熱性が不十分となる。 Ratio of the number occupied by the methyl groups out of the total number of R 3 is from 20 to 99.9999%, preferably from 40 to 99.9%. If it is less than 20 mol%, the heat resistance of the obtained cured product will be insufficient.
ａ３は０．９９８０〜０．９９９９であり、好ましくは０．９９８５〜０．９９９９であり、更に好ましくは、０．９９８７〜０．９９９９である。ｂ３は０．０００１〜０．００２であり、好ましくは０．０００１〜０．００１５であり、更に好ましくは、０．０００１〜０．００１３である。またａ３＋ｂ３＝１である。 a3 is 0.9980 to 0.9999, preferably 0.9985 to 0.9999, and more preferably 0.9987 to 0.9999. b3 is 0.0001 to 0.002, preferably 0.0001 to 0.0015, and more preferably 0.0001 to 0.0013. Further, a3 + b3 = 1.
（Ｃ）成分は、一種単独で用いても二種以上を併用してもよい。 The component (C) may be used alone or in combination of two or more.
（Ｃ）成分の配合量は、硬化物の硬度の点から、（Ａ）成分１００質量部に対して好ましくは５〜１００質量部、より好ましくは１０〜７０質量部、更に好ましくは３０〜６０質量部である。 The blending amount of the component (C) is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, and further preferably 30 to 60 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the hardness of the cured product. It is a mass part.
＜（Ｄ）成分＞
（Ｄ）成分は、有機過酸化物であり、熱により分解してラジカルを生成することで本発明の熱硬化性シリコーン組成物を硬化させるものである。
<(D) component>
The component (D) is an organic peroxide, which is decomposed by heat to generate radicals to cure the thermosetting silicone composition of the present invention.
有機過酸化物の具体例としては、ジアシルパーオキサイド、パーオキシエステル、ジアルキルパーオキサイド、パーオキシジカーボネート、パーオキシケタール、ハイドロパーオキサイド、シリルパーオキサイド等が挙げられる。 Specific examples of the organic peroxide include diacyl peroxide, peroxy ester, dialkyl peroxide, peroxy dicarbonate, peroxyketal, hydroperoxide, silyl peroxide and the like.
ジアシルパーオキサイドとしては、例えば、イソブチルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、３，５，５−トリメチルヘキサノイルパーオキサイド、オクタノイルパーオキサイド、ラウロイルパーオキサイド、ステアロイルパーオキサイド、スクシニックパーオキサイド、ベンゾイルパーオキシトルエン及びベンゾイルパーオキサイドが挙げられる。 Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and dichloromethane. , Benzoyl Peroxytoluene and Benzoyl Peroxide.
パーオキシエステルとしては、例えば、クミルパーオキシネオデカノエート、１，１，３，３−テトラメチルブチルパーオキシネオデカノエート、１−シクロヘキシル−１−メチルエチルパーオキシネオデカノエート、ｔ−ヘキシルパーオキシネオデカノエート、ｔ−ブチルパーオキシピバレート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、２，５−ジメチル−２，５−ビス（２−エチルヘキサノイルパーオキシ）ヘキサン、１−シクロヘキシル−１−メチルエチルパーオキシ−２−エチルヘキサノエート、ｔ−ヘキシルパーオキシ−２−エチルヘキサノネート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシイソブチレート、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｔ−ヘキシルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノネート、ｔ−ブチルパーオキシラウレート、２，５−ジメチル−２，５−ビス（ｍ−トルオイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート、ｔ−ヘキシルパーオキシベンゾエート、ｔ−ブチルパーオキシアセテート及びビス（ｔ−ブチルパーオキシ）ヘキサヒドロテレフタレートが挙げられる。 Examples of the peroxyester include Kumilperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, and t. -Hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis ( 2-Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanoate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-3,5,5-trimethylhexa Nonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluyl peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl Examples thereof include monocarbonate, t-hexylperoxybenzoate, t-butylperoxyacetate and bis (t-butylperoxy) hexahydroterephthalate.
ジアルキルパーオキサイドとしては、例えば、α，α’−ビス（ｔ−ブチルパーオキシ）ジイソプロピルベンゼン、ジクミルパーオキサイド、２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキサン及びｔ−ブチルクミルパーオキサイドが挙げられる。 Examples of the dialkyl peroxide include α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and t. -Butyl humyl peroxide can be mentioned.
パーオキシジカーボネートとしては、例えば、ジ−ｎ−プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、ジ−２−エトキシメトキシパーオキシジカーボネート、ビス（２−エチルヘキシルパーオキシ）ジカーボネート、ジメトキシブチルパーオキシジカーボネート及びビス（３−メチル−３−メトキシブチルパーオキシ）ジカーボネートが挙げられる。 Examples of the peroxydicarbonate include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and di-2-ethoxymethoxyperoxydicarbonate. Examples thereof include bis (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate and bis (3-methyl-3-methoxybutylperoxy) dicarbonate.
パーオキシケタールとしては、例えば、１，６−ビス（ｔ−ブチルパーオキシカルボニルオキシ）ヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−（ｔ−ブチルパーオキシ）シクロドデカン及び２，２−ビス（ｔ−ブチルパーオキシ）デカンが挙げられる。 Examples of the peroxyketal include 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1,1-. Bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (t-butylperoxy) cyclododecane and 2,2- Bis (t-butylperoxy) decane can be mentioned.
ハイドロパーオキサイドとしては、例えば、ジイソプロピルベンゼンハイドロパーオキサイド及びクメンハイドロパーオキサイドが挙げられる。 Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
シリルパーオキサイドとしては、例えば、ｔ−ブチルトリメチルシリルパーオキサイド、ビス（ｔ−ブチル）ジメチルシリルパーオキサイド、ｔ−ブチルトリビニルシリルパーオキサイド、ビス（ｔ−ブチル）ジビニルシリルパーオキサイド、トリス（ｔ−ブチル）ビニルシリルパーオキサイド、ｔ−ブチルトリアリルシリルパーオキサイド、ビス（ｔ−ブチル）ジアリルシリルパーオキサイド及びトリス（ｔ−ブチル）アリルシリルパーオキサイドが挙げられる。 Examples of the silyl peroxide include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, and tris (t-butyl). Examples thereof include butyl) vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis (t-butyl) diallylsilyl peroxide and tris (t-butyl) allylsilyl peroxide.
（Ｄ）成分としては、未硬化状態における安定性の点から、１００℃における半減期が１時間以上の有機過酸化物が好ましい。 As the component (D), an organic peroxide having a half-life of 1 hour or more at 100 ° C. is preferable from the viewpoint of stability in an uncured state.
（Ｄ）成分は、一種単独で用いても二種以上を併用してもよい。 The component (D) may be used alone or in combination of two or more.
（Ｄ）成分の配合量は、有効量（即ち、所謂触媒量）でよいが、（Ａ）成分１００質量部に対して０．０１〜１０質量部が好ましく、特に０．１〜５質量部を配合することが好ましい。 The blending amount of the component (D) may be an effective amount (that is, a so-called catalyst amount), but is preferably 0.01 to 10 parts by mass, particularly 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A). Is preferably blended.
＜（Ｅ）成分＞
（Ｅ）成分の溶剤は、本組成物を構成する上記（Ａ）〜（Ｄ）成分を溶解するものであれば特に限定されるものではなく、公知の有機溶剤を使用することができる。該溶剤としては、例えば、キシレン、トルエン、ベンゼン等の芳香族炭化水素系溶剤、ヘプタン、ヘキサン等の脂肪族炭化水素系溶剤、トリクロロエチレン、パークロロエチレン、塩化メチレン等のハロゲン化炭化水素系溶剤、酢酸エチル等のエステル系溶剤、メチルイソブチルケトン、メチルエチルケトン等のケトン系溶剤、エタノール、イソプロパノール、ブタノール等のアルコール系溶剤、リグロイン、シクロヘキサノン、ジエチルエーテル、ゴム揮発油、シリコーン系溶剤などが挙げられる。中でもトルエン、ヘプタン、酢酸エチルが好適に用いられる。
<(E) component>
The solvent of the component (E) is not particularly limited as long as it dissolves the above-mentioned components (A) to (D) constituting the present composition, and a known organic solvent can be used. Examples of the solvent include aromatic hydrocarbon solvents such as xylene, toluene and benzene, aliphatic hydrocarbon solvents such as heptane and hexane, and halogenated hydrocarbon solvents such as trichloroethylene, perchloroethylene and methylene chloride. Examples thereof include ester solvents such as ethyl acetate, ketone solvents such as methylisobutylketone and methylethylketone, alcohol solvents such as ethanol, isopropanol and butanol, ligroin, cyclohexanone, diethyl ether, rubber volatile oil and silicone solvents. Of these, toluene, heptane, and ethyl acetate are preferably used.
（Ｅ）成分は、本発明の熱硬化性シリコーン組成物の塗布作業時の蒸発速度に応じて、１種を単独で用いても２種以上を組合せて混合溶剤として用いてもよい。 As the component (E), one type may be used alone or two or more types may be used as a mixed solvent depending on the evaporation rate at the time of coating the thermosetting silicone composition of the present invention.
（Ｅ）成分の配合量は特に制限されないが、塗布作業時の作業性の点から、（Ａ）〜（Ｄ）成分の合計１００質量部に対して好ましくは５０〜２００質量部、より好ましくは１００〜１５０質量部である。 The blending amount of the component (E) is not particularly limited, but from the viewpoint of workability at the time of coating work, it is preferably 50 to 200 parts by mass, more preferably 50 parts by mass with respect to a total of 100 parts by mass of the components (A) to (D). It is 100 to 150 parts by mass.
＜（Ｆ）成分＞
本発明の熱硬化性シリコーン組成物には、（Ｆ）蛍光体を含有させてもよい。蛍光体を熱硬化性シリコーン組成物へ混合、分散させることで、光半導体素子から発せられた光を効率的に目的の波長の光に波長変換することが可能となる。
<(F) component>
The thermosetting silicone composition of the present invention may contain (F) a phosphor. By mixing and dispersing the phosphor in the thermosetting silicone composition, it is possible to efficiently convert the light emitted from the optical semiconductor device into light having a target wavelength.
蛍光体は、光半導体素子から放出される青色光、紫色光、紫外光を吸収して波長を変換し、光半導体素子から放出される光と異なる波長の赤、橙色、黄色、緑色、青色領域の波長の光を放出するものである。これにより、光半導体素子から放出される光の一部と、蛍光体から放出される光の一部とが混合して、白色を含む多色系の光半導体デバイスが得られる。 The phosphor absorbs blue light, purple light, and ultraviolet light emitted from the optical semiconductor element to convert the wavelength, and has a red, orange, yellow, green, and blue region having a wavelength different from the light emitted from the optical semiconductor element. It emits light of the same wavelength. As a result, a part of the light emitted from the optical semiconductor element and a part of the light emitted from the phosphor are mixed to obtain a multicolored optical semiconductor device containing white.
上述のような蛍光体には、緑色に発光する蛍光体、青色に発光する蛍光体、黄色に発光する蛍光体、赤色に発光する蛍光体等の種々の蛍光体がある。本発明に用いられる具体的な蛍光体としては、有機蛍光体、無機蛍光体、蛍光顔料、蛍光染料等公知の蛍光体が挙げられる。有機蛍光体としては、アリルスルホアミド・メラミンホルムアルデヒド共縮合染色物やペリレン系蛍光体等を挙げることができ、長期間使用可能な点からペリレン系蛍光体が好ましく用いられる。本発明に特に好ましく用いられる蛍光物質としては、無機蛍光体が挙げられる。以下に本発明に用いられる無機蛍光体について記載するが、これに限定されるわけではない。 The phosphors as described above include various phosphors such as a fluorescent substance that emits green light, a fluorescent substance that emits blue light, a fluorescent substance that emits yellow light, and a fluorescent substance that emits red light. Specific examples of the fluorescent substance used in the present invention include known fluorescent substances such as organic fluorescent substances, inorganic fluorescent substances, fluorescent pigments, and fluorescent dyes. Examples of the organic phosphor include an allylsulfoamide / melamine formaldehyde cocondensation dyed product, a perylene-based fluorescent substance, and the like, and a perylene-based fluorescent substance is preferably used because it can be used for a long period of time. Examples of the fluorescent substance particularly preferably used in the present invention include an inorganic fluorescent substance. The inorganic fluorescent material used in the present invention will be described below, but the present invention is not limited thereto.
緑色に発光する蛍光体として、例えば、ＳｒＡｌ２Ｏ４：Ｅｕ、Ｙ２ＳｉＯ５：Ｃｅ，Ｔｂ、ＭｇＡｌ１１Ｏ１９：Ｃｅ，Ｔｂ、Ｓｒ７Ａｌ１２Ｏ２５：Ｅｕ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも１以上）Ｇａ２Ｓ４：Ｅｕなどが挙げられる。 Examples of the fluorescent substance that emits green light include SrAl 2 O 4 : Eu, Y 2 SiO 5 : Ce, Tb, MgAl 11 O 19 : Ce, Tb, Sr 7 Al1 2 O 25 : Eu, (Mg, Ca, Sr). , At least one of Ba) Ga 2 S 4 : Eu and the like.
青色に発光する蛍光体として、例えば、Ｓｒ５（ＰＯ４）３Ｃｌ：Ｅｕ、（ＳｒＣａＢａ）５（ＰＯ４）３Ｃｌ：Ｅｕ、（ＢａＣａ）５（ＰＯ４）３Ｃｌ：Ｅｕ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも１以上）２Ｂ５Ｏ９Ｃｌ：Ｅｕ，Ｍｎ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも１以上）（ＰＯ４）６Ｃｌ２：Ｅｕ，Ｍｎなどが挙げられる。 Examples of the fluorescent substance that emits blue light include Sr 5 (PO 4 ) 3 Cl: Eu, (SrCaBa) 5 (PO 4 ) 3 Cl: Eu, (BaCa) 5 (PO 4 ) 3 Cl: Eu, (Mg,). (At least 1 or more of Ca, Sr, Ba) 2 B 5 O 9 Cl: Eu, Mn, (at least 1 or more of Mg, Ca, Sr, Ba) (PO 4 ) 6 C l2 : Eu, Mn, etc. Be done.
緑色から黄色に発光する蛍光体として、少なくともセリウムで賦活されたイットリウム・アルミニウム酸化物蛍光体、少なくともセリウムで賦括されたイットリウム・ガドリニウム・アルミニウム酸化物蛍光体、少なくともセリウムで賦活されたイットリウム・アルミニウム・ガーネット酸化物蛍光体、及び、少なくともセリウムで賦活されたイットリウム・ガリウム・アルミニウム酸化物蛍光体などが挙げられる（いわゆるＹＡＧ系蛍光体）。具体的には、Ｌｎ３Ｍ５Ｏ１２：Ａ（Ｌｎは、Ｙ、Ｇｄ、Ｌａから選ばれる少なくとも１以上である。Ｍは、Ａｌ、Ｃａの少なくともいずれか一方を含む。Ａは、ランタノイド系である。）、（Ｙ１−ｘＧａｘ）３（Ａｌ１−ｙＧａｙ）５Ｏ１２：Ａ（Ａは、Ｃｅ、Ｔｂ、Ｐｒ、Ｓｍ、Ｅｕ、Ｄｙ、Ｈｏから選ばれる少なくとも１以上である。０＜ｘ＜０．５、０＜ｙ＜０．５である。）を使用することができる。 Yttrium-aluminum oxide phosphors activated at least with cerium, yttrium-gadrinium-aluminum oxide phosphors with at least cerium, and yttrium-aluminum activated with at least cerium as phosphors that emit green to yellow light. Examples thereof include a garnet oxide phosphor and at least a yttrium / gallium / aluminum oxide phosphor activated with cerium (so-called YAG-based phosphor). Specifically, Ln 3 M 5 O 12 : A (Ln is at least one selected from Y, Gd, and La. M contains at least one of Al and Ca. A is a lanthanoid type. (Y 1-x G a x ) 3 (Al 1-y G a y ) 5 O 12 : A (A is at least one selected from Ce, Tb, Pr, Sm, Eu, Dy, Ho). 0 <x <0.5, 0 <y <0.5) can be used.
赤色に発光する蛍光体として、例えば、Ｙ２Ｏ２Ｓ：Ｅｕ、Ｌａ２Ｏ２Ｓ：Ｅｕ、Ｙ２Ｏ３：Ｅｕ、Ｇｄ２Ｏ２Ｓ：Ｅｕなどが挙げられる。 Examples of the phosphor that emits red light include Y 2 O 2 S: Eu, La 2 O 2 S: Eu, Y 2 O 3 : Eu, and Gd 2 O 2 S: Eu.
また、青色ＬＥＤに対応し発光する蛍光体としては、Ｙ３（Ａｌ，Ｇａ）５Ｏ１２：Ｃｅ、（Ｙ，Ｇｄ）３Ａｌ５Ｏ１２：Ｃｅ、Ｌｕ３Ａｌ５Ｏ１２：Ｃｅ、Ｙ３Ａｌ５Ｏ１２：ＣｅなどのＹＡＧ系蛍光体、Ｔｂ３Ａｌ５Ｏ１２：ＣｅなどのＴＡＧ系蛍光体、（Ｂａ，Ｓｒ）２ＳｉＯ４：Ｅｕ系蛍光体やＣａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ系蛍光体、（Ｓｒ，Ｂａ，Ｍｇ）２ＳｉＯ４：Ｅｕなどのシリケート系蛍光体、（Ｃａ，Ｓｒ）２Ｓｉ５Ｎ８：Ｅｕ、（Ｃａ，Ｓｒ）ＡｌＳｉＮ３：Ｅｕ、ＣａＳｉＡｌＮ３：Ｅｕ等のナイトライド系蛍光体、Ｃａｘ（Ｓｉ，Ａｌ）１２（Ｏ，Ｎ）１６：Ｅｕなどのオキシナイトライド系蛍光体、さらには（Ｂａ，Ｓｒ，Ｃａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ系蛍光体、Ｃａ８ＭｇＳｉ４Ｏ１６Ｃｌ２：Ｅｕ系蛍光体、ＳｒＡｌ２Ｏ４：Ｅｕ，Ｓｒ４Ａｌ１４Ｏ２５：Ｅｕ等の蛍光体が挙げられる。 The phosphors that emit light corresponding to the blue LED include Y 3 (Al, Ga) 5 O 12 : Ce, (Y, Gd) 3 Al 5 O 12 : Ce, Lu 3 Al 5 O 12 : Ce, Y. 3 Al 5 O 12 : YAG-based fluorescent material such as Ce, Tb 3 Al 5 O 12 : TAG-based fluorescent material such as Ce, (Ba, Sr) 2 SiO 4 : Eu-based fluorescent material and Ca 3 Sc 2 Si 3 O 12 : Ce-based fluorophore, (Sr, Ba, Mg) 2 SiO 4 : Silicate-based phosphor such as Eu, (Ca, Sr) 2 Si 5 N 8 : Eu, (Ca, Sr) AlSiN 3 : Eu, CaSiAlN 3 : Nitride-based fluorescent material such as Eu, Cax (Si, Al) 12 (O, N) 16 : Oxynitride-based fluorescent material such as Eu, and further (Ba, Sr, Ca) Si 2 O 2 N 2 : Eu-based fluorescent material, Ca 8 MgSi 4 O 16 Cl 2 : Eu-based fluorescent material, SrAl 2 O 4 : Eu, Sr 4 Al 14 O 25 : Eu or the like.
これらの中では、ＹＡＧ系蛍光体、ＴＡＧ系蛍光体、シリケート系蛍光体が、発光効率や輝度などの点で好ましく用いられる。 Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used in terms of luminous efficiency, brightness, and the like.
上記以外にも、用途や目的とする発光色に応じて公知の蛍光体を用いることができる。 In addition to the above, known phosphors can be used depending on the intended use and the desired emission color.
蛍光体の粒子サイズは、特に制限はないが、Ｄ５０が０．０５μｍ以上のものが好ましく、３μｍ以上のものがより好ましい。また、Ｄ５０が３０μｍ以下のものが好ましく、２０μｍ以下のものがより好ましい。ここでＤ５０とは、レーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布において、小粒径側からの通過分積算が５０％となるときの粒子径のことをいう。Ｄ５０が上記範囲であると、本発明の熱硬化性シリコーン組成物（例えば、ウェハーレベル光半導体デバイス用樹脂組成物）中の蛍光体の分散性が良好で、安定な発光が得られる。 The particle size of the phosphor is not particularly limited, but the one having a D 50 of 0.05 μm or more is preferable, and the one having a D 50 of 3 μm or more is more preferable. Further, the one having a D 50 of 30 μm or less is preferable, and the one having a D 50 of 20 μm or less is more preferable. Here, D 50 refers to the particle size when the total amount of passage from the small particle size side is 50% in the volume-based particle size distribution obtained by measuring by the laser diffraction / scattering type particle size distribution measurement method. When D 50 is in the above range, the dispersibility of the phosphor in the thermosetting silicone composition of the present invention (for example, the resin composition for a wafer level optical semiconductor device) is good, and stable light emission can be obtained.
上記蛍光体は、１種又は２種以上を混合して用いてもよい。 The fluorescent substance may be used alone or in combination of two or more.
（Ｆ）成分の含有量は、（Ａ）〜（Ｅ）成分の合計１００質量部に対し２０〜５００質量部であることが好ましく、５０〜４００質量部以上であることがより好ましく、８０〜３００質量部であることがさらに好ましい。蛍光体含有量を上記範囲とすることで、光変換効率を高めることができる。 The content of the component (F) is preferably 20 to 500 parts by mass, more preferably 50 to 400 parts by mass or more, and 80 to 80 to 100 parts by mass with respect to 100 parts by mass of the total of the components (A) to (E). It is more preferably 300 parts by mass. By setting the phosphor content in the above range, the light conversion efficiency can be improved.
本発明の熱硬化性シリコーン組成物は、蛍光体を配合することにより、蛍光体シートとしてＬＥＤの表面被覆用途に特に好ましく用いられる。その際、蛍光体シート中の蛍光体の含有量が上記範囲であることで、優れた性能を示すＬＥＤ発光装置を得ることができる。 The thermosetting silicone composition of the present invention is particularly preferably used as a phosphor sheet for surface coating of LEDs by blending a fluorescent substance. At that time, when the content of the phosphor in the phosphor sheet is within the above range, it is possible to obtain an LED light emitting device showing excellent performance.
＜任意成分＞
本発明の熱硬化性シリコーン組成物には、上記（Ａ）〜（Ｆ）成分以外にも、以下に例示する接着性向上剤を含有してもよい。
<Arbitrary ingredient>
In addition to the above components (A) to (F), the thermosetting silicone composition of the present invention may contain the adhesiveness improving agent exemplified below.
接着性向上剤としては、ケイ素原子に結合したアルコキシ基を一分子中に少なくとも１個、好ましくは２個以上有するオルガノポリシロキサン又はオルガノシラン化合物、もしくはエポキシ部位を有する基を含有するオルガノポリシロキサン又はオルガノシラン化合物が好ましい。 The adhesiveness improving agent includes an organopolysiloxane or an organosilane compound having at least one, preferably two or more alkoxy groups bonded to a silicon atom in one molecule, or an organopolysiloxane containing a group having an epoxy moiety. Organosilane compounds are preferred.
アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メトキシエトキシ基が例示され、特に、メトキシ基であることが好ましい。また、この有機ケイ素化合物のケイ素原子に結合するアルコキシ基以外の基としては、上記Ｒ１等において例示した、上記アルキル基、上記アルケニル基、上記アリール基、上記アラルキル基、上記ハロゲン化アルキル基等の置換もしくは非置換の一価炭化水素基；３−メタクリロキシプロピル基等のアクリル基含有一価有機基；水素原子が例示される。具体的には（メタ）アクリル基含有シランカップリング剤等のシランカップリング剤やその部分加水分解縮合物（シランカップリング剤のオリゴマー）等が例示される。より具体的には、３−メタクリロキシプロピルトリメトキシシラン等のシラン化合物；一分子中にケイ素原子結合アルケニル基もしくはケイ素原子結合水素原子、及びケイ素原子結合アルコキシ基をそれぞれ少なくとも１個ずつ有するシロキサン化合物、ケイ素原子結合アルコキシ基を少なくとも１個有するシラン化合物又はシロキサン化合物と一分子中にケイ素原子結合ヒドロキシ基とケイ素原子結合アルケニル基をそれぞれ少なくとも１個ずつ有するシロキサン化合物との混合物、メチルポリシリケート、エチルポリシリケート、エポキシ基含有エチルポリシリケートが例示される。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. As the groups other than alkoxy groups bonded to the silicon atom of the organosilicon compound, exemplified in the above R 1 or the like, the alkyl group, the alkenyl group, the aryl group, the aralkyl group, the halogenated alkyl group such as Already substituted or unsubstituted monovalent hydrocarbon group; acrylic group-containing monovalent organic group such as 3-methacryloxypropyl group; hydrogen atom is exemplified. Specific examples thereof include a silane coupling agent such as a (meth) acrylic group-containing silane coupling agent and a partially hydrolyzed condensate thereof (oligomer of the silane coupling agent). More specifically, a silane compound such as 3-methacryloxypropyltrimethoxysilane; a siloxane compound having at least one silicon atom-bonded alkenyl group or silicon atom-bonded hydrogen atom and one silicon atom-bonded alkoxy group in one molecule. , A mixture of a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group and a siloxane compound having at least one silicon atom-bonded hydroxy group and one silicon atom-bonded alkenyl group in one molecule, methylpolysilicate, ethyl. Examples thereof include polysaccharides and ethyl polysilicates containing an epoxy group.
エポキシ部位を有する基としては、３−グリシドキシプロピル基、４−グリシドキシブチル基等のグリシドキシアルキル基；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）プロピル基等のエポキシシクロヘキシルアルキル基；４−オキシラニルブチル基、８−オキシラニルオクチル基等のオキシラニルアルキル基等のエポキシ基含有一価有機基が挙げられる。 Groups having an epoxy moiety include glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4). -Epoxycyclohexyl) An epoxycyclohexylalkyl group such as a propyl group; an epoxy group-containing monovalent organic group such as an oxylanylalkyl group such as a 4-oxylanylbutyl group and an 8-oxylanyloctyl group can be mentioned.
接着性向上剤は低粘度液状であることが好ましく、その粘度は限定されないが、２３℃において１〜５００ｍＰａ・ｓの範囲内であることが好ましい。 The adhesiveness improver is preferably a low-viscosity liquid, and its viscosity is not limited, but is preferably in the range of 1 to 500 mPa · s at 23 ° C.
接着性向上剤の含有量は限定されないが、上記（Ａ）成分１００質量部に対して０．０１〜１０質量部であることが好ましい。 The content of the adhesiveness improving agent is not limited, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).
また、本発明の熱硬化性シリコーン組成物には、ヒュームドシリカ、溶融石英ガラス、アルミナ、酸化亜鉛等の（Ｆ）成分以外の無機充填剤；ポリメタクリレート樹脂等の有機樹脂微粉末；耐熱剤、染料、顔料、難燃性付与剤等を含有してもよい。 Further, the thermosetting silicone composition of the present invention contains an inorganic filler other than the component (F) such as fumed silica, fused silica glass, alumina and zinc oxide; organic resin fine powder such as polymethacrylate resin; and a heat resistant agent. , Dyes, pigments, flame retardant-imparting agents and the like may be contained.
（Ｆ）成分以外の無機充填剤を使用する場合の配合量は、上記（Ａ）成分１００質量部に対し、好ましくは５〜５００質量部であり、より好ましくは１０〜２００質量部である。このような範囲であると、本発明の組成物は流動性がより優れたものとなる。 When an inorganic filler other than the component (F) is used, the blending amount is preferably 5 to 500 parts by mass, and more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the component (A). Within such a range, the composition of the present invention has better fluidity.
本発明の熱硬化性シリコーン組成物の２５℃における粘度は、好ましくは１０〜５，０００ｍＰａ・ｓであり、より好ましくは２０〜２，０００ｍＰａ・ｓである。このような範囲であると、得られる組成物は、作業性・取扱い性が良好となりやすく、成形、硬化時に泡や空気の巻き込みが発生しにくい。なお、本発明において、粘度は回転粘度計で測定したときの値とすることができる。 The viscosity of the thermosetting silicone composition of the present invention at 25 ° C. is preferably 10 to 5,000 mPa · s, more preferably 20 to 2,000 mPa · s. Within such a range, the obtained composition tends to have good workability and handleability, and bubbles and air are less likely to be entrained during molding and curing. In the present invention, the viscosity can be a value measured by a rotational viscometer.
本発明の熱硬化性シリコーン組成物の粘度は、（Ａ）〜（Ｅ）成分およびその他の成分の配合量、粘度、ならびに（Ｆ）成分の配合量および平均粒径などにより調節される。 The viscosity of the thermosetting silicone composition of the present invention is adjusted by the blending amount and viscosity of the components (A) to (E) and other components, and the blending amount and average particle size of the component (F).
本発明の熱硬化性シリコーン組成物であれば、反応制御剤を添加しなくても未硬化状態における安定性に優れ、高硬度の硬化物を与えるため、広範な用途への応用が可能であり、ＬＥＤ素子等の光半導体装置の表面被覆用途に特に有用なものとなる。但し、本発明の熱硬化性シリコーン組成物は（Ａ）〜（Ｅ）成分を含むものであれば、目的に応じ反応制御剤を含むことは差し支えない。 The thermosetting silicone composition of the present invention has excellent stability in an uncured state without adding a reaction control agent and gives a cured product having high hardness, so that it can be applied to a wide range of applications. , Which is particularly useful for surface coating applications of optical semiconductor devices such as LED elements. However, as long as the thermosetting silicone composition of the present invention contains the components (A) to (E), it may contain a reaction control agent depending on the purpose.
［シート］
本発明では、上述の熱硬化性シリコーン組成物から形成されたものであるシートを提供する。シートは組成物が硬化したもの、もしくは未硬化のもののいずれであってもよいが、未硬化のものとする方が好ましい。本発明のシートであれば、ＬＥＤ素子等の光半導体装置の表面被覆用途に特に有用なものとなる。
[Sheet]
The present invention provides a sheet formed from the thermosetting silicone composition described above. The sheet may be either a cured composition or an uncured composition, but it is preferable that the sheet is uncured. The sheet of the present invention is particularly useful for surface coating applications of optical semiconductor devices such as LED elements.
本発明のシートを作製する方法としては特に限定はされない。例えば、本発明の熱硬化性シリコーン組成物を、該組成物が硬化する温度未満の温度で加熱して（Ｅ）溶剤を揮発させることによって、シート（未硬化のシート）を得ることができる。 The method for producing the sheet of the present invention is not particularly limited. For example, a sheet (uncured sheet) can be obtained by heating the thermosetting silicone composition of the present invention at a temperature lower than the temperature at which the composition cures to volatilize the (E) solvent.
［シリコーン硬化物］
本発明の熱硬化性シリコーン組成物を成形、硬化させることにより、硬化物を得ることができる。成形方法としては、インジェクションモールド法やトランスファーモールド法など、従来用いられている方法を適用することができる。さらに、本発明の熱硬化性シリコーン組成物は、高い流動性を有するため、ディスペンス法、ポッティング法や各種コーティング法により成形することができる。
[Silicone cured product]
A cured product can be obtained by molding and curing the thermosetting silicone composition of the present invention. As the molding method, a conventionally used method such as an injection molding method or a transfer molding method can be applied. Further, since the thermosetting silicone composition of the present invention has high fluidity, it can be molded by a dispensing method, a potting method or various coating methods.
本発明の熱硬化性シリコーン組成物は、加熱により硬化が進行するが、迅速に硬化させるためには高い温度で加熱することが好ましい。硬化条件は、成形物の形状や硬化方法等により異なり、特に制限されないが、硬化温度は１３０〜２００℃の範囲内であることが好ましく、硬化時間は好ましくは１分〜２４時間、より好ましくは５分〜５時間である。 The thermosetting silicone composition of the present invention is cured by heating, but it is preferable to heat it at a high temperature in order to cure it quickly. The curing conditions vary depending on the shape of the molded product, the curing method, and the like, and are not particularly limited, but the curing temperature is preferably in the range of 130 to 200 ° C., and the curing time is preferably 1 minute to 24 hours, more preferably. 5 minutes to 5 hours.
また、本発明のシリコーン硬化物の硬さは、ショアＤで２０以上であることが好ましく、特に３０〜７０であることが好ましい。 Further, the hardness of the cured silicone product of the present invention is preferably 20 or more in Shore D, and particularly preferably 30 to 70.
以下、実施例及び比較例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
［実施例１］
構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４０（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０５で表わされる（Ａ）成分１００質量部、構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４５で表わされる（Ｂ）成分４０質量部、構成単位比（（ＣＨ３）２ＳｉＯ）０．９９９６（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０００４で表わされる（Ｃ）成分５０質量部、（Ｄ）成分として、有機過酸化物（化薬アクゾ株式会社製カヤレン６−７０）３．５質量部、（Ｅ）成分としてトルエン２００質量部を混合し、熱硬化性シリコーン組成物を調製した。
[Example 1]
Constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) Represented by 0.05 (A) 100 parts by mass of component, constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) Represented by 0.45 (B) 40 parts by mass of component, constituent unit ratio ((CH 3 ) 2 SiO ) 0.9996 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) 50 parts by mass of component (C) represented by 0.0004 , organic peroxide (chemical peroxide Axo stock) as component (D) A thermosetting silicone composition was prepared by mixing 3.5 parts by mass of Kayalen 6-70) manufactured by the same company and 200 parts by mass of toluene as a component (E).
［実施例２］
実施例１で得られた熱硬化性シリコーン組成物１００質量部に対し、ＹＡＧ蛍光体を１５０質量部混合し、蛍光体含有熱硬化性シリコーン組成物を調製した。
[Example 2]
A thermosetting silicone composition containing a phosphor was prepared by mixing 150 parts by mass of a YAG phosphor with 100 parts by mass of the thermosetting silicone composition obtained in Example 1.
［実施例３］
構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４０（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０５で表わされる（Ａ）成分１００質量部、構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４５で表わされる（Ｂ）成分２５質量部、構成単位比（（ＣＨ３）２ＳｉＯ）０．９９９６（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０００４で表わされる（Ｃ）成分４０質量部、（Ｄ）成分として有機過酸化物（化薬アクゾ株式会社製カヤレン６−７０）３質量部、（Ｅ）成分としてトルエン１７０質量部を混合し、熱硬化性シリコーン組成物を調製した。
[Example 3]
Constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) Represented by 0.05 (A) 100 parts by mass of component, constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) Represented by 0.45 (B) 25 parts by mass of component, constituent unit ratio ((CH 3 ) 2 SiO ) 0.9996 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) 40 parts by mass of component (C) represented by 0.0004, organic peroxide as component (D) Kayalen 6-70) manufactured by 3 parts by mass and 170 parts by mass of toluene as a component (E) were mixed to prepare a thermosetting silicone composition.
［実施例４］
実施例３で得られた熱硬化性シリコーン組成物１００質量部に対し、ＹＡＧ蛍光体を１５０質量部混合し、蛍光体含有熱硬化性シリコーン組成物を調製した。
[Example 4]
A thermosetting silicone composition containing a phosphor was prepared by mixing 150 parts by mass of a YAG phosphor with 100 parts by mass of the thermosetting silicone composition obtained in Example 3.
［比較例１］
構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４０（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０５で表わされる（Ａ）成分１００質量部、構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４５で表わされる（Ｂ）成分４０質量部、構成単位比（（ＣＨ３）２ＳｉＯ）０．９９９６（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０００４で表わされる（Ｃ）成分５０質量部、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錯体（（Ａ）〜（Ｃ）成分の合計に対し、本錯体中の白金金属が質量単位で１０ｐｐｍとなる量）、下記式（４）で表わされるオルガノハイドロジェンポリシロキサン７質量部、反応制御剤としてエチニルシクロヘキサノール０．２質量部、（Ｅ）成分としてトルエン２００質量部を混合し、熱硬化性シリコーン組成物を調製した。
Constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) Represented by 0.05 (A) 100 parts by mass of component, constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) Represented by 0.45 (B) 40 parts by mass of component, constituent unit ratio ((CH 3 ) 2 SiO ) 0.9996 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) 50 parts by mass of (C) component represented by 0.0004, 1,3-divinyl-1,1,3,3 of platinum -Tetramethyldisiloxane complex (amount of platinum metal in this complex is 10 ppm by mass with respect to the total of the components (A) to (C)), organohydrogenpolysiloxane 7 represented by the following formula (4) A thermosetting silicone composition was prepared by mixing 0.2 parts by mass of ethynylcyclohexanol as a reaction control agent and 200 parts by mass of toluene as a component (E).
［比較例２］
構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４５で表わされる（Ｂ）成分１００質量部、構成単位比（（ＣＨ３）２ＳｉＯ）０．９９９６（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０００４で表わされる（Ｃ）成分５０質量部、（Ｄ）成分として有機過酸化物（化薬アクゾ株式会社製カヤレン６−７０）３．５質量部、（Ｅ）成分としてトルエン１５０質量部を混合し、熱硬化性シリコーン組成物を調製した。
[Comparative Example 2]
Constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) (B) 100 parts by mass of component represented by 0.45 , constituent unit ratio ((CH 3 ) 2 SiO) 0.9996 ( (CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) 50 parts by mass of (C) component represented by 0.0004 , organic peroxide as (D) component (Kayaren 6-70 manufactured by Kayaku Akzo Corporation) ) 3.5 parts by mass and 150 parts by mass of toluene as the component (E) were mixed to prepare a thermosetting silicone composition.
［比較例３］
構成単位比（ＳｉＯ２）０．５５（（ＣＨ３）３ＳｉＯ１／２）０．４０（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０５で表わされる（Ａ）成分１００質量部、構成単位比（（ＣＨ３）２ＳｉＯ）０．９９９６（（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２）０．０００４で表わされる（Ｃ）成分５０質量部、（Ｄ）成分として有機過酸化物（化薬アクゾ株式会社製カヤレン６−７０）３質量部、（Ｅ）成分としてトルエン１５０質量部を混合し、熱硬化性シリコーン組成物を調製した。
[Comparative Example 3]
Constituent unit ratio (SiO 2 ) 0.55 ((CH 3 ) 3 SiO 1/2 ) 0.40 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) Represented by 0.05 (A) 100 parts by mass of component, constituent unit ratio ((CH 3 ) 2 SiO) 0.9996 ((CH 2 = CH) (CH 3 ) 2 SiO 1/2 ) 50 parts by mass of (C) component represented by 0.0004, A thermosetting silicone composition was prepared by mixing 3 parts by mass of an organic peroxide (Kayalen 6-70 manufactured by Kayaku Akzo Corporation) as a component (D) and 150 parts by mass of toluene as a component (E).
上記実施例１〜４および比較例１〜３で得られた組成物について、厚み２ｍｍのテフロン（登録商標）製の枠に流し込み、６０℃１時間、８０℃１時間、１００℃１時間の順に加熱することにより溶剤を揮発させ、シートを作製した。得られたシートについて以下の試験（１）、（２）を行い、物性を確認した。その結果を表１に示す。 The compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were poured into a Teflon (registered trademark) frame having a thickness of 2 mm, and were poured in the order of 60 ° C. for 1 hour, 80 ° C. for 1 hour, and 100 ° C. for 1 hour. The solvent was volatilized by heating to prepare a sheet. The following tests (1) and (2) were performed on the obtained sheet to confirm the physical properties. The results are shown in Table 1.
試験（１）：シートを１２０℃に１０分間晒した後、トルエンに可溶か否かを確認した。
試験（２）：シートを１５０℃で３時間硬化し、得られた硬化物の外観を観察し、硬さを測定した。
・外観：目視にて亀裂の有無を観察した。
亀裂無し（○），亀裂有り（×）
・硬さ：上島製作所（株）製デュロメータタイプＤ型硬度計にて測定した。
Test (1): After exposing the sheet to 120 ° C. for 10 minutes, it was confirmed whether or not the sheet was soluble in toluene.
Test (2): The sheet was cured at 150 ° C. for 3 hours, the appearance of the obtained cured product was observed, and the hardness was measured.
-Appearance: The presence or absence of cracks was visually observed.
No crack (○), with crack (×)
-Hardness: Measured with a durometer type D type hardness tester manufactured by Ueshima Seisakusho Co., Ltd.
表１に示されるように、実施例１〜４で得られたシートは、１２０℃１０分間の加熱後においてもトルエンに可溶であり、未硬化状態を保っていた。また、１５０℃で３時間加熱することにより高硬度の硬化物を与えることが示された。 As shown in Table 1, the sheets obtained in Examples 1 to 4 were soluble in toluene even after heating at 120 ° C. for 10 minutes and remained in an uncured state. It was also shown that heating at 150 ° C. for 3 hours gives a hardened product of high hardness.
一方、ヒドロシリル化による硬化性組成物である比較例１では、反応制御剤が存在していても１２０℃１０分間の加熱により硬化し、未硬化状態を保つことができなかった。また、（Ａ）成分を含有しない比較例２では硬化物の硬度が著しく低下し、（Ｂ）成分を含有しない比較例３では硬化物に亀裂が発生した。 On the other hand, in Comparative Example 1, which is a curable composition by hydrosilylation, even in the presence of the reaction control agent, it was cured by heating at 120 ° C. for 10 minutes, and the uncured state could not be maintained. Further, in Comparative Example 2 containing no component (A), the hardness of the cured product was significantly reduced, and in Comparative Example 3 containing no component (B), cracks were generated in the cured product.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any of the above-described embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.
Claims (6)
（ＳｉＯ２）ａ１（Ｒ１ ３ＳｉＯ１／２）ｂ１（Ｘ１Ｏ１／２）ｃ１ （１）
（式中、Ｒ１は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ１の全数のうち５０〜９９．９％はメチル基であり、かつ、０．１〜５０％はアルケニル基であり、Ｘ１は水素原子又はアルキル基である。ａ１は０．２〜０．８、ｂ１は０．２〜０．８、ｃ１は０〜０．１であり、ａ１＋ｂ１＋ｃ１＝１である。）
（Ｂ）下記平均単位式（２）で表されるオルガノポリシロキサン、
（ＳｉＯ２）ａ２（Ｒ２ ３ＳｉＯ１／２）ｂ２（Ｘ１Ｏ１／２）ｃ２ （２）
（式中、Ｒ２は同一又は異なっていても良い、置換又は非置換のアルケニル基を含まない一価炭化水素基であり、Ｘ１は水素原子又はアルキル基である。ａ２は０．２〜０．８、ｂ２は０．２〜０．８、ｃ２は０〜０．１であり、ａ２＋ｂ２＋ｃ２＝１である。）
（Ｃ）下記平均単位式（３）で表されるオルガノポリシロキサン、
（Ｒ３ ２ＳｉＯ）ａ３（Ｒ３ ３ＳｉＯ１／２）ｂ３ （３）
（式中、Ｒ３は同一又は異なっていても良い、置換又は非置換の一価炭化水素基であり、Ｒ３の全数のうち２０％以上がメチル基であり、かつ、０.０００１〜２５％はアルケニル基であり、ａ３は０．９９８０〜０．９９９９、ｂ３は０．０００１〜０．００２であり、ａ３＋ｂ３＝１である。）
（Ｄ）有機過酸化物
（Ｅ）溶剤
を含むものであることを特徴とする熱硬化性シリコーン組成物。 (A) Organopolysiloxane represented by the following average unit formula (1),
(SiO 2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 (1)
(In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 50 to 99.9% of the total number of R 1 is a methyl group, and 0. 1 to 50% are alkenyl groups, X 1 is a hydrogen atom or an alkyl group. A1 is 0.2 to 0.8, b1 is 0.2 to 0.8, and c1 is 0 to 0.1. , A1 + b1 + c1 = 1)
(B) Organopolysiloxane represented by the following average unit formula (2),
(SiO 2 ) a2 (R 2 3 SiO 1/2 ) b2 (X 1 O 1/2 ) c2 (2)
(In the formula, R 2 is a monovalent hydrocarbon group containing no substituted or unsubstituted alkenyl group, which may be the same or different, and X 1 is a hydrogen atom or an alkyl group. A2 is 0.2 to 0.2. 0.8 and b2 are 0.2 to 0.8, c2 is 0 to 0.1, and a2 + b2 + c2 = 1).
(C) Organopolysiloxane represented by the following average unit formula (3),
(R 3 2 SiO) a3 (R 3 3 SiO 1/2 ) b3 (3)
(In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and 20% or more of the total number of R 3 is a methyl group, and 0.001 to 25. % Is an alkenyl group, a3 is 0.9980 to 0.9999, b3 is 0.0001 to 0.002, and a3 + b3 = 1).
(D) A thermosetting silicone composition comprising an organic peroxide (E) solvent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06306294A (en) * | 1993-04-09 | 1994-11-01 | General Electric Co <Ge> | Improved thermosetting elastomer composition based on vinyl-functional resin, polymer chain-terminated with single vinyl and polymer having vinyl in chain |
| US6342324B1 (en) * | 2000-02-16 | 2002-01-29 | Imation Corp. | Release layers and compositions for forming the same |
| JP2016108396A (en) * | 2014-12-03 | 2016-06-20 | 富士フイルム株式会社 | Composition for acoustic wave probe, silicone resin for acoustic wave probe, acoustic wave probe and ultrasonic probe using the composition, acoustic wave measurement device, ultrasonic diagnosis device, photoacoustic wave measurement device and ultrasonic endoscope, and production method of silicone resin for acoustic wave probe |
| JP2016124967A (en) * | 2014-12-26 | 2016-07-11 | 東レ・ダウコーニング株式会社 | Curable silicone composition, semiconductor sealant comprising the same and semiconductor device |
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| JP5287935B2 (en) | 2011-06-16 | 2013-09-11 | 東レ株式会社 | Phosphor-containing sheet, LED light-emitting device using the same, and manufacturing method thereof |
| JP2014116598A (en) | 2012-11-15 | 2014-06-26 | Toray Ind Inc | Light emitting diode sealing composition, phosphor sheet, led package employing the same and manufacturing method thereof |
| JP2014114446A (en) | 2012-11-16 | 2014-06-26 | Toray Ind Inc | Polyorganosiloxane composition, hardened product of the composition, phosphor sheet, method of producing the phosphor sheet, light-emitting device and method of producing the light-emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06306294A (en) * | 1993-04-09 | 1994-11-01 | General Electric Co <Ge> | Improved thermosetting elastomer composition based on vinyl-functional resin, polymer chain-terminated with single vinyl and polymer having vinyl in chain |
| US6342324B1 (en) * | 2000-02-16 | 2002-01-29 | Imation Corp. | Release layers and compositions for forming the same |
| JP2016108396A (en) * | 2014-12-03 | 2016-06-20 | 富士フイルム株式会社 | Composition for acoustic wave probe, silicone resin for acoustic wave probe, acoustic wave probe and ultrasonic probe using the composition, acoustic wave measurement device, ultrasonic diagnosis device, photoacoustic wave measurement device and ultrasonic endoscope, and production method of silicone resin for acoustic wave probe |
| JP2016124967A (en) * | 2014-12-26 | 2016-07-11 | 東レ・ダウコーニング株式会社 | Curable silicone composition, semiconductor sealant comprising the same and semiconductor device |
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