WO2018235811A1 - Curable silicone resin composition and cured product thereof - Google Patents
Curable silicone resin composition and cured product thereof Download PDFInfo
- Publication number
- WO2018235811A1 WO2018235811A1 PCT/JP2018/023275 JP2018023275W WO2018235811A1 WO 2018235811 A1 WO2018235811 A1 WO 2018235811A1 JP 2018023275 W JP2018023275 W JP 2018023275W WO 2018235811 A1 WO2018235811 A1 WO 2018235811A1
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- WIPO (PCT)
- Prior art keywords
- group
- resin composition
- silicone resin
- curable silicone
- formula
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 283
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 269
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 167
- 125000003118 aryl group Chemical group 0.000 claims abstract description 121
- -1 polysiloxane Polymers 0.000 claims abstract description 85
- 239000003566 sealing material Substances 0.000 claims abstract description 32
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 24
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 125
- 239000004065 semiconductor Substances 0.000 claims description 112
- 230000003287 optical effect Effects 0.000 claims description 99
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 95
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- 238000007789 sealing Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 abstract description 73
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 57
- 229910052717 sulfur Inorganic materials 0.000 abstract description 57
- 239000011593 sulfur Substances 0.000 abstract description 56
- 230000035939 shock Effects 0.000 abstract description 35
- 239000000463 material Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 description 121
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 80
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 77
- 125000002947 alkylene group Chemical group 0.000 description 63
- 150000002430 hydrocarbons Chemical group 0.000 description 62
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 61
- 229910052710 silicon Inorganic materials 0.000 description 48
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 33
- 238000002156 mixing Methods 0.000 description 30
- 239000007787 solid Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- 239000011701 zinc Substances 0.000 description 23
- 238000001723 curing Methods 0.000 description 22
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 20
- 229910052725 zinc Inorganic materials 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 14
- 239000000565 sealant Substances 0.000 description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 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 12
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 125000000962 organic group Chemical group 0.000 description 11
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 229910004283 SiO 4 Inorganic materials 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 150000008282 halocarbons Chemical group 0.000 description 6
- 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 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002683 reaction inhibitor Substances 0.000 description 6
- 125000005372 silanol group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 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 5
- 239000000126 substance Substances 0.000 description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 4
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 0 CC(C)(C)CC(C)(C)C(C)(CC(C1CC1)C=*)CC1CCCC1 Chemical compound CC(C)(C)CC(C)(C)C(C)(CC(C1CC1)C=*)CC1CCCC1 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 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 3
- 239000011521 glass Substances 0.000 description 3
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004590 silicone sealant Substances 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 239000000758 substrate Substances 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
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- DVSILEVINNCNTQ-UHFFFAOYSA-L zinc;3-oxobutanoate Chemical compound [Zn+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O DVSILEVINNCNTQ-UHFFFAOYSA-L 0.000 description 2
- LFOXXKXKYHIANI-UHFFFAOYSA-L zinc;7,7-dimethyloctanoate Chemical compound [Zn+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O LFOXXKXKYHIANI-UHFFFAOYSA-L 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000006649 (C2-C20) alkynyl group Chemical group 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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- KCHZPZSUZAOTIQ-UHFFFAOYSA-N 1-(ethoxy-methyl-propylsilyl)oxyethyl prop-2-enoate Chemical compound C(C=C)(=O)OC(C)O[Si](OCC)(C)CCC KCHZPZSUZAOTIQ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- FGRQBMHHOXESRC-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione;zinc Chemical compound [Zn].CC(C)(C)C(=O)CC(=O)C(C)(C)C.CC(C)(C)C(=O)CC(=O)C(C)(C)C FGRQBMHHOXESRC-UHFFFAOYSA-N 0.000 description 1
- WKRJCCZAZDZNJL-UHFFFAOYSA-N 2-methoxyethoxysilicon Chemical compound COCCO[Si] WKRJCCZAZDZNJL-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
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- HMVBQEAJQVQOTI-UHFFFAOYSA-N 3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)C=C(C)C#C HMVBQEAJQVQOTI-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- MQSZOZMNAJHVML-UHFFFAOYSA-N 3-phenylbut-1-yn-1-ol Chemical compound OC#CC(C)C1=CC=CC=C1 MQSZOZMNAJHVML-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WBEBYGPEPAQNCX-UHFFFAOYSA-N C(C)O[SiH](OCC)OCC.SC=CC Chemical compound C(C)O[SiH](OCC)OCC.SC=CC WBEBYGPEPAQNCX-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical class P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005091 alkenylcarbonylamino group Chemical group 0.000 description 1
- 125000005193 alkenylcarbonyloxy group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000005088 alkynylcarbonylamino group Chemical group 0.000 description 1
- 125000005198 alkynylcarbonyloxy group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- RMTGISUVUCWJIT-UHFFFAOYSA-N n-[3-[3-aminopropoxy(dimethoxy)silyl]propyl]-1-phenylprop-2-en-1-amine;hydrochloride Chemical compound Cl.NCCCO[Si](OC)(OC)CCCNC(C=C)C1=CC=CC=C1 RMTGISUVUCWJIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000005386 organosiloxy group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical class P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 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
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- UERZMVLKPKHGER-UHFFFAOYSA-N prop-1-ene-1-thiol trimethoxysilane Chemical compound CO[SiH](OC)OC.SC=CC UERZMVLKPKHGER-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
-
- 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- 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
-
- 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
Definitions
- the present invention relates to a curable silicone resin composition and a cured product thereof, a sealant using the curable silicone resin composition, and a semiconductor device (particularly, an optical semiconductor device) sealed using the sealant.
- the present invention relates to a semiconductor device (particularly, an optical semiconductor device) obtained by stopping.
- a sealing material for covering and protecting a semiconductor element in a semiconductor device such as an optical semiconductor device.
- a silicone resin having high heat resistance and light resistance is used as the resin of the sealing material.
- the phenyl silicone sealant has a high sulfur barrier property as compared with the methyl silicone sealant conventionally used, its properties are still insufficient.
- the corrosion of the electrode due to the corrosive gas proceeds with time, causing a problem that the current-carrying characteristics deteriorate.
- the thermal shock resistance may be lowered.
- the object of the present invention is to maintain the heat resistance and the thermal shock resistance by curing without causing the above-mentioned problems of solid deposition, and in particular, the barrier property against corrosive gas (for example, SO X gas)
- a curable silicone resin composition capable of forming a material (cured product) excellent in sulfur barrier properties.
- Another object of the present invention is to provide a material (cured product) which is particularly excellent in sulfur barrier properties while maintaining heat resistance and thermal shock resistance.
- another object of the present invention is a sealing agent using the above-mentioned curable resin composition, and a quality obtained by sealing a semiconductor element (particularly an optical semiconductor element) using the sealing agent. And providing a semiconductor device (particularly, an optical semiconductor device) excellent in durability.
- another object of the present invention is to provide an optical semiconductor device excellent in quality and durability, including a lens formed of the above-mentioned cured product.
- Polysiloxane which is at least one selected from the group consisting of polyorganosiloxysil alkylene (polyorganosiloxane having a sil alkylene bond), and one or more hydrosilyl groups in the molecule and aliphatic unsaturated group
- a composition comprising, as essential components, a polyorganosiloxane which does not react, an isocyanurate compound having a specific structure, and a branched polyorganosiloxane having one or more alkenyl groups in the molecule (curable silicone resin composition Heat resistance, by curing, without causing the problems of solid precipitation described above). While maintaining thermal shock resistance, it found to be able to form a material (cured product) having excellent sulfur barrier properties, and completed the present invention.
- the present invention provides a curable silicone resin composition
- a curable silicone resin composition comprising the following components (A), (B), (C) and (D).
- Polysiloxane (B) which is at least one selected from the group consisting of silalkylene
- A2 polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group
- C) Isocyanurate compound represented by the following formula (1) [In Formula (1), R a , R b , and R c are the same or different and each represents a group represented by Formula (1a), a group represented by Formula (1b), a hydrogen atom, or an alkyl group Show.
- R a , R b and R c is a group represented by Formula (1a).
- R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
- s represents an integer of 2 to 10.
- R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
- t represents an integer of 1 to 10.
- D branched polyorganosiloxane having one or more alkenyl groups in the molecule
- the curable silicone resin composition may contain the following component (E).
- the curable silicone resin composition may contain the following component (G).
- G isocyanurate compound represented by the following formula (2)
- R f , R g , and R h are the same or different and each represents a group represented by Formula (2a) or a group represented by Formula (2b). However, at least one of R f , R g and R h is a group represented by formula (2b).
- R i represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
- R j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]
- the curable silicone resin composition may contain the following component (F).
- the said curable silicone resin composition may contain the following (H) component.
- the curable silicone resin composition may further contain a phosphor.
- the present invention also provides a cured product of a curable silicone resin composition.
- the curable silicone resin composition may be a resin composition for encapsulating an optical semiconductor.
- the curable silicone resin composition may be a resin composition for forming a lens for an optical semiconductor.
- the present invention is characterized by including an optical semiconductor element and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the resin composition for optical semiconductor sealing.
- the sealing material is a cured product of the resin composition for optical semiconductor sealing.
- the present invention provides an optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the resin composition for forming the lens for optical semiconductor.
- the curable silicone resin composition of the present invention Since the curable silicone resin composition of the present invention has the above configuration, there is no problem of precipitation of solids in the curable silicone resin composition (for example, curable silicone resin composition temperature-controlled at room temperature). Therefore, the curable silicone resin composition of the present invention is easy to prepare and handle. In addition, since the curable silicone resin composition of the present invention has the above-mentioned constitution, by curing it, heat resistance (for example, moisture absorption reflow resistance) and thermal shock resistance are maintained, and in particular, corrosive gas (for example, SOx) It is possible to form a cured product excellent in barrier properties (sulfur barrier properties) to gas).
- heat resistance for example, moisture absorption reflow resistance
- thermal shock resistance for example, corrosive gas (for example, SOx)
- SOx corrosive gas
- the curable silicone resin composition of the present invention is preferably used particularly as a material (sealing agent) for forming a sealing material of an optical semiconductor element (LED element) in an optical semiconductor device and a resin composition for forming a lens. can do.
- An optical semiconductor device obtained by using the curable silicone resin composition of the present invention as a sealing agent or a resin composition for forming a lens has excellent quality and durability.
- FIG. 2 is a chart of 1 H-NMR spectrum of the product (polyorganosilsesquioxane having vinyl group) obtained in Synthesis Example 1.
- FIG. 2 is a chart of an FT-IR spectrum of a product (polyorganosilsesquioxane having a vinyl group) obtained in Synthesis Example 1.
- the curable silicone resin composition of the present invention is a curable composition containing the following components (A), (B), (C) and (D) as essential components. That is, the curable silicone resin composition of the present invention is an addition-curable silicone resin composition that can be cured by a hydrosilylation reaction.
- the curable silicone resin composition of the present invention contains optional components other than these essential components, such as component (E), component (F), component (G) and component (H) described below. It is also good.
- (C) Isocyanurate compound represented by the following formula (1) [In Formula (1), R a , R b , and R c are the same or different and each represents a group represented by Formula (1a), a group represented by Formula (1b), a hydrogen atom, or an alkyl group Show.
- R a , R b and R c is a group represented by Formula (1a).
- R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
- s represents an integer of 2 to 10.
- R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms.
- t represents an integer of 1 to 10.
- D branched polyorganosiloxane having one or more alkenyl groups in the molecule
- the component (A) which is an essential component of the curable silicone resin composition of the present invention, is a polyorganosiloxane (A1) (A1) having two or more alkenyl groups and one or more aryl groups in the molecule.
- A1 polyorganosiloxane
- A2 polyorganosiloxysil alkylene
- A2 polyorganosiloxane
- the component (A) is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (B) and the like).
- the component (A) does not include those corresponding to the components (D) and (F) described later. Since the curable silicone resin composition of the present invention contains such component (A), it can form a cured product excellent in sulfur barrier property and thermal shock resistance. For this reason, the quality of the optical semiconductor device which uses this as a sealing material improves.
- polyorganosiloxysil alkylene means, in addition to -Si-O-Si- (siloxane bond) as a main chain, -Si- RA -Si- (sil alkylene bond: RA is alkylene Groups are shown)).
- polyorganosiloxane (A1) in this specification is polyorganosiloxane which does not contain the said silalkylene bond as a principal chain.
- the polyorganosiloxane (A1) has two or more alkenyl groups and one or more aryl groups in the molecule, and has -Si-O-Si- (siloxane bond) as a main chain, and a silalkylene bond It is a polyorganosiloxane which does not contain it.
- polyorganosiloxane (A1) examples include those having a linear, partially branched linear, branched, or network molecular structure.
- polyorganosiloxane (A1) can also be used individually by 1 type, and can also be used combining 2 or more types.
- two or more kinds of polyorganosiloxanes (A1) having different molecular structures can be used in combination, for example, linear polyorganosiloxane (A1) and branched polyorganosiloxane (A1) Can also be used in combination.
- numerator substituted or unsubstituted alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, pentenyl group, a hexenyl group, are mentioned.
- substituent include a halogen atom, a hydroxy group and a carboxy group.
- a vinyl group is preferable as the alkenyl group.
- the polyorganosiloxane (A1) may have only one type of alkenyl group or may have two or more types of alkenyl groups.
- the alkenyl group contained in the polyorganosiloxane (A1) is preferably bonded to a silicon atom.
- Examples of the aryl group which the polyorganosiloxane (A1) has in the molecule include substituted or unsubstituted C 6 such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group (for example, benzyl group, phenethyl group etc.) And -14 aryl group and the like.
- Examples of the substituent in the substituted aryl group include a substituted or unsubstituted C 1-8 alkyl group, a halogen atom, a hydroxy group, a carboxy group and the like. Among them, a phenyl group is preferable as the above-mentioned aryl group.
- the polyorganosiloxane (A1) may have only one type of aryl group or may have two or more types of aryl groups.
- the aryl group contained in the polyorganosiloxane (A1) is not particularly limited, but is preferably a group bonded to a silicon atom. By having one or more aryl groups in the molecule, the polyorganosiloxane (A1) can form a cured product having excellent sulfur barrier properties as compared to a polyorganosiloxane having no aryl group.
- Examples of groups other than the alkenyl group and the aryl group that the polyorganosiloxane (A1) has include a hydrogen atom, an organic group and the like.
- an organic group for example, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group etc.), a cycloalkyl group (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group) , A cyclododecyl group etc.) cycloalkyl-alkyl group (eg a cyclohexyl methyl group, a methylcyclohexyl group etc.), a halogenated hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group is substituted by a halogen atom (eg chloro And monovalent substituted or unsubstituted hydrocarbon groups
- the polyorganosiloxane (A1) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
- the property of the polyorganosiloxane (A1) is not particularly limited, and may be liquid or solid at 25 ° C., for example.
- R 1a SiO 3/2 As polyorganosiloxane (A1), the following average unit formula: (R 1a SiO 3/2 ) a1 (R 1a 2 SiO 2/2 ) a2 (R 1a 3 SiO 1/2 ) a3 (SiO 4/2 ) a4 (X 1a O 1/2 ) a5
- the polyorganosiloxane represented by is preferable.
- R 1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl and aryl groups.
- a part of R 1a is an alkenyl group (in particular, a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule.
- the proportion of the alkenyl group to the total amount (100 mol%) of R 1a is preferably 0.1 to 40 mol%.
- a part of R 1a is an aryl group (in particular, a phenyl group), and the ratio thereof is controlled to a range of 1 or more in the molecule.
- the proportion of the aryl group to the total amount (100 mol%) of R 1a is preferably 30 to 70 mol%.
- the sulfur barrier properties of the cured product tend to be further improved.
- R 1a other than an alkenyl group and an aryl group an alkyl group (especially a methyl group) is preferable.
- X 1 is a hydrogen atom or an alkyl group.
- an alkyl group a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned, Especially a methyl group is preferable.
- a1 is 0 or a positive number
- a2 is 0 or a positive number
- a3 is 0 or a positive number
- a4 is 0 or a positive number
- a5 is 0 or a positive number
- (a1 + a2 + a3) is a positive It is a number.
- polyorganosiloxane (A1) is, for example, a linear polyorganosiloxane having two or more alkenyl groups and one or more aryl groups in the molecule.
- alkenyl group which this linear polyorganosiloxane has
- a vinyl group is preferable.
- it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups.
- aryl group is mentioned as an aryl group which this linear polyorganosiloxane has, a phenyl group is especially preferable.
- alkenyl group in the linear polyorganosiloxane and the group bonded to a silicon atom other than the aryl group include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group ( Particularly preferred is a methyl group).
- the ratio of the alkenyl group to the total amount (100 mol%) of the groups bonded to the silicon atom in the linear polyorganosiloxane is preferably 0.1 to 40 mol%.
- the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 40 to 60 mol%.
- the proportion of the aryl group (particularly, phenyl group) is preferably 30 to 70 mol% with respect to the total amount (100 mol%) of the groups bonded to the silicon atom.
- the proportion of aryl groups (especially phenyl groups) relative to the total amount (100 mol%) of groups bonded to silicon atoms as the linear polyorganosiloxane is 40 mol% or more (for example, 45 to 70 mol%)
- the sulfur barrier properties of the cured product tend to be further improved.
- a cured product is obtained by using a compound in which the proportion of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 55 to 60 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
- the linear polyorganosiloxane is represented by, for example, the following formula (I-1).
- R 11 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 11 are alkenyl groups, and at least one is an aryl group.
- m1 is an integer of 5 to 1000]
- polyorganosiloxane (A1) is a siloxane unit (T unit) having two or more alkenyl groups and one or more aryl groups in the molecule and represented by R a SiO 3/2 And branched polyorganosiloxanes having.
- the branched polyorganosiloxane does not include those corresponding to the component (F) described later.
- R a is a monovalent substituted or unsubstituted hydrocarbon group.
- the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this branched polyorganosiloxane has, Especially a vinyl group is preferable.
- aryl group may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups.
- aryl group may have only 1 type of aryl group, and may have 2 or more types of aryl groups.
- examples of the alkenyl group in the branched polyorganosiloxane and the group bonded to a silicon atom other than the aryl group include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group ( Particularly preferred is a methyl group).
- an aryl group particularly, a phenyl group is particularly preferable.
- the ratio of the alkenyl group to the total amount (100 mol%) of the group bonded to the silicon atom in the branched polyorganosiloxane is 0.1 to 40 mol% from the viewpoint of the curability of the curable silicone resin composition. preferable.
- the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 40 to 60 mol%.
- the proportion of the aryl group (particularly, phenyl group) is preferably 30 to 70 mol% with respect to the total amount (100 mol%) of the groups bonded to the silicon atom.
- the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 70 mol%) as the branched polyorganosiloxane
- the sulfur barrier properties of the cured product tend to be further improved.
- a cured product is obtained by using a compound in which the proportion of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 55 to 60 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
- the branched polyorganosiloxane can be represented by the above average unit formula in which a1 is a positive number.
- a2 / a1 is a number from 0 to 10
- a3 / a1 is a number from 0 to 0.5
- a4 / (a1 + a2 + a3 + a4) is a number from 0 to 0.3
- a5 / (a1 + a2 + a3 + a4) is 0 to 0.4
- the number of is preferred.
- the molecular weight of the branched polyorganosiloxane is preferably 500 to 10,000, more preferably 700 to 3,000, in terms of weight average molecular weight in terms of standard polystyrene by GPC.
- the polyorganosiloxane (A1) can be produced by a known or conventional method, and as a product containing the polyorganosiloxane (A1), for example, trade name "OE 6630" (manufactured by Toray Dow Corning Co., Ltd.), etc. Are available.
- the polyorganosiloxane (A1) can be used singly or in combination of two or more.
- two or more of polyorganosiloxanes (A1) having different molecular structures can be used in combination, and more specifically, linear polyorganosiloxane (A1) and branched polyorganosiloxane (A1) And the like.
- Polyorganosiloxycyl alkylene (A2) Polyorganosiloxycyl alkylene (A2) has two or more alkenyl groups and one or more aryl groups in the molecule, and in addition to -Si-O-Si- (siloxane bond) as the main chain, -Si -R a -Si- (silalkylene bond: R a represents an alkylene group) polyorganosiloxanes comprising (poly organosiloxy sill alkylene). That is, polyorganosiloxysil alkylene (A2) does not include polyorganosiloxane having no silalkylene bond such as polyorganosiloxane (A1).
- the curable silicone resin composition of the present invention contains such a polyorganosiloxysil alkylene (A2), it can form a cured product excellent in sulfur barrier properties and thermal shock resistance. Furthermore, by curing, a cured product having high sulfur barrier properties, resistance to yellowing and low tack or no tackiness can be obtained, so that the quality of an optical semiconductor device using this as a sealing material is improved.
- A2 polyorganosiloxysil alkylene
- Examples of the alkylene group in the silalkylene bond that polyorganosiloxycyl alkylene (A2) has in the molecule include linear or branched C 1-12 alkylene groups such as methylene, ethylene and propylene. Among them, a C.sub.2-4 alkylene group (particularly, an ethylene group) is preferable.
- the polyorganosiloxycyl alkylene (A2) is less likely to form a low molecular weight ring in the production process as compared to a polyorganosiloxane having a main chain consisting of only a siloxane bond and having no silalkylene bond, and is decomposed by heating or the like.
- the surface tackiness (tackiness) of the cured product of the curable silicone resin composition is reduced by using polyorganosiloxysil alkylene (A2), and yellowing is further caused. It tends to be difficult to change.
- polyorganosiloxycyl alkylene (A2) those having a linear or branched (for example, a partially branched linear, branched, network, etc.) molecular structure can be mentioned.
- polyorganosiloxycyl alkylene (A2) one having a branched molecular structure is preferable from the viewpoint of mechanical strength of a cured product.
- alkenyl group which polyorgano siloxy cyl alkylene (A2) has in a molecule substituted or unsubstituted alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, etc. are mentioned.
- a substituent in the said substituted alkenyl group a halogen atom, a hydroxyl group, a carboxy group etc. are mentioned.
- a vinyl group is preferable as the above-mentioned alkenyl group.
- the polyorganosiloxycyl alkylene (A2) may have only one type of alkenyl group or may have two or more types of alkenyl groups.
- the alkenyl group contained in the polyorganosiloxysil alkylene (A2) is not particularly limited, but is preferably a group bonded to a silicon atom.
- Examples of the aryl group which polyorganosiloxycyl alkylene (A2) has in the molecule thereof include substituted or unsubstituted such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group (for example, benzyl group, phenethyl group etc.) C 6-14 aryl group etc. are mentioned.
- Examples of the substituent in the substituted aryl group include a substituted or unsubstituted C 1-8 alkyl group, a halogen atom, a hydroxy group, a carboxy group and the like. Among them, a phenyl group is preferable as the above-mentioned aryl group.
- the polyorganosiloxycyl alkylene (A2) may have only one type of aryl group or may have two or more types of aryl groups.
- the aryl group contained in the polyorganosiloxysil alkylene (A2) is not particularly limited, but is preferably a group bonded to a silicon atom. By having one or more aryl groups in the molecule, the polyorganosiloxysil alkylene (A2) can form a cured product having excellent sulfur barrier properties as compared to a polyorganosiloxane having no aryl group.
- an alkyl group for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group etc.
- a cycloalkyl group for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , A cyclododecyl group etc.
- a cycloalkyl-alkyl group eg, a cyclohexyl methyl group, a methylcyclohexyl group etc.
- a halogenated hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group is substituted with a halogen atom eg, Monovalent substituted or unsubstituted hydrocarbon groups and the like can be mentioned, such as chloroalkyl, 3-chloropropyl, and halogenated alkyl groups such as 3,3,3-trifluoropropyl.
- the polyorganosiloxycyl alkylene (A2) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
- the property of the polyorganosiloxysil alkylene (A2) is not particularly limited, and may be liquid or solid at 25 ° C., for example.
- polyorganosiloxycyl alkylene (A2) As polyorganosiloxycyl alkylene (A2), the following average unit formula: (R 1 b 2 SiO 2/2 ) b 1 (R 1 b 3 SiO 1/2 ) b 2 (R 1 b SiO 3/2 ) b 3 (SiO 4/2 ) b 4 (R A ) b 5 (X 1 b O) b 6
- the polyorganosiloxycyl alkylene represented by is preferable.
- R 1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl and aryl groups.
- a part of R 1b is an alkenyl group (especially a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule.
- the proportion of the alkenyl group to the total amount (100 mol%) of R 1b is preferably 0.1 to 40 mol%.
- R 1b is an aryl group (particularly, a phenyl group), and the ratio thereof is controlled to a range of 1 or more in the molecule.
- the proportion of the aryl group to the total amount (100 mol%) of R 1b is preferably 10 to 50 mol%.
- R 1b other than an alkenyl group and an aryl group an alkyl group (especially a methyl group) is preferable.
- R A is an alkylene group as described above. Particularly preferred is an ethylene group.
- X 1b is a hydrogen atom or an alkyl group.
- an alkyl group a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned, for example, Especially a methyl group is preferable.
- b1 is a positive number
- b2 is a positive number
- b3 is 0 or a positive number
- b4 is 0 or a positive number
- b5 is a positive number
- b6 is 0 or a positive number.
- b1 is preferably 1 to 200
- b2 is preferably 1 to 200
- b3 is preferably 0 to 10
- b4 is preferably 0 to 5
- b5 is preferably 1 to 100.
- (b3 + b4) is a positive number
- the polyorganosiloxysil alkylene (A2) has a branched chain (branched main chain), and the mechanical strength of the cured product tends to be further improved.
- polyorganosiloxycyl alkylene (A2) examples include polyorganosiloxycyl alkylene having a structure represented by the following formula (I-2).
- R 12 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
- R 12 include the above-mentioned specific examples of the monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated hydrocarbon group and the like), and the above-mentioned alkenyl group and aryl group.
- at least two of R 12 are alkenyl groups (particularly, a vinyl group), and at least one of R 12 is an aryl group (particularly, a phenyl group).
- R 12 other than an alkenyl group and an aryl group an alkyl group (particularly a methyl group) is preferable.
- R A represents an alkylene group as described above, and among them, a C 2-4 alkylene group (in particular, an ethylene group) is preferable.
- a C 2-4 alkylene group in particular, an ethylene group
- RA when several RA exists, these may be the same and may differ.
- r1 represents an integer of 1 or more (for example, 1 to 100).
- r1 is an integer of 2 or more, the structures in the parentheses with r1 may be identical to or different from each other.
- r2 represents an integer of 1 or more (for example, 1 to 400).
- r2 is an integer of 2 or more, the structures in the parentheses with r2 attached thereto may be identical to or different from each other.
- r3 represents an integer of 0 or 1 (eg, 0 to 50).
- r3 is an integer of 2 or more, the structures in the brackets with r3 may be identical to or different from each other.
- r 4 represents an integer of 0 or 1 (eg, 0 to 50).
- r4 is an integer of 2 or more, the structures in the brackets with r4 may be identical to or different from each other.
- r5 represents an integer of 0 or 1 (eg, 0 to 50).
- r5 is an integer of 2 or more, the structures in the parentheses with r5 attached thereto may be identical to or different from each other.
- each structural unit in the above formula (I-2) is not particularly limited, and may be a random type or a block type. Further, the order of arrangement of each structural unit is not particularly limited.
- the terminal structure of the polyorganosiloxycyl alkylene having the structure represented by the formula (I-2) is not particularly limited, but, for example, silanol group, alkoxysilyl group, trialkylsilyl group (for example, brackets with r5 attached) Inner structure, trimethylsilyl group etc.).
- Various groups such as an alkenyl group and a hydrosilyl group may be introduced at the end of the polyorganosiloxycyl alkylene.
- the polyorganosiloxysil alkylene (A2) can be produced by a known or conventional method, and the production method thereof is not particularly limited. For example, it can be produced by the method described in JP-A-2012-140617.
- products containing polyorganosiloxycyl alkylene (A2) for example, trade names “ETERLED GS5155”, “ETERLED GS5145”, “ETERLED GS5135”, “ETERLED GS5120” (all manufactured by Changxing Materials Co., Ltd.), etc. can be obtained It is.
- polyorganosiloxycyl alkylene (A2) can be used alone or in combination of two or more.
- polyorganosiloxysil alkylene (A2) having different molecular structures can be used in combination, and specifically, linear polyorganosiloxysil alkylene (A2) and branched polyorganosiloxy The embodiment etc. which use silalkylene (A2) together are mentioned.
- the content (blending amount) of the component (A) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.1 to 60% by weight based on the curable silicone resin composition (100% by weight) Is more preferably 0.1 to 55% by weight, still more preferably 0.1 to 50% by weight.
- the thermal shock resistance of the cured product tends to be further improved.
- polyorganosiloxysil alkylene (A2) is used as the component (A)
- the tackiness of the cured product is reduced, so that the quality of the optical semiconductor device tends to be improved.
- the content of the component (A) is 60% by weight or less, the yellowing resistance of the cured product tends to be further improved, and the effect of increasing the amounts of the components (B) to (D) There is a tendency to improve the properties, to improve the sulfur barrier properties, to improve the adhesion, etc. efficiently.
- polyorganosiloxane (A1) As the component (A) in the curable silicone resin composition of the present invention, only polyorganosiloxane (A1) can be used, or only polyorganosiloxysil alkylene (A2) can be used, and The polyorganosiloxane (A1) and the polyorganosiloxysil alkylene (A2) can also be used in combination.
- polyorganosiloxane (A1) and polyorganosiloxycyl alkylene (A2) in combination the ratio of these is not particularly limited, and can be set appropriately.
- the component (B) in the curable silicone resin composition of the present invention is a polyorganosiloxane having one or more hydrosilyl groups (Si-H) in the molecule and having no aliphatic unsaturated group. Accordingly, the component (B) in the curable silicone resin composition of the present invention is a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, the component (A) and the like).
- the curable silicone resin composition of the present invention contains the component (B), the curing reaction by the hydrosilylation reaction can be efficiently advanced. In addition, the cured product exhibits excellent sulfur barrier properties.
- the number of hydrosilyl groups that the component (B) has in the molecule may be one or more, and is not particularly limited, but from the viewpoint of the curability of the curable silicone resin composition, two or more (for example, 2 to 50) Is preferred.
- the component (B) is not particularly limited, but it is a polyorganosiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule and having no aliphatic unsaturated group and no silalkylene bond (simply It is preferable that it may be called polyorganosiloxane (B1).
- (B) component does not have an aliphatic unsaturated group in a molecule
- the aliphatic unsaturated group is an aliphatic hydrocarbon group having a nonaromatic carbon-carbon unsaturated bond, and examples thereof include an ethylenically unsaturated group and an acetylenic unsaturated group.
- Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group and 5-hexenyl group (for example, C 2-20 alkenyl group (particularly C 2-10 alkenyl group))
- An alkadienyl group such as a 1,3-butadienyl group (in particular, a C 4-10 alkadienyl group etc.); an alkenylcarbonyloxy group such as an acryloyloxy group or a methacryloyloxy group; an alkenylcarbonylamino group such as an acrylamide group.
- alkynyl groups such as ethynyl group and propargyl group (for example, C 2-20 alkynyl group (especially C 2-10 alkynyl group) and the like); alkynyl carbonyloxy groups such as ethynyl carbonyloxy group And alkynylcarbonylamino groups such as ethynylcarbonylamino group.
- polyorganosiloxane (B1) examples include those having a linear or branched (a partially branched linear, branched, network, etc.) molecular structure.
- polyorganosiloxane (B1) can also be used individually by 1 type, and can also be used combining 2 or more types.
- two or more kinds of polyorganosiloxanes (B1) having different molecular structures can be used in combination, and specifically, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane (B1) And the like.
- groups other than hydrogen atoms are not particularly limited, but, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (however, aliphatic unsaturated groups) And the above-mentioned aryl group, more specifically, an alkyl group, an aryl group, a halogenated hydrocarbon group and the like. Among them, alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferable.
- the component (B1) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
- the properties of the polyorganosiloxane (B1) are not particularly limited, and may be liquid or solid at 25 ° C., for example. Among them, a liquid is preferable, and a liquid having a viscosity of 0.1 to 1 billion mPa ⁇ s at 25 ° C. is more preferable.
- polyorganosiloxane (B1) As polyorganosiloxane (B1), the following average unit formula: (R 2 SiO 3/2 ) c 1 (R 2 2 SiO 2/2 ) c 2 (R 2 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (X 2 O 1/2 ) c 5
- the polyorganosiloxane represented by is preferable.
- R 2 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups), for example, a hydrogen atom, Specific examples (for example, an alkyl group, a halogenated alkyl group etc.) of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group and the above-mentioned aryl group can be mentioned.
- a part of R 2 is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in such a range that the hydrosilyl group is one or more (preferably two or more) in the molecule.
- the ratio of hydrogen atoms to the total amount (100 mol%) of R 2 is preferably 0.1 to 40 mol%.
- R 2 other than a hydrogen atom an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.
- X 2 is a hydrogen atom or an alkyl group as in the case of X 1 above.
- alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.
- c1 is 0 or a positive number
- c2 is 0 or a positive number
- c3 is 0 or a positive number
- c4 is 0 or a positive number
- c5 is 0 or a positive number
- (c1 + c2 + c3) is a positive It is a number.
- polyorganosiloxane (B1) is, for example, a linear polyorganosiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule.
- group bonded to a silicon atom other than a hydrogen atom in the linear polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (however, aliphatic unsaturated groups are excluded) and the above-mentioned
- an aryl group is mentioned, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable among them.
- the proportion of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount (100 mol%) of the groups bonded to silicon atoms in the linear polyorganosiloxane is not particularly limited, but it is 0.1 to 40 mol% Is preferred. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but it is preferably 20 to 99 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but 10 to 50 mol% is preferable.
- the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 mol% or more (for example, 20 to 50 mol%)
- the sulfur barrier properties of the cured product tend to be further improved.
- a cured product is obtained by using a compound in which the proportion of alkyl groups (especially methyl groups) is 90 mol% or more (for example, 95 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
- the linear polyorganosiloxane is represented by, for example, the following formula (II-1).
- R 21 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups). However, at least one (preferably at least two) of R 21 is a hydrogen atom.
- m2 is an integer of 5 to 1000.
- R 21 may be a hydroxy group or an alkoxy group.
- the monovalent substituted or unsubstituted hydrocarbon group in the above R 21 may have a hydroxy group or an alkoxy group.
- polyorganosiloxane (B1) is a siloxane unit (T unit) having one or more (preferably two or more) hydrosilyl groups in the molecule and represented by R b SiO 3/2. And branched polyorganosiloxanes having.
- the branched polyorganosiloxane also includes a polyorganosiloxane having a three-dimensional structure such as a network.
- R b is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, aliphatic unsaturated groups are excluded).
- Examples of the group bonded to a silicon atom other than a hydrogen atom in the branched polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (however, aliphatic unsaturated groups are excluded) and the above-mentioned Although an aryl group is mentioned, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable among them. Furthermore, as R b in the above T unit, a hydrogen atom, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups) and the above-mentioned aryl group can be mentioned.
- Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred.
- the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of R b in the T unit is not particularly limited, but is preferably 30 mol% or more from the viewpoint of the sulfur barrier property of the cured product.
- the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms in the branched polyorganosiloxane is not particularly limited, but is preferably 70 to 95 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but 10 to 70 mol% is preferable.
- the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 10 mol% or more (for example, 10 to 70 mol%) as the branched polyorganosiloxane
- the sulfur barrier properties of the cured product tend to be further improved.
- a cured product is obtained by using a compound in which the proportion of alkyl groups (especially methyl groups) is 50 mol% or more (for example, 50 to 90 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
- the branched polyorganosiloxane can be represented, for example, by the above average unit formula in which c1 is a positive number.
- c2 / c1 is a number of 0 to 10
- c3 / c1 is a number of 0 to 0.5
- c4 / (c1 + c2 + c3 + c4) is a number of 0 to 0.3
- c5 / (c1 + c2 + c3 + c4) is not particularly limited. It is preferable that it is a number of 0 to 0.4.
- the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, and more preferably 500 to 3,000.
- (B) component can also be used individually by 1 type, and can also be used combining 2 or more types.
- the content (blending amount) of the component (B) in the curable silicone resin composition of the present invention is not particularly limited, but preferably 1 to 60% by weight with respect to the curable silicone resin composition (100% by weight). More preferably, it is 5 to 55% by weight, still more preferably 10 to 50% by weight.
- the content of the component (B) is 1% by weight or more, the curability of the curable silicone resin composition is further improved, and the sulfur barrier property tends to be further improved.
- the content of the component (B) is 60% by weight or less, the thermal shock resistance of the cured product tends to be further improved.
- the component (C) in the curable silicone resin composition of the present invention is a compound represented by the above formula (1).
- the curable silicone resin composition of the present invention can form a cured product having excellent sulfur barrier properties by including the component (C) as an essential component.
- the component (C) is considered to be because the solubility in the curable silicone resin composition of the present invention is good, but it precipitates as a solid even when the amount is increased or when the curable silicone resin composition is not heated. Does not occur. Therefore, in the curable silicone resin composition of the present invention, the problem of solid deposition does not occur and the sulfur barrier property of the cured product is compatible at a very high level.
- the component having the effect of improving the sulfur barrier property of the cured product causes a problem of solid precipitation when it is increased to improve the above-mentioned sulfur barrier property, it is difficult to achieve both of the above-mentioned characteristics.
- R a , R b and R c are the same or different and each represents a group represented by formula (1a), a group represented by formula (1b), a hydrogen atom or an alkyl group . However, at least one of R a , R b and R c is a group represented by Formula (1a).
- R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group).
- a linear or branched C 1-8 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned.
- linear or branched C 1-3 alkyl groups such as methyl, ethyl, propyl and isopropyl groups are preferable.
- a hydrogen atom is particularly preferred.
- s represents an integer of 2 to 10.
- the integer of 2 to 8 is preferable, the integer of 2 to 6 is more preferable, and the integer of 2 to 4 is more preferable.
- R a , R b and R c in the formula (1) are a group represented by the formula (1a), the group represented by the formula (1a) is It may be the same or different.
- R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group).
- a linear or branched C 1-8 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned.
- alkyl groups linear or branched C 1-3 alkyl groups such as methyl, ethyl, propyl and isopropyl groups are preferable.
- a hydrogen atom is particularly preferable as R e .
- T in Formula (1b) represents an integer of 1 to 10. Among them, the integer of 1 to 6 is preferable.
- R a , R b and R c in the formula (1) are a group represented by the formula (1 b), the groups represented by the formula (1 b) are the same. It may be different or different. Moreover, the isocyanurate compound (C) may not have a group represented by Formula (1b).
- the alkyl group as R a , R b and R c may be linear, branched or cyclic and is not particularly limited.
- the cured product can exhibit the sulfur barrier property, regardless of the state in which it is reacted with other components and the unreacted state. It is speculated that the isocyanurate skeleton in component (C) is for trapping corrosive gases such as SOx gas.
- a compound in which one of R a , R b and R c in the formula (1) is a group represented by the formula (1a), R a and R in the formula (1) Compounds in which two of b and R c are a group represented by formula (1a), and all of R a , R b , and R c in formula (1) are a group represented by formula (1a) Certain compounds are mentioned. In particular, a compound in which two or three of R a , R b and R c in the formula (1) are a group represented by the formula (1a) is preferable, and more preferable in that the problem of solid precipitation hardly occurs. Is a compound in which all of R a , R b and R c in formula (1) are a group represented by formula (1a).
- the component (C) is presumed to have a group represented by the above-mentioned formula (1a) as an essential group in the molecule, but one having no such group (for example, triglycidyl isocyanurate,
- the other components especially in the curable silicone resin composition of the present invention (in particular, as compared to those having no such group, while having the effect of improving the sulfur barrier property equal to or more than monoallyl diglycidyl isocyanurate).
- the compatibility with the component A), component (B) is very good, and as a result, the problem of solid precipitation in the curable silicone resin composition does not occur, and it is also possible to other components during preparation. It can be easily dissolved. For this reason, the productivity of the curable silicone resin composition is improved.
- even when the content of the component (C) is increased, the above-mentioned problem of solid precipitation does not occur, so that the sulfur barrier property of the cured product can be significantly improved by increasing the amount of the component (C).
- the component (C) can also be used after being modified by reaction with a compound that reacts with an epoxy group, such as alcohol or acid anhydride.
- the component (C) has a group represented by the formula (1b), for example, it can be used after previously reacting (hydrosilylation reaction) with a compound having a hydrosilyl group.
- hydrosilylation reaction for example, those which are reacted in the presence of a hydrosilylation catalyst which is the component (E) together with ladder type silsesquioxane which is the component (F) described later are used as a component of the curable silicone resin composition of the present invention
- the component (C) one type can be used alone, or two or more types can be used in combination.
- commercially available products such as trade name “TEPIC-VL” (manufactured by Nissan Chemical Industries, Ltd.) can also be obtained.
- the content (compounding amount) of the component (C) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 10% by weight with respect to the curable silicone resin composition (100% by weight) Is more preferably 0.03 to 5% by weight, still more preferably 0.05 to 3% by weight, and particularly preferably 0.1 to 2% by weight.
- the sulfur barrier properties of the cured product tend to be further improved.
- the content of the component (C) is 10% by weight or less, there is a tendency to obtain a cured product which is more excellent in heat resistance, toughness, transparency and the like.
- the component (D) in the curable silicone resin composition of the present invention may be a branched polyorganosiloxane having one or more alkenyl groups in the molecule (referred to as "component (D)”. Yes).
- the component (D) in the curable silicone resin composition of the present invention is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (B) and the like) together with the component (A).
- the curable silicone resin composition of the present invention contains the component (D)
- the heat resistance, thermal shock resistance and sulfur barrier properties of the cured product may be further improved.
- the component (D) has one or more alkenyl groups in the molecule, and further has —Si—O—Si— (siloxane bond) as a main chain, and is a branched polyorgano having no silalkylene bond. Siloxane (polyorganosiloxane having a branched main chain). In addition, polyorganosiloxane of three-dimensional structures, such as mesh shape, is also contained in (D) component. However, the component (D) does not include the component (F) described later.
- numerator the above-mentioned substituted or unsubstituted alkenyl group is mentioned, Especially, a vinyl group is preferable.
- the component (D) may have only one type of alkenyl group, or may have two or more types of alkenyl groups.
- the alkenyl group contained in the component (D) is not particularly limited, but is preferably bonded to a silicon atom.
- the number of alkenyl groups that component (D) has in the molecule may be one or more, and is not particularly limited, but from the viewpoint of the curability of the curable silicone resin composition, two or more (for example, 2 to 50) Is preferred.
- bonded with silicon atoms other than the alkenyl group which (D) component has is not specifically limited,
- a hydrogen atom, an organic group, etc. are mentioned.
- the organic group include the above-mentioned organic groups (for example, substituted or unsubstituted hydrocarbons such as alkyl group, cycloalkyl group, cycloalkyl-alkyl group, halogenated hydrocarbon group etc.) and the above-mentioned aryl group. .
- the component (D) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
- the property of the component (D) is not particularly limited, and may be liquid or solid at 25 ° C., for example.
- R 8 SiO 3/2) d1 R 8 2 SiO 2/2) d2 (R 8 3 SiO 1/2) d3 (SiO 4/2) d4 (X 3 O 1/2) d5
- R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl groups, and the above-mentioned aryl groups.
- R 8 is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule.
- the proportion of the alkenyl group to the total amount (100 mol%) of R 8 is preferably 0.1 to 40 mol%.
- R 8 other than an alkenyl group an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.
- X 3 is a hydrogen atom or an alkyl group as in the case of X 1a above.
- alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.
- d1 is 0 or a positive number
- d2 is 0 or a positive number
- d3 is 0 or a positive number
- d4 is 0 or a positive number
- d5 is 0 or a positive number
- (d1 + d2 + d3) and Each of d1 + d4) is a positive number.
- component (D) examples include branched polyorganosiloxanes having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by R c SiO 3/2. .
- R c is a monovalent substituted or unsubstituted hydrocarbon group.
- the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this branched polyorganosiloxane has, Especially a vinyl group is preferable. In addition, it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups.
- examples of the group bonded to a silicon atom other than the alkenyl group in the branched polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an aryl group), among which Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred.
- Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred.
- R c in the T unit among them, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.
- the ratio of the alkenyl group to the total amount (100 mol%) of the group bonded to the silicon atom in the branched polyorganosiloxane is not particularly limited, but from the viewpoint of the curability of the curable silicone resin composition 0.1 -40 mol% is preferable. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but it is preferably 20 to 60 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but preferably 5 to 70 mol%.
- the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 60 mol%) as the branched polyorganosiloxane
- the sulfur barrier properties of the cured product tend to be further improved.
- a cured product is obtained by using a compound in which the ratio of alkyl groups (particularly methyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 30 mol% or more (for example, 35 to 60 mol%). Thermal shock resistance tends to be further improved.
- the branched polyorganosiloxane can be represented by the above average unit formula in which d1 is a positive number.
- d2 / d1 is a number from 0 to 10
- d3 / d1 is a number from 0 to 0.5
- d4 / (d1 + d2 + d3 + d4) is a number from 0 to 0.3
- d5 / (d1 + d2 + d3 + d4) is It is preferable that it is a number of 0 to 0.4.
- the molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, and more preferably 700 to 3,000.
- (D) component in the curable silicone resin composition of this invention, can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content (blending amount) of the component (D) in the curable silicone resin composition of the present invention is not particularly limited, but 50 to 200 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B). It is preferably part, more preferably 75 to 175 parts by weight, still more preferably 100 to 150 parts by weight.
- the curable silicone resin composition of the present invention may contain a hydrosilylation catalyst (sometimes referred to as "(E) component") containing a platinum group metal. That is, the component (E) is a hydrosilylation catalyst containing at least one metal (platinum group metal) selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum.
- the curable silicone resin composition of the present invention contains the component (E), the hydrosilylation reaction between the alkenyl group and the hydrosilyl group in the curable silicone resin composition can be efficiently advanced by heating.
- hydrosilylation catalysts for example, platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, etc.
- platinum-based catalysts for example, platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, etc.
- Platinum-vinylmethylsiloxane complexes such as disiloxane complexes and platinum-cyclovinylmethylsiloxane complexes
- platinum-based catalysts such as platinum-phosphine complexes and platinum-phosphite complexes, and palladium atoms or platinum atoms
- a platinum-based catalyst hydrosilylation catalyst containing platinum
- a platinum-based catalyst hydrosilylation catalyst containing platinum
- a platinum-vinylmethylsiloxane complex a platinum-carbonylvinylmethyl complex
- a complex of chloroplatinic acid with alcohol and aldehyde It is preferable because the reaction rate is good.
- (E) component can also be used individually by 1 type, and can also be used combining 2 or more types.
- the content (blending amount) of the component (E) in the curable silicone resin composition of the present invention is not particularly limited, but it is based on 1 mole (per mole) of the total amount of alkenyl groups contained in the curable silicone resin composition.
- the molar ratio is preferably 1 ⁇ 10 -8 to 1 ⁇ 10 -2 mol, more preferably 1.0 ⁇ 10 -6 to 1.0 ⁇ 10 -3 mol.
- the content (blending amount) of the component (E) in the curable silicone resin composition of the present invention is not particularly limited, but, for example, 0.01 to 1000 ppm by weight of platinum group metal in the hydrosilylation catalyst Preferably, the amount is in the range of 0.1 to 500 ppm.
- the content of the component (E) is in such a range, a cured product can be more efficiently formed, and a cured product having more excellent hue tends to be obtained.
- the curable silicone resin composition of the present invention may contain ladder-type polyorganosilsesquioxane (sometimes referred to as "component (F)") having one or more alkenyl groups in the molecule.
- component (F) the sulfur barrier properties (in particular, the SO X barrier properties) of the cured product tend to be remarkably improved.
- component (F) polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups in the molecule and having a ladder structure -Si-O-Si- skeleton There is no particular limitation.
- the component (F) for example, the following ladder type polyorganosilsesquioxane (a) and ladder type polyorganosilsesquioxane (b) can be mentioned.
- the component (F) is not limited to the following ladder type polyorganosilsesquioxane.
- -Ladder type polyorganosilsesquioxane having two or more alkenyl groups in the molecule, having a number average molecular weight of 500 to 1,500 in terms of standard polystyrene equivalent by gel permeation chromatography, and a molecular weight dispersity (Mw / Ladder-type polyorganosilsesquioxane having a Mn of 1.00 to 1.40.
- -Ladder-type polyorganosilsesquioxane (b): A structural unit (T-III) represented by the formula (III-3-1) in part or all of the molecular chain end of the polyorganosilsesquioxane having a ladder structure Unit) and a polyorganosilsesquioxane residue ("polyorganosilsesquioxane residue (R)") containing a constitutional unit (M unit) represented by the formula (III-3-2) Ladder-type polyorganosilsesquioxanes).
- T-III represented by the formula (III-3-1) in part or all of the molecular chain end of the polyorganosilsesquioxane having a ladder structure Unit
- polyorganosilsesquioxane residue (R)" containing a constitutional unit (M unit) represented by the formula (III-3-2) Ladder-type polyorganosilsesquioxanes).
- Component (F) has a ladder structure, this near 1050 cm -1 in the FT-IR spectrum (e.g., 1000 ⁇ 1100 cm -1) and 1150 cm -1 vicinity (e.g., 1200 cm -1 from more than 1100 cm -1 Each have an intrinsic absorption peak (ie, at least two absorption peaks at 1000 to 1200 cm.sup.- 1 ) [Ref. H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)].
- the FT-IR spectrum can be measured, for example, by the following apparatus and conditions. Measuring device: Brand name "FT-720" (manufactured by Horiba, Ltd.) Measurement method: Transmission method Resolution: 4 cm -1 Measurement wave number range: 400 to 4000 cm -1 Accumulated number: 16 times
- Ladder type polyorganosilsesquioxane (a)
- the ladder type polyorganosilsesquioxane (a) may have another silsesquioxane structure such as a cage structure or a random structure.
- the number average molecular weight (Mn) in terms of standard polystyrene conversion by gel permeation chromatography of ladder-type polyorganosilsesquioxane (a) is 500 to 1,500, preferably 550 to 1450, more preferably 600 to 1400. . If the Mn is less than 500, for example, the physical properties (heat resistance, sulfur barrier property, etc.) of the cured product tend to be lowered. On the other hand, when Mn exceeds 1,500, it tends to be solid at room temperature, and the handleability tends to decrease. In addition, the compatibility with other components may be deteriorated.
- the molecular weight dispersion (Mw / Mn) in terms of standard polystyrene conversion by gel permeation chromatography of ladder-type polyorganosilsesquioxane (a) is 1.00 to 1.40, and preferably 1.35 or less (for example, 1.05 to 1.35), more preferably 1.30 or less (eg, 1.10 to 1.30).
- Mw / Mn molecular weight dispersion degree exceeds 1.40, for example, low molecular weight siloxane tends to increase, and the adhesion of the cured product, the sulfur barrier property, and the like tend to be lowered.
- the liquid (liquid) may be easily formed at room temperature, and the handleability may be improved.
- the number average molecular weight of ladder-type polyorgano silsesquioxane (a) and molecular weight dispersion degree are measured by the following apparatus and conditions.
- Measuring device Brand name "LC-20AD” (manufactured by Shimadzu Corporation)
- Eluent THF, sample concentration 0.1 to 0.2% by weight
- Flow rate 1 mL / min
- Detector UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
- Molecular weight Standard polystyrene equivalent
- the 5% weight loss temperature (T d5 ) of the ladder type polyorganosilsesquioxane (a) in a nitrogen atmosphere is not particularly limited, but is preferably 150 ° C. or more, more preferably 240 ° C. or more, still more preferably 260 to The temperature is 500 ° C., particularly preferably 262 ° C. or more, and most preferably 265 ° C. or more.
- the 5% weight loss temperature is the temperature at which 5% of the weight before heating decreases when heated at a constant temperature rising rate, and serves as an indicator of heat resistance.
- the 5% weight loss temperature is measured by TGA (thermogravimetric analysis) under a nitrogen atmosphere at a temperature rising rate of 20 ° C./minute.
- the ladder-type polyorganosilsesquioxane (a) is not particularly limited, but is preferably a liquid at room temperature (25 ° C.).
- the viscosity at 25 ° C. is not particularly limited, but is preferably 30000 Pa ⁇ s or less (eg, 1 to 30000 Pa ⁇ s), more preferably 25000 Pa ⁇ s or less, still more preferably 10000 Pa ⁇ s or less .
- the viscosity is measured using a viscometer (trade name “MCR301”, manufactured by Anton Paar Co., Ltd.) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25 ° C.
- the ladder-type polyorganosilsesquioxane (a) is, for example, represented by the following formula (III-2) and has two or more alkenyl groups in the molecule, and is converted to standard polystyrene by gel permeation chromatography And ladder-type polyorganosilsesquioxanes having a number average molecular weight (Mn) of 500 to 1,500 and a molecular weight dispersion degree (Mw / Mn) of 1.00 to 1.40.
- Mn number average molecular weight
- Mw / Mn molecular weight dispersion degree
- R 42 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
- R 42 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including alkenyl and aryl groups).
- the ladder-type polyorganosilsesquioxane (a) may or may not have an alkenyl group as R 42 .
- the ladder-type polyorganosilsesquioxane (a) has at least one group selected from the group consisting of an alkyl group and an aryl group as R 42 other than the alkenyl group in the above formula (III-2) Are preferred, and it is more preferred to have at least one group selected from the group consisting of phenyl and methyl.
- the proportion (total content) of phenyl group, vinyl group and methyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) is although not particularly limited, it is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 80 to 100% by weight.
- the proportion (content) of the phenyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but it is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, and still more preferably 5 to 100% by weight.
- the proportion (content) of the vinyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) is not particularly limited, but it is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, still more preferably 5 to 90% by weight, and particularly preferably 10 to 80% by weight.
- the proportion (content) of methyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) is not particularly limited, but it is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, and still more preferably 5 to 100% by weight.
- composition of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) has, for example, an NMR spectrum (for example, 1 H-NMR spectrum can be calculated by measurement or the like.
- R 43 's are the same or different and each represents a hydrogen atom, an alkyl group, a monovalent group represented by the following formula (III-2-1), a following formula (III-2-2) Or a monovalent group represented by the following formula (III-2-3).
- R 44 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
- R 44 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including an alkenyl group and an aryl group), among which an alkyl group is preferable.
- R 45 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group.
- R 45 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including an alkenyl group and an aryl group), among which an alkyl group is preferable.
- n1 represents an integer of 0 or more. As n1, 0 to 5 is preferable, more preferably 0 to 3, and still more preferably 0.
- R 44 is the same as or different from R 44 in formula (III-2-1), and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group is there. Among them, an alkyl group is preferable as R 44 . Further, in the formula (III-2-2), R 45, like R 45 in formula (III-2-1), the same or different, it is a monovalent substituted or unsubstituted hydrocarbon group. Among them, an alkyl group is preferable as R 45 . In the above formula (III-2-2), R 46 is an alkenyl group, preferably a vinyl group. In the above formula (III-2-2), n2 represents an integer of 0 or more. As n 2, 0 to 5 is preferable, more preferably 0 to 3, and still more preferably 0.
- R 44 is the same as or different from R 44 in formula (III-2-1), and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group is there. Among them, an alkyl group is preferable as R 44 .
- R 47 is the same or different and is a monovalent saturated aliphatic hydrocarbon group, and examples thereof include an alkyl group and a cycloalkyl group. Groups (especially methyl groups) are preferred.
- n3 represents an integer of 0 or more. As n 3, 0 to 5 is preferable, more preferably 0 to 3 and still more preferably 0.
- n represents an integer of 0 or more.
- the above n is usually an even number of 0 or more (for example, an even number of 2 or more).
- the above n is not particularly limited as long as the number average molecular weight of the ladder type polyorganosilsesquioxane (a) is controlled to 500 to 1,500 and the molecular weight dispersion degree is controlled to 1.00 to 1.40.
- the ladder-type polyorganosilsesquioxane (a) is generally a poly represented by the formula (III-2) It is an organosilsesquioxane, which is a mixture of two or more different n.
- the ladder-type polyorganosilsesquioxane (a) preferably contains a component in which n is 1 or more (particularly 2 or more) as an essential component.
- the ladder-type polyorganosilsesquioxane (a) has two or more alkenyl groups in the molecule. Especially as a alkenyl group which ladder type polyorgano silsesquioxane (a) has, a vinyl group is preferable.
- the ladder-type polyorganosilsesquioxane (a) is represented by the formula (III-2), for example, those in which any one of R 42 in the formula (III-2) is an alkenyl group, R 44 and R 45 Wherein R 44 has a monovalent group represented by the formula (III-2-1) in which any of the groups is an alkenyl group, one having a monovalent group represented by the formula (III-2-2), R 44 And the like, which have a monovalent group represented by the formula (III-2-3) in which any one of them is an alkenyl group, and the like.
- the ladder-type polyorganosilsesquioxane (a) can be produced by a well-known and commonly used method and is not particularly limited.
- JP-A-4-28722, JP-A-2010-518182, JP-A-5-39357 Patent Publication Nos. 2004-99872, WO 1997/007156, JP 11-2466662, JP 9-20826, WO 2006/033147, JP 2005-239829 It can manufacture by the method etc. which were disclosed by documents, such as the international publication 2013/176238.
- Ladder type polyorganosilsesquioxane (b)
- the polyorganosilsesquioxane having a ladder structure in the ladder type polyorganosilsesquioxane (b) is represented, for example, by the following formula (III-3).
- p represents an integer of 1 or more (for example, 1 to 5000), preferably an integer of 1 to 2000, and more preferably an integer of 1 to 1000.
- R 48 in the formula (III-3) is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. T represents a terminal group.
- the group (for example, R 48 in the formula (III-3)) directly bonded to a silicon atom in the above polyorganosilsesquioxane in the ladder type polyorganosilsesquioxane (b) is not particularly limited, but the above group
- the ratio of the monovalent substituted or unsubstituted hydrocarbon group to the total amount (100 mol%) of is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more.
- a substituted or unsubstituted C 1-10 alkyl group in particular, a C 1-4 alkyl group such as a methyl group or an ethyl group
- a substituted or unsubstituted C 6- The total amount of 10 aryl groups (particularly, phenyl group) and substituted or unsubstituted C 7-10 aralkyl groups (especially benzyl group) is preferably 50 mol% or more, more preferably 80 mol% or more. More preferably, it is 90 mol% or more.
- the ladder-type polyorganosilsesquioxane (b) has a polyorganosilsesquioxane residue (R) at part or all of the molecular chain terminals of the polyorganosilsesquioxane having the above ladder structure.
- a polyorganosilsesquioxane residue (R) at part or all of the molecular chain terminals of the polyorganosilsesquioxane having the above ladder structure.
- the polyorganosilsesquioxane residue (R) is, as described above, at least a constituent unit represented by the formula (III-3-1) and a constituent unit represented by the formula (III-3-2) It is the residue which contains.
- R 49 in the above formula (III-3-1) represents an alkenyl group.
- Specific examples of the above-mentioned alkenyl groups are given as the above-mentioned alkenyl group, and among them, a C 2-10 alkenyl group is preferable, a C 2-4 alkenyl group is more preferable, and a vinyl group is more preferable.
- R 50 in the above formula (III-3-2) is the same or different and represents a monovalent substituted or unsubstituted hydrocarbon group.
- substituted or unsubstituted hydrocarbon group the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (Alkenyl group, an aryl group is also included) etc. are mentioned.
- R 50 is preferably an alkyl group, more preferably a C 1-20 alkyl group, still more preferably a C 1-10 alkyl group, particularly preferably a C 1-4 alkyl group, and most preferably a methyl group.
- the polyorganosilsesquioxane residue (R) is not limited to the structural unit represented by the above formula (III-3-1) and the structural unit represented by the above formula (III-3-2), for example, And a structural unit represented by the following formula (III- 3 1 ′):
- R 49 ′ in the above formula (III-3-1 ′) represents a monovalent group excluding an alkenyl group. Specific examples thereof include a hydrogen atom, a halogen atom, a monovalent organic group other than an alkenyl group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, and a monovalent sulfur atom-containing group.
- the amount of silicon atoms bonded to three oxygen atoms represented by the formula (III-3-1) in the above polyorganosilsesquioxane residue (R) is not particularly limited, but the polyorganosilsesquioxane residue is not particularly limited.
- the amount is preferably 20 to 80 mol%, more preferably 25 to 60 mol%, based on the total amount (100 mol%) of silicon atoms constituting the group (R). If the content is less than 20 mol%, the amount of the alkenyl group contained in the ladder-type polyorganosilsesquioxane (b) may be insufficient, and the hardness of the cured product may not be sufficiently obtained.
- the amount of silicon atom to which one oxygen atom represented by the formula (III-3-2) in the above polyorganosilsesquioxane residue (R) is bonded is not particularly limited, but the polyorganosilsesquioxane residue is The amount is preferably 20 to 85 mol%, more preferably 30 to 75 mol%, based on the total amount (100 mol%) of silicon atoms constituting the group (R).
- the content is less than 20 mol%, silanol groups and hydrolyzable silyl groups easily remain in the ladder-type polyorganosilsesquioxane (b), and the ladder-type polyorganosilsesquioxane (b) is liquid May not be obtained at Furthermore, since the condensation reaction proceeds between the ladder-type polyorganosilsesquioxane (b) and the molecular weight is easily changed, the storage stability may be deteriorated. On the other hand, when the content exceeds 85 mol%, the amount of the alkenyl group of the ladder-type polyorganosilsesquioxane (b) may be insufficient, and the hardness of the cured product may not be sufficiently obtained.
- the Si-O-Si structure (skeleton) of the polyorganosilsesquioxane residue (R) is not particularly limited, and examples thereof include a ladder structure, a cage structure, and a random structure.
- the ladder type polyorganosilsesquioxane (b) can be represented, for example, by the following formula (III-3 ′).
- formula (III-3 ′) As p and R 48 in the formula (III-3 ′), those similar to the above formula (III-3) are exemplified.
- a in Formula (III-3 ′) represents a polyorganosilsesquioxane residue (R), or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group, and a part or all of A is a polyorgano. It is a silsesquioxane residue (R).
- Four A may be identical to or different from each other.
- the number of alkenyl groups in the molecule in the ladder-type polyorganosilsesquioxane (b) is not particularly limited as long as it is one or more, and is preferably two or more (for example, 2 to 50), more preferably Is 2 to 30 pieces.
- the number of alkenyl groups can be calculated, for example, by 1 H-NMR spectrum measurement or the like.
- the content of the alkenyl group in the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 0.7 to 5.5 mmol / g, more preferably 1.1 to 4.4 mmol / g. is there.
- the proportion (by weight) of the alkenyl group contained in the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 2.0 to 15.0% by weight in terms of vinyl group, more preferably Is 3.0 to 12.0% by weight.
- the weight average molecular weight (Mw) of the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, particularly preferably Is from 500 to 8000, most preferably from 1700 to 7000.
- Mw The heat resistance of hardened
- the Mw is 800,000 or less, the compatibility with other components does not easily decrease.
- said Mw is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.
- the number average molecular weight (Mn) of the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 800 to 800,000, more preferably 150 to 100,000, still more preferably 250 to 10,000, particularly preferably Is from 400 to 8000, most preferably from 1500 to 7000.
- cured material does not fall easily that Mn is 80 or more.
- Mn is 800,000 or less, the compatibility with other components is unlikely to decrease.
- said Mn is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.
- the ladder-type polyorganosilsesquioxane (b) is preferably liquid at normal temperature (about 25 ° C.). More specifically, the viscosity at 23 ° C. is preferably 100 to 100,000 mPa ⁇ s, more preferably 500 to 10,000 mPa ⁇ s, and still more preferably 1000 to 8000 mPa ⁇ s.
- cured material does not fall easily that a viscosity is 100 mPa * s or more. On the other hand, when the viscosity is 100,000 mPa ⁇ s or less, preparation and handling of the curable silicone resin composition are easy.
- the method for producing the ladder-type polyorganosilsesquioxane (b) is not particularly limited.
- it has a ladder structure, and has a silanol group and / or a hydrolyzable silyl group (a silanol group and a hydrolyzable group at the molecular chain terminal)
- the method of forming the said silsesquioxane residue (R) with respect to the molecular chain terminal of the polyorgano silsesquioxane which has any one or both of silyl groups is mentioned.
- it can be manufactured by the method disclosed in the document such as WO 2013/176238.
- the ladder-type polyorganosilsesquioxane (a) and (b) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
- the component (F) one type can be used alone, or two or more types can be used in combination.
- the curable silicone resin composition of the present invention preferably contains the component (F), more preferably a ladder-type polyorganosilsesquioxane (a), from the viewpoint of the sulfur barrier property and the strength (resin strength) of the cured product. And / or ladder type polyorganosilsesquioxane (b).
- the content (blending amount) of the component (F) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 100 parts by weight in total of the components (A) and (B).
- the amount is preferably 50 parts by weight, more preferably 0.01 to 45 parts by weight, and still more preferably 0.01 to 40 parts by weight.
- the content (blending amount) of the component (F) is preferably 0.1 to 20% by weight, more preferably 0 based on 100% by weight of the curable silicone resin composition. 1 to 15% by weight, more preferably 0.2 to 10% by weight.
- the curable silicone resin composition of the present invention may contain an isocyanurate compound (sometimes referred to as "(G) component”) represented by the following formula (2).
- the curable silicone resin composition of the present invention contains the component (G), the adhesion of the cured product to the adherend is further improved, and the sulfur barrier property tends to be further enhanced.
- R f , R g and R h are the same or different and each represents a group represented by formula (2a) or a group represented by formula (2b). However, at least one of R f , R g and R h is a group represented by formula (2b).
- R i represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group).
- a linear or branched C 1-8 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned.
- alkyl groups linear or branched C 1-3 alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group are preferable.
- R i a hydrogen atom is particularly preferred.
- R j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group).
- a linear or branched C 1-8 alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned.
- alkyl groups linear or branched C 1-3 alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group are preferable.
- a hydrogen atom is particularly preferable as R j .
- R f , R g and R h in the formula (2) are a group represented by the formula (2b), the group represented by the formula (2b) is It may be the same or different.
- a compound in which one of R f , R g and R h in the formula (2) is a group represented by the formula (2b) (“monoallyl diglycidyl isocyanurate compound” Or a compound represented by the formula (2b) in which two of R f , R g and R h in the formula (2) are represented by the formula (2b) (sometimes referred to as “diallyl monoglycidyl isocyanurate compound”) And compounds in which all of R f , R g , and R h in Formula (2) are represented by Formula (2b) (sometimes referred to as “triallyl isocyanurate compound”).
- monoallyl diglycidyl isocyanurate compound examples include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl) Propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methyl epoxypropyl) isocyanurate and the like.
- diallyl monoglycidyl isocyanurate compound examples include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, and 1,3-bis (2-methyl).
- triallyl isocyanurate compound examples include triallyl isocyanurate, tris (2-methylpropenyl) isocyanurate and the like.
- component (G) one type can be used alone, or two or more types can be used in combination.
- Component (G) can be obtained, for example, as a commercial product.
- the component (G) When the component (G) has a group represented by the formula (2a), it may be used after being reacted with a compound that reacts with an epoxy group, such as alcohol or acid anhydride, for example. it can.
- a compound that reacts with an epoxy group such as alcohol or acid anhydride, for example. it can.
- the component (G) has a group represented by the formula (2b), for example, it can be used after being reacted (hydrosilylation reaction) with a compound having a hydrosilyl group in advance.
- the curable silicone resin composition of the present invention is obtained by reacting the above monoallyl diglycidyl isocyanurate compound with ladder type polyorganosilsesquioxane which is the above-mentioned component (F) in the presence of a hydrosilylation catalyst. It can also be used as a component of an object.
- the component (G) can be mixed with the silane coupling agent which is the component (H) in advance, as described later, and then blended into the other components. .
- the content (blending amount) of the component (G) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 6% by weight with respect to the curable silicone resin composition (100% by weight) Is more preferably 0.05 to 4% by weight, still more preferably 0.1 to 3% by weight.
- the content of the component (G) is 0.01% by weight or more, the sulfur barrier properties of the cured product and the adhesion to the adherend tend to be further improved.
- the content of the component (G) to 6% by weight or less, the problem of solid precipitation in the curable silicone resin composition tends to be suppressed.
- the total (total content) of the content of the components (C) and (G) is not particularly limited, but the curable silicone resin composition
- the amount is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 3% by weight, and particularly preferably 0.4 to 2% by weight.
- the sulfur barrier properties of the cured product tend to be remarkably improved.
- the content of the total content is 15% by weight or less, the problem of solid precipitation in the curable silicone resin composition tends to be further suppressed.
- the curable silicone resin composition of the present invention may contain a silane coupling agent (sometimes referred to as "(H) component").
- a silane coupling agent sometimes referred to as "(H) component”
- the adhesion of the cured product to the adherend tends to be improved.
- the component (H) has good compatibility with the components (A), (B), (C), (D), (F), (G), etc.
- a composition of the (G) component and the (H) component is formed in advance and then blended with the other components to obtain a uniform curable silicone resin composition. It is easy to be
- silane coupling agents can be used and are not particularly limited.
- 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silane coupling agents such as trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-triethoxysilyl-N- (1,3-dimethyl-)
- epoxy group-containing silane coupling agents in particular, 3-glycidoxypropyltrimethoxysilane
- (H) component can be used individually by 1 type or in combination of 2 or more types.
- the content (blending amount) of the component (H) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 15% by weight with respect to the curable silicone resin composition (100% by weight) Is more preferably 0.1 to 10% by weight, still more preferably 0.4 to 5% by weight.
- the content of the component (H) is 0.01% by weight or more, the adhesion to the adherend is improved, and in particular, when the component (G) is used in a compatible manner, the curing is more sufficient. Prone.
- the content of the component (H) is 15% by weight or less, curing is unlikely to be insufficient, and the sulfur barrier properties and thermal shock resistance of the cured product are more likely to be improved.
- the curable silicone resin composition of the present invention is at least one member selected from the group consisting of zinc carboxylate and a zinc complex or a zinc salt represented by the following formula (3) (with the exception of zinc bisacetylacetonate). Or a zinc compound of the formula (which may be referred to simply as "component (I)").
- the sulfur barrier property tends to be improved.
- the amount of the zinc complex or zinc salt represented by the above formula (3) as component (I) (but excluding zinc bisacetylacetonate) is increased.
- the solubility to silicone resins (especially, the above components (A), (B), (D), (F) components, etc.) is good, and the sulfur barrier property when it is made a cured product by adding it, especially not only barrier properties against hydrogen sulfide, barrier property even higher for SO X.
- Examples of zinc carboxylates in component (I) include zinc naphthenate, zinc octylate, zinc acetoacetate, zinc (meth) acrylate, zinc neodecanate and the like, with zinc naphthenate and zinc octylate being preferred, and octylate Zinc is more preferred.
- R 31 represents a substituted or unsubstituted C 1-30 alkyl group, and as the C 1-30 alkyl group, a C 1-20 alkyl group is preferable, and a C 2-15 alkyl group is more preferable. Preferably, a C 3-10 alkyl group is more preferable, and a branched C 3-10 alkyl group is particularly preferable.
- Examples of the branched C 3-10 alkyl group include isopropyl, isobutyl, t-butyl, s-butyl, isopentyl, t-pentyl, isohexyl, t-hexyl, isoheptyl, t- Examples include heptyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, isononyl group, isodecyl group and the like. Among these groups, isopropyl, isobutyl, t-butyl, s-butyl, isopentyl and t-pentyl are most preferable. As said substituent, a halogen atom, a hydroxyl group, a carboxy group etc. are mentioned.
- R 32 represents a hydrogen atom or a substituted or unsubstituted C 1-30 alkyl group, and as the C 1-30 alkyl group, the groups mentioned above for R 31 are preferable, but in R 32 The most preferred group is a hydrogen atom.
- the above substituents are the same as those recited for R 31 above.
- R 33 represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 34 group.
- R 34 represents a substituted or unsubstituted C 1-30 alkyl group.
- the same groups as those mentioned above for R 31 are preferable.
- the aromatic heterocyclic group include pyridyl, pyrimidinyl, pyrazolyl, pyridazinyl, pyrazinyl, triazinyl, furanyl, thienyl, indolyl, oxazolyl, thiazolyl, imidazolyl and the like.
- Be The above substituents are the same as those recited for R 31 above.
- the R 31 and R 32 may be bonded to each other to form a ring, and the R 32 and R 33 may be bonded to each other to form a ring.
- the anion in the anion or enolate anion of the ⁇ -diketone or ⁇ -keto ester of the above formula (3a) is a structure represented by the formula (3a ′), and the enolate anion is a structure represented by the formula (3a ′ ′) R 31 , R 32 and R 33 in the formula (3a ′) and the formula (3a ′ ′) are the same as above.
- a compound represented by the following formula (3 ′) is preferable as the component (I).
- R 35 represents a substituted or unsubstituted C 1-30 alkyl group
- R 36 represents a hydrogen atom, or a substituted or unsubstituted C 1-30 alkyl group
- R 37 Represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 38 group.
- R 38 represents a substituted or unsubstituted C 1-30 alkyl group.
- R 35 and R 36 may be bonded to each other to form a ring
- R 36 and R 37 may be bonded to each other to form a ring
- R 35, R 36, R 37 , and C 1-30 alkyl substituted or unsubstituted C 1-30 alkyl group in R 38 are preferably the aromatic heterocyclic
- the formula group is the same group as that mentioned above for R 33 , and the above-mentioned substituent is the same as the group mentioned above for R 31 .
- component (I) a compound represented by the following formula (3-1) [zinc bis (2,2,7-trimethyl-3,5-octanedionate)] among others, a compound represented by the formula (3-2)
- the compound represented [Zn (DPM) 2 : zinc bis dipivaloyl methane] is particularly preferred.
- the component (I) one type can be used alone, or two or more types can be used in combination. Moreover, as a component (I), a commercial item can also be used.
- the content (blending amount) of the component (I) in the curable silicone resin composition of the present invention is preferably 0.01 to 5% by weight, and more preferably, with respect to the curable silicone resin composition (100% by weight). Is preferably 0.05 to 3% by weight, more preferably 0.1 to 2% by weight, and particularly preferably 0.1 to 1.5% by weight.
- the content (blending amount) of the component (I) is preferably 0.02 to 10 parts by weight, more preferably 0.05 to 6 parts by weight, still more preferably 100 parts by weight of the component (A). Is 0.1 to 4 parts by weight, particularly preferably 0.1 to 3 parts by weight.
- the curable silicone resin composition of the present invention is not limited to the components (A), (D), and (F) described above, and other polyorganosiloxanes having an alkenyl group in the molecule ("Other polyorgano May be referred to as "siloxane". By containing other polyorganosiloxanes, it may be possible to adjust the viscosity of the curable silicone resin composition or to adjust the balance of physical properties (for example, mechanical properties) of the cured product.
- polyorganosiloxanes for example, linear polyorganosiloxanes having one or more alkenyl groups in the molecule (having one or more alkenyl groups in the molecule, and having a siloxane bond as a main chain, And linear polyorganosiloxanes having no silalkylene bond.
- the above linear polyorganosiloxanes can be used alone or in combination of two or more.
- numerator the above-mentioned substituted or unsubstituted alkenyl group is mentioned, Especially, a vinyl group is preferable.
- the linear polyorganosiloxane may have only one type of alkenyl group or may have two or more types of alkenyl groups.
- the alkenyl group contained in the linear polyorganosiloxane is not particularly limited, but is preferably one bonded to a silicon atom.
- the number of alkenyl groups which the above linear polyorganosiloxane has in the molecule may be one or more, and is not particularly limited. However, from the viewpoint of the curability of the curable silicone resin composition, two or more (for example, 2 to 50) is preferable.
- bonded with silicon atoms other than the alkenyl group which the said linear polyorganosiloxane has is not specifically limited,
- a hydrogen atom, an organic group, etc. are mentioned.
- the organic group include the above-mentioned organic groups (for example, substituted or unsubstituted hydrocarbon groups such as an alkyl group, a cycloalkyl group, a cycloalkyl-alkyl group, a halogenated hydrocarbon group, etc.) and the above-mentioned aryl group.
- the linear polyorganosiloxane may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
- the properties of the linear polyorganosiloxane are not particularly limited, and may be liquid or solid at 25 ° C., for example.
- R 4 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl groups, and the above-mentioned aryl groups.
- R 4 is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule.
- the proportion of the alkenyl group to the total amount (100 mol%) of R 4 is preferably 0.1 to 40 mol%.
- R 4 other than an alkenyl group an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.
- X 4 is a hydrogen atom or an alkyl group as in the case of X 1a above.
- alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.
- e1 is a positive number
- e2 is 0 or a positive number
- e3 is 0 or a positive number
- the linear polyorganosiloxane which has a 2 or more alkenyl group in a molecule
- numerator is mentioned, for example.
- the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this linear polyorganosiloxane has, Especially a vinyl group is preferable.
- it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups.
- examples of the group bonded to a silicon atom other than the alkenyl group in the linear polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an aryl group), among which Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred.
- the proportion of the alkenyl group to the total amount (100 mol%) of the group bonded to the silicon atom in the linear polyorganosiloxane is not particularly limited, but preferably 0.1 to 40 mol%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but it is preferably 1 to 20 mol%. Further, the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 30 to 90 mol%.
- the proportion of aryl groups (especially phenyl groups) relative to the total amount (100 mol%) of groups bonded to silicon atoms as the linear polyorganosiloxane is 40 mol% or more (for example, 45 to 80 mol%)
- the sulfur barrier properties of the cured product tend to be further improved.
- a cured product is obtained by using a compound in which the proportion of alkyl groups (especially methyl groups) is 90 mol% or more (for example, 95 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
- the linear polyorganosiloxane is represented, for example, by the following formula (IV-1).
- R 51 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least one (preferably at least two) of R 51 is an alkenyl group.
- m3 is an integer of 5 to 1000.
- the content (blending amount) of the other polyorganosiloxane in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 30 wt% with respect to the curable silicone resin composition (100 wt%) % Is preferable, more preferably 0.1 to 20% by weight.
- the content of other polyorganosiloxanes in the above range it may be possible to adjust the balance of the viscosity of the curable silicone resin composition and the physical properties of the cured product.
- the curable silicone resin composition of the present invention may contain a hydrosilylation reaction inhibitor to adjust the rate of the curing reaction (hydrosilylation reaction).
- a hydrosilylation reaction inhibitor known or commonly used hydrosilylation reaction inhibitors can be used and are not particularly limited.
- the said hydrosilylation reaction inhibitor can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- content (blending amount) of the above hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the curable silicone resin composition and the like, practically it is 0. 0 as a content relative to the curable silicone resin composition (100% by weight). The range of 00001 to 5% by weight is preferable.
- the curable silicone resin composition of the present invention can be obtained, for example, as a siloxane compound other than the above-mentioned polyorganosiloxane (component (A), component (B), component (D), component (F), other polyorganosiloxanes). And cyclic siloxanes having two or more aliphatic carbon-carbon double bonds (in particular, alkenyl groups) in the molecule.
- the curable silicone resin composition of this invention may contain the cyclic siloxane which has a 2 or more hydrosilyl group in a molecule
- Each of the above cyclic siloxanes can be used alone or in combination of two or more.
- the content (compounding amount) of the above-mentioned cyclic siloxane in the curable silicone resin composition of the present invention is not particularly limited, but 0.01 to 30% by weight with respect to the curable silicone resin composition (100% by weight) Preferably, it is 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.
- the curable silicone resin composition of the present invention may contain a solvent.
- the solvent include known or commonly used organic solvents, water and the like, and not particularly limited, examples thereof include toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate and the like.
- a solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content is not specifically limited, It can select suitably.
- the curable silicone resin composition of the present invention may contain a phosphor.
- phosphors known or commonly used phosphors (for example, phosphors known in the field of optical semiconductor devices etc.) can be used, and there is no particular limitation.
- a general formula A 3 B 5 O 12 : M wherein A is selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm B represents a single or more elements selected from the group consisting of Al, Ga and In, and M represents a group consisting of Ce, Pr, Eu, Cr, Nd and Er Represents one or more selected elements] (for example, Y 3 Al 5 O 12 : Ce phosphor fine particles, (Y, Gd, Tb) 3 (Al, Ga) 5 O 12: Ce phosphor particles, etc.); based phosphor particles (e.g., (Sr, Ca Ba) 2 SiO 4: Eu, etc.), and the like.
- the phosphor may be one that has been subjected to well-known and commonly used surface treatment.
- fluorescent substance can also be used individually by 1 type, and can also be used combining 2 or more types.
- the content (blending amount) of the phosphor in the curable silicone resin composition of the present invention is not particularly limited, but is preferably 0.01 to 20% by weight with respect to the curable silicone resin composition (100% by weight). And more preferably 0.5 to 10% by weight.
- the wavelength conversion function of light by the sealing material can be sufficiently exhibited in the optical semiconductor device, and the viscosity of the curable silicone resin composition does not become too high, and curing occurs. There is a tendency that the workability at the time of object preparation (in particular, sealing operation) is further improved.
- the curable silicone resin composition of the present invention may contain components (sometimes referred to as "other components") other than the components described above.
- Other components are not particularly limited, and examples thereof include silica filler, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and the like.
- Inorganic fillers inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; fine powders of organic resins such as silicone resins, epoxy resins and fluorine resins; silver, copper, etc.
- Fillers such as conductive metal powders, stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants) Etc.), flame retardant aids, reinforcements (other fillers etc.), nucleating agents, coupling agents other than silane coupling agents, lubricants, waxes, Agents, mold release agents, impact modifiers, color modifiers, flow improvers, colorants (dyes, pigments etc.), surface conditioners (eg various polyether modified silicones, polyester modified silicones, phenyl modified silicones, Compounds such as alkyl-modified silicones, dispersants, antifoaming agents, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, and other well-known and commonly used additives such as functional additives .
- One of these other components may be used alone, or two or more thereof may be used in combination.
- content
- the curable silicone resin composition of the present invention is not particularly limited, but the composition is such that 0.2 to 4 moles of alkenyl groups are contained with respect to 1 mole of hydrosilyl groups present in the curable silicone resin composition
- the composition is 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles.
- the total amount (total content) of the component (A), the component (B), the component (D), the component (F) and the other polyorganosiloxanes contained in the curable silicone resin composition of the present invention is not particularly limited. Is preferably 70% by weight or more (eg, 70% by weight or more and less than 100% by weight), more preferably 80% by weight or more (eg, 80 to 99% by weight) based on 100% by weight of the curable silicone resin composition. %, More preferably 90% by weight or more (eg, 90 to 99% by weight). By setting the total amount to 70% by weight or more, the heat resistance and the transparency of the cured product tend to be further improved.
- the curable silicone resin composition of the present invention is not particularly limited, the curable silicone resin The amount is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, and still more preferably 60 to 80% by weight, based on 100% by weight of the resin composition.
- the total amount is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, and still more preferably 60 to 80% by weight, based on 100% by weight of the resin composition.
- the content (blending amount) of the component (B) in the curable silicone resin composition of the present invention is not particularly limited, the content of the components (A), (D), (F), and other polyorganosiloxanes is not particularly limited.
- the amount is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total amount (total content).
- Component (A) relative to the total amount (total content; 100% by weight) of component (A), component (D), component (F) and other polyorganosiloxanes contained in the curable silicone resin composition of the present invention
- the proportion is not particularly limited, but is preferably 10% by weight or more (eg, 10 to 100% by weight), more preferably 15% by weight or more (eg, 15 to 90% by weight), and still more preferably 20% by weight or more (eg, , 20-80% by weight).
- Component (D) based on the total amount (total content; 100% by weight) of components (A), (D), (F) and other polyorganosiloxanes contained in the curable silicone resin composition of the present invention
- the proportion (total proportion) of component (F) is not particularly limited, but it is preferably more than 0% by weight and 90% by weight, more preferably 5 to 85% by weight, and still more preferably 10 to 80% by weight.
- the ratio to 90% by weight or less the component (A) can be relatively increased, so the thermal shock resistance of the cured product may be further improved, and the tack may be reduced.
- the ratio to 10% by weight or more the balance of the mechanical properties and the optical properties of the cured product may be better.
- the proportion of the component (A) is not particularly limited, but is preferably 5% by weight or more (eg, 5 to 100% by weight), more preferably 10% by weight or more, and still more preferably 15 to 50% by weight. By setting the ratio to 5% by weight or more, the tackiness of the cured product tends to be further reduced, and the thermal shock resistance tends to be good.
- the curable silicone resin composition of the present invention is not particularly limited, it can be prepared, for example, by stirring and mixing the above-mentioned components at room temperature (or while heating as required).
- the curable silicone resin composition of the present invention can be used as a one-component composition in which one in which all the components are all mixed in advance is used as it is, for example, 2 separately prepared It can also be used as a multi-liquid (for example, two-liquid) composition in which the above components are mixed and used at a predetermined ratio before use.
- the curable silicone resin composition of the present invention is not particularly limited, but is preferably liquid at normal temperature (about 25 ° C.). More specifically, the curable silicone resin composition of the present invention preferably has a viscosity at 25 ° C. of 300 to 20,000 mPa ⁇ s, more preferably 500 to 10,000 mPa ⁇ s, still more preferably 1000 to 8000 mPa. ⁇ S. When the viscosity is 300 mPa ⁇ s or more, the heat resistance of the cured product tends to be further improved.
- the viscosity of the curable silicone resin composition is measured by the same method as the viscosity of the ladder-type polyorganosilsesquioxane (a) described above.
- a cured product By curing (in particular, curing by a hydrosilylation reaction) the curable silicone resin composition of the present invention, a cured product (sometimes referred to as "the cured product of the present invention") is obtained.
- the conditions for curing are not particularly limited and can be appropriately selected from conventionally known conditions.
- the temperature (curing temperature) is 25 to 180 ° C. (more preferably 60 to 150) from the viewpoint of the reaction rate. ° C) is preferred, and the time (curing time) is preferably 5 to 720 minutes.
- the cured product of the present invention has thermal shock resistance, adhesion to adherends, and sulfur barrier properties, in particular, only barrier properties to hydrogen sulfide. without excellent barrier property against SO X, further, if it contains the component (G), the cured product is obtained having a particularly excellent thermal shock resistance.
- the curable silicone resin composition of the present invention is, in particular, a resin composition for sealing an optical semiconductor element (LED element) in an optical semiconductor device (resin composition for optical semiconductor sealing) ("sealing agent of the present invention" Can be preferably used).
- the sealing material (cured product) obtained by curing the sealing agent of the present invention has high heat resistance and transparency unique to polysiloxane materials, as well as thermal shock resistance and adhesion to adherends.
- sulfur barrier properties in particular not only barrier properties against hydrogen sulfide, but also barrier properties against SO x .
- the sealing agent of the present invention can be preferably used particularly as a sealing agent for optical semiconductor devices with high brightness and short wavelength.
- an optical semiconductor device By sealing an optical semiconductor element using the sealing agent of the present invention, an optical semiconductor device (sometimes referred to as “the optical semiconductor device of the present invention”) can be obtained. That is, the optical semiconductor device of the present invention comprises at least an optical semiconductor element and a sealing material for sealing the optical semiconductor element, and the sealing material is the curable silicone resin composition of the present invention (the sealing of the present invention Optical semiconductor device which is a cured product (cured product of the present invention) of
- sealing of an optical-semiconductor element can be implemented by the well-known thru
- the curing temperature and the curing time are not particularly limited, and can be appropriately set in the same range as in the preparation of the cured product.
- An example of the optical semiconductor device of the present invention is shown in FIG.
- 100 is a reflector (resin composition for light reflection)
- 101 is a metal wiring (electrode)
- 102 is an optical semiconductor element
- 103 is a bonding wire
- 104 is a cured product (sealing material).
- the curable silicone resin composition of the present invention is a composition for forming a lens (lens for optical semiconductor) provided in an optical semiconductor device (composition for forming a lens for optical semiconductor) ("lens of the present invention It may be preferably used as "forming composition”.
- the lens obtained by curing the composition for forming a lens of the present invention has, in addition to high heat resistance and transparency, adhesion to an adherend and sulfur barrier property, in particular, only barrier property to hydrogen sulfide. Also, the barrier property to SO X is excellent.
- the composition for forming a lens of the present invention comprises at least an optical semiconductor element and a lens, and the lens is a cured product of the curable silicone resin composition of the present invention (composition for forming a lens of the present invention) Semiconductor device).
- manufacture of the lens for optical semiconductors using the composition for lens formation of this invention can be implemented by a well-known thru
- the composition for lens formation of this invention It can be carried out by a method of injection into the inside and heat curing under predetermined conditions, or a method of applying by a dispenser or the like and heat curing under predetermined conditions.
- the curing temperature and the curing time are not particularly limited, and can be appropriately set in the same range as in the preparation of the cured product.
- the aspect in which the optical semiconductor device of the present invention includes the above lens is not particularly limited.
- the optical semiconductor device of the present invention when it has a sealing material, it is disposed on part or all of the surface of the sealing material.
- the above-described aspect may be an aspect in which the optical semiconductor element of the optical semiconductor device is sealed (that is, an aspect in which the cured product of the present invention serves both as a sealing material and a lens) or the like. More specifically, for example, the embodiments disclosed in WO 2012/147342, JP 2012-188627 A, JP 2011-233605 A etc. may be mentioned.
- the optical semiconductor device of the present invention comprises an optical semiconductor element, a sealing material for sealing the optical semiconductor element, and a lens
- the sealing material is a curable silicone resin composition of the present invention (the sealing of the present invention A cured product of the curing agent of the present invention (the cured product of the present invention)
- the lens is a cured product of the curable silicone resin composition of the present invention (the composition for forming a lens of the present invention) (the cured product of the present invention) It may be an optical semiconductor device.
- the curable silicone resin composition of the present invention is not limited to the above-mentioned sealant application (application for encapsulant of optical semiconductor element) and application for forming lens (application for forming lens in optical semiconductor device), for example, die bonding agent application (For example, use as die bonding agent for optical semiconductors), Sealant for semiconductor elements in semiconductor devices other than optical semiconductor devices, functional coating agent, heat resistant plastic lens, transparent equipment, adhesive (heat resistant transparent adhesive etc.), electrical insulation Materials (insulation film etc.), laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical films, optical elements, optical lenses, optical members, optical molding, electronic paper, touch panels, It can be preferably used in applications related to optics and semiconductors such as solar cell substrates, optical waveguides, light guide plates and holographic memories.
- the curable silicone resin composition of the present invention is a sealing material for covering an optical semiconductor element in an optical semiconductor device with high brightness and short wavelength, which has been difficult to cope with conventional resin materials, It can be preferably used for applications such as sealing materials for covering semiconductor elements in high withstand voltage semiconductor devices (power semiconductors and the like).
- the 1 H-NMR analysis of the products and products produced in the synthesis example was carried out with a JEOL ECA 500 (500 MHz). Moreover, the measurement of the number average molecular weight and the weight average molecular weight of the above product and the product can be carried out according to Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskgel GMH HR -M ⁇ 2 (Tosoh (strain) ) Ltd.), guard column: Tskgel guard column H HR L (manufactured by Tosoh Corporation), column oven: cOLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measuring conditions: 40 ° C., were performed by standard polystyrene .
- Synthesis example 1 [Production of Polyorganosilsesquioxane Having Vinyl Group] Under a nitrogen stream, 9.64 g (65 mmol) of vinyltrimethoxysilane and 38.67 g (195 mmol) of phenyltrimethoxysilane in a 100 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube. And 8.31 g of methyl isobutyl ketone (MIBK) were charged, and the mixture was cooled to 10 ° C. or less.
- MIBK methyl isobutyl ketone
- FIG. 2 shows a chart (solvent: deuterated chloroform) of 1 H-NMR spectrum of the above-mentioned product.
- FIG. 3 shows a chart of the FT-IR spectrum of the above product.
- the above-mentioned product product after silylation reaction
- Ladder-type polyorganosilsesquioxane (F) (Synthesis example 1): Compound obtained in Synthesis example 1 [component (F)]
- Isocyanurate compound (MA-DGIC) trade name "MA-DGIC” [component (G)], a compound represented by the following formula, manufactured by Shikoku Kasei Kogyo Co., Ltd.
- TPIC Isocyanurate compound
- Octylic acid zinc (Nikkotics zinc): Brand name “Nikkotics zinc” [Zinc 2-ethylhexanoate], Nippon Chemical Industrial Co., Ltd.
- Silane coupling agent (OFS-6040): Brand name “XIAMETER OFS- 6040 "[3-glycidoxypropyltrimethoxysilane, (H) component], manufactured by Dow Corning
- Example 1 [Production of a curable silicone resin composition] First, as shown in Table 1, 20 parts by weight of trade name "ETERLED GS5145A” and a trade name “TEPIC-VL” (0.1 parts by weight) are mixed and stirred at 40 ° C for 2 hours to prepare agent A. did.
- agent B 80 parts by weight of trade name "ETERLED GS5145B” as agent B is mixed with 20.1 parts by weight of agent A obtained above, and a self-revolution stirring device (brand name "Awatori Neritaro", ( Kneader Co., Ltd., Model No .: ARE-310) was used for kneading for 5 minutes with stirring and 2 minutes of defoaming to produce a curable silicone resin composition which is a uniform liquid.
- a self-revolution stirring device brand name "Awatori Neritaro", ( Kneader Co., Ltd., Model No .: ARE-310) was used for kneading for 5 minutes with stirring and 2 minutes of defoaming to produce a curable silicone resin composition which is a uniform liquid.
- the curable silicone resin composition obtained above is injected into the LED package (InGaN device, 3.0 mm ⁇ 3.0 mm) of the embodiment shown in FIG. 1, and the solution is heated at 60 ° C. for 1 hour, then at 80 ° C. for 1 hour Furthermore, by heating at 150 ° C. for 4 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable silicone resin composition was manufactured.
- Examples 2 to 10, Comparative Examples 1 to 5 A curable silicone resin composition and an optical semiconductor device were produced in the same manner as in Example 1 except that the composition of the curable silicone resin composition was changed as shown in Table 1.
- Thermal shock test The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable silicone resin composition. In addition, the sample was used after confirming that it lights up, when an electric current of 20 mA is supplied before a test. About the above sample, using a thermal shock tester (manufactured by ESPEC Co., Ltd., model number: TSB-21), the thermal cycle is a cycle of exposing for 5 minutes at a temperature of -40 ° C and then for 5 minutes at a temperature of 100 ° C. Shock application was performed for 1000 cycles. Thereafter, a current of 20 mA was applied to the sample after the thermal shock of 1000 cycles was applied, and the number of samples which did not light was counted. And, when the number of samples not lit is 0, ⁇ (good heat shock resistance), when the number of samples not lit is 1 or more, x (heat shock resistance is poor) Yes). The results are shown in Table 1.
- Moisture absorption reflow test The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable silicone resin composition. In addition, the sample was used after confirming that it lights up, when an electric current of 20 mA is supplied before a test.
- the above sample was placed in a constant temperature and humidity chamber (manufactured by Espec Corp., model number “SH-641”) adjusted to 30 ° C. and 60% RH, and taken out after 192 hours. Subsequently, heat treatment was performed twice at 260 ° C. for 10 seconds using each of the above samples using a reflow furnace (manufactured by ANTOM Co., Ltd., model number “UNI-5016F”).
- a curable silicone resin composition comprising the following components (A), (B), (C) and (D).
- R a , R b and R c are a group represented by Formula (1a).
- R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom).
- s represents an integer of 2 to 10 (preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4).
- R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom).
- t represents an integer of 1 to 10 (preferably 1 to 6).
- the polyorganosiloxane (A1) has the following average unit formula: (R 1a SiO 3/2 ) a1 (R 1a 2 SiO 2/2 ) a2 (R 1a 3 SiO 1/2 ) a3 (SiO 4/2 ) a4 (X 1a O 1/2 ) a5 [In the unit formula, R 1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R 1a is an alkenyl group (preferably a vinyl group), and the ratio is 2 or more in the molecule. A part of R 1a is an aryl group (preferably a phenyl group), and the proportion is at least one in the molecule.
- X 1 is a hydrogen atom or an alkyl group (preferably a methyl group).
- a1 is 0 or a positive number
- a2 is 0 or a positive number
- a3 is 0 or a positive number
- a4 is 0 or a positive number
- a5 is 0 or a positive number
- (a1 + a2 + a3) is a positive number.
- the curable silicone resin composition as described in said [1] or [2] which is a polyorganosiloxane represented by these.
- the polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) in the molecule.
- the curable silicone resin composition according to any one of the above [1] to [6]. [8] The curable silicone resin composition as described in [7] above, wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).
- the proportion of aryl group is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms
- R 11 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 11 are alkenyl groups (preferably vinyl groups), and at least one is an aryl group (preferably phenyl group).
- m1 is an integer of 5 to 1000]
- the polyorganosiloxane (A1) has two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) in the molecule, and R a SiO 3/2 [ Ra is a monovalent substituted or unsubstituted hydrocarbon group.
- the proportion of aryl groups is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms
- the curable silicone resin composition according to any one of the above [13] to [16], which is
- the alkylene group in the silalkylene bond which the polyorganosiloxysil alkylene (A2) has in the molecule is a linear or branched C 1-12 alkylene group (preferably a C 2-4 alkylene group, more preferably Is an ethylene group).
- the polyorganosiloxycyl alkylene (A2) has the following average unit formula: (R 1 b 2 SiO 2/2 ) b 1 (R 1 b 3 SiO 1/2 ) b 2 (R 1 b SiO 3/2 ) b 3 (SiO 4/2 ) b 4 (R A ) b 5 (X 1 b O) b 6 [In the unit formula, R 1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R 1b is an alkenyl group (preferably a vinyl group), and the ratio is 2 or more in the molecule.
- R 1b is an aryl group (preferably a phenyl group), and the proportion is at least one in the molecule.
- R A is an alkylene group (preferably an ethylene group).
- X 1 b is a hydrogen atom or an alkyl group (preferably a methyl group).
- b1 is a positive number (preferably 1 to 200)
- b2 is a positive number (preferably 1 to 200)
- b3 is 0 or a positive number (preferably 0 to 10)
- b4 is 0 or a positive number (preferably 0 to 5)
- B5 is a positive number (preferably 1 to 100)
- b6 is 0 or a positive number.
- the polyorganosiloxycyl alkylene (A2) is a polyorganosiloxycyl alkylene having a structure represented by the following formula (I-2) Curable silicone resin composition as described.
- R 12 is the same or different and is a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 12 are an alkenyl group (preferably a vinyl group), and at least one of R 12 is an aryl group (preferably a phenyl group).
- R A is an alkylene group (preferably a C 2-4 alkylene group, more preferably an ethylene group).
- r1 represents an integer of 1 or more (preferably 1 to 100).
- r2 represents an integer of 1 or more (preferably 1 to 400).
- r3 represents 0 or an integer of 1 or more (preferably 0 to 50).
- r4 represents 0 or an integer of 1 or more (preferably 0 to 50).
- r5 represents 0 or an integer of 1 or more (preferably 0 to 50).
- the content (blending amount) of the component (A) is 0.1 to 60% by weight (preferably 0.1 to 55% by weight) with respect to the curable silicone resin composition (100% by weight),
- the polyorganosiloxane (B1) has the following average unit formula: (R 2 SiO 3/2 ) c 1 (R 2 2 SiO 2/2 ) c 2 (R 2 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (X 2 O 1/2 ) c 5 [In the above average unit formula, R 2 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, aliphatic unsaturated groups are excluded).
- R 2 is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the proportion thereof is that the hydrosilyl group is one or more (preferably two or more) in the molecule.
- X 2 is a hydrogen atom or an alkyl group (preferably a methyl group).
- c1 is 0 or a positive number
- c2 is 0 or a positive number
- c3 is 0 or a positive number
- c4 is 0 or a positive number
- c5 is 0 or a positive number
- (c1 + c2 + c3) is a positive number.
- the curable silicone resin composition according to any one of the above [1] to [25], which is a polyorganosiloxane represented by [27] The curable silicone resin composition as described in [26] above, wherein the ratio of hydrogen atoms to the total amount (100 mol%) of R 2 is 0.1 to 40 mol%. [28] to the above [26] or [27], wherein R 2 other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
- the polyorganosiloxane (B1) is a linear polyorganosiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule.
- the curable silicone resin composition as described in one.
- the group bonded to a silicon atom other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
- the ratio of an aryl group (preferably a phenyl group) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 to 50 mol% (preferably 20 to 50 mol%) [30]
- the polyorganosiloxane (B1) has one or more (preferably two or more) hydrosilyl groups in the molecule, R b SiO 3/2 [R b is a hydrogen atom or a monovalent atom. Or a substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups).
- T unit siloxane unit
- the group bonded to a silicon atom other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
- the ratio of the alkyl group (preferably methyl group) to the total amount (100 mol%) of groups bonded to silicon atoms is 70 to 95 mol% (preferably 50 mol% or more, more preferably 50 to 90 mol%)
- the curable silicone resin composition according to the above [36], which is [38] The curability according to the above [36] or [37], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 10 to 70 mol% Silicone resin composition.
- the content (blending amount) of the component (B) is 1 to 60% by weight (preferably 5 to 55% by weight, more preferably 10) to the curable silicone resin composition (100% by weight).
- the content (blending amount) of the component (C) is 0.01 to 10% by weight (preferably 0.03 to 5% by weight) with respect to the curable silicone resin composition (100% by weight),
- the component (D) has the following average unit formula: (R 8 SiO 3/2) d1 ( R 8 2 SiO 2/2) d2 (R 8 3 SiO 1/2) d3 (SiO 4/2) d4 (X 3 O 1/2) d5 [In the above average unit formula, R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, a part of R 8 is an alkenyl group (preferably a vinyl group), and the ratio is 1 or more (preferably 2 or more) in the molecule.
- X 3 is a hydrogen atom or an alkyl group (preferably a methyl group).
- d1 is 0 or a positive number
- d2 is 0 or a positive number
- d3 is 0 or a positive number
- d4 is 0 or a positive number
- d5 is 0 or a positive number
- (d1 + d2 + d3) and (d1 + d4) are each a positive number It is.
- the group bonded to a silicon atom other than an alkenyl group in the component (D) is at least one selected from the group consisting of an alkyl group (preferably a methyl group) and an aryl group (preferably a phenyl group)
- the proportion of alkyl group (preferably methyl group) is 20 to 60 mol% (preferably 30 mol% or more, more preferably 35 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms
- the proportion of the aryl group (preferably phenyl group) is 5 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms
- the content (blending amount) of the component (D) is 50 to 200 parts by weight (preferably 75 to 175 parts by weight) based on 100 parts by weight of the total of the components (A) and (B).
- the content (blending amount) of the component (E) is the total amount (per mole) of alkenyl groups contained in the curable silicone resin composition.
- the curable silicone resin composition according to the above [46] which is 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 2 mole (preferably 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 3 mole) object.
- the content (blending amount) of the component (E) is such that the weight of the platinum group metal in the hydrosilylation catalyst is in the range of 0.01 to 1000 ppm (preferably 0.1 to 500 ppm)
- R j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom).
- the content (blending amount) of the component (G) is 0.01 to 6% by weight (preferably 0.05 to 4% by weight) based on 100% by weight of the curable silicone resin composition, The curable silicone resin composition according to the above [49], which is more preferably 0.1 to 3% by weight).
- the total (total content) of the content of the component (C) and the component (G) is 0.01 to 15% by weight (preferably 0.1 to 15% by weight) based on the curable silicone resin composition.
- the curable silicone resin composition according to the above [49] or [50] which is 10% by weight, more preferably 0.2 to 3% by weight, still more preferably 0.4 to 2% by weight.
- the curable silicone resin composition according to any one of the above [1] to [51], which comprises the following component (F): (F): Ladder-type polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups (preferably vinyl groups) in the molecule [53]
- the component (F) has two in the molecule.
- ladder-type polyorganosilsesquioxane (a) has a polystyrene-equivalent number average molecular weight (Mn) of 550 to 1450 (preferably 600 to 1400),
- Mn polystyrene-equivalent number average molecular weight
- the molecular weight dispersion degree (Mw / Mn) in terms of standard polystyrene equivalent by gel permeation chromatography of the ladder type polyorganosilsesquioxane (a) is 1.05 to 1.35 (preferably 1.10 to The curable silicone resin composition as described in said [53] or [54] which is 1.30).
- the ladder-type polyorganosilsesquioxane (a) is represented by the following formula (III-2) and has two or more alkenyl groups in the molecule, and is a standard polystyrene by gel permeation chromatography [53] to [55], which is a ladder-type polyorganosilsesquioxane having a converted number average molecular weight (Mn) of 500 to 1,500 and a molecular weight dispersion degree (Mw / Mn) of 1.00 to 1.40.
- Mn converted number average molecular weight
- Mw / Mn molecular weight dispersion degree
- R 42 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group.
- R 43 is the same or different, and is a hydrogen atom, an alkyl group, a monovalent group represented by the following formula (III-2-1), a monovalent group represented by the following formula (III-2-2) Or a monovalent group represented by the following formula (III-2-3): n is an integer of 0 or more (preferably an even number of 2 or more).
- R 44 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group).
- R 45 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group).
- n1 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, further preferably 0).
- R 44 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group).
- R 45 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group).
- R 46 is an alkenyl group (preferably a vinyl group).
- n2 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, further preferably 0).
- R 44 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group).
- R 47 is the same or different and is a monovalent saturated aliphatic hydrocarbon group (preferably an alkyl group, more preferably a methyl group).
- n3 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, further preferably 0).
- the content (blending amount) of the component (F) is preferably 0.01 to 50 parts by weight (preferably 0.01) to 100 parts by weight in total of the components (A) and (B).
- the content (blending amount) of the component (H) is 0.01 to 15% by weight (preferably 0.1 to 10% by weight) with respect to the curable silicone resin composition (100% by weight),
- R 32 represents a hydrogen atom or a substituted or unsubstituted C 1-30 alkyl group (preferably a hydrogen atom).
- R 33 represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 34 group.
- R 34 represents a substituted or unsubstituted C 1-30 alkyl group.
- R 31 and R 32 may be bonded to each other to form a ring, and the R 32 and R 33 may be bonded to each other to form a ring.
- the curable silicone resin composition according to the above [61] which is at least one selected from the group consisting of [63]
- R 35 represents a substituted or unsubstituted C 1-30 alkyl group (preferably a C 3-10 alkyl group having a branched chain), and R 36 represents a hydrogen atom, or a substitution or unsubstituted C 1-30 alkyl group (preferably a hydrogen atom) indicates
- R 37 is a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or -OR 38 Indicates a group.
- R 38 represents a substituted or unsubstituted C 1-30 alkyl group.
- the component (I) is at least one member selected from the group consisting of zinc bis (2,2,7-trimethyl-3,5-octanedionate) and zinc bisdipivaloylmethane,
- the curable silicone resin composition according to any one of the above [61] to [63].
- the content (blending amount) of the component (I) is 0.01 to 5% by weight (preferably 0.05 to 3% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to any one of the above [61] to [64], which is more preferably 0.1 to 2% by weight, still more preferably 0.1 to 1.5% by weight.
- the content (blending amount) of the component (I) is preferably 0.02 to 10 parts by weight (preferably 0.05 to 6 parts by weight, more preferably 100 parts by weight of the component (A)).
- the curable silicone resin composition according to any one of the above [61] to [65] which is 0.1 to 4 parts by weight, more preferably 0.1 to 3 parts by weight.
- the content (blending amount) of the phosphor is 0.01 to 20% by weight (preferably 0.5 to 10% by weight) based on 100% by weight of the curable silicone resin composition.
- the curable silicone resin composition according to any one of the above [1] to [68] which is a resin composition for semiconductor encapsulation.
- the curable silicone resin composition according to any one of the above [1] to [68] which is a resin composition for forming a lens for an optical semiconductor.
- An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable silicone resin composition according to [72].
- the curable silicone resin composition of the present invention is particularly preferable as a sealing material for an optical semiconductor element (LED element) in an optical semiconductor device or a material for forming an optical lens (sealing agent, resin composition for forming a lens) It can be used.
- Reflector resin composition for light reflection
- Metal wiring electrode
- Optical semiconductor device 102: Optical semiconductor device
- Bonding wire 104: Cured product (sealing material)
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Abstract
The purpose of the present invention is to provide a curable silicone resin composition for forming a material (a sealing material, a lens, etc.) which has excellent sulfur barrier properties and maintains thermal shock resistance. The present invention provides a curable silicone resin composition containing components (A), (B), (C), and (D). (A): A polysiloxane having two or more alkenyl groups and one or more aryl groups in the molecule, (B): a polyorganosiloxane having one or more hydrosilyl groups and not having an aliphatic unsaturated group in the molecule, (C): an isocyanurate compound represented by formula (1), (D): a branched polyorganosiloxane having one or more alkenyl groups in the molecule [In each formula, symbols are as defined in the description].
Description
本発明は、硬化性シリコーン樹脂組成物及びその硬化物、上記硬化性シリコーン樹脂組成物を使用した封止剤、並びに、上記封止剤を使用して半導体素子（特に、光半導体素子）を封止して得られる半導体装置（特に、光半導体装置）に関する。本願は、２０１７年６月２０日に日本に出願した、特願２０１７－１２０４４５の優先権を主張し、その内容をここに援用する。
The present invention relates to a curable silicone resin composition and a cured product thereof, a sealant using the curable silicone resin composition, and a semiconductor device (particularly, an optical semiconductor device) sealed using the sealant. The present invention relates to a semiconductor device (particularly, an optical semiconductor device) obtained by stopping. Priority is claimed on Japanese Patent Application No. 2017-120445, filed on June 20, 2017, the content of which is incorporated herein by reference.
光半導体装置等の半導体装置における半導体素子を被覆して保護するための封止材としては、各種の樹脂材料が使用されている。近年、光半導体装置の高電流化が進んでおり、このような光半導体装置の封止材には、高い耐熱性、耐光性が求められるようになっている。従って、上記封止材の樹脂としては、高い耐熱性、耐光性を有するシリコーン樹脂が用いられている。
Various resin materials are used as a sealing material for covering and protecting a semiconductor element in a semiconductor device such as an optical semiconductor device. In recent years, the increase in current of optical semiconductor devices has progressed, and high heat resistance and light resistance are required for sealing materials of such optical semiconductor devices. Therefore, a silicone resin having high heat resistance and light resistance is used as the resin of the sealing material.
しかしながら、一般的なシリコーン樹脂はガスの透過性が高いため、光半導体装置に用いた場合、電極がＳＯXや硫化水素等の硫黄化合物によって硫化され、光度の低下を招くことがあった。このため、光半導体装置における封止材としては、これら硫黄化合物に対するバリア性（以下、「硫黄バリア性」と称する場合がある）に優れる材料（硬化物）を形成することができるフェニルシリコーン系封止材が用いられるようになってきている。
However, general silicone resin has high gas permeability, when used in a optical semiconductor device, electrodes are sulfurized by sulfur compounds such as SO X or hydrogen sulfide, was sometimes lowering the luminosity. For this reason, as a sealing material in an optical semiconductor device, a phenyl silicone-based sealing capable of forming a material (cured product) excellent in barrier properties against these sulfur compounds (hereinafter sometimes referred to as "sulfur barrier properties") Stoppers are being used.
しかし、フェニルシリコーン系封止材は、従来使用されていたメチルシリコーン系封止材に比べると硫黄バリア性は高いものの、その特性は未だ不十分である。実際に、フェニルシリコーン系封止材を使用した場合であっても、光半導体装置において腐食性ガスによる電極の腐食が経時で進行し、通電特性が悪化するという問題が生じていた。
また、硫黄バリア性を高めるため、ラダー型シルセスキオキサンを添加する方法があるが、耐熱衝撃性の低下を招く場合がある。 However, although the phenyl silicone sealant has a high sulfur barrier property as compared with the methyl silicone sealant conventionally used, its properties are still insufficient. In fact, even in the case of using a phenylsilicone-based sealing material, in the optical semiconductor device, the corrosion of the electrode due to the corrosive gas proceeds with time, causing a problem that the current-carrying characteristics deteriorate.
Moreover, although there is a method of adding ladder type silsesquioxane to improve the sulfur barrier property, the thermal shock resistance may be lowered.
また、硫黄バリア性を高めるため、ラダー型シルセスキオキサンを添加する方法があるが、耐熱衝撃性の低下を招く場合がある。 However, although the phenyl silicone sealant has a high sulfur barrier property as compared with the methyl silicone sealant conventionally used, its properties are still insufficient. In fact, even in the case of using a phenylsilicone-based sealing material, in the optical semiconductor device, the corrosion of the electrode due to the corrosive gas proceeds with time, causing a problem that the current-carrying characteristics deteriorate.
Moreover, although there is a method of adding ladder type silsesquioxane to improve the sulfur barrier property, the thermal shock resistance may be lowered.
封止材の硫黄バリア性に対するバリア性を高めるために、特定の成分を封止剤（封止材を形成するための硬化性組成物）に配合する手法も存在する。例えば、モノアリルジグリシジルイソシアヌレート及びトリグリシジルイソシアヌレート等のイソシアヌレート化合物の添加が上述の硫黄バリア性向上の効果を奏することが報告されている（例えば、特許文献１）。
There is also a method of blending a specific component into a sealant (curable composition for forming a sealant) in order to increase the barrier property to the sulfur barrier property of the sealant. For example, it has been reported that the addition of isocyanurate compounds such as monoallyl diglycidyl isocyanurate and triglycidyl isocyanurate exerts the above-mentioned effect of improving the sulfur barrier property (for example, Patent Document 1).
しかしながら、モノアリルジグリシジルイソシアヌレートは室温で固体であり、加熱しながら混合しない限り均一な封止剤を得ることができない。また、配合量を増量すると、封止剤においてモノアリルジグリシジルイソシアヌレートの固体が析出するという問題が生じていた。一方、トリグリシジルイソシアヌレートも同様に室温で固体であり、特に封止剤における溶解性が低いために、加熱によっても均一な封止剤を得にくい。また、いったんは溶解させた場合であっても、封止剤を室温に戻すとトリグリシジルイソシアヌレートの固体が析出するという問題が生じていた。このように、封止材の腐食性ガスに対するバリア性を効率的に高めることができる成分であって上述の固体析出の問題を生じさせないものは、現状見出されていない。
However, monoallyl diglycidyl isocyanurate is solid at room temperature and can not obtain a uniform sealant unless mixed while heating. In addition, when the compounding amount is increased, there is a problem that solid of monoallyl diglycidyl isocyanurate precipitates in the sealing agent. On the other hand, triglycidyl isocyanurate is also solid at room temperature and, in particular, has low solubility in the sealant, so that it is difficult to obtain a uniform sealant even by heating. In addition, even if it was once dissolved, there was a problem that when the sealant was returned to room temperature, a solid of triglycidyl isocyanurate was precipitated. As described above, there is currently not found any component that can efficiently enhance the barrier property against the corrosive gas of the sealing material and does not cause the above-described problem of solid deposition.
従って、本発明の目的は、上述の固体析出の問題が生じることなく、硬化させることにより、耐熱性、耐熱衝撃性を維持しつつ、特に腐食性ガス（例えば、ＳＯXガス）に対するバリア性（硫黄バリア性）に優れた材料（硬化物）を形成できる硬化性シリコーン樹脂組成物を提供することにある。
また、本発明の他の目的は、耐熱性、耐熱衝撃性を維持しつつ、特に硫黄バリア性に優れた材料（硬化物）を提供することにある。
さらに、本発明の他の目的は、上記硬化性樹脂組成物を使用した封止剤、及び該封止剤を使用して半導体素子（特に光半導体素子）を封止することにより得られる、品質と耐久性に優れた半導体装置（特に光半導体装置）を提供することにある。
さらに、本発明の他の目的は、上記硬化物により形成されたレンズを含む、品質と耐久性に優れた光半導体装置を提供することにある。 Therefore, the object of the present invention is to maintain the heat resistance and the thermal shock resistance by curing without causing the above-mentioned problems of solid deposition, and in particular, the barrier property against corrosive gas (for example, SO X gas) ( It is an object of the present invention to provide a curable silicone resin composition capable of forming a material (cured product) excellent in sulfur barrier properties).
Another object of the present invention is to provide a material (cured product) which is particularly excellent in sulfur barrier properties while maintaining heat resistance and thermal shock resistance.
Furthermore, another object of the present invention is a sealing agent using the above-mentioned curable resin composition, and a quality obtained by sealing a semiconductor element (particularly an optical semiconductor element) using the sealing agent. And providing a semiconductor device (particularly, an optical semiconductor device) excellent in durability.
Furthermore, another object of the present invention is to provide an optical semiconductor device excellent in quality and durability, including a lens formed of the above-mentioned cured product.
また、本発明の他の目的は、耐熱性、耐熱衝撃性を維持しつつ、特に硫黄バリア性に優れた材料（硬化物）を提供することにある。
さらに、本発明の他の目的は、上記硬化性樹脂組成物を使用した封止剤、及び該封止剤を使用して半導体素子（特に光半導体素子）を封止することにより得られる、品質と耐久性に優れた半導体装置（特に光半導体装置）を提供することにある。
さらに、本発明の他の目的は、上記硬化物により形成されたレンズを含む、品質と耐久性に優れた光半導体装置を提供することにある。 Therefore, the object of the present invention is to maintain the heat resistance and the thermal shock resistance by curing without causing the above-mentioned problems of solid deposition, and in particular, the barrier property against corrosive gas (for example, SO X gas) ( It is an object of the present invention to provide a curable silicone resin composition capable of forming a material (cured product) excellent in sulfur barrier properties).
Another object of the present invention is to provide a material (cured product) which is particularly excellent in sulfur barrier properties while maintaining heat resistance and thermal shock resistance.
Furthermore, another object of the present invention is a sealing agent using the above-mentioned curable resin composition, and a quality obtained by sealing a semiconductor element (particularly an optical semiconductor element) using the sealing agent. And providing a semiconductor device (particularly, an optical semiconductor device) excellent in durability.
Furthermore, another object of the present invention is to provide an optical semiconductor device excellent in quality and durability, including a lens formed of the above-mentioned cured product.
本発明者らは、分子内に２個以上のアルケニル基及び１個以上のアリール基を有する特定のポリオルガノシロキサン及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有する特定のポリオルガノシロキシシルアルキレン（シルアルキレン結合を有するポリオルガノシロキサン）からなる群より選択される少なくとも１種であるポリシロキサンと、分子内に１個以上のヒドロシリル基を有し脂肪族不飽和基を有しないポリオルガノシロキサンと、特定の構造を有するイソシアヌレート化合物と、分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサンと、を必須成分として含む組成物（硬化性シリコーン樹脂組成物）によると、上述の固体析出の問題が生じることなく、硬化させることにより、耐熱性、耐熱衝撃性を維持しつつ、硫黄バリア性に優れる材料（硬化物）を形成できることを見出し、本発明を完成させた。
We have identified certain polyorganosiloxanes having more than one alkenyl group and more than one aryl group in the molecule and certain polyorganosiloxanes having more than one alkenyl group and more than one aryl group in the molecule. Polysiloxane which is at least one selected from the group consisting of polyorganosiloxysil alkylene (polyorganosiloxane having a sil alkylene bond), and one or more hydrosilyl groups in the molecule and aliphatic unsaturated group A composition comprising, as essential components, a polyorganosiloxane which does not react, an isocyanurate compound having a specific structure, and a branched polyorganosiloxane having one or more alkenyl groups in the molecule (curable silicone resin composition Heat resistance, by curing, without causing the problems of solid precipitation described above). While maintaining thermal shock resistance, it found to be able to form a material (cured product) having excellent sulfur barrier properties, and completed the present invention.
すなわち、本発明は、下記の（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を含むことを特徴とする硬化性シリコーン樹脂組成物を提供する。
（Ａ）：分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
［式（１）中、Ｒa、Ｒb、及びＲcは、同一又は異なって、式（１ａ）で表される基、式（１ｂ）で表される基、水素原子、又はアルキル基を示す。但し、Ｒa、Ｒb、及びＲcのうち少なくとも１個は、式（１ａ）で表される基である。
［式（１ａ）中、Ｒdは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基を示す。ｓは２～１０の整数を示す。］
［式（１ｂ）中、Ｒeは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基を示す。ｔは１～１０の整数を示す。］］
（Ｄ）：分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン That is, the present invention provides a curable silicone resin composition comprising the following components (A), (B), (C) and (D).
(A): Polyorganosiloxane (A1) having two or more alkenyl groups and one or more aryl groups in the molecule and polyorganosiloxy having two or more alkenyl groups and one or more aryl groups in the molecule Polysiloxane (B) which is at least one selected from the group consisting of silalkylene (A2): polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group (C) : Isocyanurate compound represented by the following formula (1)
[In Formula (1), R a , R b , and R c are the same or different and each represents a group represented by Formula (1a), a group represented by Formula (1b), a hydrogen atom, or an alkyl group Show. However, at least one of R a , R b and R c is a group represented by Formula (1a).
[In the formula (1a), R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. s represents an integer of 2 to 10. ]
[In the formula (1b), R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. t represents an integer of 1 to 10. ]]
(D): branched polyorganosiloxane having one or more alkenyl groups in the molecule
（Ａ）：分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
（Ｄ）：分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン That is, the present invention provides a curable silicone resin composition comprising the following components (A), (B), (C) and (D).
(A): Polyorganosiloxane (A1) having two or more alkenyl groups and one or more aryl groups in the molecule and polyorganosiloxy having two or more alkenyl groups and one or more aryl groups in the molecule Polysiloxane (B) which is at least one selected from the group consisting of silalkylene (A2): polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group (C) : Isocyanurate compound represented by the following formula (1)
(D): branched polyorganosiloxane having one or more alkenyl groups in the molecule
前記硬化性シリコーン樹脂組成物は、下記の（Ｅ）成分を含んでいてもよい。
（Ｅ）：白金族金属を含むヒドロシリル化触媒 The curable silicone resin composition may contain the following component (E).
(E): hydrosilylation catalyst containing platinum group metal
（Ｅ）：白金族金属を含むヒドロシリル化触媒 The curable silicone resin composition may contain the following component (E).
(E): hydrosilylation catalyst containing platinum group metal
前記硬化性シリコーン樹脂組成物は、下記の（Ｇ）成分を含んでいてもよい。
（Ｇ）：下記式（２）で表されるイソシアヌレート化合物
［式（２）中、Ｒf、Ｒg、及びＲhは、同一又は異なって、式（２ａ）で表される基、又は式（２ｂ）で表される基を示す。但し、Ｒf、Ｒg、及びＲhのうち少なくとも１個は、式（２ｂ）で表される基である。］
［式（２ａ）中、Ｒiは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基を示す。］
［式（２ｂ）中、Ｒjは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基を示す。］］
The curable silicone resin composition may contain the following component (G).
(G): isocyanurate compound represented by the following formula (2)
[In Formula (2), R f , R g , and R h are the same or different and each represents a group represented by Formula (2a) or a group represented by Formula (2b). However, at least one of R f , R g and R h is a group represented by formula (2b). ]
[In the formula (2a), R i represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]
[In the formula (2b), R j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. ]]
（Ｇ）：下記式（２）で表されるイソシアヌレート化合物
(G): isocyanurate compound represented by the following formula (2)
前記硬化性シリコーン樹脂組成物は、下記の（Ｆ）成分を含んでいてもよい。
（Ｆ）：分子内に１個以上のアルケニル基を有するラダー型ポリオルガノシルセスキオキサン The curable silicone resin composition may contain the following component (F).
(F): Ladder-type polyorganosilsesquioxane having one or more alkenyl groups in the molecule
（Ｆ）：分子内に１個以上のアルケニル基を有するラダー型ポリオルガノシルセスキオキサン The curable silicone resin composition may contain the following component (F).
(F): Ladder-type polyorganosilsesquioxane having one or more alkenyl groups in the molecule
前記硬化性シリコーン樹脂組成物は、下記の（Ｈ）成分を含んでいてもよい。
（Ｈ）：シランカップリング剤 The said curable silicone resin composition may contain the following (H) component.
(H): Silane coupling agent
（Ｈ）：シランカップリング剤 The said curable silicone resin composition may contain the following (H) component.
(H): Silane coupling agent
前記硬化性シリコーン樹脂組成物は、さらに蛍光体を含んでいてもよい。
The curable silicone resin composition may further contain a phosphor.
また、本発明は、硬化性シリコーン樹脂組成物の硬化物を提供する。
The present invention also provides a cured product of a curable silicone resin composition.
前記硬化性シリコーン樹脂組成物は、光半導体封止用樹脂組成物であってもよい。
The curable silicone resin composition may be a resin composition for encapsulating an optical semiconductor.
前記硬化性シリコーン樹脂組成物は、光半導体用レンズの形成用樹脂組成物であってもよい。
The curable silicone resin composition may be a resin composition for forming a lens for an optical semiconductor.
また、本発明は、光半導体素子と、該光半導体素子を封止する封止材とを含み、前記封止材が前記光半導体封止用樹脂組成物の硬化物であることを特徴とする光半導体装置を提供する。
In addition, the present invention is characterized by including an optical semiconductor element and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the resin composition for optical semiconductor sealing. Provided is an optical semiconductor device.
さらに、本発明は、光半導体素子とレンズとを含み、前記レンズが前記光半導体用レンズの形成用樹脂組成物の硬化物であることを特徴とする光半導体装置を提供する。
Furthermore, the present invention provides an optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the resin composition for forming the lens for optical semiconductor.
本発明の硬化性シリコーン樹脂組成物は上記構成を有するため、硬化性シリコーン樹脂組成物（例えば、室温に調温した硬化性シリコーン樹脂組成物等）において固体が析出する問題が生じない。従って、本発明の硬化性シリコーン樹脂組成物は、その調製が容易であり、取り扱いやすい。また、本発明の硬化性シリコーン樹脂組成物は上記構成を有するため、硬化させることによって、耐熱性（例えば、耐吸湿リフロー性）、耐熱衝撃性を維持しつつ、特に腐食性ガス（例えば、ＳＯｘガス）に対するバリア性（硫黄バリア性）に優れた硬化物を形成できる。このため、上記硬化物を半導体装置における半導体素子の封止材やレンズとして使用した場合、上記半導体装置の電極の腐食が高度に抑制され、上記半導体装置の耐久性が著しく向上する。従って、本発明の硬化性シリコーン樹脂組成物は、特に光半導体装置における光半導体素子（ＬＥＤ素子）の封止材を形成するための材料（封止剤）やレンズ形成用樹脂組成物として好ましく使用することができる。本発明の硬化性シリコーン樹脂組成物を封止剤やレンズ形成用樹脂組成物として使用して得られる光半導体装置は、優れた品質と耐久性とを備える。
Since the curable silicone resin composition of the present invention has the above configuration, there is no problem of precipitation of solids in the curable silicone resin composition (for example, curable silicone resin composition temperature-controlled at room temperature). Therefore, the curable silicone resin composition of the present invention is easy to prepare and handle. In addition, since the curable silicone resin composition of the present invention has the above-mentioned constitution, by curing it, heat resistance (for example, moisture absorption reflow resistance) and thermal shock resistance are maintained, and in particular, corrosive gas (for example, SOx) It is possible to form a cured product excellent in barrier properties (sulfur barrier properties) to gas). Therefore, when the cured product is used as a sealing material or a lens of a semiconductor element in a semiconductor device, corrosion of an electrode of the semiconductor device is highly suppressed, and the durability of the semiconductor device is significantly improved. Therefore, the curable silicone resin composition of the present invention is preferably used particularly as a material (sealing agent) for forming a sealing material of an optical semiconductor element (LED element) in an optical semiconductor device and a resin composition for forming a lens. can do. An optical semiconductor device obtained by using the curable silicone resin composition of the present invention as a sealing agent or a resin composition for forming a lens has excellent quality and durability.
＜硬化性シリコーン樹脂組成物＞
本発明の硬化性シリコーン樹脂組成物は、下記の（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を必須成分として含む硬化性組成物である。即ち、本発明の硬化性シリコーン樹脂組成物は、ヒドロシリル化反応により硬化させることができる付加硬化型のシリコーン樹脂組成物である。なお、本発明の硬化性シリコーン樹脂組成物は、これら必須成分以外の、例えば、後述の（Ｅ）成分、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分等の任意成分を含んでいてもよい。
（Ａ）：分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
［式（１）中、Ｒa、Ｒb、及びＲcは、同一又は異なって、式（１ａ）で表される基、式（１ｂ）で表される基、水素原子、又はアルキル基を示す。但し、Ｒa、Ｒb、及びＲcのうち少なくとも１個は、式（１ａ）で表される基である。
［式（１ａ）中、Ｒdは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基を示す。ｓは２～１０の整数を示す。］
［式（１ｂ）中、Ｒeは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基を示す。ｔは１～１０の整数を示す。］］
（Ｄ）：分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン <Curable silicone resin composition>
The curable silicone resin composition of the present invention is a curable composition containing the following components (A), (B), (C) and (D) as essential components. That is, the curable silicone resin composition of the present invention is an addition-curable silicone resin composition that can be cured by a hydrosilylation reaction. The curable silicone resin composition of the present invention contains optional components other than these essential components, such as component (E), component (F), component (G) and component (H) described below. It is also good.
(A): Polyorganosiloxane (A1) having two or more alkenyl groups and one or more aryl groups in the molecule and polyorganosiloxy having two or more alkenyl groups and one or more aryl groups in the molecule Polysiloxane (B) which is at least one selected from the group consisting of silalkylene (A2): polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group (C) : Isocyanurate compound represented by the following formula (1)
[In Formula (1), R a , R b , and R c are the same or different and each represents a group represented by Formula (1a), a group represented by Formula (1b), a hydrogen atom, or an alkyl group Show. However, at least one of R a , R b and R c is a group represented by Formula (1a).
[In the formula (1a), R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. s represents an integer of 2 to 10. ]
[In the formula (1b), R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. t represents an integer of 1 to 10. ]]
(D): branched polyorganosiloxane having one or more alkenyl groups in the molecule
本発明の硬化性シリコーン樹脂組成物は、下記の（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を必須成分として含む硬化性組成物である。即ち、本発明の硬化性シリコーン樹脂組成物は、ヒドロシリル化反応により硬化させることができる付加硬化型のシリコーン樹脂組成物である。なお、本発明の硬化性シリコーン樹脂組成物は、これら必須成分以外の、例えば、後述の（Ｅ）成分、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分等の任意成分を含んでいてもよい。
（Ａ）：分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
（Ｄ）：分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン <Curable silicone resin composition>
The curable silicone resin composition of the present invention is a curable composition containing the following components (A), (B), (C) and (D) as essential components. That is, the curable silicone resin composition of the present invention is an addition-curable silicone resin composition that can be cured by a hydrosilylation reaction. The curable silicone resin composition of the present invention contains optional components other than these essential components, such as component (E), component (F), component (G) and component (H) described below. It is also good.
(A): Polyorganosiloxane (A1) having two or more alkenyl groups and one or more aryl groups in the molecule and polyorganosiloxy having two or more alkenyl groups and one or more aryl groups in the molecule Polysiloxane (B) which is at least one selected from the group consisting of silalkylene (A2): polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group (C) : Isocyanurate compound represented by the following formula (1)
(D): branched polyorganosiloxane having one or more alkenyl groups in the molecule
［（Ａ）成分］
本発明の硬化性シリコーン樹脂組成物の必須成分である（Ａ）成分は、上述のように、分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）（以下、単に「ポリオルガノシロキサン（Ａ１）」と称する場合がある）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）（以下、単に「ポリオルガノシロキシシルアルキレン（Ａ２）」と称する場合がある）からなる群より選択される少なくとも１種であるポリシロキサンである。従って、本発明の硬化性シリコーン樹脂組成物において（Ａ）成分は、ヒドロシリル基を有する成分（例えば、（Ｂ）成分等）とヒドロシリル化反応を生じる成分である。但し、（Ａ）成分には、後述の（Ｄ）成分、（Ｆ）成分に当たるものは含まれない。
本発明の硬化性シリコーン樹脂組成物はこのような（Ａ）成分を含むために、硫黄バリア性と耐熱衝撃性とに優れた硬化物を形成できる。このため、これを封止材とする光半導体装置の品質が向上する。 [(A) component]
As described above, the component (A), which is an essential component of the curable silicone resin composition of the present invention, is a polyorganosiloxane (A1) (A1) having two or more alkenyl groups and one or more aryl groups in the molecule. Hereinafter, it may be simply referred to as “polyorganosiloxane (A1)” and polyorganosiloxysil alkylene (A2) having two or more alkenyl groups and one or more aryl groups in the molecule (hereinafter, simply referred to as “polyorganosiloxane”) Or a polysiloxane which is at least one selected from the group consisting of organosiloxysil alkylene (A2). Accordingly, in the curable silicone resin composition of the present invention, the component (A) is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (B) and the like). However, the component (A) does not include those corresponding to the components (D) and (F) described later.
Since the curable silicone resin composition of the present invention contains such component (A), it can form a cured product excellent in sulfur barrier property and thermal shock resistance. For this reason, the quality of the optical semiconductor device which uses this as a sealing material improves.
本発明の硬化性シリコーン樹脂組成物の必須成分である（Ａ）成分は、上述のように、分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）（以下、単に「ポリオルガノシロキサン（Ａ１）」と称する場合がある）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）（以下、単に「ポリオルガノシロキシシルアルキレン（Ａ２）」と称する場合がある）からなる群より選択される少なくとも１種であるポリシロキサンである。従って、本発明の硬化性シリコーン樹脂組成物において（Ａ）成分は、ヒドロシリル基を有する成分（例えば、（Ｂ）成分等）とヒドロシリル化反応を生じる成分である。但し、（Ａ）成分には、後述の（Ｄ）成分、（Ｆ）成分に当たるものは含まれない。
本発明の硬化性シリコーン樹脂組成物はこのような（Ａ）成分を含むために、硫黄バリア性と耐熱衝撃性とに優れた硬化物を形成できる。このため、これを封止材とする光半導体装置の品質が向上する。 [(A) component]
As described above, the component (A), which is an essential component of the curable silicone resin composition of the present invention, is a polyorganosiloxane (A1) (A1) having two or more alkenyl groups and one or more aryl groups in the molecule. Hereinafter, it may be simply referred to as “polyorganosiloxane (A1)” and polyorganosiloxysil alkylene (A2) having two or more alkenyl groups and one or more aryl groups in the molecule (hereinafter, simply referred to as “polyorganosiloxane”) Or a polysiloxane which is at least one selected from the group consisting of organosiloxysil alkylene (A2). Accordingly, in the curable silicone resin composition of the present invention, the component (A) is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (B) and the like). However, the component (A) does not include those corresponding to the components (D) and (F) described later.
Since the curable silicone resin composition of the present invention contains such component (A), it can form a cured product excellent in sulfur barrier property and thermal shock resistance. For this reason, the quality of the optical semiconductor device which uses this as a sealing material improves.
本明細書におけるポリオルガノシロキシシルアルキレン（Ａ２）とは、主鎖として－Ｓｉ－Ｏ－Ｓｉ－（シロキサン結合）に加えて、－Ｓｉ－ＲA－Ｓｉ－（シルアルキレン結合：ＲAはアルキレン基を示す）を含むポリオルガノシロキサンである。そして、本明細書におけるポリオルガノシロキサン（Ａ１）は、主鎖として上記シルアルキレン結合を含まないポリオルガノシロキサンである。
In the present specification, polyorganosiloxysil alkylene (A2) means, in addition to -Si-O-Si- (siloxane bond) as a main chain, -Si- RA -Si- (sil alkylene bond: RA is alkylene Groups are shown)). And polyorganosiloxane (A1) in this specification is polyorganosiloxane which does not contain the said silalkylene bond as a principal chain.
（ポリオルガノシロキサン（Ａ１））
ポリオルガノシロキサン（Ａ１）は、分子内に２個以上のアルケニル基及び１個以上のアリール基を有し、主鎖として－Ｓｉ－Ｏ－Ｓｉ－（シロキサン結合）を有し、シルアルキレン結合を含まないポリオルガノシロキサンである。 (Polyorganosiloxane (A1))
The polyorganosiloxane (A1) has two or more alkenyl groups and one or more aryl groups in the molecule, and has -Si-O-Si- (siloxane bond) as a main chain, and a silalkylene bond It is a polyorganosiloxane which does not contain it.
ポリオルガノシロキサン（Ａ１）は、分子内に２個以上のアルケニル基及び１個以上のアリール基を有し、主鎖として－Ｓｉ－Ｏ－Ｓｉ－（シロキサン結合）を有し、シルアルキレン結合を含まないポリオルガノシロキサンである。 (Polyorganosiloxane (A1))
The polyorganosiloxane (A1) has two or more alkenyl groups and one or more aryl groups in the molecule, and has -Si-O-Si- (siloxane bond) as a main chain, and a silalkylene bond It is a polyorganosiloxane which does not contain it.
ポリオルガノシロキサン（Ａ１）としては、直鎖状、一部分岐を有する直鎖状、分岐鎖状、網目状の分子構造を有するものが挙げられる。なお、ポリオルガノシロキサン（Ａ１）は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。具体的には、分子構造が異なるポリオルガノシロキサン（Ａ１）の２種以上を併用することができ、例えば、直鎖状のポリオルガノシロキサン（Ａ１）と分岐鎖状のポリオルガノシロキサン（Ａ１）とを併用することもできる。
Examples of the polyorganosiloxane (A1) include those having a linear, partially branched linear, branched, or network molecular structure. In addition, polyorganosiloxane (A1) can also be used individually by 1 type, and can also be used combining 2 or more types. Specifically, two or more kinds of polyorganosiloxanes (A1) having different molecular structures can be used in combination, for example, linear polyorganosiloxane (A1) and branched polyorganosiloxane (A1) Can also be used in combination.
ポリオルガノシロキサン（Ａ１）を分子内に有する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、ヘキセニル基等の置換又は無置換アルケニル基が挙げられる。置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。中でも、アルケニル基としては、ビニル基が好ましい。また、ポリオルガノシロキサン（Ａ１）は、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。ポリオルガノシロキサン（Ａ１）が有するアルケニル基は、ケイ素原子に結合したものが好ましい。
As an alkenyl group which has polyorganosiloxane (A1) in a molecule | numerator, substituted or unsubstituted alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, pentenyl group, a hexenyl group, are mentioned. Examples of the substituent include a halogen atom, a hydroxy group and a carboxy group. Among them, a vinyl group is preferable as the alkenyl group. The polyorganosiloxane (A1) may have only one type of alkenyl group or may have two or more types of alkenyl groups. The alkenyl group contained in the polyorganosiloxane (A1) is preferably bonded to a silicon atom.
ポリオルガノシロキサン（Ａ１）が分子内に有するアリール基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基、アラルキル基（例えば、ベンジル基、フェネチル基等）等の置換又は無置換Ｃ6-14アリール基等が挙げられる。当該置換アリール基における置換基としては、置換又は無置換Ｃ1-8アルキル基、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。中でも、上記アリール基としては、フェニル基が好ましい。また、ポリオルガノシロキサン（Ａ１）は、１種のみのアリール基を有するものであってもよいし、２種以上のアリール基を有するものであってもよい。ポリオルガノシロキサン（Ａ１）が有するアリール基は、特に限定されないが、ケイ素原子に結合した基であることが好ましい。ポリオルガノシロキサン（Ａ１）は、分子内に１個以上のアリール基を有することにより、アリール基を有しないポリオルガノシロキサンと比較して、硫黄バリア性に優れた硬化物を形成できる。
Examples of the aryl group which the polyorganosiloxane (A1) has in the molecule include substituted or unsubstituted C 6 such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group (for example, benzyl group, phenethyl group etc.) And -14 aryl group and the like. Examples of the substituent in the substituted aryl group include a substituted or unsubstituted C 1-8 alkyl group, a halogen atom, a hydroxy group, a carboxy group and the like. Among them, a phenyl group is preferable as the above-mentioned aryl group. The polyorganosiloxane (A1) may have only one type of aryl group or may have two or more types of aryl groups. The aryl group contained in the polyorganosiloxane (A1) is not particularly limited, but is preferably a group bonded to a silicon atom. By having one or more aryl groups in the molecule, the polyorganosiloxane (A1) can form a cured product having excellent sulfur barrier properties as compared to a polyorganosiloxane having no aryl group.
ポリオルガノシロキサン（Ａ１）が有するアルケニル基及びアリール基以外の基は、例えば、水素原子、有機基等が挙げられる。有機基としては、例えば、アルキル基（例えば、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）、シクロアルキル基（例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロドデシル基等）シクロアルキル－アルキル基（例えば、シクロへキシルメチル基、メチルシクロヘキシル基等）、炭化水素基における１以上の水素原子がハロゲン原子で置換されたハロゲン化炭化水素基（例えば、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基等）等の一価の置換又は無置換炭化水素基等が挙げられる。なお、本明細書において「ケイ素原子に結合した基」とは、通常、ケイ素原子を含まない基を指すものとする。中でも、アルキル基（特に、メチル基）が好ましい。
Examples of groups other than the alkenyl group and the aryl group that the polyorganosiloxane (A1) has include a hydrogen atom, an organic group and the like. As an organic group, for example, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group etc.), a cycloalkyl group (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group) , A cyclododecyl group etc.) cycloalkyl-alkyl group (eg a cyclohexyl methyl group, a methylcyclohexyl group etc.), a halogenated hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group is substituted by a halogen atom (eg chloro And monovalent substituted or unsubstituted hydrocarbon groups and the like, such as methyl alkyl, halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl, etc., and the like. In the present specification, “a group bonded to a silicon atom” usually refers to a group not containing a silicon atom. Among them, an alkyl group (in particular, a methyl group) is preferable.
また、ポリオルガノシロキサン（Ａ１）は、ケイ素原子に結合した基として、ヒドロキシ基、アルコキシ基を有していてもよい。
In addition, the polyorganosiloxane (A1) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
ポリオルガノシロキサン（Ａ１）の性状は、特に限定されず、例えば２５℃において、液状であってもよいし、固体状であってもよい。
The property of the polyorganosiloxane (A1) is not particularly limited, and may be liquid or solid at 25 ° C., for example.
ポリオルガノシロキサン（Ａ１）としては、下記平均単位式：
（Ｒ1aＳｉＯ3/2）a1（Ｒ1a 2ＳｉＯ2/2）a2（Ｒ1a 3ＳｉＯ1/2）a3（ＳｉＯ4/2）a4（Ｘ1aＯ1/2）a5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、Ｒ1aは、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、及び上述のアルケニル基、アリール基が挙げられる。但し、Ｒ1aの一部はアルケニル基（特にビニル基）であり、その割合は、分子内に２個以上となる範囲に制御される。例えば、Ｒ1aの全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、Ｒ1aの一部はアリール基（特にフェニル基）であり、その割合は、分子内に１個以上となる範囲に制御される。例えば、Ｒ1aの全量（１００モル％）に対するアリール基の割合は、３０～７０モル％が好ましい。アリール基の割合を上記範囲に制御することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、アルケニル基、アリール基以外のＲ1aとしては、アルキル基（特にメチル基）が好ましい。 As polyorganosiloxane (A1), the following average unit formula:
(R 1a SiO 3/2 ) a1 (R 1a 2 SiO 2/2 ) a2 (R 1a 3 SiO 1/2 ) a3 (SiO 4/2 ) a4 (X 1a O 1/2 ) a5
The polyorganosiloxane represented by is preferable. In the above average unit formula, R 1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl and aryl groups. However, a part of R 1a is an alkenyl group (in particular, a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 1a is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, a part of R 1a is an aryl group (in particular, a phenyl group), and the ratio thereof is controlled to a range of 1 or more in the molecule. For example, the proportion of the aryl group to the total amount (100 mol%) of R 1a is preferably 30 to 70 mol%. By controlling the proportion of the aryl group to the above range, the sulfur barrier properties of the cured product tend to be further improved. Moreover, as R 1a other than an alkenyl group and an aryl group, an alkyl group (especially a methyl group) is preferable.
（Ｒ1aＳｉＯ3/2）a1（Ｒ1a 2ＳｉＯ2/2）a2（Ｒ1a 3ＳｉＯ1/2）a3（ＳｉＯ4/2）a4（Ｘ1aＯ1/2）a5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、Ｒ1aは、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、及び上述のアルケニル基、アリール基が挙げられる。但し、Ｒ1aの一部はアルケニル基（特にビニル基）であり、その割合は、分子内に２個以上となる範囲に制御される。例えば、Ｒ1aの全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、Ｒ1aの一部はアリール基（特にフェニル基）であり、その割合は、分子内に１個以上となる範囲に制御される。例えば、Ｒ1aの全量（１００モル％）に対するアリール基の割合は、３０～７０モル％が好ましい。アリール基の割合を上記範囲に制御することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、アルケニル基、アリール基以外のＲ1aとしては、アルキル基（特にメチル基）が好ましい。 As polyorganosiloxane (A1), the following average unit formula:
(R 1a SiO 3/2 ) a1 (R 1a 2 SiO 2/2 ) a2 (R 1a 3 SiO 1/2 ) a3 (SiO 4/2 ) a4 (X 1a O 1/2 ) a5
The polyorganosiloxane represented by is preferable. In the above average unit formula, R 1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl and aryl groups. However, a part of R 1a is an alkenyl group (in particular, a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 1a is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, a part of R 1a is an aryl group (in particular, a phenyl group), and the ratio thereof is controlled to a range of 1 or more in the molecule. For example, the proportion of the aryl group to the total amount (100 mol%) of R 1a is preferably 30 to 70 mol%. By controlling the proportion of the aryl group to the above range, the sulfur barrier properties of the cured product tend to be further improved. Moreover, as R 1a other than an alkenyl group and an aryl group, an alkyl group (especially a methyl group) is preferable.
上記平均単位式中、Ｘ1は、水素原子又はアルキル基である。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、ヘキシル基等が挙げられ、特にメチル基が好ましい。
In the above average unit formula, X 1 is a hydrogen atom or an alkyl group. As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned, Especially a methyl group is preferable.
上記平均単位式中、ａ１は０又は正数、ａ２は０又は正数、ａ３は０又は正数、ａ４は０又は正数、ａ５は０又は正数であり、かつ、（ａ１＋ａ２＋ａ３）は正数である。
In the above average unit formula, a1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1 + a2 + a3) is a positive It is a number.
ポリオルガノシロキサン（Ａ１）の一例としては、例えば、分子内に２個以上のアルケニル基及び１個以上のアリール基を有する直鎖状ポリオルガノシロキサンが挙げられる。この直鎖状ポリオルガノシロキサンが有するアルケニル基としては、上述のアルケニル基の具体例が挙げられるが、中でもビニル基が好ましい。なお、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。また、この直鎖状ポリオルガノシロキサンが有するアリール基としては、上述のアリール基の具体例が挙げられるが、中でもフェニル基が好ましい。なお、１種のみのアリール基を有するものであってもよいし、２種以上のアリール基を有するものであってもよい。また、上記直鎖状ポリオルガノシロキサンにおけるアルケニル基、アリール基以外のケイ素原子に結合した基としては、例えば、上述の一価の置換又は無置換炭化水素基が挙げられるが、中でも、アルキル基（特にメチル基）が好ましい。
An example of the polyorganosiloxane (A1) is, for example, a linear polyorganosiloxane having two or more alkenyl groups and one or more aryl groups in the molecule. Although the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this linear polyorganosiloxane has, Especially a vinyl group is preferable. In addition, it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Moreover, although the specific example of the above-mentioned aryl group is mentioned as an aryl group which this linear polyorganosiloxane has, a phenyl group is especially preferable. In addition, it may have only 1 type of aryl group, and may have 2 or more types of aryl groups. Moreover, examples of the alkenyl group in the linear polyorganosiloxane and the group bonded to a silicon atom other than the aryl group include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group ( Particularly preferred is a methyl group).
上記直鎖状ポリオルガノシロキサンにおける、ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合は、４０～６０モル％が好ましい。さらに、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、３０～７０モル％が好ましい。特に、上記直鎖状ポリオルガノシロキサンとして、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合が４０モル％以上（例えば、４５～７０モル％）であるものを使用することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合が５０モル％以上（例えば、５５～６０モル％）であるものを使用することにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The ratio of the alkenyl group to the total amount (100 mol%) of the groups bonded to the silicon atom in the linear polyorganosiloxane is preferably 0.1 to 40 mol%. The ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 40 to 60 mol%. Further, the proportion of the aryl group (particularly, phenyl group) is preferably 30 to 70 mol% with respect to the total amount (100 mol%) of the groups bonded to the silicon atom. In particular, the proportion of aryl groups (especially phenyl groups) relative to the total amount (100 mol%) of groups bonded to silicon atoms as the linear polyorganosiloxane is 40 mol% or more (for example, 45 to 70 mol%) By using one, the sulfur barrier properties of the cured product tend to be further improved. In addition, a cured product is obtained by using a compound in which the proportion of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 55 to 60 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
上記直鎖状ポリオルガノシロキサンは、例えば、下記式（Ｉ－１）で表される。
［上記式中、Ｒ11は、同一又は異なって、一価の置換又は無置換の炭化水素基である。但し、Ｒ11の少なくとも２個はアルケニル基であり、少なくとも１個はアリール基である。ｍ１は、５～１０００の整数である］
The linear polyorganosiloxane is represented by, for example, the following formula (I-1).
[In the above formula, R 11 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 11 are alkenyl groups, and at least one is an aryl group. m1 is an integer of 5 to 1000]
ポリオルガノシロキサン（Ａ１）の他の例としては、分子内に２個以上のアルケニル基及び１個以上のアリール基を有し、ＲaＳｉＯ3/2で表されるシロキサン単位（Ｔ単位）を有する分岐鎖状ポリオルガノシロキサンが挙げられる。但し、上述のように、当該分岐鎖状ポリオルガノシロキサンには、後述の（Ｆ）成分に当たるものは含まれない。なお、Ｒaは、一価の置換又は無置換炭化水素基である。この分岐鎖状ポリオルガノシロキサンが有するアルケニル基としては、上述のアルケニル基の具体例が挙げられるが、中でもビニル基が好ましい。なお、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。また、この分岐鎖状ポリオルガノシロキサンが有するアリール基としては、上述のアリール基の具体例が挙げられるが、中でもフェニル基が好ましい。なお、１種のみのアリール基を有するものであってもよいし、２種以上のアリール基を有するものであってもよい。また、上記分岐鎖状ポリオルガノシロキサンにおけるアルケニル基、アリール基以外のケイ素原子に結合した基としては、例えば、上述の一価の置換又は無置換炭化水素基が挙げられるが、中でも、アルキル基（特にメチル基）が好ましい。さらに、上記Ｔ単位中のＲaとしては、中でも、アリール基（特にフェニル基）が好ましい。
Another example of the polyorganosiloxane (A1) is a siloxane unit (T unit) having two or more alkenyl groups and one or more aryl groups in the molecule and represented by R a SiO 3/2 And branched polyorganosiloxanes having. However, as described above, the branched polyorganosiloxane does not include those corresponding to the component (F) described later. R a is a monovalent substituted or unsubstituted hydrocarbon group. Although the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this branched polyorganosiloxane has, Especially a vinyl group is preferable. In addition, it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Moreover, although the specific example of the above-mentioned aryl group is mentioned as an aryl group which this branched polyorganosiloxane has, a phenyl group is especially preferable. In addition, it may have only 1 type of aryl group, and may have 2 or more types of aryl groups. Moreover, examples of the alkenyl group in the branched polyorganosiloxane and the group bonded to a silicon atom other than the aryl group include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group, and among them, an alkyl group ( Particularly preferred is a methyl group). Furthermore, as R a in the above T unit, an aryl group (particularly, a phenyl group) is particularly preferable.
上記分岐鎖状ポリオルガノシロキサンにおける、ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基の割合は、硬化性シリコーン樹脂組成物の硬化性の観点で、０．１～４０モル％が好ましい。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合は、４０～６０モル％が好ましい。さらに、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、３０～７０モル％が好ましい。特に、上記分岐鎖状ポリオルガノシロキサンとして、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合が４０モル％以上（例えば、４５～７０モル％）であるものを使用することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合が５０モル％以上（例えば、５５～６０モル％）であるものを使用することにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The ratio of the alkenyl group to the total amount (100 mol%) of the group bonded to the silicon atom in the branched polyorganosiloxane is 0.1 to 40 mol% from the viewpoint of the curability of the curable silicone resin composition. preferable. The ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is preferably 40 to 60 mol%. Further, the proportion of the aryl group (particularly, phenyl group) is preferably 30 to 70 mol% with respect to the total amount (100 mol%) of the groups bonded to the silicon atom. In particular, the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 70 mol%) as the branched polyorganosiloxane By using one, the sulfur barrier properties of the cured product tend to be further improved. In addition, a cured product is obtained by using a compound in which the proportion of alkyl groups (particularly methyl groups) is 50 mol% or more (for example, 55 to 60 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
上記分岐鎖状ポリオルガノシロキサンは、ａ１が正数である上記平均単位式で表すことができる。この場合、ａ２／ａ１は０～１０の数、ａ３／ａ１は０～０．５の数、ａ４／（ａ１＋ａ２＋ａ３＋ａ４）は０～０．３の数、ａ５／（ａ１＋ａ２＋ａ３＋ａ４）は０～０．４の数が好ましい。また、上記分岐鎖状ポリオルガノシロキサンの分子量は、ＧＰＣによる標準ポリスチレン換算の重量平均分子量が５００～１万が好ましく、より好ましくは７００～３０００である。
The branched polyorganosiloxane can be represented by the above average unit formula in which a1 is a positive number. In this case, a2 / a1 is a number from 0 to 10, a3 / a1 is a number from 0 to 0.5, a4 / (a1 + a2 + a3 + a4) is a number from 0 to 0.3, and a5 / (a1 + a2 + a3 + a4) is 0 to 0.4 The number of is preferred. Further, the molecular weight of the branched polyorganosiloxane is preferably 500 to 10,000, more preferably 700 to 3,000, in terms of weight average molecular weight in terms of standard polystyrene by GPC.
ポリオルガノシロキサン（Ａ１）は公知乃至慣用の方法により製造することができ、また、ポリオルガノシロキサン（Ａ１）を含む製品として、例えば、商品名「ＯＥ６６３０」（東レ・ダウコーニング（株）製）等が入手可能である。
The polyorganosiloxane (A1) can be produced by a known or conventional method, and as a product containing the polyorganosiloxane (A1), for example, trade name "OE 6630" (manufactured by Toray Dow Corning Co., Ltd.), etc. Are available.
なお、本発明の硬化性シリコーン樹脂組成物においてポリオルガノシロキサン（Ａ１）は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。例えば、分子構造が異なるポリオルガノシロキサン（Ａ１）の２種以上を併用することができ、具体的には、直鎖状のポリオルガノシロキサン（Ａ１）と分岐鎖状のポリオルガノシロキサン（Ａ１）とを併用する態様等が挙げられる。
In the curable silicone resin composition of the present invention, the polyorganosiloxane (A1) can be used singly or in combination of two or more. For example, two or more of polyorganosiloxanes (A1) having different molecular structures can be used in combination, and more specifically, linear polyorganosiloxane (A1) and branched polyorganosiloxane (A1) And the like.
（ポリオルガノシロキシシルアルキレン（Ａ２））
ポリオルガノシロキシシルアルキレン（Ａ２）は、分子内に２個以上のアルケニル基及び１個以上のアリール基を有し、主鎖として－Ｓｉ－Ｏ－Ｓｉ－（シロキサン結合）に加えて、－Ｓｉ－ＲA－Ｓｉ－（シルアルキレン結合：ＲAはアルキレン基を示す）を含むポリオルガノシロキサン（ポリオルガノシロキシシルアルキレン）である。即ち、ポリオルガノシロキシシルアルキレン（Ａ２）には、ポリオルガノシロキサン（Ａ１）のようなシルアルキレン結合を有しないポリオルガノシロキサンは含まれない。本発明の硬化性シリコーン樹脂組成物はこのようなポリオルガノシロキシシルアルキレン（Ａ２）を含むために、硫黄バリア性と耐熱衝撃性とに優れた硬化物を形成できる。さらに、硬化させることにより、硫黄バリア性が高く、黄変し難く、タックの低い又は無い硬化物とすることができるため、これを封止材とする光半導体装置の品質が向上する。 (Polyorganosiloxycyl alkylene (A2))
Polyorganosiloxycyl alkylene (A2) has two or more alkenyl groups and one or more aryl groups in the molecule, and in addition to -Si-O-Si- (siloxane bond) as the main chain, -Si -R a -Si- (silalkylene bond: R a represents an alkylene group) polyorganosiloxanes comprising (poly organosiloxy sill alkylene). That is, polyorganosiloxysil alkylene (A2) does not include polyorganosiloxane having no silalkylene bond such as polyorganosiloxane (A1). Since the curable silicone resin composition of the present invention contains such a polyorganosiloxysil alkylene (A2), it can form a cured product excellent in sulfur barrier properties and thermal shock resistance. Furthermore, by curing, a cured product having high sulfur barrier properties, resistance to yellowing and low tack or no tackiness can be obtained, so that the quality of an optical semiconductor device using this as a sealing material is improved.
ポリオルガノシロキシシルアルキレン（Ａ２）は、分子内に２個以上のアルケニル基及び１個以上のアリール基を有し、主鎖として－Ｓｉ－Ｏ－Ｓｉ－（シロキサン結合）に加えて、－Ｓｉ－ＲA－Ｓｉ－（シルアルキレン結合：ＲAはアルキレン基を示す）を含むポリオルガノシロキサン（ポリオルガノシロキシシルアルキレン）である。即ち、ポリオルガノシロキシシルアルキレン（Ａ２）には、ポリオルガノシロキサン（Ａ１）のようなシルアルキレン結合を有しないポリオルガノシロキサンは含まれない。本発明の硬化性シリコーン樹脂組成物はこのようなポリオルガノシロキシシルアルキレン（Ａ２）を含むために、硫黄バリア性と耐熱衝撃性とに優れた硬化物を形成できる。さらに、硬化させることにより、硫黄バリア性が高く、黄変し難く、タックの低い又は無い硬化物とすることができるため、これを封止材とする光半導体装置の品質が向上する。 (Polyorganosiloxycyl alkylene (A2))
Polyorganosiloxycyl alkylene (A2) has two or more alkenyl groups and one or more aryl groups in the molecule, and in addition to -Si-O-Si- (siloxane bond) as the main chain, -Si -R a -Si- (silalkylene bond: R a represents an alkylene group) polyorganosiloxanes comprising (poly organosiloxy sill alkylene). That is, polyorganosiloxysil alkylene (A2) does not include polyorganosiloxane having no silalkylene bond such as polyorganosiloxane (A1). Since the curable silicone resin composition of the present invention contains such a polyorganosiloxysil alkylene (A2), it can form a cured product excellent in sulfur barrier properties and thermal shock resistance. Furthermore, by curing, a cured product having high sulfur barrier properties, resistance to yellowing and low tack or no tackiness can be obtained, so that the quality of an optical semiconductor device using this as a sealing material is improved.
ポリオルガノシロキシシルアルキレン（Ａ２）が分子内に有するシルアルキレン結合におけるアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基等の直鎖又は分岐鎖状のＣ1-12アルキレン基等が挙げられ、中でも、Ｃ2-4アルキレン基（特に、エチレン基）が好ましい。ポリオルガノシロキシシルアルキレン（Ａ２）は、主鎖がシロキサン結合のみからなり、シルアルキレン結合を有しないポリオルガノシロキサンと比較して、製造工程において低分子量の環を生じ難く、また、加熱等により分解してシラノール基（－ＳｉＯＨ）を生じ難いため、ポリオルガノシロキシシルアルキレン（Ａ２）を使用することにより、硬化性シリコーン樹脂組成物の硬化物の表面粘着性（タック性）が低減され、より黄変し難くなる傾向がある。
Examples of the alkylene group in the silalkylene bond that polyorganosiloxycyl alkylene (A2) has in the molecule include linear or branched C 1-12 alkylene groups such as methylene, ethylene and propylene. Among them, a C.sub.2-4 alkylene group (particularly, an ethylene group) is preferable. The polyorganosiloxycyl alkylene (A2) is less likely to form a low molecular weight ring in the production process as compared to a polyorganosiloxane having a main chain consisting of only a siloxane bond and having no silalkylene bond, and is decomposed by heating or the like. Since it is difficult to form silanol groups (-SiOH), the surface tackiness (tackiness) of the cured product of the curable silicone resin composition is reduced by using polyorganosiloxysil alkylene (A2), and yellowing is further caused. It tends to be difficult to change.
ポリオルガノシロキシシルアルキレン（Ａ２）としては、直鎖状、分岐鎖状（例えば、一部分岐を有する直鎖状、分岐鎖状、網目状等）の分子構造を有するもの等が挙げられる。中でも、ポリオルガノシロキシシルアルキレン（Ａ２）としては、分岐鎖状の分子構造を有するものが、硬化物の機械強度の観点で好ましい。
As the polyorganosiloxycyl alkylene (A2), those having a linear or branched (for example, a partially branched linear, branched, network, etc.) molecular structure can be mentioned. Among them, as the polyorganosiloxycyl alkylene (A2), one having a branched molecular structure is preferable from the viewpoint of mechanical strength of a cured product.
ポリオルガノシロキシシルアルキレン（Ａ２）が分子内に有する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、ヘキセニル基等の置換又は無置換アルケニル基が挙げられる。当該置換アルケニル基における置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。中でも、上記アルケニル基としては、ビニル基が好ましい。また、ポリオルガノシロキシシルアルキレン（Ａ２）は、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。ポリオルガノシロキシシルアルキレン（Ａ２）が有するアルケニル基は、特に限定されないが、ケイ素原子に結合した基であることが好ましい。
As an alkenyl group which polyorgano siloxy cyl alkylene (A2) has in a molecule, substituted or unsubstituted alkenyl groups, such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, etc. are mentioned. As a substituent in the said substituted alkenyl group, a halogen atom, a hydroxyl group, a carboxy group etc. are mentioned. Among them, a vinyl group is preferable as the above-mentioned alkenyl group. The polyorganosiloxycyl alkylene (A2) may have only one type of alkenyl group or may have two or more types of alkenyl groups. The alkenyl group contained in the polyorganosiloxysil alkylene (A2) is not particularly limited, but is preferably a group bonded to a silicon atom.
ポリオルガノシロキシシルアルキレン（Ａ２）が分子内に有するアリール基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基、アラルキル基（例えば、ベンジル基、フェネチル基等）等の置換又は無置換Ｃ6-14アリール基等が挙げられる。当該置換アリール基における置換基としては、置換又は無置換Ｃ1-8アルキル基、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。中でも、上記アリール基としては、フェニル基が好ましい。また、ポリオルガノシロキシシルアルキレン（Ａ２）は、１種のみのアリール基を有するものであってもよいし、２種以上のアリール基を有するものであってもよい。ポリオルガノシロキシシルアルキレン（Ａ２）が有するアリール基は、特に限定されないが、ケイ素原子に結合した基であることが好ましい。ポリオルガノシロキシシルアルキレン（Ａ２）は、分子内に１個以上のアリール基を有することにより、アリール基を有しないポリオルガノシロキサンと比較して、硫黄バリア性に優れた硬化物を形成できる。
Examples of the aryl group which polyorganosiloxycyl alkylene (A2) has in the molecule thereof include substituted or unsubstituted such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group (for example, benzyl group, phenethyl group etc.) C 6-14 aryl group etc. are mentioned. Examples of the substituent in the substituted aryl group include a substituted or unsubstituted C 1-8 alkyl group, a halogen atom, a hydroxy group, a carboxy group and the like. Among them, a phenyl group is preferable as the above-mentioned aryl group. The polyorganosiloxycyl alkylene (A2) may have only one type of aryl group or may have two or more types of aryl groups. The aryl group contained in the polyorganosiloxysil alkylene (A2) is not particularly limited, but is preferably a group bonded to a silicon atom. By having one or more aryl groups in the molecule, the polyorganosiloxysil alkylene (A2) can form a cured product having excellent sulfur barrier properties as compared to a polyorganosiloxane having no aryl group.
ポリオルガノシロキシシルアルキレン（Ａ２）が分子内に有するアルケニル基及びアリール基以外のケイ素原子に結合した基としては、特に限定されないが、例えば、水素原子、有機基等が挙げられる。有機基としては、例えば、アルキル基［例えば、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］、シクロアルキル基［例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロドデシル基等］、シクロアルキル－アルキル基［例えば、シクロへキシルメチル基、メチルシクロヘキシル基等］、炭化水素基における１以上の水素原子がハロゲン原子で置換されたハロゲン化炭化水素基［例えば、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基等］等の一価の置換又は無置換炭化水素基等が挙げられる。なお、本明細書において「ケイ素原子に結合した基」とは、通常、ケイ素原子を含まない基を指すものとする。中でも、アルキル基（特にメチル基）が好ましい。
Although it does not specifically limit as group which couple | bonded with silicon atoms other than the alkenyl group which the polyorgano siloxy cyl alkylene (A2) has in a molecule | numerator, and an aryl group, For example, a hydrogen atom, an organic group etc. are mentioned. As an organic group, for example, an alkyl group [for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group etc.], a cycloalkyl group [for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group , A cyclododecyl group etc., a cycloalkyl-alkyl group [eg, a cyclohexyl methyl group, a methylcyclohexyl group etc.], a halogenated hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group is substituted with a halogen atom [eg, Monovalent substituted or unsubstituted hydrocarbon groups and the like can be mentioned, such as chloroalkyl, 3-chloropropyl, and halogenated alkyl groups such as 3,3,3-trifluoropropyl. In the present specification, “a group bonded to a silicon atom” usually refers to a group not containing a silicon atom. Among them, an alkyl group (in particular, a methyl group) is preferable.
また、ポリオルガノシロキシシルアルキレン（Ａ２）は、ケイ素原子に結合した基として、ヒドロキシ基、アルコキシ基を有していてもよい。
The polyorganosiloxycyl alkylene (A2) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
ポリオルガノシロキシシルアルキレン（Ａ２）の性状は、特に限定されず、例えば２５℃において、液状であってもよいし、固体状であってもよい。
The property of the polyorganosiloxysil alkylene (A2) is not particularly limited, and may be liquid or solid at 25 ° C., for example.
ポリオルガノシロキシシルアルキレン（Ａ２）としては、下記平均単位式：
（Ｒ1b 2ＳｉＯ2/2）b1（Ｒ1b 3ＳｉＯ1/2）b2（Ｒ1bＳｉＯ3/2）b3（ＳｉＯ4/2）b4（ＲA）b5（Ｘ1bＯ）b6
で表されるポリオルガノシロキシシルアルキレンが好ましい。上記平均単位式中、Ｒ1bは、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化アルキル基等）、及び上述のアルケニル基、アリール基が挙げられる。但し、Ｒ1bの一部はアルケニル基（特にビニル基）であり、その割合は、分子内に２個以上となる範囲に制御される。例えば、Ｒ1bの全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、Ｒ1bの一部はアリール基（特にフェニル基）であり、その割合は、分子内に１個以上となる範囲に制御される。例えば、Ｒ1bの全量（１００モル％）に対するアリール基の割合は、１０～５０モル％が好ましい。アリール基の割合を上記範囲に制御することにより、硬化物の硫黄バリア性がより向上する傾向がある。アルケニル基、アリール基以外のＲ1bとしては、アルキル基（特にメチル基）が好ましい。 As polyorganosiloxycyl alkylene (A2), the following average unit formula:
(R 1 b 2 SiO 2/2 ) b 1 (R 1 b 3 SiO 1/2 ) b 2 (R 1 b SiO 3/2 ) b 3 (SiO 4/2 ) b 4 (R A ) b 5 (X 1 b O) b 6
The polyorganosiloxycyl alkylene represented by is preferable. In the above average unit formula, R 1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl and aryl groups. However, a part of R 1b is an alkenyl group (especially a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 1b is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, a part of R 1b is an aryl group (particularly, a phenyl group), and the ratio thereof is controlled to a range of 1 or more in the molecule. For example, the proportion of the aryl group to the total amount (100 mol%) of R 1b is preferably 10 to 50 mol%. By controlling the proportion of the aryl group to the above range, the sulfur barrier properties of the cured product tend to be further improved. As R 1b other than an alkenyl group and an aryl group, an alkyl group (especially a methyl group) is preferable.
（Ｒ1b 2ＳｉＯ2/2）b1（Ｒ1b 3ＳｉＯ1/2）b2（Ｒ1bＳｉＯ3/2）b3（ＳｉＯ4/2）b4（ＲA）b5（Ｘ1bＯ）b6
で表されるポリオルガノシロキシシルアルキレンが好ましい。上記平均単位式中、Ｒ1bは、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化アルキル基等）、及び上述のアルケニル基、アリール基が挙げられる。但し、Ｒ1bの一部はアルケニル基（特にビニル基）であり、その割合は、分子内に２個以上となる範囲に制御される。例えば、Ｒ1bの全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、Ｒ1bの一部はアリール基（特にフェニル基）であり、その割合は、分子内に１個以上となる範囲に制御される。例えば、Ｒ1bの全量（１００モル％）に対するアリール基の割合は、１０～５０モル％が好ましい。アリール基の割合を上記範囲に制御することにより、硬化物の硫黄バリア性がより向上する傾向がある。アルケニル基、アリール基以外のＲ1bとしては、アルキル基（特にメチル基）が好ましい。 As polyorganosiloxycyl alkylene (A2), the following average unit formula:
(
The polyorganosiloxycyl alkylene represented by is preferable. In the above average unit formula, R 1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl and aryl groups. However, a part of R 1b is an alkenyl group (especially a vinyl group), and the ratio is controlled to a range of 2 or more in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 1b is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, a part of R 1b is an aryl group (particularly, a phenyl group), and the ratio thereof is controlled to a range of 1 or more in the molecule. For example, the proportion of the aryl group to the total amount (100 mol%) of R 1b is preferably 10 to 50 mol%. By controlling the proportion of the aryl group to the above range, the sulfur barrier properties of the cured product tend to be further improved. As R 1b other than an alkenyl group and an aryl group, an alkyl group (especially a methyl group) is preferable.
上記平均単位式中、ＲAは、上述のようにアルキレン基である。特にエチレン基が好ましい。
In the above average unit formula, R A is an alkylene group as described above. Particularly preferred is an ethylene group.
上記平均単位式中、Ｘ1bは、水素原子又はアルキル基である。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられ、特にメチル基が好ましい。
In the above average unit formula, X 1b is a hydrogen atom or an alkyl group. As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. are mentioned, for example, Especially a methyl group is preferable.
上記平均単位式中、ｂ１は正数、ｂ２は正数、ｂ３は０又は正数、ｂ４は０又は正数、ｂ５は正数、ｂ６は０又は正数である。中でも、ｂ１は１～２００が好ましく、ｂ２は１～２００が好ましく、ｂ３は０～１０が好ましく、ｂ４は０～５が好ましく、ｂ５は１～１００が好ましい。特に、（ｂ３＋ｂ４）が正数の場合には、ポリオルガノシロキシシルアルキレン（Ａ２）が分岐鎖（分岐状の主鎖）を有し、硬化物の機械強度がより向上する傾向がある。
In the above average unit formula, b1 is a positive number, b2 is a positive number, b3 is 0 or a positive number, b4 is 0 or a positive number, b5 is a positive number, and b6 is 0 or a positive number. Among them, b1 is preferably 1 to 200, b2 is preferably 1 to 200, b3 is preferably 0 to 10, b4 is preferably 0 to 5, and b5 is preferably 1 to 100. In particular, when (b3 + b4) is a positive number, the polyorganosiloxysil alkylene (A2) has a branched chain (branched main chain), and the mechanical strength of the cured product tends to be further improved.
ポリオルガノシロキシシルアルキレン（Ａ２）としては、より具体的には、例えば、下記式（Ｉ－２）で表される構造を有するポリオルガノシロキシシルアルキレンが挙げられる。
More specific examples of the polyorganosiloxycyl alkylene (A2) include polyorganosiloxycyl alkylene having a structure represented by the following formula (I-2).
上記式（Ｉ－２）中、Ｒ12は、同一又は異なって、水素原子、又は一価の置換若しくは無置換炭化水素基である。Ｒ12としては、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、及び上述のアルケニル基、アリール基が挙げられる。但し、Ｒ12の少なくとも２個はアルケニル基（特にビニル基）であり、Ｒ12の少なくとも１個はアリール基（特にフェニル基）である。また、アルケニル基及びアリール基以外のＲ12としては、アルキル基（特にメチル基）が好ましい。
In the above formula (I-2), R 12 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Examples of R 12 include the above-mentioned specific examples of the monovalent substituted or unsubstituted hydrocarbon group (for example, an alkyl group, a halogenated hydrocarbon group and the like), and the above-mentioned alkenyl group and aryl group. However, at least two of R 12 are alkenyl groups (particularly, a vinyl group), and at least one of R 12 is an aryl group (particularly, a phenyl group). In addition, as R 12 other than an alkenyl group and an aryl group, an alkyl group (particularly a methyl group) is preferable.
上記式（Ｉ－２）中、ＲAは、上記と同じく、アルキレン基を示し、中でも、Ｃ2-4アルキレン基（特に、エチレン基）が好ましい。なお、複数のＲAが存在する場合、これらは同一であってもよいし、異なっていてもよい。
In the above formula (I-2), R A represents an alkylene group as described above, and among them, a C 2-4 alkylene group (in particular, an ethylene group) is preferable. In addition, when several RA exists, these may be the same and may differ.
上記式（Ｉ－２）中、ｒ１は１以上の整数（例えば、１～１００）を示す。なお、ｒ１が２以上の整数の場合、ｒ１が付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。
In the above formula (I-2), r1 represents an integer of 1 or more (for example, 1 to 100). When r1 is an integer of 2 or more, the structures in the parentheses with r1 may be identical to or different from each other.
上記式（Ｉ－２）中、ｒ２は１以上の整数（例えば、１～４００）を示す。なお、ｒ２が２以上の整数の場合、ｒ２が付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。
In the above formula (I-2), r2 represents an integer of 1 or more (for example, 1 to 400). When r2 is an integer of 2 or more, the structures in the parentheses with r2 attached thereto may be identical to or different from each other.
上記式（Ｉ－２）中、ｒ３は０又は１以上の整数（例えば、０～５０）を示す。なお、ｒ３が２以上の整数の場合、ｒ３が付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。
In the above formula (I-2), r3 represents an integer of 0 or 1 (eg, 0 to 50). When r3 is an integer of 2 or more, the structures in the brackets with r3 may be identical to or different from each other.
上記式（Ｉ－２）中、ｒ４は０又は１以上の整数（例えば、０～５０）を示す。なお、ｒ４が２以上の整数の場合、ｒ４が付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。
In the above formula (I-2), r 4 represents an integer of 0 or 1 (eg, 0 to 50). When r4 is an integer of 2 or more, the structures in the brackets with r4 may be identical to or different from each other.
上記式（Ｉ－２）中、ｒ５は０又は１以上の整数（例えば、０～５０）を示す。なお、ｒ５が２以上の整数の場合、ｒ５が付された括弧内の構造はそれぞれ同一であってもよいし、異なっていてもよい。
In the above formula (I-2), r5 represents an integer of 0 or 1 (eg, 0 to 50). When r5 is an integer of 2 or more, the structures in the parentheses with r5 attached thereto may be identical to or different from each other.
また、上記式（Ｉ－２）における各構造単位の付加形態は特に限定されず、ランダム型であってもよいし、ブロック型であってもよい。また、各構造単位の配列の順番も特に限定されない。
Further, the addition form of each structural unit in the above formula (I-2) is not particularly limited, and may be a random type or a block type. Further, the order of arrangement of each structural unit is not particularly limited.
式（Ｉ－２）で表される構造を有するポリオルガノシロキシシルアルキレンの末端構造は、特に限定されないが、例えば、シラノール基、アルコキシシリル基、トリアルキルシリル基（例えば、ｒ５が付された括弧内の構造、トリメチルシリル基等）等が挙げられる。上記ポリオルガノシロキシシルアルキレンの末端には、アルケニル基やヒドロシリル基等の各種の基が導入されていてもよい。
The terminal structure of the polyorganosiloxycyl alkylene having the structure represented by the formula (I-2) is not particularly limited, but, for example, silanol group, alkoxysilyl group, trialkylsilyl group (for example, brackets with r5 attached) Inner structure, trimethylsilyl group etc.). Various groups such as an alkenyl group and a hydrosilyl group may be introduced at the end of the polyorganosiloxycyl alkylene.
ポリオルガノシロキシシルアルキレン（Ａ２）は公知乃至慣用の方法により製造することができ、その製造方法は特に限定されないが、例えば、特開２０１２－１４０６１７号公報に記載の方法により製造できる。また、ポリオルガノシロキシシルアルキレン（Ａ２）を含む製品として、例えば、商品名「ＥＴＥＲＬＥＤ ＧＳ５１５５」、「ＥＴＥＲＬＥＤ ＧＳ５１４５」、「ＥＴＥＲＬＥＤ ＧＳ５１３５」、「ＥＴＥＲＬＥＤ ＧＳ５１２０」（いずれも長興材料工業製）等が入手可能である。
The polyorganosiloxysil alkylene (A2) can be produced by a known or conventional method, and the production method thereof is not particularly limited. For example, it can be produced by the method described in JP-A-2012-140617. In addition, as products containing polyorganosiloxycyl alkylene (A2), for example, trade names “ETERLED GS5155”, “ETERLED GS5145”, “ETERLED GS5135”, “ETERLED GS5120” (all manufactured by Changxing Materials Co., Ltd.), etc. can be obtained It is.
なお、本発明の硬化性シリコーン樹脂組成物においてポリオルガノシロキシシルアルキレン（Ａ２）は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。例えば、分子構造が異なるポリオルガノシロキシシルアルキレン（Ａ２）の２種以上を併用することができ、具体的には、直鎖状のポリオルガノシロキシシルアルキレン（Ａ２）と分岐鎖状のポリオルガノシロキシシルアルキレン（Ａ２）とを併用する態様等が挙げられる。
In the curable silicone resin composition of the present invention, polyorganosiloxycyl alkylene (A2) can be used alone or in combination of two or more. For example, two or more kinds of polyorganosiloxysil alkylene (A2) having different molecular structures can be used in combination, and specifically, linear polyorganosiloxysil alkylene (A2) and branched polyorganosiloxy The embodiment etc. which use silalkylene (A2) together are mentioned.
本発明の硬化性シリコーン樹脂組成物における（Ａ）成分の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．１～６０重量％が好ましく、より好ましくは０．１～５５重量％、さらに好ましくは０．１～５０重量％である。（Ａ）成分の含有量を０．１重量％以上とすることにより、硬化物の耐熱衝撃性がより向上する傾向がある。また、（Ａ）成分としてポリオルガノシロキシシルアルキレン（Ａ２）を使用した場合には、硬化物のタックが低減されるため、光半導体装置の品質が向上する傾向もある。一方、（Ａ）成分の含有量を６０重量％以下とすることにより、硬化物の耐黄変性がより向上する傾向があり、また、（Ｂ）～（Ｄ）成分の増量による効果（例えば硬化性向上、硫黄バリア性向上、密着性向上等）を効率的に得られる傾向がある。
The content (blending amount) of the component (A) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.1 to 60% by weight based on the curable silicone resin composition (100% by weight) Is more preferably 0.1 to 55% by weight, still more preferably 0.1 to 50% by weight. By making the content of the component (A) 0.1% by weight or more, the thermal shock resistance of the cured product tends to be further improved. In addition, when polyorganosiloxysil alkylene (A2) is used as the component (A), the tackiness of the cured product is reduced, so that the quality of the optical semiconductor device tends to be improved. On the other hand, when the content of the component (A) is 60% by weight or less, the yellowing resistance of the cured product tends to be further improved, and the effect of increasing the amounts of the components (B) to (D) There is a tendency to improve the properties, to improve the sulfur barrier properties, to improve the adhesion, etc. efficiently.
本発明の硬化性シリコーン樹脂組成物における（Ａ）成分としては、ポリオルガノシロキサン（Ａ１）のみを使用することもできるし、ポリオルガノシロキシシルアルキレン（Ａ２）のみを使用することもできるし、また、ポリオルガノシロキサン（Ａ１）とポリオルガノシロキシシルアルキレン（Ａ２）とを併用することもできる。ポリオルガノシロキサン（Ａ１）とポリオルガノシロキシシルアルキレン（Ａ２）とを併用する場合、これらの割合は特に限定されず、適宜設定可能である。
As the component (A) in the curable silicone resin composition of the present invention, only polyorganosiloxane (A1) can be used, or only polyorganosiloxysil alkylene (A2) can be used, and The polyorganosiloxane (A1) and the polyorganosiloxysil alkylene (A2) can also be used in combination. When using polyorganosiloxane (A1) and polyorganosiloxycyl alkylene (A2) in combination, the ratio of these is not particularly limited, and can be set appropriately.
［（Ｂ）成分］
本発明の硬化性シリコーン樹脂組成物における（Ｂ）成分は、分子内に１個以上のヒドロシリル基（Ｓｉ－Ｈ）を有し、脂肪族不飽和基を有しないポリオルガノシロキサンである。従って、本発明の硬化性シリコーン樹脂組成物において（Ｂ）成分は、アルケニル基を有する成分（例えば、（Ａ）成分等）とヒドロシリル化反応を生じる成分である。本発明の硬化性シリコーン樹脂組成物が（Ｂ）成分を含むことにより、ヒドロシリル化反応による硬化反応を効率的に進行させることができる。また、その硬化物が優れた硫黄バリア性を発揮する。 [(B) component]
The component (B) in the curable silicone resin composition of the present invention is a polyorganosiloxane having one or more hydrosilyl groups (Si-H) in the molecule and having no aliphatic unsaturated group. Accordingly, the component (B) in the curable silicone resin composition of the present invention is a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, the component (A) and the like). When the curable silicone resin composition of the present invention contains the component (B), the curing reaction by the hydrosilylation reaction can be efficiently advanced. In addition, the cured product exhibits excellent sulfur barrier properties.
本発明の硬化性シリコーン樹脂組成物における（Ｂ）成分は、分子内に１個以上のヒドロシリル基（Ｓｉ－Ｈ）を有し、脂肪族不飽和基を有しないポリオルガノシロキサンである。従って、本発明の硬化性シリコーン樹脂組成物において（Ｂ）成分は、アルケニル基を有する成分（例えば、（Ａ）成分等）とヒドロシリル化反応を生じる成分である。本発明の硬化性シリコーン樹脂組成物が（Ｂ）成分を含むことにより、ヒドロシリル化反応による硬化反応を効率的に進行させることができる。また、その硬化物が優れた硫黄バリア性を発揮する。 [(B) component]
The component (B) in the curable silicone resin composition of the present invention is a polyorganosiloxane having one or more hydrosilyl groups (Si-H) in the molecule and having no aliphatic unsaturated group. Accordingly, the component (B) in the curable silicone resin composition of the present invention is a component that causes a hydrosilylation reaction with a component having an alkenyl group (for example, the component (A) and the like). When the curable silicone resin composition of the present invention contains the component (B), the curing reaction by the hydrosilylation reaction can be efficiently advanced. In addition, the cured product exhibits excellent sulfur barrier properties.
（Ｂ）成分が分子内に有するヒドロシリル基の数は、１個以上であればよく、特に限定されないが、硬化性シリコーン樹脂組成物の硬化性の観点で、２個以上（例えば２～５０個）が好ましい。
The number of hydrosilyl groups that the component (B) has in the molecule may be one or more, and is not particularly limited, but from the viewpoint of the curability of the curable silicone resin composition, two or more (for example, 2 to 50) Is preferred.
（Ｂ）成分としては、特に限定されないが、分子内に１個以上（好ましくは２個以上）のヒドロシリル基を有し、脂肪族不飽和基及びシルアルキレン結合を有しないポリオルガノシロキサン（単に「ポリオルガノシロキサン（Ｂ１）」と称する場合がある）であることが好ましい。
The component (B) is not particularly limited, but it is a polyorganosiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule and having no aliphatic unsaturated group and no silalkylene bond (simply It is preferable that it may be called polyorganosiloxane (B1).
なお、（Ｂ）成分は、上述のように、分子内に脂肪族不飽和基を有しない。上記脂肪族不飽和基とは、非芳香族性の炭素－炭素不飽和結合を有する脂肪族炭化水素基であり、例えば、エチレン性不飽和基、アセチレン性不飽和基等が挙げられる。エチレン性不飽和基としては、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、５－ヘキセニル基等のアルケニル基（例えば、Ｃ2-20アルケニル基（特にＣ2-10アルケニル基）等）；１，３－ブタジエニル基等のアルカジエニル基（特に、Ｃ4-10アルカジエニル基等）；アクリロイルオキシ基、メタクリロイルオキシ基等のアルケニルカルボニルオキシ基；アクリルアミド基等のアルケニルカルボニルアミノ基等が挙げられる。アセチレン性不飽和基としては、例えば、エチニル基、プロパルギル基等のアルキニル基（例えば、Ｃ2-20アルキニル基（特にＣ2-10アルキニル基）等）；エチニルカルボニルオキシ基等のアルキニルカルボニルオキシ基；エチニルカルボニルアミノ基等のアルキニルカルボニルアミノ基が挙げられる。
In addition, as above-mentioned, (B) component does not have an aliphatic unsaturated group in a molecule | numerator. The aliphatic unsaturated group is an aliphatic hydrocarbon group having a nonaromatic carbon-carbon unsaturated bond, and examples thereof include an ethylenically unsaturated group and an acetylenic unsaturated group. Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group and 5-hexenyl group (for example, C 2-20 alkenyl group (particularly C 2-10 alkenyl group)) An alkadienyl group such as a 1,3-butadienyl group (in particular, a C 4-10 alkadienyl group etc.); an alkenylcarbonyloxy group such as an acryloyloxy group or a methacryloyloxy group; an alkenylcarbonylamino group such as an acrylamide group. As the acetylenic unsaturated group, for example, alkynyl groups such as ethynyl group and propargyl group (for example, C 2-20 alkynyl group (especially C 2-10 alkynyl group) and the like); alkynyl carbonyloxy groups such as ethynyl carbonyloxy group And alkynylcarbonylamino groups such as ethynylcarbonylamino group.
ポリオルガノシロキサン（Ｂ１）としては、直鎖状、分岐鎖状（一部分岐を有する直鎖状、分岐鎖状、網目状等）の分子構造を有するもの等が挙げられる。なお、ポリオルガノシロキサン（Ｂ１）は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。例えば、分子構造が異なるポリオルガノシロキサン（Ｂ１）の２種以上を併用することができ、具体的には、直鎖状のポリオルガノシロキサン（Ｂ１）と分岐鎖状のポリオルガノシロキサン（Ｂ１）とを併用する態様等が挙げられる。
Examples of the polyorganosiloxane (B1) include those having a linear or branched (a partially branched linear, branched, network, etc.) molecular structure. In addition, polyorganosiloxane (B1) can also be used individually by 1 type, and can also be used combining 2 or more types. For example, two or more kinds of polyorganosiloxanes (B1) having different molecular structures can be used in combination, and specifically, a linear polyorganosiloxane (B1) and a branched polyorganosiloxane (B1) And the like.
ポリオルガノシロキサン（Ｂ１）が有するケイ素原子に結合した基の中でも水素原子以外の基は、特に限定されないが、例えば、上述の一価の置換又は無置換炭化水素基（但し、脂肪族不飽和基は除かれる）及び上述のアリール基、より詳しくは、アルキル基、アリール基、ハロゲン化炭化水素基等が挙げられる。中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。
Among the groups bonded to the silicon atom of the polyorganosiloxane (B1), groups other than hydrogen atoms are not particularly limited, but, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (however, aliphatic unsaturated groups) And the above-mentioned aryl group, more specifically, an alkyl group, an aryl group, a halogenated hydrocarbon group and the like. Among them, alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferable.
また、（Ｂ１）成分は、ケイ素原子に結合した基として、ヒドロキシ基、アルコキシ基を有していてもよい。
The component (B1) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
ポリオルガノシロキサン（Ｂ１）の性状は、特に限定されず、例えば２５℃において、液状であってもよいし、固体状であってもよい。中でも液状であることが好ましく、２５℃における粘度が０．１～１０億ｍＰａ・ｓの液状であることがより好ましい。
The properties of the polyorganosiloxane (B1) are not particularly limited, and may be liquid or solid at 25 ° C., for example. Among them, a liquid is preferable, and a liquid having a viscosity of 0.1 to 1 billion mPa · s at 25 ° C. is more preferable.
ポリオルガノシロキサン（Ｂ１）としては、下記平均単位式：
（Ｒ2ＳｉＯ3/2）c1（Ｒ2 2ＳｉＯ2/2）c2（Ｒ2 3ＳｉＯ1/2）c3（ＳｉＯ4/2）c4（Ｘ2Ｏ1/2）c5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、Ｒ2は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）であり、例えば、水素原子、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化アルキル基等）、及び上述のアリール基が挙げられる。但し、Ｒ2の一部は水素原子（ヒドロシリル基を構成する水素原子）であり、その割合は、ヒドロシリル基が分子内に１個以上（好ましくは２個以上）となる範囲に制御される。例えば、Ｒ2の全量（１００モル％）に対する水素原子の割合は、０．１～４０モル％が好ましい。水素原子の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、水素原子以外のＲ2としては、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。 As polyorganosiloxane (B1), the following average unit formula:
(R 2 SiO 3/2 ) c 1 (R 2 2 SiO 2/2 ) c 2 (R 2 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (X 2 O 1/2 ) c 5
The polyorganosiloxane represented by is preferable. In the above average unit formula, R 2 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups), for example, a hydrogen atom, Specific examples (for example, an alkyl group, a halogenated alkyl group etc.) of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group and the above-mentioned aryl group can be mentioned. However, a part of R 2 is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in such a range that the hydrosilyl group is one or more (preferably two or more) in the molecule. For example, the ratio of hydrogen atoms to the total amount (100 mol%) of R 2 is preferably 0.1 to 40 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. Further, as R 2 other than a hydrogen atom, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.
（Ｒ2ＳｉＯ3/2）c1（Ｒ2 2ＳｉＯ2/2）c2（Ｒ2 3ＳｉＯ1/2）c3（ＳｉＯ4/2）c4（Ｘ2Ｏ1/2）c5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、Ｒ2は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）であり、例えば、水素原子、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化アルキル基等）、及び上述のアリール基が挙げられる。但し、Ｒ2の一部は水素原子（ヒドロシリル基を構成する水素原子）であり、その割合は、ヒドロシリル基が分子内に１個以上（好ましくは２個以上）となる範囲に制御される。例えば、Ｒ2の全量（１００モル％）に対する水素原子の割合は、０．１～４０モル％が好ましい。水素原子の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、水素原子以外のＲ2としては、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。 As polyorganosiloxane (B1), the following average unit formula:
(R 2 SiO 3/2 ) c 1 (R 2 2 SiO 2/2 ) c 2 (R 2 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (X 2 O 1/2 ) c 5
The polyorganosiloxane represented by is preferable. In the above average unit formula, R 2 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups), for example, a hydrogen atom, Specific examples (for example, an alkyl group, a halogenated alkyl group etc.) of the above-mentioned monovalent substituted or unsubstituted hydrocarbon group and the above-mentioned aryl group can be mentioned. However, a part of R 2 is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in such a range that the hydrosilyl group is one or more (preferably two or more) in the molecule. For example, the ratio of hydrogen atoms to the total amount (100 mol%) of R 2 is preferably 0.1 to 40 mol%. By controlling the proportion of hydrogen atoms within the above range, the curability of the curable silicone resin composition tends to be further improved. Further, as R 2 other than a hydrogen atom, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.
上記平均単位式中、Ｘ2は、上記Ｘ1と同じく、水素原子又はアルキル基である。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、ヘキシル基等が挙げられ、特にメチル基であることが好ましい。
In the above average unit formula, X 2 is a hydrogen atom or an alkyl group as in the case of X 1 above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.
上記平均単位式中、ｃ１は０又は正数、ｃ２は０又は正数、ｃ３は０又は正数、ｃ４は０又は正数、ｃ５は０又は正数であり、かつ、（ｃ１＋ｃ２＋ｃ３）は正数である。
In the above average unit formula, c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1 + c2 + c3) is a positive It is a number.
ポリオルガノシロキサン（Ｂ１）の一例としては、例えば、分子内に１個以上（好ましくは２個以上）のヒドロシリル基を有する直鎖状ポリオルガノシロキサンが挙げられる。上記直鎖状ポリオルガノシロキサンにおける水素原子以外のケイ素原子に結合した基としては、例えば、上述の一価の置換又は無置換炭化水素基（但し、脂肪族不飽和基は除かれる）及び上述のアリール基が挙げられるが、中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。
An example of the polyorganosiloxane (B1) is, for example, a linear polyorganosiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule. Examples of the group bonded to a silicon atom other than a hydrogen atom in the linear polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (however, aliphatic unsaturated groups are excluded) and the above-mentioned Although an aryl group is mentioned, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable among them.
上記直鎖状ポリオルガノシロキサンにおける、ケイ素原子に結合した基の全量（１００モル％）に対する水素原子（ケイ素原子に結合した水素原子）の割合は、特に限定されないが、０．１～４０モル％が好ましい。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合は、特に限定されないが、２０～９９モル％が好ましい。さらに、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、特に限定されないが、１０～５０モル％が好ましい。特に、上記直鎖状ポリオルガノシロキサンとして、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合が１０モル％以上（例えば、２０～５０モル％）であるものを使用することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合が９０モル％以上（例えば、９５～９９モル％）であるものを使用することにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The proportion of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount (100 mol%) of the groups bonded to silicon atoms in the linear polyorganosiloxane is not particularly limited, but it is 0.1 to 40 mol% Is preferred. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but it is preferably 20 to 99 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but 10 to 50 mol% is preferable. In particular, as the linear polyorganosiloxane, the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 mol% or more (for example, 20 to 50 mol%) By using one, the sulfur barrier properties of the cured product tend to be further improved. In addition, a cured product is obtained by using a compound in which the proportion of alkyl groups (especially methyl groups) is 90 mol% or more (for example, 95 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
上記直鎖状ポリオルガノシロキサンは、例えば、下記式（ＩＩ－１）で表される。
［上記式中、Ｒ21は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）である。但し、Ｒ21の少なくとも１個（好ましくは少なくとも２個）は水素原子である。ｍ２は、５～１０００の整数である。］
The linear polyorganosiloxane is represented by, for example, the following formula (II-1).
[In the above-mentioned formula, R 21 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups). However, at least one (preferably at least two) of R 21 is a hydrogen atom. m2 is an integer of 5 to 1000. ]
なお、上記式（ＩＩ－１）で表される直鎖状ポリオルガノシロキサンにおいて、上記Ｒ21は、ヒドロキシ基、アルコキシ基であってもよい。また、上記Ｒ21における一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）がヒドロキシ基やアルコキシ基を有していてもよい。
In the linear polyorganosiloxane represented by the formula (II-1), R 21 may be a hydroxy group or an alkoxy group. In addition, the monovalent substituted or unsubstituted hydrocarbon group in the above R 21 (however, aliphatic unsaturated groups are excluded) may have a hydroxy group or an alkoxy group.
ポリオルガノシロキサン（Ｂ１）の他の例としては、分子内に１個以上（好ましくは２個以上）のヒドロシリル基を有し、ＲbＳｉＯ3/2で表されるシロキサン単位（Ｔ単位）を有する分岐鎖状ポリオルガノシロキサンが挙げられる。この分岐鎖状ポリオルガノシロキサンには、網目状等の三次元構造のポリオルガノシロキサンも含まれる。なお、Ｒbは、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）である。上記分岐鎖状ポリオルガノシロキサンにおける水素原子以外のケイ素原子に結合した基としては、例えば、上述の一価の置換又は無置換炭化水素基（但し、脂肪族不飽和基は除かれる）及び上述のアリール基が挙げられるが、中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。さらに、上記Ｔ単位中のＲbとしては、水素原子、上述の一価の置換又は無置換炭化水素基（但し、脂肪族不飽和基は除かれる）及び上述のアリール基が挙げられるが、中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。上記Ｔ単位中のＲbの全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、特に限定されないが、硬化物の硫黄バリア性の観点で、３０モル％以上が好ましい。
Another example of the polyorganosiloxane (B1) is a siloxane unit (T unit) having one or more (preferably two or more) hydrosilyl groups in the molecule and represented by R b SiO 3/2. And branched polyorganosiloxanes having. The branched polyorganosiloxane also includes a polyorganosiloxane having a three-dimensional structure such as a network. R b is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, aliphatic unsaturated groups are excluded). Examples of the group bonded to a silicon atom other than a hydrogen atom in the branched polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (however, aliphatic unsaturated groups are excluded) and the above-mentioned Although an aryl group is mentioned, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable among them. Furthermore, as R b in the above T unit, a hydrogen atom, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups) and the above-mentioned aryl group can be mentioned. Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred. The ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of R b in the T unit is not particularly limited, but is preferably 30 mol% or more from the viewpoint of the sulfur barrier property of the cured product.
上記分岐鎖状ポリオルガノシロキサンにおける、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合は、特に限定されないが、７０～９５モル％が好ましい。さらに、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、特に限定されないが、１０～７０モル％が好ましい。特に、上記分岐鎖状ポリオルガノシロキサンとして、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合が１０モル％以上（例えば、１０～７０モル％）であるものを使用することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合が５０モル％以上（例えば、５０～９０モル％）であるものを使用することにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms in the branched polyorganosiloxane is not particularly limited, but is preferably 70 to 95 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but 10 to 70 mol% is preferable. In particular, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 10 mol% or more (for example, 10 to 70 mol%) as the branched polyorganosiloxane By using one, the sulfur barrier properties of the cured product tend to be further improved. In addition, a cured product is obtained by using a compound in which the proportion of alkyl groups (especially methyl groups) is 50 mol% or more (for example, 50 to 90 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
上記分岐鎖状ポリオルガノシロキサンは、例えば、ｃ１が正数である上記平均単位式で表すことができる。この場合、特に限定されないが、ｃ２／ｃ１は０～１０の数、ｃ３／ｃ１は０～０．５の数、ｃ４／（ｃ１＋ｃ２＋ｃ３＋ｃ４）は０～０．３の数、ｃ５／（ｃ１＋ｃ２＋ｃ３＋ｃ４）は０～０．４の数であることが好ましい。また、上記分岐鎖状ポリオルガノシロキサンの分子量は特に限定されないが、標準ポリスチレン換算の重量平均分子量が３００～１万であることが好ましく、より好ましくは５００～３０００である。
The branched polyorganosiloxane can be represented, for example, by the above average unit formula in which c1 is a positive number. In this case, c2 / c1 is a number of 0 to 10, c3 / c1 is a number of 0 to 0.5, c4 / (c1 + c2 + c3 + c4) is a number of 0 to 0.3, c5 / (c1 + c2 + c3 + c4) is not particularly limited. It is preferable that it is a number of 0 to 0.4. The molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 300 to 10,000, and more preferably 500 to 3,000.
なお、本発明の硬化性シリコーン樹脂組成物において（Ｂ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。
In addition, in the curable silicone resin composition of this invention, (B) component can also be used individually by 1 type, and can also be used combining 2 or more types.
本発明の硬化性シリコーン樹脂組成物における（Ｂ）成分の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、１～６０重量％が好ましく、より好ましくは５～５５重量％、さらに好ましくは１０～５０重量％である。（Ｂ）成分の含有量を１重量％以上とすることにより、硬化性シリコーン樹脂組成物の硬化性がより向上し、硫黄バリア性がより向上する傾向がある。一方、（Ｂ）成分の含有量を６０重量％以下とすることにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The content (blending amount) of the component (B) in the curable silicone resin composition of the present invention is not particularly limited, but preferably 1 to 60% by weight with respect to the curable silicone resin composition (100% by weight). More preferably, it is 5 to 55% by weight, still more preferably 10 to 50% by weight. By setting the content of the component (B) to 1% by weight or more, the curability of the curable silicone resin composition is further improved, and the sulfur barrier property tends to be further improved. On the other hand, when the content of the component (B) is 60% by weight or less, the thermal shock resistance of the cured product tends to be further improved.
［（Ｃ）成分］
本発明の硬化性シリコーン樹脂組成物における（Ｃ）成分は、上記式（１）で表される化合物である。本発明の硬化性シリコーン樹脂組成物は（Ｃ）成分を必須成分として含むことにより、硫黄バリア性に優れた硬化物を形成できる。また、（Ｃ）成分は、本発明の硬化性シリコーン樹脂組成物における溶解性が良好であるためと考えられるが、増量した場合や硬化性シリコーン樹脂組成物を加熱しない場合にも、固体として析出を生じない。このため、本発明の硬化性シリコーン樹脂組成物は、固体析出の問題が生じないことと、硬化物の硫黄バリア性とが、非常に高いレベルで両立される。従来、硬化物の硫黄バリア性の向上効果を有する成分は、上記硫黄バリア性を向上させるために増量すると固体析出の問題を生じるため、上述の両特性の両立をすることは困難であった。 [(C) ingredient]
The component (C) in the curable silicone resin composition of the present invention is a compound represented by the above formula (1). The curable silicone resin composition of the present invention can form a cured product having excellent sulfur barrier properties by including the component (C) as an essential component. The component (C) is considered to be because the solubility in the curable silicone resin composition of the present invention is good, but it precipitates as a solid even when the amount is increased or when the curable silicone resin composition is not heated. Does not occur. Therefore, in the curable silicone resin composition of the present invention, the problem of solid deposition does not occur and the sulfur barrier property of the cured product is compatible at a very high level. Heretofore, since the component having the effect of improving the sulfur barrier property of the cured product causes a problem of solid precipitation when it is increased to improve the above-mentioned sulfur barrier property, it is difficult to achieve both of the above-mentioned characteristics.
本発明の硬化性シリコーン樹脂組成物における（Ｃ）成分は、上記式（１）で表される化合物である。本発明の硬化性シリコーン樹脂組成物は（Ｃ）成分を必須成分として含むことにより、硫黄バリア性に優れた硬化物を形成できる。また、（Ｃ）成分は、本発明の硬化性シリコーン樹脂組成物における溶解性が良好であるためと考えられるが、増量した場合や硬化性シリコーン樹脂組成物を加熱しない場合にも、固体として析出を生じない。このため、本発明の硬化性シリコーン樹脂組成物は、固体析出の問題が生じないことと、硬化物の硫黄バリア性とが、非常に高いレベルで両立される。従来、硬化物の硫黄バリア性の向上効果を有する成分は、上記硫黄バリア性を向上させるために増量すると固体析出の問題を生じるため、上述の両特性の両立をすることは困難であった。 [(C) ingredient]
The component (C) in the curable silicone resin composition of the present invention is a compound represented by the above formula (1). The curable silicone resin composition of the present invention can form a cured product having excellent sulfur barrier properties by including the component (C) as an essential component. The component (C) is considered to be because the solubility in the curable silicone resin composition of the present invention is good, but it precipitates as a solid even when the amount is increased or when the curable silicone resin composition is not heated. Does not occur. Therefore, in the curable silicone resin composition of the present invention, the problem of solid deposition does not occur and the sulfur barrier property of the cured product is compatible at a very high level. Heretofore, since the component having the effect of improving the sulfur barrier property of the cured product causes a problem of solid precipitation when it is increased to improve the above-mentioned sulfur barrier property, it is difficult to achieve both of the above-mentioned characteristics.
式（１）中、Ｒa、Ｒb、及びＲcは、同一又は異なって、式（１ａ）で表される基、式（１ｂ）で表される基、水素原子、又はアルキル基を示す。但し、Ｒa、Ｒb、及びＲcのうち少なくとも１個は、式（１ａ）で表される基である。
In formula (1), R a , R b and R c are the same or different and each represents a group represented by formula (1a), a group represented by formula (1b), a hydrogen atom or an alkyl group . However, at least one of R a , R b and R c is a group represented by Formula (1a).
式（１ａ）中、Ｒdは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（直鎖又は分岐鎖状のＣ1-8アルキル基）を示す。直鎖又は分岐鎖状のＣ1-8アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基等が挙げられる。上記アルキル基の中でも、メチル基、エチル基、プロピル基、イソプロピル基等の直鎖又は分岐鎖状のＣ1-3アルキル基が好ましい。中でもＲdとしては、水素原子が特に好ましい。
In the formula (1a), R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group). As a linear or branched C 1-8 alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned. Among the above alkyl groups, linear or branched C 1-3 alkyl groups such as methyl, ethyl, propyl and isopropyl groups are preferable. Of these examples of R d, a hydrogen atom is particularly preferred.
式（１ａ）中、ｓは、２～１０の整数を示す。中でも、２～８の整数が好ましく、より好ましくは２～６の整数、さらに好ましくは２～４の整数である。ｓが上記範囲にあることにより、硬化性シリコーン樹脂組成物における固体析出の抑制と、硬化物の硫黄バリア性とが、より高いレベルで両立される傾向がある。
In formula (1a), s represents an integer of 2 to 10. Among them, the integer of 2 to 8 is preferable, the integer of 2 to 6 is more preferable, and the integer of 2 to 4 is more preferable. When s is in the above range, suppression of solid deposition in the curable silicone resin composition and sulfur barrier properties of the cured product tend to be compatible at a higher level.
なお、式（１）におけるＲa、Ｒb、及びＲcのうち２個又は３個が式（１ａ）で表される基である場合、これらの式（１ａ）で表される基は、同一であってもよいし、異なっていてもよい。
When two or three of R a , R b and R c in the formula (1) are a group represented by the formula (1a), the group represented by the formula (1a) is It may be the same or different.
式（１ｂ）中、Ｒeは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（直鎖又は分岐鎖状のＣ1-8アルキル基）を示す。直鎖又は分岐鎖状のＣ1-8アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基等が挙げられる。上記アルキル基の中でも、メチル基、エチル基、プロピル基、イソプロピル基等の直鎖又は分岐鎖状のＣ1-3アルキル基が好ましい。中でもＲeとしては、水素原子が特に好ましい。
In the formula (1b), R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group). As a linear or branched C 1-8 alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned. Among the above alkyl groups, linear or branched C 1-3 alkyl groups such as methyl, ethyl, propyl and isopropyl groups are preferable. Among them, a hydrogen atom is particularly preferable as R e .
式（１ｂ）におけるｔは、１～１０の整数を示す。中でも１～６の整数が好ましい。
T in Formula (1b) represents an integer of 1 to 10. Among them, the integer of 1 to 6 is preferable.
なお、式（１）におけるＲa、Ｒb、及びＲcのうち２個が式（１ｂ）で表される基である場合、これらの式（１ｂ）で表される基は、同一であってもよいし、異なっていてもよい。また、イソシアヌレート化合物（Ｃ）は、式（１ｂ）で表される基を有していなくてもよい。
When two of R a , R b and R c in the formula (1) are a group represented by the formula (1 b), the groups represented by the formula (1 b) are the same. It may be different or different. Moreover, the isocyanurate compound (C) may not have a group represented by Formula (1b).
Ｒa、Ｒb、及びＲcとしてのアルキル基は、直鎖、分岐鎖、環状のいずれであってもよく、特に限定されないが、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基等の直鎖又は分岐鎖状のアルキル基（例えば、直鎖又は分岐鎖状のＣ1-8アルキル基）；シクロヘキシル基、メチルシクロヘキシル基、ジメチルシクロヘキシル基等の環状のアルキル基（シクロアルキル基）等が挙げられる。
The alkyl group as R a , R b and R c may be linear, branched or cyclic and is not particularly limited. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group Or branched or straight chain alkyl group such as isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group (for example, linear or branched C 1-8 alkyl) Group); and cyclic alkyl groups (cycloalkyl groups) such as cyclohexyl, methylcyclohexyl and dimethylcyclohexyl.
本発明の硬化性シリコーン樹脂組成物が（Ｃ）成分を含むことにより、その硬化物が硫黄バリア性を発揮できるのは、他の成分と反応した状態及び未反応の状態に関わらず、硬化物中で（Ｃ）成分におけるイソシアヌレート骨格がＳＯｘガス等の腐食性ガスをトラップするためであると推測される。
When the curable silicone resin composition of the present invention contains the component (C), the cured product can exhibit the sulfur barrier property, regardless of the state in which it is reacted with other components and the unreacted state. It is speculated that the isocyanurate skeleton in component (C) is for trapping corrosive gases such as SOx gas.
（Ｃ）成分としては、例えば、式（１）におけるＲa、Ｒb、及びＲcのうち１個が式（１ａ）で表される基である化合物、式（１）におけるＲa、Ｒb、及びＲcのうち２個が式（１ａ）で表される基である化合物、式（１）におけるＲa、Ｒb、及びＲcの全てが式（１ａ）で表される基である化合物が挙げられる。特に固体析出の問題が生じにくい点で、式（１）におけるＲa、Ｒb、及びＲcのうち２個又は３個が式（１ａ）で表される基である化合物が好ましく、より好ましくは式（１）におけるＲa、Ｒb、及びＲcの全てが式（１ａ）で表される基である化合物である。
As the component (C), for example, a compound in which one of R a , R b and R c in the formula (1) is a group represented by the formula (1a), R a and R in the formula (1) Compounds in which two of b and R c are a group represented by formula (1a), and all of R a , R b , and R c in formula (1) are a group represented by formula (1a) Certain compounds are mentioned. In particular, a compound in which two or three of R a , R b and R c in the formula (1) are a group represented by the formula (1a) is preferable, and more preferable in that the problem of solid precipitation hardly occurs. Is a compound in which all of R a , R b and R c in formula (1) are a group represented by formula (1a).
（Ｃ）成分は、分子内に上述の式（１ａ）で表される基を必須の基として有するものであるためと推測されるが、当該基を有しないもの（例えば、トリグリシジルイソシアヌレート、モノアリルジグリシジルイソシアヌレート等）と同等以上の硫黄バリア性の向上効果を有しながら、上記基を有しないものに比べて、本発明の硬化性シリコーン樹脂組成物における他の成分（特に、（Ａ）成分、（Ｂ）成分）との相溶性が非常に良好であり、その結果、硬化性シリコーン樹脂組成物における固体析出の問題が生じることなく、また、調製時にも他の成分に対して容易に溶解させることができる。このため、硬化性シリコーン樹脂組成物の生産性が向上する。また、（Ｃ）成分の含有量を多くした場合であっても上述の固体析出の問題が生じないため、（Ｃ）成分の増量による硬化物の硫黄バリア性の著しい向上が可能となる。
The component (C) is presumed to have a group represented by the above-mentioned formula (1a) as an essential group in the molecule, but one having no such group (for example, triglycidyl isocyanurate, The other components (especially in the curable silicone resin composition of the present invention) (in particular, as compared to those having no such group, while having the effect of improving the sulfur barrier property equal to or more than monoallyl diglycidyl isocyanurate). The compatibility with the component A), component (B) is very good, and as a result, the problem of solid precipitation in the curable silicone resin composition does not occur, and it is also possible to other components during preparation. It can be easily dissolved. For this reason, the productivity of the curable silicone resin composition is improved. In addition, even when the content of the component (C) is increased, the above-mentioned problem of solid precipitation does not occur, so that the sulfur barrier property of the cured product can be significantly improved by increasing the amount of the component (C).
（Ｃ）成分は、例えば、アルコールや酸無水物等のエポキシ基と反応する化合物と反応させて、変性した上で使用することもできる。
The component (C) can also be used after being modified by reaction with a compound that reacts with an epoxy group, such as alcohol or acid anhydride.
（Ｃ）成分が式（１ｂ）で表される基を有するものである場合は、例えば、ヒドロシリル基を有する化合物とあらかじめ反応（ヒドロシリル化反応）させた上で使用することもできる。例えば、後述の（Ｆ）成分であるラダー型シルセスキオキサンとともに（Ｅ）成分であるヒドロシリル化触媒の存在下で反応させたものを、本発明の硬化性シリコーン樹脂組成物の構成成分として使用することもできる。
When the component (C) has a group represented by the formula (1b), for example, it can be used after previously reacting (hydrosilylation reaction) with a compound having a hydrosilyl group. For example, those which are reacted in the presence of a hydrosilylation catalyst which is the component (E) together with ladder type silsesquioxane which is the component (F) described later are used as a component of the curable silicone resin composition of the present invention You can also
本発明の硬化性シリコーン樹脂組成物において（Ｃ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。また、（Ｃ）成分は、商品名「ＴＥＰＩＣ－ＶＬ」（日産化学工業（株）製）等の市販品を入手することもできる。
In the curable silicone resin composition of the present invention, as the component (C), one type can be used alone, or two or more types can be used in combination. In addition, as the component (C), commercially available products such as trade name “TEPIC-VL” (manufactured by Nissan Chemical Industries, Ltd.) can also be obtained.
本発明の硬化性シリコーン樹脂組成物における（Ｃ）成分の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～１０重量％が好ましく、より好ましくは０．０３～５重量％、さらに好ましくは０．０５～３重量％、特に好ましくは０．１～２重量％である。（Ｃ）成分の含有量を０．０１重量％以上とすることにより、硬化物の硫黄バリア性がより向上する傾向がある。一方、（Ｃ）成分の含有量を１０重量％以下とすることにより、耐熱性、強靭性、透明性等により優れる硬化物が得られる傾向がある。
The content (compounding amount) of the component (C) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 10% by weight with respect to the curable silicone resin composition (100% by weight) Is more preferably 0.03 to 5% by weight, still more preferably 0.05 to 3% by weight, and particularly preferably 0.1 to 2% by weight. By setting the content of the component (C) to 0.01% by weight or more, the sulfur barrier properties of the cured product tend to be further improved. On the other hand, when the content of the component (C) is 10% by weight or less, there is a tendency to obtain a cured product which is more excellent in heat resistance, toughness, transparency and the like.
［（Ｄ）成分］
本発明の硬化性シリコーン樹脂組成物における（Ｄ）成分は、上述のように、分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン（「（Ｄ）成分」と称する場合がある）である。本発明の硬化性シリコーン樹脂組成物において（Ｄ）成分は、（Ａ）成分とともに、ヒドロシリル基を有する成分（例えば、（Ｂ）成分等）とヒドロシリル化反応を生じる成分である。本発明の硬化性シリコーン樹脂組成物が（Ｄ）成分を含むことにより、硬化物の耐熱性、耐熱衝撃性、硫黄バリア性がさらに向上する場合がある。 [(D) component]
As described above, the component (D) in the curable silicone resin composition of the present invention may be a branched polyorganosiloxane having one or more alkenyl groups in the molecule (referred to as "component (D)". Yes). The component (D) in the curable silicone resin composition of the present invention is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (B) and the like) together with the component (A). When the curable silicone resin composition of the present invention contains the component (D), the heat resistance, thermal shock resistance and sulfur barrier properties of the cured product may be further improved.
本発明の硬化性シリコーン樹脂組成物における（Ｄ）成分は、上述のように、分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン（「（Ｄ）成分」と称する場合がある）である。本発明の硬化性シリコーン樹脂組成物において（Ｄ）成分は、（Ａ）成分とともに、ヒドロシリル基を有する成分（例えば、（Ｂ）成分等）とヒドロシリル化反応を生じる成分である。本発明の硬化性シリコーン樹脂組成物が（Ｄ）成分を含むことにより、硬化物の耐熱性、耐熱衝撃性、硫黄バリア性がさらに向上する場合がある。 [(D) component]
As described above, the component (D) in the curable silicone resin composition of the present invention may be a branched polyorganosiloxane having one or more alkenyl groups in the molecule (referred to as "component (D)". Yes). The component (D) in the curable silicone resin composition of the present invention is a component that causes a hydrosilylation reaction with a component having a hydrosilyl group (for example, the component (B) and the like) together with the component (A). When the curable silicone resin composition of the present invention contains the component (D), the heat resistance, thermal shock resistance and sulfur barrier properties of the cured product may be further improved.
（Ｄ）成分は、分子内に１個以上のアルケニル基を有し、なおかつ主鎖として－Ｓｉ－Ｏ－Ｓｉ－（シロキサン結合）を有し、シルアルキレン結合を有しない分岐鎖状のポリオルガノシロキサン（分岐状の主鎖を有するポリオルガノシロキサン）である。なお、（Ｄ）成分には、網目状等の三次元構造のポリオルガノシロキサンも含まれる。但し、（Ｄ）成分には、後述の（Ｆ）成分は含まれない。
The component (D) has one or more alkenyl groups in the molecule, and further has —Si—O—Si— (siloxane bond) as a main chain, and is a branched polyorgano having no silalkylene bond. Siloxane (polyorganosiloxane having a branched main chain). In addition, polyorganosiloxane of three-dimensional structures, such as mesh shape, is also contained in (D) component. However, the component (D) does not include the component (F) described later.
（Ｄ）成分が分子内に有するアルケニル基としては、上述の置換又は無置換アルケニル基が挙げられ、中でも、ビニル基が好ましい。また、（Ｄ）成分は、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。（Ｄ）成分が有するアルケニル基は、特に限定されないが、ケイ素原子に結合したものであることが好ましい。
As an alkenyl group which (D) component has in a molecule | numerator, the above-mentioned substituted or unsubstituted alkenyl group is mentioned, Especially, a vinyl group is preferable. The component (D) may have only one type of alkenyl group, or may have two or more types of alkenyl groups. The alkenyl group contained in the component (D) is not particularly limited, but is preferably bonded to a silicon atom.
（Ｄ）成分が分子内に有するアルケニル基の数は、１個以上であればよく、特に限定されないが、硬化性シリコーン樹脂組成物の硬化性の観点で、２個以上（例えば２～５０個）が好ましい。
The number of alkenyl groups that component (D) has in the molecule may be one or more, and is not particularly limited, but from the viewpoint of the curability of the curable silicone resin composition, two or more (for example, 2 to 50) Is preferred.
（Ｄ）成分が有するアルケニル基以外のケイ素原子に結合した基は、特に限定されないが、例えば、水素原子、有機基等が挙げられる。有機基としては、例えば、上述の有機基（例えば、アルキル基、シクロアルキル基、シクロアルキル－アルキル基、ハロゲン化炭化水素基等の置換又は無置換炭化水素等）及び上述のアリール基が挙げられる。
Although the group couple | bonded with silicon atoms other than the alkenyl group which (D) component has is not specifically limited, For example, a hydrogen atom, an organic group, etc. are mentioned. Examples of the organic group include the above-mentioned organic groups (for example, substituted or unsubstituted hydrocarbons such as alkyl group, cycloalkyl group, cycloalkyl-alkyl group, halogenated hydrocarbon group etc.) and the above-mentioned aryl group. .
また、（Ｄ）成分は、ケイ素原子に結合した基として、ヒドロキシ基、アルコキシ基を有していてもよい。
The component (D) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
（Ｄ）成分の性状は、特に限定されず、例えば２５℃において、液状であってもよいし、固体状であってもよい。
The property of the component (D) is not particularly limited, and may be liquid or solid at 25 ° C., for example.
（Ｄ）成分としては、下記平均単位式：
（Ｒ8ＳｉＯ3/2）d1（Ｒ8 2ＳｉＯ2/2）d2（Ｒ8 3ＳｉＯ1/2）d3（ＳｉＯ4/2）d4（Ｘ3Ｏ1/2）d5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、Ｒ8は、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、上述のアルケニル基、及び上述のアリール基が挙げられる。但し、Ｒ8の一部はアルケニル基（特にビニル基）であり、その割合は、分子内に１個以上（好ましくは２個以上）となる範囲に制御される。例えば、Ｒ8の全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、アルケニル基以外のＲ8としては、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。 As the component (D), the following average unit formula:
(R 8 SiO 3/2) d1 ( R 8 2 SiO 2/2) d2 (R 8 3SiO 1/2) d3 (SiO 4/2) d4 (X 3 O 1/2) d5
The polyorganosiloxane represented by is preferable. In the above average unit formula, R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl groups, and the above-mentioned aryl groups. However, a part of R 8 is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 8 is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R 8 other than an alkenyl group, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.
（Ｒ8ＳｉＯ3/2）d1（Ｒ8 2ＳｉＯ2/2）d2（Ｒ8 3ＳｉＯ1/2）d3（ＳｉＯ4/2）d4（Ｘ3Ｏ1/2）d5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、Ｒ8は、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、上述のアルケニル基、及び上述のアリール基が挙げられる。但し、Ｒ8の一部はアルケニル基（特にビニル基）であり、その割合は、分子内に１個以上（好ましくは２個以上）となる範囲に制御される。例えば、Ｒ8の全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、アルケニル基以外のＲ8としては、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。 As the component (D), the following average unit formula:
(R 8 SiO 3/2) d1 ( R 8 2 SiO 2/2) d2 (R 8 3
The polyorganosiloxane represented by is preferable. In the above average unit formula, R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl groups, and the above-mentioned aryl groups. However, a part of R 8 is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 8 is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R 8 other than an alkenyl group, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.
上記平均単位式中、Ｘ3は、上記Ｘ1aと同様、水素原子又はアルキル基である。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、ヘキシル基等が挙げられ、特にメチル基であることが好ましい。
In the above average unit formula, X 3 is a hydrogen atom or an alkyl group as in the case of X 1a above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.
上記平均単位式中、ｄ１は０又は正数、ｄ２は０又は正数、ｄ３は０又は正数、ｄ４は０又は正数、ｄ５は０又は正数であり、かつ、（ｄ１＋ｄ２＋ｄ３）及び（ｄ１＋ｄ４）がそれぞれ正数である。
In the above average unit formula, d1 is 0 or a positive number, d2 is 0 or a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is 0 or a positive number, and (d1 + d2 + d3) and Each of d1 + d4) is a positive number.
（Ｄ）成分の具体例としては、分子内に２個以上のアルケニル基を有し、ＲcＳｉＯ3/2で表されるシロキサン単位（Ｔ単位）を有する分岐鎖状ポリオルガノシロキサンが挙げられる。なお、Ｒcは、一価の置換又は無置換炭化水素基である。この分岐鎖状ポリオルガノシロキサンが有するアルケニル基としては、上述のアルケニル基の具体例が挙げられるが、中でもビニル基が好ましい。なお、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。また、上記分岐鎖状ポリオルガノシロキサンにおけるアルケニル基以外のケイ素原子に結合した基としては、例えば、上述の一価の置換又は無置換炭化水素基（アリール基も含まれる）が挙げられるが、中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。さらに、上記Ｔ単位中のＲcとしては、中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。
Specific examples of the component (D) include branched polyorganosiloxanes having two or more alkenyl groups in the molecule and having a siloxane unit (T unit) represented by R c SiO 3/2. . R c is a monovalent substituted or unsubstituted hydrocarbon group. Although the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this branched polyorganosiloxane has, Especially a vinyl group is preferable. In addition, it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Further, examples of the group bonded to a silicon atom other than the alkenyl group in the branched polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an aryl group), among which Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred. Furthermore, as R c in the T unit, among them, an alkyl group (especially methyl group) and an aryl group (especially phenyl group) are preferable.
上記分岐鎖状ポリオルガノシロキサンにおける、ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基の割合は、特に限定されないが、硬化性シリコーン樹脂組成物の硬化性の観点で、０．１～４０モル％が好ましい。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合は、特に限定されないが、２０～６０モル％が好ましい。さらに、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、特に限定されないが、５～７０モル％が好ましい。特に、上記分岐鎖状ポリオルガノシロキサンとして、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合が４０モル％以上（例えば、４５～６０モル％）であるものを使用することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合が３０モル％以上（例えば、３５～６０モル％）であるものを使用することにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The ratio of the alkenyl group to the total amount (100 mol%) of the group bonded to the silicon atom in the branched polyorganosiloxane is not particularly limited, but from the viewpoint of the curability of the curable silicone resin composition 0.1 -40 mol% is preferable. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but it is preferably 20 to 60 mol%. Further, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but preferably 5 to 70 mol%. In particular, the ratio of the aryl group (especially phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 40 mol% or more (for example, 45 to 60 mol%) as the branched polyorganosiloxane By using one, the sulfur barrier properties of the cured product tend to be further improved. In addition, a cured product is obtained by using a compound in which the ratio of alkyl groups (particularly methyl groups) to the total amount (100 mol%) of groups bonded to silicon atoms is 30 mol% or more (for example, 35 to 60 mol%). Thermal shock resistance tends to be further improved.
上記分岐鎖状ポリオルガノシロキサンは、ｄ１が正数である上記平均単位式で表すことができる。この場合、特に限定されないが、ｄ２／ｄ１は０～１０の数、ｄ３／ｄ１は０～０．５の数、ｄ４／（ｄ１＋ｄ２＋ｄ３＋ｄ４）は０～０．３の数、ｄ５／（ｄ１＋ｄ２＋ｄ３＋ｄ４）は０～０．４の数であることが好ましい。また、上記分岐鎖状ポリオルガノシロキサンの分子量は特に限定されないが、標準ポリスチレン換算の重量平均分子量が５００～１万であることが好ましく、より好ましくは７００～３０００である。
The branched polyorganosiloxane can be represented by the above average unit formula in which d1 is a positive number. In this case, although not particularly limited, d2 / d1 is a number from 0 to 10, d3 / d1 is a number from 0 to 0.5, d4 / (d1 + d2 + d3 + d4) is a number from 0 to 0.3, d5 / (d1 + d2 + d3 + d4) is It is preferable that it is a number of 0 to 0.4. The molecular weight of the branched polyorganosiloxane is not particularly limited, but the weight average molecular weight in terms of standard polystyrene is preferably 500 to 10,000, and more preferably 700 to 3,000.
なお、本発明の硬化性シリコーン樹脂組成物において（Ｄ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。
In addition, in the curable silicone resin composition of this invention, (D) component can also be used individually by 1 type, and can also be used in combination of 2 or more type.
本発明の硬化性シリコーン樹脂組成物における（Ｄ）成分の含有量（配合量）は、特に限定されないが、（Ａ）成分及び（Ｂ）成分の合計１００重量部に対して、５０～２００重量部が好ましく、より好ましくは７５～１７５重量部、さらに好ましくは１００～１５０重量部である。（Ｄ）成分の含有量を上記範囲に制御することにより、硬化物の耐熱衝撃性、硫黄バリア性、及び耐熱性がさらに向上する場合がある。
The content (blending amount) of the component (D) in the curable silicone resin composition of the present invention is not particularly limited, but 50 to 200 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B). It is preferably part, more preferably 75 to 175 parts by weight, still more preferably 100 to 150 parts by weight. By controlling the content of the component (D) in the above range, the thermal shock resistance, sulfur barrier properties, and heat resistance of the cured product may be further improved.
［（Ｅ）成分］
本発明の硬化性シリコーン樹脂組成物は、白金族金属を含むヒドロシリル化触媒（「（Ｅ）成分」と称する場合がある）を含んでいてもよい。即ち、（Ｅ）成分は、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、及び白金からなる群より選択される少なくとも１種の金属（白金族金属）を含むヒドロシリル化触媒である。本発明の硬化性シリコーン樹脂組成物が（Ｅ）成分を含むことにより、加熱により硬化性シリコーン樹脂組成物中のアルケニル基とヒドロシリル基の間のヒドロシリル化反応を効率的に進行させることができる。 [(E) ingredient]
The curable silicone resin composition of the present invention may contain a hydrosilylation catalyst (sometimes referred to as "(E) component") containing a platinum group metal. That is, the component (E) is a hydrosilylation catalyst containing at least one metal (platinum group metal) selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum. When the curable silicone resin composition of the present invention contains the component (E), the hydrosilylation reaction between the alkenyl group and the hydrosilyl group in the curable silicone resin composition can be efficiently advanced by heating.
本発明の硬化性シリコーン樹脂組成物は、白金族金属を含むヒドロシリル化触媒（「（Ｅ）成分」と称する場合がある）を含んでいてもよい。即ち、（Ｅ）成分は、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、及び白金からなる群より選択される少なくとも１種の金属（白金族金属）を含むヒドロシリル化触媒である。本発明の硬化性シリコーン樹脂組成物が（Ｅ）成分を含むことにより、加熱により硬化性シリコーン樹脂組成物中のアルケニル基とヒドロシリル基の間のヒドロシリル化反応を効率的に進行させることができる。 [(E) ingredient]
The curable silicone resin composition of the present invention may contain a hydrosilylation catalyst (sometimes referred to as "(E) component") containing a platinum group metal. That is, the component (E) is a hydrosilylation catalyst containing at least one metal (platinum group metal) selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum. When the curable silicone resin composition of the present invention contains the component (E), the hydrosilylation reaction between the alkenyl group and the hydrosilyl group in the curable silicone resin composition can be efficiently advanced by heating.
（Ｅ）成分としては、公知乃至慣用のヒドロシリル化触媒（例えば、白金系触媒、ロジウム系触媒、パラジウム系触媒等）を使用することができ、具体的には、白金微粉末、白金黒、白金担持シリカ微粉末、白金担持活性炭、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金のオレフィン錯体、白金－カルボニルビニルメチル錯体等の白金のカルボニル錯体、白金－ジビニルテトラメチルジシロキサン錯体や白金－シクロビニルメチルシロキサン錯体等の白金－ビニルメチルシロキサン錯体、白金－ホスフィン錯体、白金－ホスファイト錯体等の白金系触媒、並びに上記白金系触媒において白金原子の代わりにパラジウム原子又はロジウム原子を含有するパラジウム系触媒又はロジウム系触媒等が挙げられる。中でも、（Ｅ）成分としては、白金系触媒（白金を含むヒドロシリル化触媒）が好ましく、特に、白金－ビニルメチルシロキサン錯体や白金－カルボニルビニルメチル錯体や塩化白金酸とアルコール、アルデヒドとの錯体が、反応速度が良好であるため好ましい。
As component (E), known or commonly used hydrosilylation catalysts (for example, platinum-based catalysts, rhodium-based catalysts, palladium-based catalysts, etc.) can be used. Specifically, fine platinum powder, platinum black, platinum Supported fine silica powder, supported platinum platinum active carbon, chloroplatinic acid, complex of chloroplatinic acid with alcohol, aldehyde, ketone etc., olefin complex of platinum, carbonyl complex of platinum such as platinum-carbonylvinyl methyl complex etc, platinum-divinyl tetramethyl methyl complex Platinum-vinylmethylsiloxane complexes such as disiloxane complexes and platinum-cyclovinylmethylsiloxane complexes, platinum-based catalysts such as platinum-phosphine complexes and platinum-phosphite complexes, and palladium atoms or platinum atoms instead of platinum atoms in the above-mentioned platinum-based catalysts A palladium-based catalyst or a rhodium-based catalyst containing a rhodium atom may, for example, be mentioned. Among them, as the component (E), a platinum-based catalyst (hydrosilylation catalyst containing platinum) is preferable, and in particular, a platinum-vinylmethylsiloxane complex, a platinum-carbonylvinylmethyl complex, a complex of chloroplatinic acid with alcohol and aldehyde It is preferable because the reaction rate is good.
なお、本発明の硬化性シリコーン樹脂組成物において（Ｅ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。
In addition, in the curable silicone resin composition of this invention, (E) component can also be used individually by 1 type, and can also be used combining 2 or more types.
本発明の硬化性シリコーン樹脂組成物における（Ｅ）成分の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物に含まれるアルケニル基の全量１モル（１モル当たり）に対して、１×１０-8～１×１０-2モルが好ましく、より好ましくは１．０×１０-6～１．０×１０-3モルである。（Ｅ）成分の含有量を１×１０-8モル以上とすることにより、より効率的に硬化物を形成させることができる傾向がある。一方、（Ｅ）成分の含有量を１×１０-2モル以下とすることにより、より色相に優れた（着色の少ない）硬化物を得ることができる傾向がある。
The content (blending amount) of the component (E) in the curable silicone resin composition of the present invention is not particularly limited, but it is based on 1 mole (per mole) of the total amount of alkenyl groups contained in the curable silicone resin composition. The molar ratio is preferably 1 × 10 -8 to 1 × 10 -2 mol, more preferably 1.0 × 10 -6 to 1.0 × 10 -3 mol. By setting the content of the component (E) to 1 × 10 −8 mol or more, a cured product tends to be able to be formed more efficiently. On the other hand, by setting the content of the component (E) to 1 × 10 −2 mol or less, there is a tendency to be able to obtain a cured product which is more excellent in hue (less colored).
また、本発明の硬化性シリコーン樹脂組成物における（Ｅ）成分の含有量（配合量）は、特に限定されないが、例えば、ヒドロシリル化触媒中の白金族金属が重量単位で、０．０１～１０００ｐｐｍの範囲内となる量が好ましく、０．１～５００ｐｐｍの範囲内となる量がより好ましい。（Ｅ）成分の含有量がこのような範囲にあると、より効率的に硬化物を形成させることができ、また、より色相に優れた硬化物を得ることができる傾向がある。
Further, the content (blending amount) of the component (E) in the curable silicone resin composition of the present invention is not particularly limited, but, for example, 0.01 to 1000 ppm by weight of platinum group metal in the hydrosilylation catalyst Preferably, the amount is in the range of 0.1 to 500 ppm. When the content of the component (E) is in such a range, a cured product can be more efficiently formed, and a cured product having more excellent hue tends to be obtained.
［（Ｆ）成分］
本発明の硬化性シリコーン樹脂組成物は、分子内に１個以上のアルケニル基を有するラダー型ポリオルガノシルセスキオキサン（「（Ｆ）成分」と称する場合がある）を含んでいてもよい。本発明の硬化性シリコーン樹脂組成物が（Ｆ）成分を含むことにより、硬化物の硫黄バリア性（特に、ＳＯXバリア性）が著しく向上する傾向がある。（Ｆ）成分としては、分子内に１個以上（好ましくは２個以上）のアルケニル基を有し、ラダー構造の－Ｓｉ－Ｏ－Ｓｉ－骨格を有するポリオルガノシルセスキオキサンを使用することができ、特に限定されない。（Ｆ）成分の特に好ましい態様として、例えば、下記のラダー型ポリオルガノシルセスキオキサン（ａ）、ラダー型ポリオルガノシルセスキオキサン（ｂ）が挙げられる。但し、（Ｆ）成分は、以下のラダー型ポリオルガノシルセスキオキサンには限定されない。
・ラダー型ポリオルガノシルセスキオキサン（ａ）：分子内に２個以上のアルケニル基を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサン。
・ラダー型ポリオルガノシルセスキオキサン（ｂ）：ラダー構造を有するポリオルガノシルセスキオキサンの分子鎖末端の一部又は全部に、式（ＩＩＩ－３－１）で表される構成単位（Ｔ単位）及び式（ＩＩＩ－３－２）で表される構成単位（Ｍ単位）を含むポリオルガノシルセスキオキサン残基（「ポリオルガノシルセスキオキサン残基（Ｒ）」と称する場合がある）を有するラダー型ポリオルガノシルセスキオキサン。
[(F) component]
The curable silicone resin composition of the present invention may contain ladder-type polyorganosilsesquioxane (sometimes referred to as "component (F)") having one or more alkenyl groups in the molecule. When the curable silicone resin composition of the present invention contains the component (F), the sulfur barrier properties (in particular, the SO X barrier properties) of the cured product tend to be remarkably improved. As component (F), polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups in the molecule and having a ladder structure -Si-O-Si- skeleton There is no particular limitation. As a particularly preferable embodiment of the component (F), for example, the following ladder type polyorganosilsesquioxane (a) and ladder type polyorganosilsesquioxane (b) can be mentioned. However, the component (F) is not limited to the following ladder type polyorganosilsesquioxane.
-Ladder type polyorganosilsesquioxane (a): having two or more alkenyl groups in the molecule, having a number average molecular weight of 500 to 1,500 in terms of standard polystyrene equivalent by gel permeation chromatography, and a molecular weight dispersity (Mw / Ladder-type polyorganosilsesquioxane having a Mn of 1.00 to 1.40.
-Ladder-type polyorganosilsesquioxane (b): A structural unit (T-III) represented by the formula (III-3-1) in part or all of the molecular chain end of the polyorganosilsesquioxane having a ladder structure Unit) and a polyorganosilsesquioxane residue ("polyorganosilsesquioxane residue (R)") containing a constitutional unit (M unit) represented by the formula (III-3-2) Ladder-type polyorganosilsesquioxanes).
本発明の硬化性シリコーン樹脂組成物は、分子内に１個以上のアルケニル基を有するラダー型ポリオルガノシルセスキオキサン（「（Ｆ）成分」と称する場合がある）を含んでいてもよい。本発明の硬化性シリコーン樹脂組成物が（Ｆ）成分を含むことにより、硬化物の硫黄バリア性（特に、ＳＯXバリア性）が著しく向上する傾向がある。（Ｆ）成分としては、分子内に１個以上（好ましくは２個以上）のアルケニル基を有し、ラダー構造の－Ｓｉ－Ｏ－Ｓｉ－骨格を有するポリオルガノシルセスキオキサンを使用することができ、特に限定されない。（Ｆ）成分の特に好ましい態様として、例えば、下記のラダー型ポリオルガノシルセスキオキサン（ａ）、ラダー型ポリオルガノシルセスキオキサン（ｂ）が挙げられる。但し、（Ｆ）成分は、以下のラダー型ポリオルガノシルセスキオキサンには限定されない。
・ラダー型ポリオルガノシルセスキオキサン（ａ）：分子内に２個以上のアルケニル基を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサン。
・ラダー型ポリオルガノシルセスキオキサン（ｂ）：ラダー構造を有するポリオルガノシルセスキオキサンの分子鎖末端の一部又は全部に、式（ＩＩＩ－３－１）で表される構成単位（Ｔ単位）及び式（ＩＩＩ－３－２）で表される構成単位（Ｍ単位）を含むポリオルガノシルセスキオキサン残基（「ポリオルガノシルセスキオキサン残基（Ｒ）」と称する場合がある）を有するラダー型ポリオルガノシルセスキオキサン。
The curable silicone resin composition of the present invention may contain ladder-type polyorganosilsesquioxane (sometimes referred to as "component (F)") having one or more alkenyl groups in the molecule. When the curable silicone resin composition of the present invention contains the component (F), the sulfur barrier properties (in particular, the SO X barrier properties) of the cured product tend to be remarkably improved. As component (F), polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups in the molecule and having a ladder structure -Si-O-Si- skeleton There is no particular limitation. As a particularly preferable embodiment of the component (F), for example, the following ladder type polyorganosilsesquioxane (a) and ladder type polyorganosilsesquioxane (b) can be mentioned. However, the component (F) is not limited to the following ladder type polyorganosilsesquioxane.
-Ladder type polyorganosilsesquioxane (a): having two or more alkenyl groups in the molecule, having a number average molecular weight of 500 to 1,500 in terms of standard polystyrene equivalent by gel permeation chromatography, and a molecular weight dispersity (Mw / Ladder-type polyorganosilsesquioxane having a Mn of 1.00 to 1.40.
-Ladder-type polyorganosilsesquioxane (b): A structural unit (T-III) represented by the formula (III-3-1) in part or all of the molecular chain end of the polyorganosilsesquioxane having a ladder structure Unit) and a polyorganosilsesquioxane residue ("polyorganosilsesquioxane residue (R)") containing a constitutional unit (M unit) represented by the formula (III-3-2) Ladder-type polyorganosilsesquioxanes).
（Ｆ）成分はラダー構造を有するが、このことは、ＦＴ－ＩＲスペクトルにおいて１０５０ｃｍ-1付近（例えば、１０００～１１００ｃｍ-1）と１１５０ｃｍ-1付近（例えば、１１００ｃｍ-1を超え１２００ｃｍ-1以下）にそれぞれ固有吸収ピークを有する（即ち、１０００～１２００ｃｍ-1に少なくとも２本の吸収ピークを有する）ことから確認される［参考文献：Ｒ．Ｈ.Ｒａｎｅｙ， Ｍ．Ｉｔｏｈ， Ａ．Ｓａｋａｋｉｂａｒａ ａｎｄ Ｔ．Ｓｕｚｕｋｉ， Ｃｈｅｍ． Ｒｅｖ． ９５， １４０９（１９９５）］。なお、ＦＴ－ＩＲスペクトルは、例えば、下記の装置及び条件により測定することができる。
測定装置：商品名「ＦＴ－７２０」（（株）堀場製作所製）
測定方法：透過法
分解能：４ｃｍ-1
測定波数域：４００～４０００ｃｍ-1
積算回数：１６回 Component (F) has a ladder structure, this near 1050 cm -1 in the FT-IR spectrum (e.g., 1000 ~ 1100 cm -1) and 1150 cm -1 vicinity (e.g., 1200 cm -1 from more than 1100 cm -1 Each have an intrinsic absorption peak (ie, at least two absorption peaks at 1000 to 1200 cm.sup.- 1 ) [Ref. H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. The FT-IR spectrum can be measured, for example, by the following apparatus and conditions.
Measuring device: Brand name "FT-720" (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm -1
Measurement wave number range: 400 to 4000 cm -1
Accumulated number: 16 times
測定装置：商品名「ＦＴ－７２０」（（株）堀場製作所製）
測定方法：透過法
分解能：４ｃｍ-1
測定波数域：４００～４０００ｃｍ-1
積算回数：１６回 Component (F) has a ladder structure, this near 1050 cm -1 in the FT-IR spectrum (e.g., 1000 ~ 1100 cm -1) and 1150 cm -1 vicinity (e.g., 1200 cm -1 from more than 1100 cm -1 Each have an intrinsic absorption peak (ie, at least two absorption peaks at 1000 to 1200 cm.sup.- 1 ) [Ref. H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. The FT-IR spectrum can be measured, for example, by the following apparatus and conditions.
Measuring device: Brand name "FT-720" (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm -1
Measurement wave number range: 400 to 4000 cm -1
Accumulated number: 16 times
・ラダー型ポリオルガノシルセスキオキサン（ａ）
但し、ラダー型ポリオルガノシルセスキオキサン（ａ）は、ラダー構造に加えて、さらにカゴ構造やランダム構造等のその他のシルセスキオキサン構造を有するものであってもよい。 ・ Ladder type polyorganosilsesquioxane (a)
However, in addition to the ladder structure, the ladder type polyorganosilsesquioxane (a) may have another silsesquioxane structure such as a cage structure or a random structure.
但し、ラダー型ポリオルガノシルセスキオキサン（ａ）は、ラダー構造に加えて、さらにカゴ構造やランダム構造等のその他のシルセスキオキサン構造を有するものであってもよい。 ・ Ladder type polyorganosilsesquioxane (a)
However, in addition to the ladder structure, the ladder type polyorganosilsesquioxane (a) may have another silsesquioxane structure such as a cage structure or a random structure.
ラダー型ポリオルガノシルセスキオキサン（ａ）の、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量（Ｍｎ）は５００～１５００であり、好ましくは５５０～１４５０、より好ましくは６００～１４００である。Ｍｎが５００未満であると、例えば、硬化物の物性（耐熱性、硫黄バリア性等）が低下する傾向がある。一方、Ｍｎが１５００を超えると、室温で固体となりやすく、取り扱い性が低下する傾向がある。また、他の成分との相溶性が悪化する場合もある。
The number average molecular weight (Mn) in terms of standard polystyrene conversion by gel permeation chromatography of ladder-type polyorganosilsesquioxane (a) is 500 to 1,500, preferably 550 to 1450, more preferably 600 to 1400. . If the Mn is less than 500, for example, the physical properties (heat resistance, sulfur barrier property, etc.) of the cured product tend to be lowered. On the other hand, when Mn exceeds 1,500, it tends to be solid at room temperature, and the handleability tends to decrease. In addition, the compatibility with other components may be deteriorated.
ラダー型ポリオルガノシルセスキオキサン（ａ）の、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の分子量分散度（Ｍｗ／Ｍｎ）は１．００～１．４０であり、好ましくは１．３５以下（例えば、１．０５～１．３５）、より好ましくは１．３０以下（例えば、１．１０～１．３０）である。分子量分散度が１．４０を超えると、例えば、低分子シロキサンが増加し、硬化物の密着性や硫黄バリア性等が低下する傾向がある。一方、例えば、分子量分散度を１．０５以上とすることにより、室温で液体（液状）となりやすく、取り扱い性が向上する場合がある。
The molecular weight dispersion (Mw / Mn) in terms of standard polystyrene conversion by gel permeation chromatography of ladder-type polyorganosilsesquioxane (a) is 1.00 to 1.40, and preferably 1.35 or less (for example, 1.05 to 1.35), more preferably 1.30 or less (eg, 1.10 to 1.30). When the molecular weight dispersion degree exceeds 1.40, for example, low molecular weight siloxane tends to increase, and the adhesion of the cured product, the sulfur barrier property, and the like tend to be lowered. On the other hand, for example, by setting the molecular weight dispersion degree to 1.05 or more, the liquid (liquid) may be easily formed at room temperature, and the handleability may be improved.
なお、ラダー型ポリオルガノシルセスキオキサン（ａ）の数平均分子量、分子量分散度は、下記の装置及び条件により測定される。
測定装置：商品名「ＬＣ－２０ＡＤ」（（株）島津製作所製）
カラム：Ｓｈｏｄｅｘ ＫＦ－８０１×２本、ＫＦ－８０２、及びＫＦ－８０３（昭和電工（株）製）
測定温度：４０℃
溶離液：ＴＨＦ、試料濃度０．１～０．２重量％
流量：１ｍＬ／分
検出器：ＵＶ－ＶＩＳ検出器（商品名「ＳＰＤ－２０Ａ」、（株）島津製作所製）
分子量：標準ポリスチレン換算 In addition, the number average molecular weight of ladder-type polyorgano silsesquioxane (a) and molecular weight dispersion degree are measured by the following apparatus and conditions.
Measuring device: Brand name "LC-20AD" (manufactured by Shimadzu Corporation)
Column: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1 to 0.2% by weight
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene equivalent
測定装置：商品名「ＬＣ－２０ＡＤ」（（株）島津製作所製）
カラム：Ｓｈｏｄｅｘ ＫＦ－８０１×２本、ＫＦ－８０２、及びＫＦ－８０３（昭和電工（株）製）
測定温度：４０℃
溶離液：ＴＨＦ、試料濃度０．１～０．２重量％
流量：１ｍＬ／分
検出器：ＵＶ－ＶＩＳ検出器（商品名「ＳＰＤ－２０Ａ」、（株）島津製作所製）
分子量：標準ポリスチレン換算 In addition, the number average molecular weight of ladder-type polyorgano silsesquioxane (a) and molecular weight dispersion degree are measured by the following apparatus and conditions.
Measuring device: Brand name "LC-20AD" (manufactured by Shimadzu Corporation)
Column: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1 to 0.2% by weight
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene equivalent
ラダー型ポリオルガノシルセスキオキサン（ａ）の窒素雰囲気下における５％重量減少温度（Ｔd5）は、特に限定されないが、１５０℃以上が好ましく、より好ましくは２４０℃以上、さらに好ましくは２６０～５００℃、特に好ましくは２６２℃以上、最も好ましくは２６５℃以上である。５％重量減少温度が１５０℃以上（特に、２４０℃以上）であると、多様な用途において要求される耐熱性を満たしやすくなる傾向がある。なお、５％重量減少温度は、一定の昇温速度で加熱した時に加熱前の重量の５％が減少した時点での温度であり、耐熱性の指標となる。上記５％重量減少温度は、ＴＧＡ（熱重量分析）により、窒素雰囲気下、昇温速度２０℃／分の条件で測定される。
The 5% weight loss temperature (T d5 ) of the ladder type polyorganosilsesquioxane (a) in a nitrogen atmosphere is not particularly limited, but is preferably 150 ° C. or more, more preferably 240 ° C. or more, still more preferably 260 to The temperature is 500 ° C., particularly preferably 262 ° C. or more, and most preferably 265 ° C. or more. When the 5% weight loss temperature is 150 ° C. or higher (in particular, 240 ° C. or higher), the heat resistance required for various applications tends to be satisfied easily. The 5% weight loss temperature is the temperature at which 5% of the weight before heating decreases when heated at a constant temperature rising rate, and serves as an indicator of heat resistance. The 5% weight loss temperature is measured by TGA (thermogravimetric analysis) under a nitrogen atmosphere at a temperature rising rate of 20 ° C./minute.
ラダー型ポリオルガノシルセスキオキサン（ａ）は、特に限定されないが、室温（２５℃）で液体であることが好ましい。具体的には、その２５℃における粘度は、特に限定されないが、３００００Ｐａ・ｓ以下（例えば、１～３００００Ｐａ・ｓ）が好ましく、より好ましくは２５０００Ｐａ・ｓ以下、さらに好ましくは１００００Ｐａ・ｓ以下である。上記粘度は、粘度計（商品名「ＭＣＲ３０１」、アントンパール社製）を用いて、振り角５％、周波数０．１～１００（１／ｓ）、温度：２５℃の条件で測定される。
The ladder-type polyorganosilsesquioxane (a) is not particularly limited, but is preferably a liquid at room temperature (25 ° C.). Specifically, the viscosity at 25 ° C. is not particularly limited, but is preferably 30000 Pa · s or less (eg, 1 to 30000 Pa · s), more preferably 25000 Pa · s or less, still more preferably 10000 Pa · s or less . The viscosity is measured using a viscometer (trade name “MCR301”, manufactured by Anton Paar Co., Ltd.) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25 ° C.
ラダー型ポリオルガノシルセスキオキサン（ａ）としては、例えば、下記式（ＩＩＩ－２）で表され、かつ分子内に２個以上のアルケニル基を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量（Ｍｎ）が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサンが挙げられる。
The ladder-type polyorganosilsesquioxane (a) is, for example, represented by the following formula (III-2) and has two or more alkenyl groups in the molecule, and is converted to standard polystyrene by gel permeation chromatography And ladder-type polyorganosilsesquioxanes having a number average molecular weight (Mn) of 500 to 1,500 and a molecular weight dispersion degree (Mw / Mn) of 1.00 to 1.40.
上記式（ＩＩＩ－２）中、Ｒ42は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。Ｒ42の具体例としては、上述の一価の置換又は無置換炭化水素基（アルケニル基、アリール基も含まれる）が挙げられる。
In formula (III-2) above, R 42 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R 42 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including alkenyl and aryl groups).
ラダー型ポリオルガノシルセスキオキサン（ａ）は、Ｒ42としてアルケニル基を有していてもよいし、有していなくてもよい。ラダー型ポリオルガノシルセスキオキサン（ａ）は、上記式（ＩＩＩ－２）中のアルケニル基以外のＲ42として、アルキル基及びアリール基からなる群より選択された少なくとも１種の基を有することが好ましく、フェニル基及びメチル基からなる群より選択された少なくとも１種の基を有することがより好ましい。
The ladder-type polyorganosilsesquioxane (a) may or may not have an alkenyl group as R 42 . The ladder-type polyorganosilsesquioxane (a) has at least one group selected from the group consisting of an alkyl group and an aryl group as R 42 other than the alkenyl group in the above formula (III-2) Are preferred, and it is more preferred to have at least one group selected from the group consisting of phenyl and methyl.
ラダー型ポリオルガノシルセスキオキサン（ａ）の上記式（ＩＩＩ－２）におけるＲ42の全量（１００重量％）中の、フェニル基、ビニル基、及びメチル基の割合（合計含有量）は、特に限定されないが、５０～１００重量％が好ましく、より好ましくは７０～１００重量％、さらに好ましくは８０～１００重量％である。
The proportion (total content) of phenyl group, vinyl group and methyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) is Although not particularly limited, it is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 80 to 100% by weight.
ラダー型ポリオルガノシルセスキオキサン（ａ）の上記式（ＩＩＩ－２）におけるＲ42の全量（１００重量％）中の、フェニル基の割合（含有量）は、特に限定されないが、０～１００重量％が好ましく、より好ましくは１～１００重量％、さらに好ましくは５～１００重量％である。ラダー型ポリオルガノシルセスキオキサン（ａ）の上記式（ＩＩＩ－２）におけるＲ42の全量（１００重量％）中の、ビニル基の割合（含有量）は、特に限定されないが、０～１００重量％が好ましく、より好ましくは１～１００重量％、さらに好ましくは５～９０重量％、特に好ましくは１０～８０重量％である。ラダー型ポリオルガノシルセスキオキサン（ａ）の上記式（ＩＩＩ－２）におけるＲ42の全量（１００重量％）中の、メチル基の割合（含有量）は、特に限定されないが、０～１００重量％が好ましく、より好ましくは１～１００重量％、さらに好ましくは５～１００重量％である。
The proportion (content) of the phenyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of the ladder type polyorganosilsesquioxane (a) is not particularly limited, but it is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, and still more preferably 5 to 100% by weight. The proportion (content) of the vinyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) is not particularly limited, but it is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, still more preferably 5 to 90% by weight, and particularly preferably 10 to 80% by weight. The proportion (content) of methyl group in the total amount (100% by weight) of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) is not particularly limited, but it is 0 to 100 % By weight is preferable, more preferably 1 to 100% by weight, and still more preferably 5 to 100% by weight.
なお、ラダー型ポリオルガノシルセスキオキサン（ａ）の上記式（ＩＩＩ－２）におけるＲ42の組成（例えば、フェニル基、ビニル基、メチル基の割合等）は、例えば、ＮＭＲスペクトル（例えば、1Ｈ－ＮＭＲスペクトル）測定等により算出することができる。
The composition of R 42 in the above formula (III-2) of ladder type polyorganosilsesquioxane (a) (for example, the ratio of phenyl group, vinyl group, methyl group etc.) has, for example, an NMR spectrum (for example, 1 H-NMR spectrum can be calculated by measurement or the like.
上記式（ＩＩＩ－２）中、Ｒ43は、同一又は異なって、水素原子、アルキル基、下記式（ＩＩＩ－２－１）で表される一価の基、下記式（ＩＩＩ－２－２）で表される一価の基、又は、下記式（ＩＩＩ－２－３）で表される一価の基を示す。
In the above formula (III-2), R 43 's are the same or different and each represents a hydrogen atom, an alkyl group, a monovalent group represented by the following formula (III-2-1), a following formula (III-2-2) Or a monovalent group represented by the following formula (III-2-3).
上記式（ＩＩＩ－２－１）中、Ｒ44は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。Ｒ44の具体例としては、上述の一価の置換又は無置換炭化水素基（アルケニル基、アリール基も含まれる）が挙げられ、中でもアルキル基が好ましい。また、上記式（ＩＩＩ－２－１）中、Ｒ45は、同一又は異なって、一価の置換又は無置換炭化水素基である。Ｒ45の具体例としては、上述の一価の置換又は無置換炭化水素基（アルケニル基、アリール基も含まれる）が挙げられ、中でもアルキル基が好ましい。上記式（ＩＩＩ－２－１）中、ｎ１は、０以上の整数を示す。ｎ１としては、０～５が好ましく、より好ましくは０～３、さらに好ましくは０である。
In formula (III-2-1) above, R 44 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R 44 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including an alkenyl group and an aryl group), among which an alkyl group is preferable. In the above formula (III-2-1), R 45 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. Specific examples of R 45 include the above-mentioned monovalent substituted or unsubstituted hydrocarbon groups (including an alkenyl group and an aryl group), among which an alkyl group is preferable. In the above formula (III-2-1), n1 represents an integer of 0 or more. As n1, 0 to 5 is preferable, more preferably 0 to 3, and still more preferably 0.
上記式（ＩＩＩ－２－２）中、Ｒ44は、式（ＩＩＩ－２－１）におけるＲ44と同じく、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。Ｒ44としては、中でもアルキル基が好ましい。また、上記式（ＩＩＩ－２－２）中、Ｒ45は、式（ＩＩＩ－２－１）におけるＲ45と同じく、同一又は異なって、一価の置換又は無置換炭化水素基である。Ｒ45としては、中でもアルキル基が好ましい。上記式（ＩＩＩ－２－２）中、Ｒ46はアルケニル基であり、中でもビニル基が好ましい。また、上記式（ＩＩＩ－２－２）中、ｎ２は、０以上の整数を示す。ｎ２としては、０～５が好ましく、より好ましくは０～３、さらに好ましくは０である。
In the above formula (III-2-2), R 44 is the same as or different from R 44 in formula (III-2-1), and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group is there. Among them, an alkyl group is preferable as R 44 . Further, in the formula (III-2-2), R 45, like R 45 in formula (III-2-1), the same or different, it is a monovalent substituted or unsubstituted hydrocarbon group. Among them, an alkyl group is preferable as R 45 . In the above formula (III-2-2), R 46 is an alkenyl group, preferably a vinyl group. In the above formula (III-2-2), n2 represents an integer of 0 or more. As n 2, 0 to 5 is preferable, more preferably 0 to 3, and still more preferably 0.
上記式（ＩＩＩ－２－３）中、Ｒ44は、式（ＩＩＩ－２－１）におけるＲ44と同じく、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。Ｒ44としては、中でもアルキル基が好ましい。また、上記式（ＩＩＩ－２－３）中、Ｒ47は、同一又は異なって、一価の飽和脂肪族炭化水素基であり、例えば、アルキル基、シクロアルキル基等が挙げられるが、中でもアルキル基（特にメチル基）が好ましい。上記式（ＩＩＩ－２－３）中、ｎ３は、０以上の整数を示す。ｎ３としては、０～５が好ましく、より好ましくは０～３、さらに好ましくは０である。
In the above formula (III-2-3), R 44 is the same as or different from R 44 in formula (III-2-1), and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group is there. Among them, an alkyl group is preferable as R 44 . Further, in the above formula (III-2-3), R 47 is the same or different and is a monovalent saturated aliphatic hydrocarbon group, and examples thereof include an alkyl group and a cycloalkyl group. Groups (especially methyl groups) are preferred. In the above formula (III-2-3), n3 represents an integer of 0 or more. As n 3, 0 to 5 is preferable, more preferably 0 to 3 and still more preferably 0.
上記式（ＩＩＩ－２）中、ｎは０以上の整数を示す。上記ｎは、通常、０以上の偶数（例えば、２以上の偶数）である。上記ｎは、ラダー型ポリオルガノシルセスキオキサン（ａ）の数平均分子量が５００～１５００、分子量分散度が１．００～１．４０に制御される限り、特に限定されない。ラダー型ポリオルガノシルセスキオキサン（ａ）の分子量分散度が１．００を超える場合、該ラダー型ポリオルガノシルセスキオキサン（ａ）は、一般に、式（ＩＩＩ－２）で表されるポリオルガノシルセスキオキサンであってｎが異なる２種以上の混合物である。特に、ラダー型ポリオルガノシルセスキオキサン（ａ）は、ｎが１以上（特に２以上）の成分を必須成分として含有することが好ましい。
In the above formula (III-2), n represents an integer of 0 or more. The above n is usually an even number of 0 or more (for example, an even number of 2 or more). The above n is not particularly limited as long as the number average molecular weight of the ladder type polyorganosilsesquioxane (a) is controlled to 500 to 1,500 and the molecular weight dispersion degree is controlled to 1.00 to 1.40. When the molecular weight dispersion of the ladder-type polyorganosilsesquioxane (a) exceeds 1.00, the ladder-type polyorganosilsesquioxane (a) is generally a poly represented by the formula (III-2) It is an organosilsesquioxane, which is a mixture of two or more different n. In particular, the ladder-type polyorganosilsesquioxane (a) preferably contains a component in which n is 1 or more (particularly 2 or more) as an essential component.
ラダー型ポリオルガノシルセスキオキサン（ａ）は、分子内に２個以上のアルケニル基を有する。ラダー型ポリオルガノシルセスキオキサン（ａ）が有するアルケニル基としては、特にビニル基が好ましい。ラダー型ポリオルガノシルセスキオキサン（ａ）が式（ＩＩＩ－２）で表される場合、例えば、式（ＩＩＩ－２）におけるＲ42のいずれかがアルケニル基であるもの、Ｒ44及びＲ45のいずれかがアルケニル基である式（ＩＩＩ－２－１）で表される一価の基を有するもの、式（ＩＩＩ－２－２）で表される一価の基を有するもの、Ｒ44のいずれかがアルケニル基である式（ＩＩＩ－２－３）で表される一価の基を有するもの等が挙げられる。
The ladder-type polyorganosilsesquioxane (a) has two or more alkenyl groups in the molecule. Especially as a alkenyl group which ladder type polyorgano silsesquioxane (a) has, a vinyl group is preferable. When the ladder-type polyorganosilsesquioxane (a) is represented by the formula (III-2), for example, those in which any one of R 42 in the formula (III-2) is an alkenyl group, R 44 and R 45 Wherein R 44 has a monovalent group represented by the formula (III-2-1) in which any of the groups is an alkenyl group, one having a monovalent group represented by the formula (III-2-2), R 44 And the like, which have a monovalent group represented by the formula (III-2-3) in which any one of them is an alkenyl group, and the like.
ラダー型ポリオルガノシルセスキオキサン（ａ）は、周知慣用の方法により製造でき、特に限定されないが、例えば、特開平４－２８７２２号公報、特開２０１０－５１８１８２号公報、特開平５－３９３５７号公報、特開２００４－９９８７２号公報、国際公開第１９９７／００７１５６号、特開平１１－２４６６６２号公報、特開平９－２０８２６号公報、国際公開第２００６／０３３１４７号、特開２００５－２３９８２９号公報、国際公開第２０１３／１７６２３８号等の文献に開示された方法等により製造できる。
The ladder-type polyorganosilsesquioxane (a) can be produced by a well-known and commonly used method and is not particularly limited. For example, JP-A-4-28722, JP-A-2010-518182, JP-A-5-39357 Patent Publication Nos. 2004-99872, WO 1997/007156, JP 11-2466662, JP 9-20826, WO 2006/033147, JP 2005-239829, It can manufacture by the method etc. which were disclosed by documents, such as the international publication 2013/176238.
・ラダー型ポリオルガノシルセスキオキサン（ｂ）
ラダー型ポリオルガノシルセスキオキサン（ｂ）におけるラダー構造を有するポリオルガノシルセスキオキサンは、例えば、下記式（ＩＩＩ－３）で表される。
・ Ladder type polyorganosilsesquioxane (b)
The polyorganosilsesquioxane having a ladder structure in the ladder type polyorganosilsesquioxane (b) is represented, for example, by the following formula (III-3).
ラダー型ポリオルガノシルセスキオキサン（ｂ）におけるラダー構造を有するポリオルガノシルセスキオキサンは、例えば、下記式（ＩＩＩ－３）で表される。
The polyorganosilsesquioxane having a ladder structure in the ladder type polyorganosilsesquioxane (b) is represented, for example, by the following formula (III-3).
上記式（ＩＩＩ－３）において、ｐは１以上の整数（例えば、１～５０００）を示し、好ましくは１～２０００の整数、さらに好ましくは１～１０００の整数である。式（ＩＩＩ－３）中のＲ48は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。Ｔは末端基を示す。
In the above formula (III-3), p represents an integer of 1 or more (for example, 1 to 5000), preferably an integer of 1 to 2000, and more preferably an integer of 1 to 1000. R 48 in the formula (III-3) is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. T represents a terminal group.
ラダー型ポリオルガノシルセスキオキサン（ｂ）における上記ポリオルガノシルセスキオキサン中のケイ素原子に直接結合した基（例えば、式（ＩＩＩ－３）におけるＲ48）は、特に限定されないが、上記基の全量（１００モル％）に対する一価の置換若しくは無置換炭化水素基の占める割合が５０モル％以上であることが好ましく、より好ましくは８０モル％以上、さらに好ましくは９０モル％以上である。特に、上記基の全量（１００モル％）に対する、置換又は無置換のＣ1-10アルキル基（特に、メチル基、エチル基等のＣ1-4アルキル基）、置換又は無置換のＣ6-10アリール基（特に、フェニル基）、置換又は無置換のＣ7-10アラルキル基（特に、ベンジル基）の合計量が、５０モル％以上であることが好ましく、より好ましくは８０モル％以上、さらに好ましくは９０モル％以上である。
The group (for example, R 48 in the formula (III-3)) directly bonded to a silicon atom in the above polyorganosilsesquioxane in the ladder type polyorganosilsesquioxane (b) is not particularly limited, but the above group The ratio of the monovalent substituted or unsubstituted hydrocarbon group to the total amount (100 mol%) of is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more. In particular, a substituted or unsubstituted C 1-10 alkyl group (in particular, a C 1-4 alkyl group such as a methyl group or an ethyl group) relative to the total amount (100 mol%) of the above groups, a substituted or unsubstituted C 6- The total amount of 10 aryl groups (particularly, phenyl group) and substituted or unsubstituted C 7-10 aralkyl groups (especially benzyl group) is preferably 50 mol% or more, more preferably 80 mol% or more. More preferably, it is 90 mol% or more.
ラダー型ポリオルガノシルセスキオキサン（ｂ）は、上記ラダー構造を有するポリオルガノシルセスキオキサンの分子鎖末端の一部又は全部に、ポリオルガノシルセスキオキサン残基（Ｒ）を有する。上記ポリオルガノシルセスキオキサンが上記式（ＩＩＩ－３）で表される場合、ラダー型ポリオルガノシルセスキオキサン（ｂ）は、式（ＩＩＩ－３）中のＴの一部又は全部が上記ポリオルガノシルセスキオキサン残基（Ｒ）で置換されたものである。
The ladder-type polyorganosilsesquioxane (b) has a polyorganosilsesquioxane residue (R) at part or all of the molecular chain terminals of the polyorganosilsesquioxane having the above ladder structure. When the above polyorganosilsesquioxane is represented by the above formula (III-3), in ladder type polyorganosilsesquioxane (b), a part or all of T in the formula (III-3) is the above It is substituted with a polyorganosilsesquioxane residue (R).
上記ポリオルガノシルセスキオキサン残基（Ｒ）は、上述のように、式（ＩＩＩ－３－１）で表される構成単位及び式（ＩＩＩ－３－２）で表される構成単位を少なくとも含む残基である。
The polyorganosilsesquioxane residue (R) is, as described above, at least a constituent unit represented by the formula (III-3-1) and a constituent unit represented by the formula (III-3-2) It is the residue which contains.
上記式（ＩＩＩ－３－１）におけるＲ49は、アルケニル基を示す。上記アルケニル基としては、上述のアルケニル基の具体例が挙げられ、中でも、Ｃ2-10アルケニル基が好ましく、より好ましくはＣ2-4アルケニル基、さらに好ましくはビニル基である。
R 49 in the above formula (III-3-1) represents an alkenyl group. Specific examples of the above-mentioned alkenyl groups are given as the above-mentioned alkenyl group, and among them, a C 2-10 alkenyl group is preferable, a C 2-4 alkenyl group is more preferable, and a vinyl group is more preferable.
上記式（ＩＩＩ－３－２）中のＲ50は、同一又は異なって、一価の置換若しくは無置換炭化水素基を示す。上記置換若しくは無置換炭化水素基としては、上述の一価の置換又は無置換炭化水素基（アルケニル基、アリール基も含まれる）等が挙げられる。Ｒ50としては、中でもアルキル基が好ましく、より好ましくはＣ1-20アルキル基、さらに好ましくはＣ1-10アルキル基、特に好ましくはＣ1-4アルキル基、最も好ましくはメチル基である。特に、式（ＩＩＩ－３－２）中のＲ50がいずれもメチル基であることが好ましい。
R 50 in the above formula (III-3-2) is the same or different and represents a monovalent substituted or unsubstituted hydrocarbon group. As said substituted or unsubstituted hydrocarbon group, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (Alkenyl group, an aryl group is also included) etc. are mentioned. R 50 is preferably an alkyl group, more preferably a C 1-20 alkyl group, still more preferably a C 1-10 alkyl group, particularly preferably a C 1-4 alkyl group, and most preferably a methyl group. In particular, it is preferable that all of R 50 in the formula (III-3-2) be a methyl group.
上記ポリオルガノシルセスキオキサン残基（Ｒ）は、上記式（ＩＩＩ－３－１）で表される構成単位と上記式（ＩＩＩ－３－２）で表される構成単位以外にも、例えば、下記式（ＩＩＩ－３－１’）で表される構成単位を有していてもよい。
The polyorganosilsesquioxane residue (R) is not limited to the structural unit represented by the above formula (III-3-1) and the structural unit represented by the above formula (III-3-2), for example, And a structural unit represented by the following formula (III- 3 1 ′):
上記式（ＩＩＩ－３－１’）中のＲ49’は、アルケニル基を除く一価の基を示す。具体的には、例えば、水素原子、ハロゲン原子、アルケニル基を除く一価の有機基、一価の酸素原子含有基、一価の窒素原子含有基、又は一価の硫黄原子含有基等が挙げられる。
R 49 ′ in the above formula (III-3-1 ′) represents a monovalent group excluding an alkenyl group. Specific examples thereof include a hydrogen atom, a halogen atom, a monovalent organic group other than an alkenyl group, a monovalent oxygen atom-containing group, a monovalent nitrogen atom-containing group, and a monovalent sulfur atom-containing group. Be
上記ポリオルガノシルセスキオキサン残基（Ｒ）における式（ＩＩＩ－３－１）に表された３つの酸素原子が結合したケイ素原子の量は、特に限定されないが、ポリオルガノシルセスキオキサン残基（Ｒ）を構成するケイ素原子の全量（１００モル％）に対して、２０～８０モル％が好ましく、より好ましくは２５～６０モル％である。含有量が２０モル％未満であると、ラダー型ポリオルガノシルセスキオキサン（ｂ）が有するアルケニル基の量が不十分となって、硬化物の硬度が十分得られない場合がある。一方、含有量が８０モル％を超えると、ラダー型ポリオルガノシルセスキオキサン（ｂ）中にシラノール基や加水分解性シリル基が多く残存するため、ラダー型ポリオルガノシルセスキオキサン（ｂ）が液状で得られない場合がある。さらにラダー型ポリオルガノシルセスキオキサン（ｂ）間で縮合反応が進行して分子量が変化しやすくなるため、保存安定性が悪化する場合がある。
The amount of silicon atoms bonded to three oxygen atoms represented by the formula (III-3-1) in the above polyorganosilsesquioxane residue (R) is not particularly limited, but the polyorganosilsesquioxane residue is not particularly limited. The amount is preferably 20 to 80 mol%, more preferably 25 to 60 mol%, based on the total amount (100 mol%) of silicon atoms constituting the group (R). If the content is less than 20 mol%, the amount of the alkenyl group contained in the ladder-type polyorganosilsesquioxane (b) may be insufficient, and the hardness of the cured product may not be sufficiently obtained. On the other hand, when the content exceeds 80 mol%, a large number of silanol groups and hydrolyzable silyl groups remain in the ladder-type polyorganosilsesquioxane (b), so the ladder-type polyorganosilsesquioxane (b) May not be obtained in liquid form. Furthermore, since the condensation reaction proceeds between the ladder-type polyorganosilsesquioxane (b) and the molecular weight is easily changed, the storage stability may be deteriorated.
上記ポリオルガノシルセスキオキサン残基（Ｒ）における式（ＩＩＩ－３－２）に表された１つの酸素原子が結合したケイ素原子の量は、特に限定されないが、ポリオルガノシルセスキオキサン残基（Ｒ）を構成するケイ素原子の全量（１００モル％）に対して、２０～８５モル％が好ましく、より好ましくは３０～７５モル％である。含有量が２０モル％未満であると、ラダー型ポリオルガノシルセスキオキサン（ｂ）中にシラノール基や加水分解性シリル基が残存しやすく、ラダー型ポリオルガノシルセスキオキサン（ｂ）が液状で得られない場合がある。さらにラダー型ポリオルガノシルセスキオキサン（ｂ）間で縮合反応が進行して分子量が変化しやすくなるため、保存安定性が悪化する場合がある。一方、含有量が８５モル％を超えると、ラダー型ポリオルガノシルセスキオキサン（ｂ）が有するアルケニル基の量が不十分となって、硬化物の硬度が十分得られない場合がある。
The amount of silicon atom to which one oxygen atom represented by the formula (III-3-2) in the above polyorganosilsesquioxane residue (R) is bonded is not particularly limited, but the polyorganosilsesquioxane residue is The amount is preferably 20 to 85 mol%, more preferably 30 to 75 mol%, based on the total amount (100 mol%) of silicon atoms constituting the group (R). If the content is less than 20 mol%, silanol groups and hydrolyzable silyl groups easily remain in the ladder-type polyorganosilsesquioxane (b), and the ladder-type polyorganosilsesquioxane (b) is liquid May not be obtained at Furthermore, since the condensation reaction proceeds between the ladder-type polyorganosilsesquioxane (b) and the molecular weight is easily changed, the storage stability may be deteriorated. On the other hand, when the content exceeds 85 mol%, the amount of the alkenyl group of the ladder-type polyorganosilsesquioxane (b) may be insufficient, and the hardness of the cured product may not be sufficiently obtained.
上記ポリオルガノシルセスキオキサン残基（Ｒ）が有するＳｉ－Ｏ－Ｓｉ構造（骨格）としては、特に限定されず、例えば、ラダー構造、カゴ構造、ランダム構造等が挙げられる。
The Si-O-Si structure (skeleton) of the polyorganosilsesquioxane residue (R) is not particularly limited, and examples thereof include a ladder structure, a cage structure, and a random structure.
ラダー型ポリオルガノシルセスキオキサン（ｂ）は、例えば、下記式（ＩＩＩ－３’）で表すことができる。式（ＩＩＩ－３’）中のｐ、Ｒ48としては、上記式（ＩＩＩ－３）と同様のものが例示される。式（ＩＩＩ－３’）中のＡは、ポリオルガノシルセスキオキサン残基（Ｒ）、又は、ヒドロキシ基、ハロゲン原子、アルコキシ基、若しくはアシルオキシ基を示し、Ａの一部又は全部はポリオルガノシルセスキオキサン残基（Ｒ）である。４つのＡは、それぞれ同一であってもよいし、異なっていてもよい。なお、式（ＩＩＩ－３’）中の複数（２～４個）のＡがポリオルガノシルセスキオキサン残基（Ｒ）である場合、それぞれのＡは互いに又は他の式（ＩＩＩ－３’）で表される分子が有するＡと１以上のＳｉ－Ｏ－Ｓｉ結合を介して結合していてもよい。
The ladder type polyorganosilsesquioxane (b) can be represented, for example, by the following formula (III-3 ′). As p and R 48 in the formula (III-3 ′), those similar to the above formula (III-3) are exemplified. A in Formula (III-3 ′) represents a polyorganosilsesquioxane residue (R), or a hydroxy group, a halogen atom, an alkoxy group, or an acyloxy group, and a part or all of A is a polyorgano. It is a silsesquioxane residue (R). Four A may be identical to or different from each other. In the case where a plurality (2 to 4) of A in the formula (III-3 ′) is a polyorganosilsesquioxane residue (R), the respective A may be each other or may be other formula (III-3 ′) The molecule represented by) may be bonded to A via one or more Si-O-Si bonds.
ラダー型ポリオルガノシルセスキオキサン（ｂ）における、分子内のアルケニル基の数は１個以上であればよく、特に限定されないが、２個以上（例えば、２～５０個）が好ましく、より好ましくは２～３０個である。上述の範囲でアルケニル基を有することにより、耐熱性等の各種物性、耐クラック性、硫黄化合物に対するバリア性に優れた硬化物が得られやすい傾向がある。なお、アルケニル基の数は、例えば、1Ｈ－ＮＭＲスペクトル測定等により算出できる。
The number of alkenyl groups in the molecule in the ladder-type polyorganosilsesquioxane (b) is not particularly limited as long as it is one or more, and is preferably two or more (for example, 2 to 50), more preferably Is 2 to 30 pieces. By having an alkenyl group in the above-mentioned range, there is a tendency that a cured product excellent in various physical properties such as heat resistance and the like, crack resistance, and barrier property to a sulfur compound tends to be obtained. The number of alkenyl groups can be calculated, for example, by 1 H-NMR spectrum measurement or the like.
ラダー型ポリオルガノシルセスキオキサン（ｂ）中のアルケニル基の含有量は、特に限定されないが、０．７～５．５ｍｍｏｌ／ｇが好ましく、より好ましくは１．１～４．４ｍｍｏｌ／ｇである。また、ラダー型ポリオルガノシルセスキオキサン（ｂ）に含まれるアルケニル基の割合（重量基準）は、特に限定されないが、ビニル基換算で、２．０～１５．０重量％が好ましく、より好ましくは３．０～１２．０重量％である。
The content of the alkenyl group in the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 0.7 to 5.5 mmol / g, more preferably 1.1 to 4.4 mmol / g. is there. The proportion (by weight) of the alkenyl group contained in the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 2.0 to 15.0% by weight in terms of vinyl group, more preferably Is 3.0 to 12.0% by weight.
ラダー型ポリオルガノシルセスキオキサン（ｂ）の重量平均分子量（Ｍｗ）は、特に限定されないが、１００～８０万が好ましく、より好ましくは２００～１０万、さらに好ましくは３００～１万、特に好ましくは５００～８０００、最も好ましくは１７００～７０００である。Ｍｗが１００以上であると、硬化物の耐熱性が低下しにくい。一方、Ｍｗが８０万以下であると、他の成分との相溶性が低下しにくい。なお、上記Ｍｗは、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の分子量より算出される。
The weight average molecular weight (Mw) of the ladder type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 100 to 800,000, more preferably 200 to 100,000, still more preferably 300 to 10,000, particularly preferably Is from 500 to 8000, most preferably from 1700 to 7000. The heat resistance of hardened | cured material does not fall easily that Mw is 100 or more. On the other hand, when the Mw is 800,000 or less, the compatibility with other components does not easily decrease. In addition, said Mw is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.
ラダー型ポリオルガノシルセスキオキサン（ｂ）の数平均分子量（Ｍｎ）は、特に限定されないが、８０～８０万が好ましく、より好ましくは１５０～１０万、さらに好ましくは２５０～１万、特に好ましくは４００～８０００、最も好ましくは１５００～７０００である。Ｍｎが８０以上であると、硬化物の耐熱性が低下しにくい。一方、Ｍｎが８０万以下であると、他の成分との相溶性が低下しにくい。なお、上記Ｍｎは、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の分子量より算出される。
The number average molecular weight (Mn) of the ladder-type polyorganosilsesquioxane (b) is not particularly limited, but is preferably 800 to 800,000, more preferably 150 to 100,000, still more preferably 250 to 10,000, particularly preferably Is from 400 to 8000, most preferably from 1500 to 7000. The heat resistance of hardened | cured material does not fall easily that Mn is 80 or more. On the other hand, when Mn is 800,000 or less, the compatibility with other components is unlikely to decrease. In addition, said Mn is computed from the molecular weight of standard polystyrene conversion by gel permeation chromatography.
ラダー型ポリオルガノシルセスキオキサン（ｂ）は、常温（約２５℃）で液体であることが好ましい。より具体的には、その２３℃における粘度は、１００～１０万ｍＰａ・ｓが好ましく、より好ましくは５００～１万ｍＰａ・ｓ、さらに好ましくは１０００～８０００ｍＰａ・ｓである。粘度が１００ｍＰａ・ｓ以上であると、硬化物の耐熱性が低下しにくい。一方、粘度が１０万ｍＰａ・ｓ以下であると、硬化性シリコーン樹脂組成物の調製や取り扱いが容易である。なお、２３℃における粘度は、レオメーター（商品名「Ｐｈｙｓｉｃａ ＵＤＳ－２００」、Ａｎｔｏｎ Ｐａａｒ社製）とコーンプレート（円錐直径：１６ｍｍ、テーパ角度＝０°）を用いて、温度：２３℃、回転数：２０ｒｐｍの条件で測定することができる。
The ladder-type polyorganosilsesquioxane (b) is preferably liquid at normal temperature (about 25 ° C.). More specifically, the viscosity at 23 ° C. is preferably 100 to 100,000 mPa · s, more preferably 500 to 10,000 mPa · s, and still more preferably 1000 to 8000 mPa · s. The heat resistance of hardened | cured material does not fall easily that a viscosity is 100 mPa * s or more. On the other hand, when the viscosity is 100,000 mPa · s or less, preparation and handling of the curable silicone resin composition are easy. The viscosity at 23 ° C was measured using a rheometer (trade name "Physica UDS-200" manufactured by Anton Paar) and a cone plate (cone diameter: 16 mm, taper angle = 0 °) at a temperature of 23 ° C and rotation. Number: It can be measured under the condition of 20 rpm.
ラダー型ポリオルガノシルセスキオキサン（ｂ）の製造方法は、特に限定されないが、例えば、ラダー構造を有し、分子鎖末端にシラノール基及び／又は加水分解性シリル基（シラノール基及び加水分解性シリル基のいずれか一方又は両方）を有するポリオルガノシルセスキオキサンの分子鎖末端に対して、上記シルセスキオキサン残基（Ｒ）を形成する方法が挙げられる。具体的には、国際公開第２０１３／１７６２３８号等の文献に開示された方法等により製造できる。
The method for producing the ladder-type polyorganosilsesquioxane (b) is not particularly limited. For example, it has a ladder structure, and has a silanol group and / or a hydrolyzable silyl group (a silanol group and a hydrolyzable group at the molecular chain terminal) The method of forming the said silsesquioxane residue (R) with respect to the molecular chain terminal of the polyorgano silsesquioxane which has any one or both of silyl groups is mentioned. Specifically, it can be manufactured by the method disclosed in the document such as WO 2013/176238.
また、ラダー型ポリオルガノシルセスキオキサン（ａ）及び（ｂ）は、ケイ素原子に結合した基として、ヒドロキシ基、アルコキシ基を有していてもよい。
The ladder-type polyorganosilsesquioxane (a) and (b) may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
なお、本発明の硬化性シリコーン樹脂組成物において（Ｆ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。
In the curable silicone resin composition of the present invention, as the component (F), one type can be used alone, or two or more types can be used in combination.
本発明の硬化性シリコーン樹脂組成物は、硬化物の硫黄バリア性と強度（樹脂強度）の観点で、（Ｆ）成分を含むことが好ましく、より好ましくはラダー型ポリオルガノシルセスキオキサン（ａ）及び／又はラダー型ポリオルガノシルセスキオキサン（ｂ）を含むことである。
The curable silicone resin composition of the present invention preferably contains the component (F), more preferably a ladder-type polyorganosilsesquioxane (a), from the viewpoint of the sulfur barrier property and the strength (resin strength) of the cured product. And / or ladder type polyorganosilsesquioxane (b).
本発明の硬化性シリコーン樹脂組成物における（Ｆ）成分の含有量（配合量）は、特に限定されないが、（Ａ）成分及び（Ｂ）成分の合計１００重量部に対して、０．０１～５０重量部が好ましく、より好ましくは０．０１～４５重量部、さらに好ましくは０．０１～４０重量部である。また、特に限定されないが、上記（Ｆ）成分の含有量（配合量）は、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．１～２０重量％が好ましく、より好ましくは０．１～１５重量％、さらに好ましくは０．２～１０重量％である。上記（Ｆ）成分の含有量を上記範囲に制御することにより、硬化物の硫黄バリア性が著しく向上する傾向がある。
The content (blending amount) of the component (F) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 100 parts by weight in total of the components (A) and (B). The amount is preferably 50 parts by weight, more preferably 0.01 to 45 parts by weight, and still more preferably 0.01 to 40 parts by weight. Further, although not particularly limited, the content (blending amount) of the component (F) is preferably 0.1 to 20% by weight, more preferably 0 based on 100% by weight of the curable silicone resin composition. 1 to 15% by weight, more preferably 0.2 to 10% by weight. By controlling the content of the component (F) to the above range, the sulfur barrier property of the cured product tends to be significantly improved.
［（Ｇ）成分］
本発明の硬化性シリコーン樹脂組成物は、下記式（２）で表されるイソシアヌレート化合物（「（Ｇ）成分」と称する場合がある）を含んでいてもよい。本発明の硬化性シリコーン樹脂組成物が（Ｇ）成分を含む場合には、硬化物の被着体に対する密着性がいっそう向上し、さらに、硫黄バリア性がより高くなる傾向がある。
[(G) component]
The curable silicone resin composition of the present invention may contain an isocyanurate compound (sometimes referred to as "(G) component") represented by the following formula (2). When the curable silicone resin composition of the present invention contains the component (G), the adhesion of the cured product to the adherend is further improved, and the sulfur barrier property tends to be further enhanced.
本発明の硬化性シリコーン樹脂組成物は、下記式（２）で表されるイソシアヌレート化合物（「（Ｇ）成分」と称する場合がある）を含んでいてもよい。本発明の硬化性シリコーン樹脂組成物が（Ｇ）成分を含む場合には、硬化物の被着体に対する密着性がいっそう向上し、さらに、硫黄バリア性がより高くなる傾向がある。
The curable silicone resin composition of the present invention may contain an isocyanurate compound (sometimes referred to as "(G) component") represented by the following formula (2). When the curable silicone resin composition of the present invention contains the component (G), the adhesion of the cured product to the adherend is further improved, and the sulfur barrier property tends to be further enhanced.
式（２）中、Ｒf、Ｒg、及びＲhは、同一又は異なって、式（２ａ）で表される基、又は式（２ｂ）で表される基を示す。但し、Ｒf、Ｒg、及びＲhのうち少なくとも１個は、式（２ｂ）で表される基である。
In formula (2), R f , R g and R h are the same or different and each represents a group represented by formula (2a) or a group represented by formula (2b). However, at least one of R f , R g and R h is a group represented by formula (2b).
式（２ａ）中、Ｒiは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（直鎖若しくは分岐鎖状のＣ1-8アルキル基）を示す。直鎖若しくは分岐鎖状のＣ1-8アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基等が挙げられる。上記アルキル基の中でも、メチル基、エチル基、プロピル基、イソプロピル基等の直鎖若しくは分岐鎖状のＣ1-3アルキル基が好ましい。中でもＲiとしては、水素原子が特に好ましい。
In formula (2a), R i represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group). As a linear or branched C 1-8 alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned. Among the above alkyl groups, linear or branched C 1-3 alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group are preferable. Of these examples of R i, a hydrogen atom is particularly preferred.
なお、式（２）におけるＲf、Ｒg、及びＲhのうち２個が式（２ａ）で表される基である場合、これらの式（２ａ）で表される基は、同一であってもよいし、異なっていてもよい。また、イソシアヌレート化合物（Ｄ）は、式（２ａ）で表される基を有していなくてもよい。
When two of R f , R g and R h in the formula (2) are a group represented by the formula (2a), the groups represented by these formula (2a) are the same. It may be different or different. Moreover, the isocyanurate compound (D) may not have a group represented by Formula (2a).
式（２ｂ）中、Ｒjは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（直鎖若しくは分岐鎖状のＣ1-8アルキル基）を示す。直鎖若しくは分岐鎖状のＣ1-8アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、エチルヘキシル基等が挙げられる。上記アルキル基の中でも、メチル基、エチル基、プロピル基、イソプロピル基等の直鎖若しくは分岐鎖状のＣ1-3アルキル基が好ましい。中でもＲjとしては、水素原子が特に好ましい。
In the formula (2b), R j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (a linear or branched C 1-8 alkyl group). As a linear or branched C 1-8 alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, heptyl group, An octyl group, an ethylhexyl group etc. are mentioned. Among the above alkyl groups, linear or branched C 1-3 alkyl groups such as methyl group, ethyl group, propyl group and isopropyl group are preferable. Among them, a hydrogen atom is particularly preferable as R j .
なお、式（２）におけるＲf、Ｒg、及びＲhのうち２個又は３個が式（２ｂ）で表される基である場合、これらの式（２ｂ）で表される基は、同一であってもよいし、異なっていてもよい。
When two or three of R f , R g and R h in the formula (2) are a group represented by the formula (2b), the group represented by the formula (2b) is It may be the same or different.
（Ｇ）成分としては、例えば、式（２）におけるＲf、Ｒg、及びＲhのうち１個が式（２ｂ）で表される基である化合物（「モノアリルジグリシジルイソシアヌレート化合物」と称する場合がある）、式（２）におけるＲf、Ｒg、及びＲhのうち２個が式（２ｂ）で表される化合物（「ジアリルモノグリシジルイソシアヌレート化合物」と称する場合がある）、式（２）におけるＲf、Ｒg、及びＲhの全てが式（２ｂ）で表される化合物（「トリアリルイソシアヌレート化合物」と称する場合がある）が挙げられる。
As the component (G), for example, a compound in which one of R f , R g and R h in the formula (2) is a group represented by the formula (2b) (“monoallyl diglycidyl isocyanurate compound” Or a compound represented by the formula (2b) in which two of R f , R g and R h in the formula (2) are represented by the formula (2b) (sometimes referred to as “diallyl monoglycidyl isocyanurate compound”) And compounds in which all of R f , R g , and R h in Formula (2) are represented by Formula (2b) (sometimes referred to as “triallyl isocyanurate compound”).
上記モノアリルジグリシジルイソシアヌレート化合物としては、具体的には、例えば、モノアリルジグリシジルイソシアヌレート、１－アリル－３，５－ビス（２－メチルエポキシプロピル）イソシアヌレート、１－（２－メチルプロペニル）－３，５－ジグリシジルイソシアヌレート、１－（２－メチルプロペニル）－３，５－ビス（２－メチルエポキシプロピル）イソシアヌレート等が挙げられる。
Specific examples of the monoallyl diglycidyl isocyanurate compound include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2-methyl) Propenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methyl epoxypropyl) isocyanurate and the like.
上記ジアリルモノグリシジルイソシアヌレート化合物としては、具体的には、例えば、ジアリルモノグリシジルイソシアヌレート、１，３－ジアリル－５－（２－メチルエポキシプロピル）イソシアヌレート、１，３－ビス（２－メチルプロペニル）－５－グリシジルイソシアヌレート、１，３－ビス（２－メチルプロペニル）－５－（２－メチルエポキシプロピル）イソシアヌレート等が挙げられる。
Specific examples of the diallyl monoglycidyl isocyanurate compound include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, and 1,3-bis (2-methyl). Propenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methyl epoxypropyl) isocyanurate and the like.
上記トリアリルイソシアヌレート化合物としては、具体的には、例えば、トリアリルイソシアヌレート、トリス（２－メチルプロペニル）イソシアヌレート等が挙げられる。
Specific examples of the triallyl isocyanurate compound include triallyl isocyanurate, tris (2-methylpropenyl) isocyanurate and the like.
本発明の硬化性シリコーン樹脂組成物において（Ｇ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。なお、（Ｇ）成分は、例えば、市販品として入手することが可能である。
In the curable silicone resin composition of the present invention, as the component (G), one type can be used alone, or two or more types can be used in combination. Component (G) can be obtained, for example, as a commercial product.
（Ｇ）成分が式（２ａ）で表される基を有するものである場合は、例えば、アルコールや酸無水物等のエポキシ基と反応する化合物と反応させて、変性した上で使用することもできる。
When the component (G) has a group represented by the formula (2a), it may be used after being reacted with a compound that reacts with an epoxy group, such as alcohol or acid anhydride, for example. it can.
（Ｇ）成分は式（２ｂ）で表される基を有するため、例えば、ヒドロシリル基を有する化合物とあらかじめ反応（ヒドロシリル化反応）させた上で使用することもできる。例えば、上記モノアリルジグリシジルイソシアヌレート化合物と上述の（Ｆ）成分であるラダー型ポリオルガノシルセスキオキサンとをヒドロシリル化触媒の存在下で反応させたものを、本発明の硬化性シリコーン樹脂組成物の構成成分として使用することもできる。
Since the component (G) has a group represented by the formula (2b), for example, it can be used after being reacted (hydrosilylation reaction) with a compound having a hydrosilyl group in advance. For example, the curable silicone resin composition of the present invention is obtained by reacting the above monoallyl diglycidyl isocyanurate compound with ladder type polyorganosilsesquioxane which is the above-mentioned component (F) in the presence of a hydrosilylation catalyst. It can also be used as a component of an object.
（Ｇ）成分は、他の成分との相溶性を向上させる観点から、後述のように、（Ｈ）成分であるシランカップリング剤とあらかじめ混合してから、他の成分に配合することもできる。
From the viewpoint of improving the compatibility with other components, the component (G) can be mixed with the silane coupling agent which is the component (H) in advance, as described later, and then blended into the other components. .
本発明の硬化性シリコーン樹脂組成物における（Ｇ）成分の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～６重量％が好ましく、より好ましくは０．０５～４重量％、さらに好ましくは０．１～３重量％である。（Ｇ）成分の含有量を０．０１重量％以上とすることにより、硬化物の硫黄バリア性、被着体に対する密着性がより向上する傾向がある。一方、（Ｇ）成分の含有量を６重量％以下とすることにより、硬化性シリコーン樹脂組成物における固体析出の問題が抑制される傾向がある。
The content (blending amount) of the component (G) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 6% by weight with respect to the curable silicone resin composition (100% by weight) Is more preferably 0.05 to 4% by weight, still more preferably 0.1 to 3% by weight. By setting the content of the component (G) to 0.01% by weight or more, the sulfur barrier properties of the cured product and the adhesion to the adherend tend to be further improved. On the other hand, by setting the content of the component (G) to 6% by weight or less, the problem of solid precipitation in the curable silicone resin composition tends to be suppressed.
本発明の硬化性シリコーン樹脂組成物が（Ｇ）成分を含む場合、（Ｃ）成分と（Ｇ）成分の含有量の合計（合計含有量）は、特に限定されないが、硬化性シリコーン樹脂組成物に対して、０．０１～１５重量％が好ましく、より好ましくは０．１～１０重量％、さらに好ましくは０．２～３重量％、特に好ましくは０．４～２重量％である。上記合計含有量を０．０１重量％以上とすることにより、硬化物の硫黄バリア性が著しく向上する傾向がある。一方、上記合計含有量の含有量を１５重量％以下とすることにより、硬化性シリコーン樹脂組成物における固体析出の問題がより抑制される傾向がある。
When the curable silicone resin composition of the present invention contains the component (G), the total (total content) of the content of the components (C) and (G) is not particularly limited, but the curable silicone resin composition The amount is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 3% by weight, and particularly preferably 0.4 to 2% by weight. By setting the total content to 0.01% by weight or more, the sulfur barrier properties of the cured product tend to be remarkably improved. On the other hand, when the content of the total content is 15% by weight or less, the problem of solid precipitation in the curable silicone resin composition tends to be further suppressed.
［（Ｈ）成分］
本発明の硬化性シリコーン樹脂組成物は、シランカップリング剤（「（Ｈ）成分」と称する場合がある）を含んでいてもよい。本発明の硬化性シリコーン樹脂組成物が（Ｈ）成分を含むことにより、被着体に対する硬化物の密着性が向上する傾向がある。 [(H) component]
The curable silicone resin composition of the present invention may contain a silane coupling agent (sometimes referred to as "(H) component"). When the curable silicone resin composition of the present invention contains the component (H), the adhesion of the cured product to the adherend tends to be improved.
本発明の硬化性シリコーン樹脂組成物は、シランカップリング剤（「（Ｈ）成分」と称する場合がある）を含んでいてもよい。本発明の硬化性シリコーン樹脂組成物が（Ｈ）成分を含むことにより、被着体に対する硬化物の密着性が向上する傾向がある。 [(H) component]
The curable silicone resin composition of the present invention may contain a silane coupling agent (sometimes referred to as "(H) component"). When the curable silicone resin composition of the present invention contains the component (H), the adhesion of the cured product to the adherend tends to be improved.
（Ｈ）成分は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、（Ｆ）成分、及び（Ｇ）成分等との相溶性が良好であるため、例えば、（Ｇ）成分のその他成分に対する相溶性を向上させるために、あらかじめ（Ｇ）成分と（Ｈ）成分の組成物を形成した上で、その他成分と配合すると、均一な硬化性シリコーン樹脂組成物が得られやすい。
The component (H) has good compatibility with the components (A), (B), (C), (D), (F), (G), etc. In order to improve the compatibility of the G) component with other components, a composition of the (G) component and the (H) component is formed in advance and then blended with the other components to obtain a uniform curable silicone resin composition. It is easy to be
（Ｈ）成分としては、公知乃至慣用のシランカップリング剤を使用することができ、特に限定されないが、例えば、３－グリシドキシプロピルトリメトキシシラン、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－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン等のエポキシ基含有シランカップリング剤；Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩、Ｎ－（β－アミノエチル）－γ－アミノプロピルメチルジエトキシシラン等のアミノ基含有シランカップリング剤；テトラメトキシシラン、テトラエトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス（メトキシエトキシシラン）、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、ビニルトリアセトキシシラン、γ－（メタ）アクリロキシプロピルトリエトキシシラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン、γ－（メタ）アクリロキシプロピルメチルジメトキシシラン、γ－（メタ）アクリロキシプロピルメチルジエトキシシラン、メルカプトプロピレントリメトキシシラン、メルカプトプロピレントリエトキシシラン等が挙げられる。中でも、エポキシ基含有シランカップリング剤（特に、３－グリシドキシプロピルトリメトキシシラン）が好ましい。なお、（Ｈ）成分は１種を単独で、又は２種以上を組み合わせて使用することができる。
As the component (H), known or commonly used silane coupling agents can be used and are not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silane coupling agents such as trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-triethoxysilyl-N- (1,3-dimethyl-) Phenyl) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N- (β-aminoethyl) -γ -Amino group-containing silane coupling agents such as aminopropylmethyldiethoxysilane; tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (methoxyethoxysilane) ), Phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriacetoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxy B pills methyldimethoxysilane, .gamma. (meth) acryloxy propyl methyl diethoxy silane, mercapto propylene trimethoxysilane, and the like mercapto propylene triethoxysilane. Among them, epoxy group-containing silane coupling agents (in particular, 3-glycidoxypropyltrimethoxysilane) are preferable. In addition, (H) component can be used individually by 1 type or in combination of 2 or more types.
本発明の硬化性シリコーン樹脂組成物における（Ｈ）成分の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～１５重量％が好ましく、より好ましくは０．１～１０重量％、さらに好ましくは０．４～５重量％である。（Ｈ）成分の含有量を０．０１重量％以上とすることにより、被着体に対する密着性が向上し、特に、（Ｇ）成分を相溶させて使用する際に、硬化がより十分になりやすい。一方、（Ｈ）成分の含有量を１５重量％以下とすることにより、硬化が不十分となりにくく、硬化物の硫黄バリア性、耐熱衝撃性がより向上しやすい。
The content (blending amount) of the component (H) in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 15% by weight with respect to the curable silicone resin composition (100% by weight) Is more preferably 0.1 to 10% by weight, still more preferably 0.4 to 5% by weight. By setting the content of the component (H) to 0.01% by weight or more, the adhesion to the adherend is improved, and in particular, when the component (G) is used in a compatible manner, the curing is more sufficient. Prone. On the other hand, when the content of the component (H) is 15% by weight or less, curing is unlikely to be insufficient, and the sulfur barrier properties and thermal shock resistance of the cured product are more likely to be improved.
［（Ｉ）成分］
本発明の硬化性シリコーン樹脂組成物は、カルボン酸亜鉛、及び下記式（３）で表される亜鉛錯体又は亜鉛塩（但し、亜鉛ビスアセチルアセトナートを除く）からなる群から選ばれる少なくとも１種の亜鉛化合物（単に「（Ｉ）成分」と称する場合がある）を含有していてもよい。
［Ｚｎ（Ｌ１）（Ｌ２）］ （３）
［式中、Ｌ１及びＬ２は、同一又は異なって、下記式（３ａ）
Ｒ31ＣＯＣＨＲ32ＣＯＲ33 （３ａ）
で表される、β－ジケトン又はβ－ケトエステルのアニオン若しくはエノラートアニオンを示す］
なお、上記亜鉛ビスアセチルアセトナートは、ビス（２，４－ペンタンジオナト）亜鉛とも呼ばれる。 [(I) component]
The curable silicone resin composition of the present invention is at least one member selected from the group consisting of zinc carboxylate and a zinc complex or a zinc salt represented by the following formula (3) (with the exception of zinc bisacetylacetonate). Or a zinc compound of the formula (which may be referred to simply as "component (I)").
[Zn (L1) (L2)] (3)
[Wherein,L 1 and L 2 are the same or different and the following formula (3a)
R 31 COCHR 32 COR 33 (3a)
Represents an anion or enolate anion of β-diketone or β-ketoester represented by
The above zinc bisacetylacetonate is also referred to as bis (2,4-pentanedionato) zinc.
本発明の硬化性シリコーン樹脂組成物は、カルボン酸亜鉛、及び下記式（３）で表される亜鉛錯体又は亜鉛塩（但し、亜鉛ビスアセチルアセトナートを除く）からなる群から選ばれる少なくとも１種の亜鉛化合物（単に「（Ｉ）成分」と称する場合がある）を含有していてもよい。
［Ｚｎ（Ｌ１）（Ｌ２）］ （３）
［式中、Ｌ１及びＬ２は、同一又は異なって、下記式（３ａ）
Ｒ31ＣＯＣＨＲ32ＣＯＲ33 （３ａ）
で表される、β－ジケトン又はβ－ケトエステルのアニオン若しくはエノラートアニオンを示す］
なお、上記亜鉛ビスアセチルアセトナートは、ビス（２，４－ペンタンジオナト）亜鉛とも呼ばれる。 [(I) component]
The curable silicone resin composition of the present invention is at least one member selected from the group consisting of zinc carboxylate and a zinc complex or a zinc salt represented by the following formula (3) (with the exception of zinc bisacetylacetonate). Or a zinc compound of the formula (which may be referred to simply as "component (I)").
[Zn (L1) (L2)] (3)
[Wherein,
R 31 COCHR 32 COR 33 (3a)
Represents an anion or enolate anion of β-diketone or β-ketoester represented by
The above zinc bisacetylacetonate is also referred to as bis (2,4-pentanedionato) zinc.
本発明の硬化性樹脂組成物が上記（Ｉ）成分を含むことにより、特に、硫黄バリア性が向上する傾向がある。
また、本発明の硬化性シリコーン樹脂組成物は、（Ｉ）成分としての上記式（３）で表される亜鉛錯体又は亜鉛塩（但し、亜鉛ビスアセチルアセトナートを除く）の添加量を増やしてもシリコーン樹脂（特に、上記（Ａ）成分、（Ｂ）成分、（Ｄ）成分、（Ｆ）成分等）への溶解性が良く、添加することで硬化物としたときの硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性もより高くなる。 When the curable resin composition of the present invention contains the component (I), in particular, the sulfur barrier property tends to be improved.
In the curable silicone resin composition of the present invention, the amount of the zinc complex or zinc salt represented by the above formula (3) as component (I) (but excluding zinc bisacetylacetonate) is increased. Also, the solubility to silicone resins (especially, the above components (A), (B), (D), (F) components, etc.) is good, and the sulfur barrier property when it is made a cured product by adding it, especially not only barrier properties against hydrogen sulfide, barrier property even higher for SO X.
また、本発明の硬化性シリコーン樹脂組成物は、（Ｉ）成分としての上記式（３）で表される亜鉛錯体又は亜鉛塩（但し、亜鉛ビスアセチルアセトナートを除く）の添加量を増やしてもシリコーン樹脂（特に、上記（Ａ）成分、（Ｂ）成分、（Ｄ）成分、（Ｆ）成分等）への溶解性が良く、添加することで硬化物としたときの硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性もより高くなる。 When the curable resin composition of the present invention contains the component (I), in particular, the sulfur barrier property tends to be improved.
In the curable silicone resin composition of the present invention, the amount of the zinc complex or zinc salt represented by the above formula (3) as component (I) (but excluding zinc bisacetylacetonate) is increased. Also, the solubility to silicone resins (especially, the above components (A), (B), (D), (F) components, etc.) is good, and the sulfur barrier property when it is made a cured product by adding it, especially not only barrier properties against hydrogen sulfide, barrier property even higher for SO X.
（Ｉ）成分おけるカルボン酸亜鉛としては、例えば、ナフテン酸亜鉛、オクチル酸亜鉛、アセト酢酸亜鉛、亜鉛(メタ)アクリレート、亜鉛ネオデカネート等が挙げられ、ナフテン酸亜鉛、オクチル酸亜鉛が好ましく、オクチル酸亜鉛がより好ましい。
Examples of zinc carboxylates in component (I) include zinc naphthenate, zinc octylate, zinc acetoacetate, zinc (meth) acrylate, zinc neodecanate and the like, with zinc naphthenate and zinc octylate being preferred, and octylate Zinc is more preferred.
式（３ａ）中、Ｒ31は、置換若しくは無置換のＣ1-30アルキル基を示し、Ｃ1-30アルキル基としては、Ｃ1-20アルキル基が好ましく、Ｃ2-15アルキル基がより好ましく、Ｃ3-10アルキル基がさらに好ましく、分岐鎖を有するＣ3-10アルキル基が特に好ましい。分岐鎖を有するＣ3-10アルキル基としては、イソプロピル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、イソペンチル基、ｔ－ペンチル基、イソヘキシル基、ｔ－ヘキシル基、イソヘプチル基、ｔ－ヘプチル基、イソオクチル基、ｔ－オクチル基、２－エチルヘキシル基、イソノニル基、イソデシル基等が挙げられる。これらの基では、イソプロピル基、イソブチル基、ｔ－ブチル基、ｓ－ブチル基、イソペンチル基、ｔ－ペンチル基が最も好ましい。上記置換基としては、ハロゲン原子、ヒドロキシ基、カルボキシ基等が挙げられる。
In formula (3a), R 31 represents a substituted or unsubstituted C 1-30 alkyl group, and as the C 1-30 alkyl group, a C 1-20 alkyl group is preferable, and a C 2-15 alkyl group is more preferable. Preferably, a C 3-10 alkyl group is more preferable, and a branched C 3-10 alkyl group is particularly preferable. Examples of the branched C 3-10 alkyl group include isopropyl, isobutyl, t-butyl, s-butyl, isopentyl, t-pentyl, isohexyl, t-hexyl, isoheptyl, t- Examples include heptyl group, isooctyl group, t-octyl group, 2-ethylhexyl group, isononyl group, isodecyl group and the like. Among these groups, isopropyl, isobutyl, t-butyl, s-butyl, isopentyl and t-pentyl are most preferable. As said substituent, a halogen atom, a hydroxyl group, a carboxy group etc. are mentioned.
式（３ａ）中、Ｒ32は、水素原子、又は置換若しくは無置換のＣ1-30アルキル基を示し、Ｃ1-30アルキル基としては上記Ｒ31で挙げた基が好ましいが、Ｒ32において最も好ましい基は、水素原子である。上記置換基は、上記Ｒ31で挙げたものと同じである。
In formula (3a), R 32 represents a hydrogen atom or a substituted or unsubstituted C 1-30 alkyl group, and as the C 1-30 alkyl group, the groups mentioned above for R 31 are preferable, but in R 32 The most preferred group is a hydrogen atom. The above substituents are the same as those recited for R 31 above.
式（３ａ）中、Ｒ33は、置換若しくは無置換のＣ1-30アルキル基、置換若しくは無置換の芳香族複素環式基、又は－ＯＲ34基を示す。上記Ｒ34は、置換若しくは無置換のＣ1-30アルキル基を示す。これらのＣ1-30アルキル基としては、上記Ｒ31で挙げたものと同じ基が好ましい。上記芳香族複素環式基としては、例えば、ピリジル基、ピリミジニル基、ピラゾリル基、ピリダジニル基、ピラジニル基、トリアジニル基、フラニル基、チエニル基、インドリル基、オキサゾリル基、チアゾリル基、イミダゾリル基等が挙げられる。上記置換基は、上記Ｒ31で挙げたものと同じである。上記Ｒ31及びＲ32は、互いに結合して環を形成してもよく、上記Ｒ32及びＲ33は、互いに結合して環を形成してもよい。
In formula (3a), R 33 represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 34 group. R 34 represents a substituted or unsubstituted C 1-30 alkyl group. As these C 1-30 alkyl groups, the same groups as those mentioned above for R 31 are preferable. Examples of the aromatic heterocyclic group include pyridyl, pyrimidinyl, pyrazolyl, pyridazinyl, pyrazinyl, triazinyl, furanyl, thienyl, indolyl, oxazolyl, thiazolyl, imidazolyl and the like. Be The above substituents are the same as those recited for R 31 above. The R 31 and R 32 may be bonded to each other to form a ring, and the R 32 and R 33 may be bonded to each other to form a ring.
なお、上記式（３ａ）のβ－ジケトン又はβ－ケトエステルのアニオン若しくはエノラートアニオンにおける、アニオンは式（３ａ’）で表される構造であり、エノラートアニオンは式（３ａ"）で表される構造である。式（３ａ’）及び式（３ａ"）におけるＲ31、Ｒ32、及びＲ33は上記と同じである。
The anion in the anion or enolate anion of the β-diketone or β-keto ester of the above formula (3a) is a structure represented by the formula (3a ′), and the enolate anion is a structure represented by the formula (3a ′ ′) R 31 , R 32 and R 33 in the formula (3a ′) and the formula (3a ′ ′) are the same as above.
中でも（Ｉ）成分としては、以下の式（３’）で表される化合物が好ましい。
［式（３’）中、Ｒ35は、置換若しくは無置換のＣ1-30アルキル基を示し、Ｒ36は、水素原子、又は置換若しくは無置換のＣ1-30アルキル基を示し、Ｒ37は、置換若しくは無置換のＣ1-30アルキル基、置換若しくは無置換の芳香族複素環式基、又は－ＯＲ38基を示す。Ｒ38は、置換若しくは無置換のＣ1-30アルキル基を示す。Ｒ35及びＲ36は、互いに結合して環を形成してもよく、Ｒ36及びＲ37は、互いに結合して環を形成してもよい］
Among them, as the component (I), a compound represented by the following formula (3 ′) is preferable.
[In formula (3 '), R 35 represents a substituted or unsubstituted C 1-30 alkyl group, R 36 represents a hydrogen atom, or a substituted or unsubstituted C 1-30 alkyl group, R 37 Represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 38 group. R 38 represents a substituted or unsubstituted C 1-30 alkyl group. R 35 and R 36 may be bonded to each other to form a ring, and R 36 and R 37 may be bonded to each other to form a ring]
上記Ｒ35、Ｒ36、Ｒ37、及びＲ38における置換若しくは無置換のＣ1-30アルキル基のＣ1-30アルキル基としては、上記Ｒ31で挙げた基が好ましく、上記芳香族複素環式基は、上記Ｒ33で挙げたものと同じ基であり、上記置換基は、上記Ｒ31で挙げた基と同じである。
Examples of the R 35, R 36, R 37 , and C 1-30 alkyl substituted or unsubstituted C 1-30 alkyl group in R 38, the groups listed above R 31 is preferably the aromatic heterocyclic The formula group is the same group as that mentioned above for R 33 , and the above-mentioned substituent is the same as the group mentioned above for R 31 .
上記（Ｉ）成分としては、中でも下記式（３－１）で表される化合物［亜鉛ビス（２，２，７－トリメチル－３，５－オクタンジオナート）］、式（３－２）で表される化合物［Ｚｎ（ＤＰＭ）2：亜鉛ビスジピバロイルメタン］が特に好ましい。
As the component (I), a compound represented by the following formula (3-1) [zinc bis (2,2,7-trimethyl-3,5-octanedionate)] among others, a compound represented by the formula (3-2) The compound represented [Zn (DPM) 2 : zinc bis dipivaloyl methane] is particularly preferred.
本発明の硬化性シリコーン樹脂組成物において（Ｉ）成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。また、（Ｉ）成分としては、市販品を使用することもできる。
In the curable silicone resin composition of the present invention, as the component (I), one type can be used alone, or two or more types can be used in combination. Moreover, as a component (I), a commercial item can also be used.
本発明の硬化性シリコーン樹脂組成物における（Ｉ）成分の含有量（配合量）は、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～５重量％が好ましく、より好ましくは０．０５～３重量％、さらに好ましくは０．１～２重量％、特に好ましくは０．１～１．５重量％である。（Ｉ）成分の含有量を０．０１重量％以上とすることにより、硬化物の硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性もより向上し、５重量％以下とすることにより、硬化性シリコーン樹脂組成物において（Ｉ）成分に起因する固体の析出が抑制されやすくなる傾向がある。
The content (blending amount) of the component (I) in the curable silicone resin composition of the present invention is preferably 0.01 to 5% by weight, and more preferably, with respect to the curable silicone resin composition (100% by weight). Is preferably 0.05 to 3% by weight, more preferably 0.1 to 2% by weight, and particularly preferably 0.1 to 1.5% by weight. By setting the content of the component (I) to 0.01% by weight or more, not only the barrier property against sulfur of the cured product, especially to hydrogen sulfide, but also the barrier property against SO X is further improved, and 5% by weight By setting it as the following, precipitation of solid which originates in the (I) component in the curable silicone resin composition tends to be easily suppressed.
また、（Ｉ）成分の含有量（配合量）は、上記（Ａ）成分１００重量部に対して、０．０２～１０重量部が好ましく、より好ましくは０．０５～６重量部、さらに好ましくは０．１～４重量部、特に好ましくは０．１～３重量部である。（Ｉ）成分の含有量を０．０２重量部以上とすることにより、硬化物の硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性もより向上し、１０重量部以下とすることにより、（Ｉ）成分に起因する固体の析出が抑制されやすくなる傾向がある。
The content (blending amount) of the component (I) is preferably 0.02 to 10 parts by weight, more preferably 0.05 to 6 parts by weight, still more preferably 100 parts by weight of the component (A). Is 0.1 to 4 parts by weight, particularly preferably 0.1 to 3 parts by weight. By setting the content of the component (I) to not less than 0.02 parts by weight, not only the barrier property against sulfur of the cured product, especially to hydrogen sulfide, but also the barrier property against SO X is further improved, and 10 parts by weight By setting it as follows, there exists a tendency for precipitation of the solid resulting from (I) component to become easy to be suppressed.
［その他のポリオルガノシロキサン］
本発明の硬化性シリコーン樹脂組成物は、上述の（Ａ）成分、（Ｄ）成分、及び（Ｆ）成分以外にも、分子内にアルケニル基を有するその他のポリオルガノシロキサン（「その他のポリオルガノシロキサン」と称する場合がある）を含んでいてもよい。その他のポリオルガノシロキサンを含むことにより、硬化性シリコーン樹脂組成物の粘度を調整したり、硬化物の物性（例えば、機械物性）のバランスを調整することができる場合がある。 [Other polyorganosiloxanes]
The curable silicone resin composition of the present invention is not limited to the components (A), (D), and (F) described above, and other polyorganosiloxanes having an alkenyl group in the molecule ("Other polyorgano May be referred to as "siloxane". By containing other polyorganosiloxanes, it may be possible to adjust the viscosity of the curable silicone resin composition or to adjust the balance of physical properties (for example, mechanical properties) of the cured product.
本発明の硬化性シリコーン樹脂組成物は、上述の（Ａ）成分、（Ｄ）成分、及び（Ｆ）成分以外にも、分子内にアルケニル基を有するその他のポリオルガノシロキサン（「その他のポリオルガノシロキサン」と称する場合がある）を含んでいてもよい。その他のポリオルガノシロキサンを含むことにより、硬化性シリコーン樹脂組成物の粘度を調整したり、硬化物の物性（例えば、機械物性）のバランスを調整することができる場合がある。 [Other polyorganosiloxanes]
The curable silicone resin composition of the present invention is not limited to the components (A), (D), and (F) described above, and other polyorganosiloxanes having an alkenyl group in the molecule ("Other polyorgano May be referred to as "siloxane". By containing other polyorganosiloxanes, it may be possible to adjust the viscosity of the curable silicone resin composition or to adjust the balance of physical properties (for example, mechanical properties) of the cured product.
その他のポリオルガノシロキサンとしては、例えば、分子内に１個以上のアルケニル基を有する直鎖状ポリオルガノシロキサン（分子内に１個以上のアルケニル基を有し、主鎖としてシロキサン結合を有し、シルアルキレン結合を有しない直鎖状のポリオルガノシロキサン）等が挙げられる。
As other polyorganosiloxanes, for example, linear polyorganosiloxanes having one or more alkenyl groups in the molecule (having one or more alkenyl groups in the molecule, and having a siloxane bond as a main chain, And linear polyorganosiloxanes having no silalkylene bond.
本発明の硬化性シリコーン樹脂組成物において上記直鎖状ポリオルガノシロキサンは、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。
In the curable silicone resin composition of the present invention, the above linear polyorganosiloxanes can be used alone or in combination of two or more.
上記直鎖状ポリオルガノシロキサンが分子内に有するアルケニル基としては、上述の置換又は無置換アルケニル基が挙げられ、中でも、ビニル基が好ましい。また、上記直鎖状ポリオルガノシロキサンは、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。上記直鎖状ポリオルガノシロキサンが有するアルケニル基は、特に限定されないが、ケイ素原子に結合したものであることが好ましい。
As an alkenyl group which the said linear polyorganosiloxane has in a molecule | numerator, the above-mentioned substituted or unsubstituted alkenyl group is mentioned, Especially, a vinyl group is preferable. The linear polyorganosiloxane may have only one type of alkenyl group or may have two or more types of alkenyl groups. The alkenyl group contained in the linear polyorganosiloxane is not particularly limited, but is preferably one bonded to a silicon atom.
上記直鎖状ポリオルガノシロキサンが分子内に有するアルケニル基の数は１個以上であればよく、特に限定されないが、硬化性シリコーン樹脂組成物の硬化性の観点で、２個以上（例えば２～５０個）が好ましい。
The number of alkenyl groups which the above linear polyorganosiloxane has in the molecule may be one or more, and is not particularly limited. However, from the viewpoint of the curability of the curable silicone resin composition, two or more (for example, 2 to 50) is preferable.
上記直鎖状ポリオルガノシロキサンが有するアルケニル基以外のケイ素原子に結合した基は、特に限定されないが、例えば、水素原子、有機基等が挙げられる。有機基としては、例えば、上述の有機基（例えば、アルキル基、シクロアルキル基、シクロアルキル－アルキル基、ハロゲン化炭化水素基等の置換又は無置換炭化水素基等）及び上述のアリール基が挙げられる。
Although the group couple | bonded with silicon atoms other than the alkenyl group which the said linear polyorganosiloxane has is not specifically limited, For example, a hydrogen atom, an organic group, etc. are mentioned. Examples of the organic group include the above-mentioned organic groups (for example, substituted or unsubstituted hydrocarbon groups such as an alkyl group, a cycloalkyl group, a cycloalkyl-alkyl group, a halogenated hydrocarbon group, etc.) and the above-mentioned aryl group. Be
また、上記直鎖状ポリオルガノシロキサンは、ケイ素原子に結合した基として、ヒドロキシ基、アルコキシ基を有していてもよい。
The linear polyorganosiloxane may have a hydroxy group or an alkoxy group as a group bonded to a silicon atom.
上記直鎖状ポリオルガノシロキサンの性状は、特に限定されず、例えば２５℃において、液状であってもよいし、固体状であってもよい。
The properties of the linear polyorganosiloxane are not particularly limited, and may be liquid or solid at 25 ° C., for example.
上記直鎖状ポリオルガノシロキサンとしては、下記平均単位式：
（Ｒ4 2ＳｉＯ2/2）e1（Ｒ4 3ＳｉＯ1/2）e2（Ｘ4Ｏ1/2）e3
で表されるポリオルガノシロキサンが挙げられる。上記平均単位式中、Ｒ4は、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、上述のアルケニル基、及び上述のアリール基が挙げられる。但し、Ｒ4の一部はアルケニル基（特にビニル基）であり、その割合は、分子内に１個以上（好ましくは２個以上）となる範囲に制御される。例えば、Ｒ4の全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、アルケニル基以外のＲ4としては、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。 As said linear polyorganosiloxane, the following average unit formula:
(R 4 2 SiO 2/2) e1 (R 4 3SiO 1/2) e2 (X 4 O 1/2) e3
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R 4 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl groups, and the above-mentioned aryl groups. However, a part of R 4 is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 4 is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R 4 other than an alkenyl group, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.
（Ｒ4 2ＳｉＯ2/2）e1（Ｒ4 3ＳｉＯ1/2）e2（Ｘ4Ｏ1/2）e3
で表されるポリオルガノシロキサンが挙げられる。上記平均単位式中、Ｒ4は、同一又は異なって、一価の置換又は無置換炭化水素基であり、上述の一価の置換又は無置換炭化水素基の具体例（例えば、アルキル基、ハロゲン化炭化水素基等）、上述のアルケニル基、及び上述のアリール基が挙げられる。但し、Ｒ4の一部はアルケニル基（特にビニル基）であり、その割合は、分子内に１個以上（好ましくは２個以上）となる範囲に制御される。例えば、Ｒ4の全量（１００モル％）に対するアルケニル基の割合は、０．１～４０モル％が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、アルケニル基以外のＲ4としては、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。 As said linear polyorganosiloxane, the following average unit formula:
(R 4 2 SiO 2/2) e1 (R 4 3
The polyorganosiloxane represented by these is mentioned. In the above average unit formula, R 4 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and specific examples of the monovalent substituted or unsubstituted hydrocarbon group described above (eg, alkyl group, halogen And the above-mentioned alkenyl groups, and the above-mentioned aryl groups. However, a part of R 4 is an alkenyl group (in particular, a vinyl group), and the ratio thereof is controlled in a range of 1 or more (preferably 2 or more) in the molecule. For example, the proportion of the alkenyl group to the total amount (100 mol%) of R 4 is preferably 0.1 to 40 mol%. By controlling the proportion of the alkenyl group in the above range, the curability of the curable silicone resin composition tends to be further improved. In addition, as R 4 other than an alkenyl group, an alkyl group (in particular, a methyl group) and an aryl group (in particular, a phenyl group) are preferable.
上記平均単位式中、Ｘ4は、上記Ｘ1aと同様、水素原子又はアルキル基である。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、ヘキシル基等が挙げられ、特にメチル基であることが好ましい。
In the above average unit formula, X 4 is a hydrogen atom or an alkyl group as in the case of X 1a above. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and a methyl group is particularly preferable.
上記平均単位式中、ｅ１は正数、ｅ２は０又は正数、ｅ３は０又は正数である。
In the above average unit formula, e1 is a positive number, e2 is 0 or a positive number, and e3 is 0 or a positive number.
上記直鎖状ポリオルガノシロキサンの一例としては、例えば、分子内に２個以上のアルケニル基を有する直鎖状ポリオルガノシロキサンが挙げられる。この直鎖状ポリオルガノシロキサンが有するアルケニル基としては、上述のアルケニル基の具体例が挙げられるが、中でもビニル基が好ましい。なお、１種のみのアルケニル基を有するものであってもよいし、２種以上のアルケニル基を有するものであってもよい。また、上記直鎖状ポリオルガノシロキサンにおけるアルケニル基以外のケイ素原子に結合した基としては、例えば、上述の一価の置換又は無置換炭化水素基（アリール基も含まれる）が挙げられるが、中でも、アルキル基（特にメチル基）、アリール基（特にフェニル基）が好ましい。
As an example of the said linear polyorganosiloxane, the linear polyorganosiloxane which has a 2 or more alkenyl group in a molecule | numerator is mentioned, for example. Although the specific example of the above-mentioned alkenyl group is mentioned as an alkenyl group which this linear polyorganosiloxane has, Especially a vinyl group is preferable. In addition, it may have only 1 type of alkenyl group, and may have 2 or more types of alkenyl groups. Moreover, examples of the group bonded to a silicon atom other than the alkenyl group in the linear polyorganosiloxane include, for example, the above-mentioned monovalent substituted or unsubstituted hydrocarbon group (including an aryl group), among which Alkyl groups (especially methyl groups) and aryl groups (especially phenyl groups) are preferred.
上記直鎖状ポリオルガノシロキサンにおける、ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基の割合は、特に限定されないが、０．１～４０モル％が好ましい。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合は、特に限定されないが、１～２０モル％が好ましい。さらに、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合は、特に限定されないが、３０～９０モル％が好ましい。特に、上記直鎖状ポリオルガノシロキサンとして、ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（特にフェニル基）の割合が４０モル％以上（例えば、４５～８０モル％）であるものを使用することにより、硬化物の硫黄バリア性がより向上する傾向がある。また、ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（特にメチル基）の割合が９０モル％以上（例えば、９５～９９モル％）であるものを使用することにより、硬化物の耐熱衝撃性がより向上する傾向がある。
The proportion of the alkenyl group to the total amount (100 mol%) of the group bonded to the silicon atom in the linear polyorganosiloxane is not particularly limited, but preferably 0.1 to 40 mol%. Further, the ratio of the alkyl group (especially methyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but it is preferably 1 to 20 mol%. Further, the ratio of the aryl group (particularly phenyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is not particularly limited, but is preferably 30 to 90 mol%. In particular, the proportion of aryl groups (especially phenyl groups) relative to the total amount (100 mol%) of groups bonded to silicon atoms as the linear polyorganosiloxane is 40 mol% or more (for example, 45 to 80 mol%) By using one, the sulfur barrier properties of the cured product tend to be further improved. In addition, a cured product is obtained by using a compound in which the proportion of alkyl groups (especially methyl groups) is 90 mol% or more (for example, 95 to 99 mol%) with respect to the total amount (100 mol%) of groups bonded to silicon atoms. Thermal shock resistance tends to be further improved.
上記直鎖状ポリオルガノシロキサンは、例えば、下記式（ＩＶ－１）で表される。
［上記式中、Ｒ51は、同一又は異なって、一価の置換又は無置換炭化水素基である。但し、Ｒ51の少なくとも１個（好ましくは少なくとも２個）はアルケニル基である。ｍ３は、５～１０００の整数である。］
The linear polyorganosiloxane is represented, for example, by the following formula (IV-1).
[In the above-mentioned formulae, R 51 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least one (preferably at least two) of R 51 is an alkenyl group. m3 is an integer of 5 to 1000. ]
本発明の硬化性シリコーン樹脂組成物におけるその他のポリオルガノシロキサンの含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～３０重量％が好ましく、より好ましくは０．１～２０重量％である。その他のポリオルガノシロキサンの含有量を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の粘度や硬化物の物性のバランスの調整が可能となる場合がある。
The content (blending amount) of the other polyorganosiloxane in the curable silicone resin composition of the present invention is not particularly limited, but it is 0.01 to 30 wt% with respect to the curable silicone resin composition (100 wt%) % Is preferable, more preferably 0.1 to 20% by weight. By controlling the content of other polyorganosiloxanes in the above range, it may be possible to adjust the balance of the viscosity of the curable silicone resin composition and the physical properties of the cured product.
［ヒドロシリル化反応抑制剤］
本発明の硬化性シリコーン樹脂組成物は、硬化反応（ヒドロシリル化反応）の速度を調整するために、ヒドロシリル化反応抑制剤を含んでいてもよい。上記ヒドロシリル化反応抑制剤としては、公知乃至慣用のヒドロシリル化反応抑制剤を使用でき、特に限定されないが、例えば、３－メチル－１－ブチン－３－オール、３，５－ジメチル－１－ヘキシン－３－オール、フェニルブチノ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；チアゾール、ベンゾチアゾール、ベンゾトリアゾール等が挙げられる。上記ヒドロシリル化反応抑制剤は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。上記ヒドロシリル化反応抑制剤の含有量（配合量）は、硬化性シリコーン樹脂組成物の架橋条件等により異なるが、実用上、硬化性シリコーン樹脂組成物（１００重量％）に対する含有量として、０．００００１～５重量％の範囲内が好ましい。 [Hydrosilylation reaction inhibitor]
The curable silicone resin composition of the present invention may contain a hydrosilylation reaction inhibitor to adjust the rate of the curing reaction (hydrosilylation reaction). As the hydrosilylation reaction inhibitor, known or commonly used hydrosilylation reaction inhibitors can be used and are not particularly limited. For example, 3-methyl-1-butin-3-ol, 3,5-dimethyl-1-hexyne Alkyne alcohols such as -3-ol and phenylbutynol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexene-1-yne; thiazole, benzothiazole and benzotriazole Etc. The said hydrosilylation reaction inhibitor can also be used individually by 1 type, and can also be used in combination of 2 or more type. Although the content (blending amount) of the above hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the curable silicone resin composition and the like, practically it is 0. 0 as a content relative to the curable silicone resin composition (100% by weight). The range of 00001 to 5% by weight is preferable.
本発明の硬化性シリコーン樹脂組成物は、硬化反応（ヒドロシリル化反応）の速度を調整するために、ヒドロシリル化反応抑制剤を含んでいてもよい。上記ヒドロシリル化反応抑制剤としては、公知乃至慣用のヒドロシリル化反応抑制剤を使用でき、特に限定されないが、例えば、３－メチル－１－ブチン－３－オール、３，５－ジメチル－１－ヘキシン－３－オール、フェニルブチノ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；チアゾール、ベンゾチアゾール、ベンゾトリアゾール等が挙げられる。上記ヒドロシリル化反応抑制剤は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。上記ヒドロシリル化反応抑制剤の含有量（配合量）は、硬化性シリコーン樹脂組成物の架橋条件等により異なるが、実用上、硬化性シリコーン樹脂組成物（１００重量％）に対する含有量として、０．００００１～５重量％の範囲内が好ましい。 [Hydrosilylation reaction inhibitor]
The curable silicone resin composition of the present invention may contain a hydrosilylation reaction inhibitor to adjust the rate of the curing reaction (hydrosilylation reaction). As the hydrosilylation reaction inhibitor, known or commonly used hydrosilylation reaction inhibitors can be used and are not particularly limited. For example, 3-methyl-1-butin-3-ol, 3,5-dimethyl-1-hexyne Alkyne alcohols such as -3-ol and phenylbutynol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexene-1-yne; thiazole, benzothiazole and benzotriazole Etc. The said hydrosilylation reaction inhibitor can also be used individually by 1 type, and can also be used in combination of 2 or more type. Although the content (blending amount) of the above hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the curable silicone resin composition and the like, practically it is 0. 0 as a content relative to the curable silicone resin composition (100% by weight). The range of 00001 to 5% by weight is preferable.
［環状シロキサン］
本発明の硬化性シリコーン樹脂組成物は、上述のポリオルガノシロキサン（（Ａ）成分、（Ｂ）成分、（Ｄ）成分、（Ｆ）成分、その他のポリオルガノシロキサン）以外のシロキサン化合物として、例えば、分子内に２個以上の脂肪族炭素－炭素二重結合（特に、アルケニル基）を有する環状シロキサンを含んでいてもよい。また、本発明の硬化性シリコーン樹脂組成物は、上記シロキサン化合物として、分子内に２個以上のヒドロシリル基を有する環状シロキサンを含んでいてもよい。上記各環状シロキサンは１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。本発明の硬化性シリコーン樹脂組成物における上記環状シロキサンの含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～３０重量％が好ましく、より好ましくは０．１～２０重量％、さらに好ましくは０．５～１０重量％である。 [Cyclic siloxane]
The curable silicone resin composition of the present invention can be obtained, for example, as a siloxane compound other than the above-mentioned polyorganosiloxane (component (A), component (B), component (D), component (F), other polyorganosiloxanes). And cyclic siloxanes having two or more aliphatic carbon-carbon double bonds (in particular, alkenyl groups) in the molecule. Moreover, the curable silicone resin composition of this invention may contain the cyclic siloxane which has a 2 or more hydrosilyl group in a molecule | numerator as said siloxane compound. Each of the above cyclic siloxanes can be used alone or in combination of two or more. The content (compounding amount) of the above-mentioned cyclic siloxane in the curable silicone resin composition of the present invention is not particularly limited, but 0.01 to 30% by weight with respect to the curable silicone resin composition (100% by weight) Preferably, it is 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.
本発明の硬化性シリコーン樹脂組成物は、上述のポリオルガノシロキサン（（Ａ）成分、（Ｂ）成分、（Ｄ）成分、（Ｆ）成分、その他のポリオルガノシロキサン）以外のシロキサン化合物として、例えば、分子内に２個以上の脂肪族炭素－炭素二重結合（特に、アルケニル基）を有する環状シロキサンを含んでいてもよい。また、本発明の硬化性シリコーン樹脂組成物は、上記シロキサン化合物として、分子内に２個以上のヒドロシリル基を有する環状シロキサンを含んでいてもよい。上記各環状シロキサンは１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。本発明の硬化性シリコーン樹脂組成物における上記環状シロキサンの含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～３０重量％が好ましく、より好ましくは０．１～２０重量％、さらに好ましくは０．５～１０重量％である。 [Cyclic siloxane]
The curable silicone resin composition of the present invention can be obtained, for example, as a siloxane compound other than the above-mentioned polyorganosiloxane (component (A), component (B), component (D), component (F), other polyorganosiloxanes). And cyclic siloxanes having two or more aliphatic carbon-carbon double bonds (in particular, alkenyl groups) in the molecule. Moreover, the curable silicone resin composition of this invention may contain the cyclic siloxane which has a 2 or more hydrosilyl group in a molecule | numerator as said siloxane compound. Each of the above cyclic siloxanes can be used alone or in combination of two or more. The content (compounding amount) of the above-mentioned cyclic siloxane in the curable silicone resin composition of the present invention is not particularly limited, but 0.01 to 30% by weight with respect to the curable silicone resin composition (100% by weight) Preferably, it is 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.
［溶媒］
本発明の硬化性シリコーン樹脂組成物は溶媒を含んでいてもよい。溶媒としては、公知乃至慣用の有機溶媒や水等が挙げられ、特に限定されないが、例えば、トルエン、ヘキサン、イソプロパノール、メチルイソブチルケトン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。なお、溶媒は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。また、その含有量は特に限定されず、適宜選択できる。 [solvent]
The curable silicone resin composition of the present invention may contain a solvent. Examples of the solvent include known or commonly used organic solvents, water and the like, and not particularly limited, examples thereof include toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate and the like. In addition, a solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, the content is not specifically limited, It can select suitably.
本発明の硬化性シリコーン樹脂組成物は溶媒を含んでいてもよい。溶媒としては、公知乃至慣用の有機溶媒や水等が挙げられ、特に限定されないが、例えば、トルエン、ヘキサン、イソプロパノール、メチルイソブチルケトン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。なお、溶媒は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。また、その含有量は特に限定されず、適宜選択できる。 [solvent]
The curable silicone resin composition of the present invention may contain a solvent. Examples of the solvent include known or commonly used organic solvents, water and the like, and not particularly limited, examples thereof include toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate and the like. In addition, a solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type. Moreover, the content is not specifically limited, It can select suitably.
［蛍光体］
本発明の硬化性シリコーン樹脂組成物は蛍光体を含んでいてもよい。蛍光体としては、公知乃至慣用の蛍光体（例えば、光半導体装置分野で周知の蛍光体等）を使用することができ、特に限定されないが、例えば、青色光の白色光への変換機能を封止材に対して付与したい場合には、一般式Ａ3Ｂ5Ｏ12：Ｍ［式中、Ａは、Ｙ、Ｇｄ、Ｔｂ、Ｌａ、Ｌｕ、Ｓｅ、及びＳｍからなる群より選択された１種以上の元素を示し、Ｂは、Ａｌ、Ｇａ、及びＩｎからなる群より選択された１種以上の元素を示し、Ｍは、Ｃｅ、Ｐｒ、Ｅｕ、Ｃｒ、Ｎｄ、及びＥｒからなる群より選択された１種以上の元素を示す］で表されるＹＡＧ系の蛍光体微粒子（例えば、Ｙ3Ａｌ5Ｏ12：Ｃｅ蛍光体微粒子、（Ｙ，Ｇｄ，Ｔｂ）3（Ａｌ，Ｇａ）5Ｏ12：Ｃｅ蛍光体微粒子等）；シリケート系蛍光体微粒子（例えば、（Ｓｒ，Ｃａ，Ｂａ）2ＳｉＯ4：Ｅｕ等）等が挙げられる。なお、蛍光体は、周知慣用の表面処理がされたものであってもよい。また、蛍光体は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 [Phosphor]
The curable silicone resin composition of the present invention may contain a phosphor. As phosphors, known or commonly used phosphors (for example, phosphors known in the field of optical semiconductor devices etc.) can be used, and there is no particular limitation. For example, the conversion function of blue light to white light is sealed When it is desired to add to the stopper, a general formula A 3 B 5 O 12 : M, wherein A is selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm B represents a single or more elements selected from the group consisting of Al, Ga and In, and M represents a group consisting of Ce, Pr, Eu, Cr, Nd and Er Represents one or more selected elements] (for example, Y 3 Al 5 O 12 : Ce phosphor fine particles, (Y, Gd, Tb) 3 (Al, Ga) 5 O 12: Ce phosphor particles, etc.); based phosphor particles (e.g., (Sr, Ca Ba) 2 SiO 4: Eu, etc.), and the like. The phosphor may be one that has been subjected to well-known and commonly used surface treatment. Moreover, fluorescent substance can also be used individually by 1 type, and can also be used combining 2 or more types.
本発明の硬化性シリコーン樹脂組成物は蛍光体を含んでいてもよい。蛍光体としては、公知乃至慣用の蛍光体（例えば、光半導体装置分野で周知の蛍光体等）を使用することができ、特に限定されないが、例えば、青色光の白色光への変換機能を封止材に対して付与したい場合には、一般式Ａ3Ｂ5Ｏ12：Ｍ［式中、Ａは、Ｙ、Ｇｄ、Ｔｂ、Ｌａ、Ｌｕ、Ｓｅ、及びＳｍからなる群より選択された１種以上の元素を示し、Ｂは、Ａｌ、Ｇａ、及びＩｎからなる群より選択された１種以上の元素を示し、Ｍは、Ｃｅ、Ｐｒ、Ｅｕ、Ｃｒ、Ｎｄ、及びＥｒからなる群より選択された１種以上の元素を示す］で表されるＹＡＧ系の蛍光体微粒子（例えば、Ｙ3Ａｌ5Ｏ12：Ｃｅ蛍光体微粒子、（Ｙ，Ｇｄ，Ｔｂ）3（Ａｌ，Ｇａ）5Ｏ12：Ｃｅ蛍光体微粒子等）；シリケート系蛍光体微粒子（例えば、（Ｓｒ，Ｃａ，Ｂａ）2ＳｉＯ4：Ｅｕ等）等が挙げられる。なお、蛍光体は、周知慣用の表面処理がされたものであってもよい。また、蛍光体は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 [Phosphor]
The curable silicone resin composition of the present invention may contain a phosphor. As phosphors, known or commonly used phosphors (for example, phosphors known in the field of optical semiconductor devices etc.) can be used, and there is no particular limitation. For example, the conversion function of blue light to white light is sealed When it is desired to add to the stopper, a general formula A 3 B 5 O 12 : M, wherein A is selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm B represents a single or more elements selected from the group consisting of Al, Ga and In, and M represents a group consisting of Ce, Pr, Eu, Cr, Nd and Er Represents one or more selected elements] (for example, Y 3 Al 5 O 12 : Ce phosphor fine particles, (Y, Gd, Tb) 3 (Al, Ga) 5 O 12: Ce phosphor particles, etc.); based phosphor particles (e.g., (Sr, Ca Ba) 2 SiO 4: Eu, etc.), and the like. The phosphor may be one that has been subjected to well-known and commonly used surface treatment. Moreover, fluorescent substance can also be used individually by 1 type, and can also be used combining 2 or more types.
本発明の硬化性シリコーン樹脂組成物における蛍光体の含有量（配合量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～２０重量％が好ましく、より好ましくは０．５～１０重量％である。蛍光体を上記範囲で含有することにより、光半導体装置において封止材による光の波長変換機能を十分に発揮させることができ、なおかつ、硬化性シリコーン樹脂組成物の粘度が高くなり過ぎず、硬化物作製（特に、封止作業）時の作業性がより向上する傾向がある。
The content (blending amount) of the phosphor in the curable silicone resin composition of the present invention is not particularly limited, but is preferably 0.01 to 20% by weight with respect to the curable silicone resin composition (100% by weight). And more preferably 0.5 to 10% by weight. By containing the phosphor in the above range, the wavelength conversion function of light by the sealing material can be sufficiently exhibited in the optical semiconductor device, and the viscosity of the curable silicone resin composition does not become too high, and curing occurs. There is a tendency that the workability at the time of object preparation (in particular, sealing operation) is further improved.
［その他の成分］
本発明の硬化性シリコーン樹脂組成物は、上述の成分以外の成分（「その他の成分」と称する場合がある）を含んでいてもよい。その他の成分としては、特に限定されないが、例えば、シリカフィラー、酸化チタン、アルミナ、ガラス、石英、アルミノケイ酸、酸化鉄、酸化亜鉛、炭酸カルシウム、カーボンブラック、炭化ケイ素、窒化ケイ素、窒化ホウ素等の無機質充填剤、これらの充填剤をオルガノハロシラン、オルガノアルコキシシラン、オルガノシラザン等の有機ケイ素化合物により処理した無機質充填剤；シリコーン樹脂、エポキシ樹脂、フッ素樹脂等の有機樹脂微粉末；銀、銅等の導電性金属粉末等の充填剤、安定化剤（酸化防止剤、紫外線吸収剤、耐光安定剤、熱安定化剤等）、難燃剤（リン系難燃剤、ハロゲン系難燃剤、無機系難燃剤等）、難燃助剤、補強材（他の充填剤等）、核剤、シランカップリング剤以外のカップリング剤、滑剤、ワックス、可塑剤、離型剤、耐衝撃性改良剤、色相改良剤、流動性改良剤、着色剤（染料、顔料等）、表面調整剤（例えば、各種ポリエーテル変性シリコーン、ポリエステル変性シリコーン、フェニル変性シリコーン、アルキル変性シリコーン等の化合物）、分散剤、消泡剤、脱泡剤、抗菌剤、防腐剤、粘度調整剤、増粘剤、その他の機能性添加剤等の周知慣用の添加剤等が挙げられる。これらその他の成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。なお、その他の成分の含有量（配合量）は、特に限定されず、適宜選択することが可能である。 [Other ingredients]
The curable silicone resin composition of the present invention may contain components (sometimes referred to as "other components") other than the components described above. Other components are not particularly limited, and examples thereof include silica filler, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and the like. Inorganic fillers, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; fine powders of organic resins such as silicone resins, epoxy resins and fluorine resins; silver, copper, etc. Fillers such as conductive metal powders, stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants) Etc.), flame retardant aids, reinforcements (other fillers etc.), nucleating agents, coupling agents other than silane coupling agents, lubricants, waxes, Agents, mold release agents, impact modifiers, color modifiers, flow improvers, colorants (dyes, pigments etc.), surface conditioners (eg various polyether modified silicones, polyester modified silicones, phenyl modified silicones, Compounds such as alkyl-modified silicones, dispersants, antifoaming agents, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, and other well-known and commonly used additives such as functional additives . One of these other components may be used alone, or two or more thereof may be used in combination. In addition, content (blending quantity) of another component is not specifically limited, It is possible to select suitably.
本発明の硬化性シリコーン樹脂組成物は、上述の成分以外の成分（「その他の成分」と称する場合がある）を含んでいてもよい。その他の成分としては、特に限定されないが、例えば、シリカフィラー、酸化チタン、アルミナ、ガラス、石英、アルミノケイ酸、酸化鉄、酸化亜鉛、炭酸カルシウム、カーボンブラック、炭化ケイ素、窒化ケイ素、窒化ホウ素等の無機質充填剤、これらの充填剤をオルガノハロシラン、オルガノアルコキシシラン、オルガノシラザン等の有機ケイ素化合物により処理した無機質充填剤；シリコーン樹脂、エポキシ樹脂、フッ素樹脂等の有機樹脂微粉末；銀、銅等の導電性金属粉末等の充填剤、安定化剤（酸化防止剤、紫外線吸収剤、耐光安定剤、熱安定化剤等）、難燃剤（リン系難燃剤、ハロゲン系難燃剤、無機系難燃剤等）、難燃助剤、補強材（他の充填剤等）、核剤、シランカップリング剤以外のカップリング剤、滑剤、ワックス、可塑剤、離型剤、耐衝撃性改良剤、色相改良剤、流動性改良剤、着色剤（染料、顔料等）、表面調整剤（例えば、各種ポリエーテル変性シリコーン、ポリエステル変性シリコーン、フェニル変性シリコーン、アルキル変性シリコーン等の化合物）、分散剤、消泡剤、脱泡剤、抗菌剤、防腐剤、粘度調整剤、増粘剤、その他の機能性添加剤等の周知慣用の添加剤等が挙げられる。これらその他の成分は、１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。なお、その他の成分の含有量（配合量）は、特に限定されず、適宜選択することが可能である。 [Other ingredients]
The curable silicone resin composition of the present invention may contain components (sometimes referred to as "other components") other than the components described above. Other components are not particularly limited, and examples thereof include silica filler, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and the like. Inorganic fillers, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; fine powders of organic resins such as silicone resins, epoxy resins and fluorine resins; silver, copper, etc. Fillers such as conductive metal powders, stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants) Etc.), flame retardant aids, reinforcements (other fillers etc.), nucleating agents, coupling agents other than silane coupling agents, lubricants, waxes, Agents, mold release agents, impact modifiers, color modifiers, flow improvers, colorants (dyes, pigments etc.), surface conditioners (eg various polyether modified silicones, polyester modified silicones, phenyl modified silicones, Compounds such as alkyl-modified silicones, dispersants, antifoaming agents, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, and other well-known and commonly used additives such as functional additives . One of these other components may be used alone, or two or more thereof may be used in combination. In addition, content (blending quantity) of another component is not specifically limited, It is possible to select suitably.
本発明の硬化性シリコーン樹脂組成物は、特に限定されないが、硬化性シリコーン樹脂組成物中に存在するヒドロシリル基１モルに対して、アルケニル基が０．２～４モルとなるような組成（配合組成）であることが好ましく、より好ましくは０．５～１．５モル、さらに好ましくは０．８～１．２モルである。ヒドロシリル基とアルケニル基との割合を上記範囲に制御することにより、硬化物の耐熱衝撃性、硫黄バリア性がいっそう向上する傾向がある。
The curable silicone resin composition of the present invention is not particularly limited, but the composition is such that 0.2 to 4 moles of alkenyl groups are contained with respect to 1 mole of hydrosilyl groups present in the curable silicone resin composition Preferably, the composition is 0.5 to 1.5 moles, and more preferably 0.8 to 1.2 moles. By controlling the ratio of the hydrosilyl group to the alkenyl group in the above range, the thermal shock resistance and sulfur barrier properties of the cured product tend to be further improved.
本発明の硬化性シリコーン樹脂組成物に含まれる（Ａ）成分、（Ｂ）成分、（Ｄ）成分、（Ｆ）成分、及びその他のポリオルガノシロキサンの総量（総含有量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、７０重量％以上（例えば、７０重量％以上１００重量％未満）が好ましく、より好ましくは８０重量％以上（例えば、８０～９９重量％）、さらに好ましくは９０重量％以上（例えば、９０～９９重量％）である。上記総量を７０重量％以上とすることにより、硬化物の耐熱性、透明性がより向上する傾向がある。
The total amount (total content) of the component (A), the component (B), the component (D), the component (F) and the other polyorganosiloxanes contained in the curable silicone resin composition of the present invention is not particularly limited. Is preferably 70% by weight or more (eg, 70% by weight or more and less than 100% by weight), more preferably 80% by weight or more (eg, 80 to 99% by weight) based on 100% by weight of the curable silicone resin composition. %, More preferably 90% by weight or more (eg, 90 to 99% by weight). By setting the total amount to 70% by weight or more, the heat resistance and the transparency of the cured product tend to be further improved.
本発明の硬化性シリコーン樹脂組成物に含まれる（Ａ）成分、（Ｄ）成分、（Ｆ）成分、及びその他のポリオルガノシロキサンの総量（総含有量）は、特に限定されないが、硬化性シリコーン樹脂組成物（１００重量％）に対して、４０～９０重量％が好ましく、より好ましくは５０～８５重量％、さらに好ましくは６０～８０重量％である。上記総量を４０重量％以上とすることにより、硬化物の耐久性、透明性がより向上する傾向がある。一方、上記総量を９０重量％以下とすることにより、硬化性がより向上する傾向がある。
Although the total amount (total content) of the (A) component, the (D) component, the (F) component, and the other polyorganosiloxanes contained in the curable silicone resin composition of the present invention is not particularly limited, the curable silicone resin The amount is preferably 40 to 90% by weight, more preferably 50 to 85% by weight, and still more preferably 60 to 80% by weight, based on 100% by weight of the resin composition. By setting the total amount to 40% by weight or more, the durability and the transparency of the cured product tend to be further improved. On the other hand, when the total amount is 90% by weight or less, the curability tends to be further improved.
本発明の硬化性シリコーン樹脂組成物における（Ｂ）成分の含有量（配合量）は、特に限定されないが、（Ａ）成分、（Ｄ）成分、（Ｆ）成分、及びその他のポリオルガノシロキサンの総量（総含有量）１００重量部に対して、１～２００重量部が好ましい。（Ｂ）成分の含有量を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上し、効率的に硬化物を形成することができる傾向がある。
Although the content (blending amount) of the component (B) in the curable silicone resin composition of the present invention is not particularly limited, the content of the components (A), (D), (F), and other polyorganosiloxanes is not particularly limited. The amount is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total amount (total content). By controlling the content of the component (B) in the above range, the curability of the curable silicone resin composition tends to be further improved, and a cured product can be efficiently formed.
本発明の硬化性シリコーン樹脂組成物に含まれる（Ａ）成分、（Ｄ）成分、（Ｆ）成分、及びその他のポリオルガノシロキサンの総量（総含有量；１００重量％）に対する（Ａ）成分の割合は、特に限定されないが、１０重量％以上（例えば、１０～１００重量％）が好ましく、より好ましくは１５重量％以上（例えば、１５～９０重量％）、さらに好ましくは２０重量％以上（例えば、２０～８０重量％）である。上記割合を１０重量％以上とすることにより、硬化物の耐熱衝撃性がより向上し、また、タックが低減される傾向がある。
Component (A) relative to the total amount (total content; 100% by weight) of component (A), component (D), component (F) and other polyorganosiloxanes contained in the curable silicone resin composition of the present invention The proportion is not particularly limited, but is preferably 10% by weight or more (eg, 10 to 100% by weight), more preferably 15% by weight or more (eg, 15 to 90% by weight), and still more preferably 20% by weight or more (eg, , 20-80% by weight). By setting the ratio to 10% by weight or more, the thermal shock resistance of the cured product is further improved, and the tack tends to be reduced.
本発明の硬化性シリコーン樹脂組成物に含まれる（Ａ）成分、（Ｄ）成分、（Ｆ）成分、及びその他のポリオルガノシロキサンの総量（総含有量；１００重量％）に対する、（Ｄ）成分と（Ｆ）成分の割合（合計割合）は、特に限定されないが、０重量％を超えて９０重量％が好ましく、より好ましくは５～８５重量％、さらに好ましくは１０～８０重量％である。上記割合を９０重量％以下とすることにより、相対的に（Ａ）成分を増量できるため、硬化物の耐熱衝撃性がより向上し、また、タックが低減される場合がある。一方、例えば、上記割合を１０重量％以上とすることにより、硬化物の機械特性や光学特性等のバランスがより良好となる場合がある。
Component (D) based on the total amount (total content; 100% by weight) of components (A), (D), (F) and other polyorganosiloxanes contained in the curable silicone resin composition of the present invention The proportion (total proportion) of component (F) is not particularly limited, but it is preferably more than 0% by weight and 90% by weight, more preferably 5 to 85% by weight, and still more preferably 10 to 80% by weight. By setting the ratio to 90% by weight or less, the component (A) can be relatively increased, so the thermal shock resistance of the cured product may be further improved, and the tack may be reduced. On the other hand, for example, by setting the ratio to 10% by weight or more, the balance of the mechanical properties and the optical properties of the cured product may be better.
本発明の硬化性シリコーン樹脂組成物に含まれる（Ａ）成分、（Ｂ）成分、（Ｄ）成分、（Ｆ）成分、及びその他のポリオルガノシロキサンの総量（総含有量；１００重量％）に対する、（Ａ）成分の割合は、特に限定されないが、５重量％以上（例えば、５～１００重量％）が好ましく、より好ましくは１０重量％以上、さらに好ましくは１５～５０重量％である。上記割合を５重量％以上とすることにより、硬化物のタックがより低減し、耐熱衝撃性が良好となる傾向がある。
Component (A), (B), (D), (F), and other polyorganosiloxanes in the curable silicone resin composition of the present invention relative to the total amount (total content: 100% by weight) The proportion of the component (A) is not particularly limited, but is preferably 5% by weight or more (eg, 5 to 100% by weight), more preferably 10% by weight or more, and still more preferably 15 to 50% by weight. By setting the ratio to 5% by weight or more, the tackiness of the cured product tends to be further reduced, and the thermal shock resistance tends to be good.
本発明の硬化性シリコーン樹脂組成物は、特に限定されないが、例えば、上記の各成分を室温で（又は必要に応じて加熱しながら）撹拌・混合することにより調製することができる。なお、本発明の硬化性シリコーン樹脂組成物は、各成分が全てあらかじめ混合されたものをそのまま使用する１液系の組成物として使用することもできるし、例えば、別々に調製しておいた２以上の成分を使用前に所定の割合で混合して使用する多液系（例えば、２液系）の組成物として使用することもできる。
Although the curable silicone resin composition of the present invention is not particularly limited, it can be prepared, for example, by stirring and mixing the above-mentioned components at room temperature (or while heating as required). In addition, the curable silicone resin composition of the present invention can be used as a one-component composition in which one in which all the components are all mixed in advance is used as it is, for example, 2 separately prepared It can also be used as a multi-liquid (for example, two-liquid) composition in which the above components are mixed and used at a predetermined ratio before use.
本発明の硬化性シリコーン樹脂組成物は、特に限定されないが、常温（約２５℃）で液体であることが好ましい。より具体的には、本発明の硬化性シリコーン樹脂組成物は、２５℃における粘度として、３００～２万ｍＰａ・ｓが好ましく、より好ましくは５００～１万ｍＰａ・ｓ、さらに好ましくは１０００～８０００ｍＰａ・ｓである。上記粘度が３００ｍＰａ・ｓ以上であることにより、硬化物の耐熱性がより向上する傾向がある。一方、上記粘度が２万ｍＰａ・ｓ以下であることにより、硬化性シリコーン樹脂組成物の調製がしやすく、その生産性や取り扱い性がより向上し、また、硬化物に気泡が残存しにくくなるため、硬化物（特に、封止材）の生産性や品質がより向上する傾向がある。なお、硬化性シリコーン樹脂組成物の粘度は、上述のラダー型ポリオルガノシルセスキオキサン（ａ）の粘度と同様の方法で測定される。
The curable silicone resin composition of the present invention is not particularly limited, but is preferably liquid at normal temperature (about 25 ° C.). More specifically, the curable silicone resin composition of the present invention preferably has a viscosity at 25 ° C. of 300 to 20,000 mPa · s, more preferably 500 to 10,000 mPa · s, still more preferably 1000 to 8000 mPa.・ S. When the viscosity is 300 mPa · s or more, the heat resistance of the cured product tends to be further improved. On the other hand, when the viscosity is 20,000 mPa · s or less, preparation of the curable silicone resin composition is facilitated, productivity and handleability are further improved, and bubbles are less likely to remain in the cured product. Therefore, the productivity and the quality of the cured product (in particular, the sealing material) tend to be further improved. The viscosity of the curable silicone resin composition is measured by the same method as the viscosity of the ladder-type polyorganosilsesquioxane (a) described above.
＜硬化物＞
本発明の硬化性シリコーン樹脂組成物を硬化（特に、ヒドロシリル化反応により硬化）させることによって、硬化物（「本発明の硬化物」と称する場合がある）が得られる。硬化の際の条件は、特に限定されず、従来公知の条件より適宜選択することができるが、例えば、反応速度の点から、温度（硬化温度）は２５～１８０℃（より好ましくは６０～１５０℃）が好ましく、時間（硬化時間）は５～７２０分が好ましい。本発明の硬化物は、ポリシロキサン系材料特有の高い耐熱性及び透明性を有することに加え、耐熱衝撃性、被着体に対する密着性、及び硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性にも優れ、さらに、（Ｇ）成分を含む場合には、特に優れた耐熱衝撃性を有する硬化物が得られる。 <Cured product>
By curing (in particular, curing by a hydrosilylation reaction) the curable silicone resin composition of the present invention, a cured product (sometimes referred to as "the cured product of the present invention") is obtained. The conditions for curing are not particularly limited and can be appropriately selected from conventionally known conditions. For example, the temperature (curing temperature) is 25 to 180 ° C. (more preferably 60 to 150) from the viewpoint of the reaction rate. ° C) is preferred, and the time (curing time) is preferably 5 to 720 minutes. In addition to the high heat resistance and transparency unique to polysiloxane materials, the cured product of the present invention has thermal shock resistance, adhesion to adherends, and sulfur barrier properties, in particular, only barrier properties to hydrogen sulfide. without excellent barrier property against SO X, further, if it contains the component (G), the cured product is obtained having a particularly excellent thermal shock resistance.
本発明の硬化性シリコーン樹脂組成物を硬化（特に、ヒドロシリル化反応により硬化）させることによって、硬化物（「本発明の硬化物」と称する場合がある）が得られる。硬化の際の条件は、特に限定されず、従来公知の条件より適宜選択することができるが、例えば、反応速度の点から、温度（硬化温度）は２５～１８０℃（より好ましくは６０～１５０℃）が好ましく、時間（硬化時間）は５～７２０分が好ましい。本発明の硬化物は、ポリシロキサン系材料特有の高い耐熱性及び透明性を有することに加え、耐熱衝撃性、被着体に対する密着性、及び硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性にも優れ、さらに、（Ｇ）成分を含む場合には、特に優れた耐熱衝撃性を有する硬化物が得られる。 <Cured product>
By curing (in particular, curing by a hydrosilylation reaction) the curable silicone resin composition of the present invention, a cured product (sometimes referred to as "the cured product of the present invention") is obtained. The conditions for curing are not particularly limited and can be appropriately selected from conventionally known conditions. For example, the temperature (curing temperature) is 25 to 180 ° C. (more preferably 60 to 150) from the viewpoint of the reaction rate. ° C) is preferred, and the time (curing time) is preferably 5 to 720 minutes. In addition to the high heat resistance and transparency unique to polysiloxane materials, the cured product of the present invention has thermal shock resistance, adhesion to adherends, and sulfur barrier properties, in particular, only barrier properties to hydrogen sulfide. without excellent barrier property against SO X, further, if it contains the component (G), the cured product is obtained having a particularly excellent thermal shock resistance.
＜封止剤、光半導体装置＞
本発明の硬化性シリコーン樹脂組成物は、特に、光半導体装置における光半導体素子（ＬＥＤ素子）の封止用樹脂組成物（光半導体封止用樹脂組成物）（「本発明の封止剤」と称する場合がある）として好ましく使用できる。本発明の封止剤を硬化させることにより得られる封止材（硬化物）は、ポリシロキサン系材料特有の高い耐熱性及び透明性を有することに加え、耐熱衝撃性、被着体に対する密着性、及び硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性にも優れる。このため、本発明の封止剤は、特に、高輝度、短波長の光半導体素子の封止剤等として好ましく使用できる。本発明の封止剤を使用して光半導体素子を封止することにより、光半導体装置（「本発明の光半導体装置」と称する場合がある）を得ることができる。即ち、本発明の光半導体装置は、光半導体素子と、該光半導体素子を封止する封止材とを少なくとも含み、上記封止材が本発明の硬化性シリコーン樹脂組成物（本発明の封止剤）の硬化物（本発明の硬化物）である光半導体装置である。なお、光半導体素子の封止は、公知乃至慣用の方法により実施でき、特に限定されないが、例えば、本発明の封止剤を所定の成形型内に注入し、所定の条件で加熱硬化することで実施できる。硬化温度と硬化時間は、特に限定されず、硬化物の調製時と同様の範囲で適宜設定することができる。本発明の光半導体装置の一例を図１に示す。図１において、１００はリフレクター（光反射用樹脂組成物）、１０１は金属配線（電極）、１０２は光半導体素子、１０３はボンディングワイヤ、１０４は硬化物（封止材）を示す。 Sealant, optical semiconductor device
The curable silicone resin composition of the present invention is, in particular, a resin composition for sealing an optical semiconductor element (LED element) in an optical semiconductor device (resin composition for optical semiconductor sealing) ("sealing agent of the present invention" Can be preferably used). The sealing material (cured product) obtained by curing the sealing agent of the present invention has high heat resistance and transparency unique to polysiloxane materials, as well as thermal shock resistance and adhesion to adherends. And sulfur barrier properties, in particular not only barrier properties against hydrogen sulfide, but also barrier properties against SO x . For this reason, the sealing agent of the present invention can be preferably used particularly as a sealing agent for optical semiconductor devices with high brightness and short wavelength. By sealing an optical semiconductor element using the sealing agent of the present invention, an optical semiconductor device (sometimes referred to as “the optical semiconductor device of the present invention”) can be obtained. That is, the optical semiconductor device of the present invention comprises at least an optical semiconductor element and a sealing material for sealing the optical semiconductor element, and the sealing material is the curable silicone resin composition of the present invention (the sealing of the present invention Optical semiconductor device which is a cured product (cured product of the present invention) of In addition, although sealing of an optical-semiconductor element can be implemented by the well-known thru | or conventional method and it is not specifically limited, For example, inject | pouring the sealing agent of this invention in a predetermined | prescribed shaping | molding die, heat-hardening on predetermined conditions. Can be implemented by The curing temperature and the curing time are not particularly limited, and can be appropriately set in the same range as in the preparation of the cured product. An example of the optical semiconductor device of the present invention is shown in FIG. In FIG. 1, 100 is a reflector (resin composition for light reflection), 101 is a metal wiring (electrode), 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).
本発明の硬化性シリコーン樹脂組成物は、特に、光半導体装置における光半導体素子（ＬＥＤ素子）の封止用樹脂組成物（光半導体封止用樹脂組成物）（「本発明の封止剤」と称する場合がある）として好ましく使用できる。本発明の封止剤を硬化させることにより得られる封止材（硬化物）は、ポリシロキサン系材料特有の高い耐熱性及び透明性を有することに加え、耐熱衝撃性、被着体に対する密着性、及び硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性にも優れる。このため、本発明の封止剤は、特に、高輝度、短波長の光半導体素子の封止剤等として好ましく使用できる。本発明の封止剤を使用して光半導体素子を封止することにより、光半導体装置（「本発明の光半導体装置」と称する場合がある）を得ることができる。即ち、本発明の光半導体装置は、光半導体素子と、該光半導体素子を封止する封止材とを少なくとも含み、上記封止材が本発明の硬化性シリコーン樹脂組成物（本発明の封止剤）の硬化物（本発明の硬化物）である光半導体装置である。なお、光半導体素子の封止は、公知乃至慣用の方法により実施でき、特に限定されないが、例えば、本発明の封止剤を所定の成形型内に注入し、所定の条件で加熱硬化することで実施できる。硬化温度と硬化時間は、特に限定されず、硬化物の調製時と同様の範囲で適宜設定することができる。本発明の光半導体装置の一例を図１に示す。図１において、１００はリフレクター（光反射用樹脂組成物）、１０１は金属配線（電極）、１０２は光半導体素子、１０３はボンディングワイヤ、１０４は硬化物（封止材）を示す。 Sealant, optical semiconductor device
The curable silicone resin composition of the present invention is, in particular, a resin composition for sealing an optical semiconductor element (LED element) in an optical semiconductor device (resin composition for optical semiconductor sealing) ("sealing agent of the present invention" Can be preferably used). The sealing material (cured product) obtained by curing the sealing agent of the present invention has high heat resistance and transparency unique to polysiloxane materials, as well as thermal shock resistance and adhesion to adherends. And sulfur barrier properties, in particular not only barrier properties against hydrogen sulfide, but also barrier properties against SO x . For this reason, the sealing agent of the present invention can be preferably used particularly as a sealing agent for optical semiconductor devices with high brightness and short wavelength. By sealing an optical semiconductor element using the sealing agent of the present invention, an optical semiconductor device (sometimes referred to as “the optical semiconductor device of the present invention”) can be obtained. That is, the optical semiconductor device of the present invention comprises at least an optical semiconductor element and a sealing material for sealing the optical semiconductor element, and the sealing material is the curable silicone resin composition of the present invention (the sealing of the present invention Optical semiconductor device which is a cured product (cured product of the present invention) of In addition, although sealing of an optical-semiconductor element can be implemented by the well-known thru | or conventional method and it is not specifically limited, For example, inject | pouring the sealing agent of this invention in a predetermined | prescribed shaping | molding die, heat-hardening on predetermined conditions. Can be implemented by The curing temperature and the curing time are not particularly limited, and can be appropriately set in the same range as in the preparation of the cured product. An example of the optical semiconductor device of the present invention is shown in FIG. In FIG. 1, 100 is a reflector (resin composition for light reflection), 101 is a metal wiring (electrode), 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a cured product (sealing material).
＜光半導体用レンズの形成用組成物、光半導体装置＞
また、本発明の硬化性シリコーン樹脂組成物は、光半導体装置に備えられるレンズ（光半導体用レンズ）を形成するための組成物（光半導体用レンズの形成用組成物）（「本発明のレンズ形成用組成物」と称する場合がある）としても好ましく使用できる。本発明のレンズ形成用組成物を硬化させることにより得られるレンズは、高い耐熱性及び透明性を有することに加えて、被着体に対する密着性及び硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性にも優れる。本発明のレンズ形成用組成物を使用することにより、光半導体装置（これも「本発明の光半導体装置」と称する場合がある）を得ることができる。即ち、本発明の光半導体装置は、光半導体素子とレンズとを少なくとも含み、上記レンズが本発明の硬化性シリコーン樹脂組成物（本発明のレンズ形成用組成物）の硬化物（本発明の硬化物）である光半導体装置である。なお、本発明のレンズ形成用組成物を用いた光半導体用レンズの製造は、公知乃至慣用の方法により実施でき、特に限定されないが、例えば、本発明のレンズ形成用組成物を所定の成形型内に注入して所定の条件で加熱硬化する方法や、ディスペンサー等によって塗布して所定の条件で加熱硬化する方法等によって実施できる。硬化温度と硬化時間は、特に限定されず、硬化物の調製時と同様の範囲で適宜設定することができる。本発明の光半導体装置が上記レンズを備える態様は特に限定されず、例えば、本発明の光半導体装置が封止材を有する場合には、該封止材の表面上の一部又は全部に配置された態様、上記光半導体装置の光半導体素子を封止する態様（即ち、本発明の硬化物が封止材とレンズとを兼ねる態様）等であってもよい。より具体的には、例えば、国際公開第２０１２／１４７３４２号、特開２０１２－１８８６２７号公報、特開２０１１－２３３６０５号公報等に開示された態様等が挙げられる。 <Composition for Forming Lens for Optical Semiconductor, Optical Semiconductor Device>
Further, the curable silicone resin composition of the present invention is a composition for forming a lens (lens for optical semiconductor) provided in an optical semiconductor device (composition for forming a lens for optical semiconductor) ("lens of the present invention It may be preferably used as "forming composition". The lens obtained by curing the composition for forming a lens of the present invention has, in addition to high heat resistance and transparency, adhesion to an adherend and sulfur barrier property, in particular, only barrier property to hydrogen sulfide. Also, the barrier property to SO X is excellent. By using the composition for forming a lens of the present invention, it is possible to obtain an optical semiconductor device (also referred to as "the optical semiconductor device of the present invention"). That is, the optical semiconductor device of the present invention comprises at least an optical semiconductor element and a lens, and the lens is a cured product of the curable silicone resin composition of the present invention (composition for forming a lens of the present invention) Semiconductor device). In addition, manufacture of the lens for optical semiconductors using the composition for lens formation of this invention can be implemented by a well-known thru | or conventional method, It is not specifically limited, For example, the composition for lens formation of this invention It can be carried out by a method of injection into the inside and heat curing under predetermined conditions, or a method of applying by a dispenser or the like and heat curing under predetermined conditions. The curing temperature and the curing time are not particularly limited, and can be appropriately set in the same range as in the preparation of the cured product. The aspect in which the optical semiconductor device of the present invention includes the above lens is not particularly limited. For example, when the optical semiconductor device of the present invention has a sealing material, it is disposed on part or all of the surface of the sealing material The above-described aspect may be an aspect in which the optical semiconductor element of the optical semiconductor device is sealed (that is, an aspect in which the cured product of the present invention serves both as a sealing material and a lens) or the like. More specifically, for example, the embodiments disclosed in WO 2012/147342, JP 2012-188627 A, JP 2011-233605 A etc. may be mentioned.
また、本発明の硬化性シリコーン樹脂組成物は、光半導体装置に備えられるレンズ（光半導体用レンズ）を形成するための組成物（光半導体用レンズの形成用組成物）（「本発明のレンズ形成用組成物」と称する場合がある）としても好ましく使用できる。本発明のレンズ形成用組成物を硬化させることにより得られるレンズは、高い耐熱性及び透明性を有することに加えて、被着体に対する密着性及び硫黄バリア性、特に、硫化水素に対するバリア性だけではなく、ＳＯXに対するバリア性にも優れる。本発明のレンズ形成用組成物を使用することにより、光半導体装置（これも「本発明の光半導体装置」と称する場合がある）を得ることができる。即ち、本発明の光半導体装置は、光半導体素子とレンズとを少なくとも含み、上記レンズが本発明の硬化性シリコーン樹脂組成物（本発明のレンズ形成用組成物）の硬化物（本発明の硬化物）である光半導体装置である。なお、本発明のレンズ形成用組成物を用いた光半導体用レンズの製造は、公知乃至慣用の方法により実施でき、特に限定されないが、例えば、本発明のレンズ形成用組成物を所定の成形型内に注入して所定の条件で加熱硬化する方法や、ディスペンサー等によって塗布して所定の条件で加熱硬化する方法等によって実施できる。硬化温度と硬化時間は、特に限定されず、硬化物の調製時と同様の範囲で適宜設定することができる。本発明の光半導体装置が上記レンズを備える態様は特に限定されず、例えば、本発明の光半導体装置が封止材を有する場合には、該封止材の表面上の一部又は全部に配置された態様、上記光半導体装置の光半導体素子を封止する態様（即ち、本発明の硬化物が封止材とレンズとを兼ねる態様）等であってもよい。より具体的には、例えば、国際公開第２０１２／１４７３４２号、特開２０１２－１８８６２７号公報、特開２０１１－２３３６０５号公報等に開示された態様等が挙げられる。 <Composition for Forming Lens for Optical Semiconductor, Optical Semiconductor Device>
Further, the curable silicone resin composition of the present invention is a composition for forming a lens (lens for optical semiconductor) provided in an optical semiconductor device (composition for forming a lens for optical semiconductor) ("lens of the present invention It may be preferably used as "forming composition". The lens obtained by curing the composition for forming a lens of the present invention has, in addition to high heat resistance and transparency, adhesion to an adherend and sulfur barrier property, in particular, only barrier property to hydrogen sulfide. Also, the barrier property to SO X is excellent. By using the composition for forming a lens of the present invention, it is possible to obtain an optical semiconductor device (also referred to as "the optical semiconductor device of the present invention"). That is, the optical semiconductor device of the present invention comprises at least an optical semiconductor element and a lens, and the lens is a cured product of the curable silicone resin composition of the present invention (composition for forming a lens of the present invention) Semiconductor device). In addition, manufacture of the lens for optical semiconductors using the composition for lens formation of this invention can be implemented by a well-known thru | or conventional method, It is not specifically limited, For example, the composition for lens formation of this invention It can be carried out by a method of injection into the inside and heat curing under predetermined conditions, or a method of applying by a dispenser or the like and heat curing under predetermined conditions. The curing temperature and the curing time are not particularly limited, and can be appropriately set in the same range as in the preparation of the cured product. The aspect in which the optical semiconductor device of the present invention includes the above lens is not particularly limited. For example, when the optical semiconductor device of the present invention has a sealing material, it is disposed on part or all of the surface of the sealing material The above-described aspect may be an aspect in which the optical semiconductor element of the optical semiconductor device is sealed (that is, an aspect in which the cured product of the present invention serves both as a sealing material and a lens) or the like. More specifically, for example, the embodiments disclosed in WO 2012/147342, JP 2012-188627 A, JP 2011-233605 A etc. may be mentioned.
本発明の光半導体装置は、光半導体素子と、該光半導体素子を封止する封止材と、レンズとを含み、上記封止材が本発明の硬化性シリコーン樹脂組成物（本発明の封止剤）の硬化物（本発明の硬化物）でありなおかつ、上記レンズが本発明の硬化性シリコーン樹脂組成物（本発明のレンズ形成用組成物）の硬化物（本発明の硬化物）である光半導体装置であってもよい。
The optical semiconductor device of the present invention comprises an optical semiconductor element, a sealing material for sealing the optical semiconductor element, and a lens, and the sealing material is a curable silicone resin composition of the present invention (the sealing of the present invention A cured product of the curing agent of the present invention (the cured product of the present invention), and the lens is a cured product of the curable silicone resin composition of the present invention (the composition for forming a lens of the present invention) (the cured product of the present invention) It may be an optical semiconductor device.
本発明の硬化性シリコーン樹脂組成物は、上述の封止剤用途（光半導体素子の封止剤用途）及びレンズ形成用途（光半導体装置におけるレンズ形成用途）に限定されず、例えば、ダイボンド剤用途（例えば、光半導体用ダイボンド剤用途）、光半導体装置以外の半導体装置における半導体素子の封止剤、機能性コーティング剤、耐熱プラスチックレンズ、透明機器、接着剤（耐熱透明接着剤等）、電気絶縁材（絶縁膜等）、積層板、コーティング、インク、塗料、シーラント、レジスト、複合材料、透明基材、透明シート、透明フィルム、光学素子、光学レンズ、光学部材、光造形、電子ペーパー、タッチパネル、太陽電池基板、光導波路、導光板、ホログラフィックメモリ等の光学関連や半導体関連の用途に好ましく使用できる。
The curable silicone resin composition of the present invention is not limited to the above-mentioned sealant application (application for encapsulant of optical semiconductor element) and application for forming lens (application for forming lens in optical semiconductor device), for example, die bonding agent application (For example, use as die bonding agent for optical semiconductors), Sealant for semiconductor elements in semiconductor devices other than optical semiconductor devices, functional coating agent, heat resistant plastic lens, transparent equipment, adhesive (heat resistant transparent adhesive etc.), electrical insulation Materials (insulation film etc.), laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical films, optical elements, optical lenses, optical members, optical molding, electronic paper, touch panels, It can be preferably used in applications related to optics and semiconductors such as solar cell substrates, optical waveguides, light guide plates and holographic memories.
特に、本発明の硬化性シリコーン樹脂組成物は、従来の樹脂材料では対応することが困難であった、高輝度・短波長の光半導体装置において光半導体素子を被覆する封止材、高耐熱・高耐電圧の半導体装置（パワー半導体等）において半導体素子を被覆する封止材等の用途に好ましく使用できる。
In particular, the curable silicone resin composition of the present invention is a sealing material for covering an optical semiconductor element in an optical semiconductor device with high brightness and short wavelength, which has been difficult to cope with conventional resin materials, It can be preferably used for applications such as sealing materials for covering semiconductor elements in high withstand voltage semiconductor devices (power semiconductors and the like).
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。なお、表１に示す各成分の配合割合の単位は重量部である。
EXAMPLES The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. In addition, the unit of the compounding ratio of each component shown in Table 1 is a weight part.
合成例で製造した生成物及び製品の1Ｈ－ＮＭＲ分析は、ＪＥＯＬ ＥＣＡ５００（５００ＭＨｚ）により行った。また、上記生成物並びに製品の数平均分子量及び重量平均分子量の測定は、Ａｌｌｉａｎｃｅ ＨＰＬＣシステム ２６９５（Ｗａｔｅｒｓ製）、Ｒｅｆｒａｃｔｉｖｅ Ｉｎｄｅｘ Ｄｅｔｅｃｔｏｒ ２４１４（Ｗａｔｅｒｓ製）、カラム：Ｔｓｋｇｅｌ ＧＭＨHR－Ｍ×２（東ソー（株）製）、ガードカラム：Ｔｓｋｇｅｌ ｇｕａｒｄ ｃｏｌｕｍｎ ＨHRＬ（東ソー（株）製）、カラムオーブン：ＣＯＬＵＭＮ ＨＥＡＴＥＲ Ｕ－６２０（Ｓｕｇａｉ製）、溶媒：ＴＨＦ、測定条件：４０℃、標準ポリスチレン換算により行った。
The 1 H-NMR analysis of the products and products produced in the synthesis example was carried out with a JEOL ECA 500 (500 MHz). Moreover, the measurement of the number average molecular weight and the weight average molecular weight of the above product and the product can be carried out according to Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskgel GMH HR -M × 2 (Tosoh (strain) ) Ltd.), guard column: Tskgel guard column H HR L (manufactured by Tosoh Corporation), column oven: cOLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measuring conditions: 40 ° C., were performed by standard polystyrene .
合成例１
［ビニル基を有するポリオルガノシルセスキオキサンの製造］
温度計、撹拌装置、還流冷却器、及び窒素導入管を取り付けた１００ｍｌのフラスコ（反応容器）に、窒素気流下でビニルトリメトキシシラン９．６４ｇ（６５ｍｍｏｌ）、フェニルトリメトキシシラン３８．６７ｇ（１９５ｍｍｏｌ）、及びメチルイソブチルケトン（ＭＩＢＫ）８．３１ｇを仕込み、この混合物を１０℃以下に冷却した。上記混合物に、水６．４８ｇ（３６０ｍｍｏｌ）及び５Ｎの塩酸０．２４ｇ（塩化水素として１．２ｍｍｏｌ）を滴下した。その後、ＭＩＢＫを４０ｇ添加して、反応溶液を希釈した。
次に、反応容器の温度を７０℃まで昇温した。ここに水９．３６ｇ（５２０ｍｍｏｌ）を添加し、窒素気流下で重縮合反応を行った。続いて、重縮合反応後の反応溶液にヘキサメチルジシロキサン２１．１１ｇ（１３０ｍｍｏｌ）を添加し、７０℃で撹拌してシリル化反応を行った。その後、冷却し、下層液が中性になるまで水洗を行い、上層液を分取した後、１ｍｍＨｇ、４０℃の条件で上層液から溶媒を留去し、無色透明の液状の生成物（３８．６ｇ；ビニル基を有するポリオルガノシルセスキオキサン）を得た。
上記生成物（シリル化反応後の生成物）の数平均分子量は１２８０であり、分子量分散度は１．１３であった。また、図２には、上記生成物の1Ｈ－ＮＭＲスペクトルのチャート（溶媒：重クロロホルム）を示す。さらに、上記生成物のＦＴ－ＩＲスペクトルを上述の条件で測定したところ、１０００～１２００ｃｍ-1に２本の吸収ピークを有することが確認された。図３には、上記生成物のＦＴ－ＩＲスペクトルのチャートを示す。
上記生成物（シリル化反応後の生成物）は、上述の（Ｆ）成分（詳しくは、ラダー型ポリオルガノシルセスキオキサン（ａ））に該当する。 Synthesis example 1
[Production of Polyorganosilsesquioxane Having Vinyl Group]
Under a nitrogen stream, 9.64 g (65 mmol) of vinyltrimethoxysilane and 38.67 g (195 mmol) of phenyltrimethoxysilane in a 100 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube. And 8.31 g of methyl isobutyl ketone (MIBK) were charged, and the mixture was cooled to 10 ° C. or less. To the above mixture, 6.48 g (360 mmol) of water and 0.24 g of 5 N hydrochloric acid (1.2 mmol as hydrogen chloride) were added dropwise. Thereafter, 40 g of MIBK was added to dilute the reaction solution.
Next, the temperature of the reaction vessel was raised to 70.degree. To this, 9.36 g (520 mmol) of water was added, and a polycondensation reaction was performed under a nitrogen stream. Subsequently, 21.11 g (130 mmol) of hexamethyldisiloxane was added to the reaction solution after the polycondensation reaction, and the mixture was stirred at 70 ° C. to conduct a silylation reaction. After cooling, the lower layer solution is washed with water until it becomes neutral, and the upper layer solution is separated, and then the solvent is distilled off from the upper layer solution under the conditions of 1 mmHg and 40 ° C. .6 g; polyorganosilsesquioxanes having a vinyl group were obtained.
The number average molecular weight of the product (product after silylation reaction) was 1280, and the molecular weight dispersion degree was 1.13. Further, FIG. 2 shows a chart (solvent: deuterated chloroform) of 1 H-NMR spectrum of the above-mentioned product. Furthermore, when the FT-IR spectrum of the above product was measured under the conditions described above, it was confirmed that it had two absorption peaks at 1000 to 1200 cm -1 . FIG. 3 shows a chart of the FT-IR spectrum of the above product.
The above-mentioned product (product after silylation reaction) corresponds to the above-mentioned component (F) (specifically, ladder type polyorganosilsesquioxane (a)).
［ビニル基を有するポリオルガノシルセスキオキサンの製造］
温度計、撹拌装置、還流冷却器、及び窒素導入管を取り付けた１００ｍｌのフラスコ（反応容器）に、窒素気流下でビニルトリメトキシシラン９．６４ｇ（６５ｍｍｏｌ）、フェニルトリメトキシシラン３８．６７ｇ（１９５ｍｍｏｌ）、及びメチルイソブチルケトン（ＭＩＢＫ）８．３１ｇを仕込み、この混合物を１０℃以下に冷却した。上記混合物に、水６．４８ｇ（３６０ｍｍｏｌ）及び５Ｎの塩酸０．２４ｇ（塩化水素として１．２ｍｍｏｌ）を滴下した。その後、ＭＩＢＫを４０ｇ添加して、反応溶液を希釈した。
次に、反応容器の温度を７０℃まで昇温した。ここに水９．３６ｇ（５２０ｍｍｏｌ）を添加し、窒素気流下で重縮合反応を行った。続いて、重縮合反応後の反応溶液にヘキサメチルジシロキサン２１．１１ｇ（１３０ｍｍｏｌ）を添加し、７０℃で撹拌してシリル化反応を行った。その後、冷却し、下層液が中性になるまで水洗を行い、上層液を分取した後、１ｍｍＨｇ、４０℃の条件で上層液から溶媒を留去し、無色透明の液状の生成物（３８．６ｇ；ビニル基を有するポリオルガノシルセスキオキサン）を得た。
上記生成物（シリル化反応後の生成物）の数平均分子量は１２８０であり、分子量分散度は１．１３であった。また、図２には、上記生成物の1Ｈ－ＮＭＲスペクトルのチャート（溶媒：重クロロホルム）を示す。さらに、上記生成物のＦＴ－ＩＲスペクトルを上述の条件で測定したところ、１０００～１２００ｃｍ-1に２本の吸収ピークを有することが確認された。図３には、上記生成物のＦＴ－ＩＲスペクトルのチャートを示す。
上記生成物（シリル化反応後の生成物）は、上述の（Ｆ）成分（詳しくは、ラダー型ポリオルガノシルセスキオキサン（ａ））に該当する。 Synthesis example 1
[Production of Polyorganosilsesquioxane Having Vinyl Group]
Under a nitrogen stream, 9.64 g (65 mmol) of vinyltrimethoxysilane and 38.67 g (195 mmol) of phenyltrimethoxysilane in a 100 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube. And 8.31 g of methyl isobutyl ketone (MIBK) were charged, and the mixture was cooled to 10 ° C. or less. To the above mixture, 6.48 g (360 mmol) of water and 0.24 g of 5 N hydrochloric acid (1.2 mmol as hydrogen chloride) were added dropwise. Thereafter, 40 g of MIBK was added to dilute the reaction solution.
Next, the temperature of the reaction vessel was raised to 70.degree. To this, 9.36 g (520 mmol) of water was added, and a polycondensation reaction was performed under a nitrogen stream. Subsequently, 21.11 g (130 mmol) of hexamethyldisiloxane was added to the reaction solution after the polycondensation reaction, and the mixture was stirred at 70 ° C. to conduct a silylation reaction. After cooling, the lower layer solution is washed with water until it becomes neutral, and the upper layer solution is separated, and then the solvent is distilled off from the upper layer solution under the conditions of 1 mmHg and 40 ° C. .6 g; polyorganosilsesquioxanes having a vinyl group were obtained.
The number average molecular weight of the product (product after silylation reaction) was 1280, and the molecular weight dispersion degree was 1.13. Further, FIG. 2 shows a chart (solvent: deuterated chloroform) of 1 H-NMR spectrum of the above-mentioned product. Furthermore, when the FT-IR spectrum of the above product was measured under the conditions described above, it was confirmed that it had two absorption peaks at 1000 to 1200 cm -1 . FIG. 3 shows a chart of the FT-IR spectrum of the above product.
The above-mentioned product (product after silylation reaction) corresponds to the above-mentioned component (F) (specifically, ladder type polyorganosilsesquioxane (a)).
表１に記載の各成分の説明を以下に示す。
（Ａ剤）
ポリオルガノシロキシシルアルキレン（ＧＳ５１４５Ａ）：商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ａ」［ポリオルガノシロキシシルアルキレン（Ａ２）を含むシリコーン樹脂］、長興材料工業製、アリール基（フェニル基）の割合約２４モル％、ヒドロシリル化触媒［（Ｅ）成分］を含む。
ポリオルガノシロキサン（ＯＥ－６６３０Ａ）：商品名「ＯＥ－６６３０Ａ」［ポリオルガノシロキサン（Ａ１）を含むフェニルシリコーン樹脂］、東レ・ダウコーニング（株）製、ヒドロシリル化触媒［（Ｅ）成分］を含む。
イソシアヌレート化合物（Ｃ）（ＴＥＰＩＣ－ＶＬ）：商品名「ＴＥＰＩＣ－ＶＬ」［（Ｃ）成分］、日産化学工業（株）製、下記式で表される化合物
The description of each component described in Table 1 is shown below.
(A agent)
Polyorganosiloxycyl alkylene (GS5145A): trade name "ETERLED GS5145A" [polysilicon resin containing polyorganosiloxycyl alkylene (A2)], manufactured by Chokkei Materials Co., Ltd., proportion of aryl group (phenyl group) about 24 mol%, hydrosilylation The catalyst [component (E)] is included.
Polyorganosiloxane (OE-6630A): trade name "OE-6630A" [phenylsilicone resin containing polyorganosiloxane (A1)], Toray Dow Corning Co., Ltd., containing hydrosilylation catalyst [component (E)] .
Isocyanurate compound (C) (TEPIC-VL): trade name "TEPIC-VL" [component (C)], manufactured by Nissan Chemical Industries, Ltd., a compound represented by the following formula
（Ａ剤）
ポリオルガノシロキシシルアルキレン（ＧＳ５１４５Ａ）：商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ａ」［ポリオルガノシロキシシルアルキレン（Ａ２）を含むシリコーン樹脂］、長興材料工業製、アリール基（フェニル基）の割合約２４モル％、ヒドロシリル化触媒［（Ｅ）成分］を含む。
ポリオルガノシロキサン（ＯＥ－６６３０Ａ）：商品名「ＯＥ－６６３０Ａ」［ポリオルガノシロキサン（Ａ１）を含むフェニルシリコーン樹脂］、東レ・ダウコーニング（株）製、ヒドロシリル化触媒［（Ｅ）成分］を含む。
イソシアヌレート化合物（Ｃ）（ＴＥＰＩＣ－ＶＬ）：商品名「ＴＥＰＩＣ－ＶＬ」［（Ｃ）成分］、日産化学工業（株）製、下記式で表される化合物
(A agent)
Polyorganosiloxycyl alkylene (GS5145A): trade name "ETERLED GS5145A" [polysilicon resin containing polyorganosiloxycyl alkylene (A2)], manufactured by Chokkei Materials Co., Ltd., proportion of aryl group (phenyl group) about 24 mol%, hydrosilylation The catalyst [component (E)] is included.
Polyorganosiloxane (OE-6630A): trade name "OE-6630A" [phenylsilicone resin containing polyorganosiloxane (A1)], Toray Dow Corning Co., Ltd., containing hydrosilylation catalyst [component (E)] .
Isocyanurate compound (C) (TEPIC-VL): trade name "TEPIC-VL" [component (C)], manufactured by Nissan Chemical Industries, Ltd., a compound represented by the following formula
ラダー型ポリオルガノシルセスキオキサン（Ｆ）（合成例１）：合成例１で得られた化合物［（Ｆ）成分］
イソシアヌレート化合物（ＭＡ－ＤＧＩＣ）：商品名「ＭＡ－ＤＧＩＣ」［（Ｇ）成分］、四国化成工業（株）製、下記式で表される化合物
Ladder-type polyorganosilsesquioxane (F) (Synthesis example 1): Compound obtained in Synthesis example 1 [component (F)]
Isocyanurate compound (MA-DGIC): trade name "MA-DGIC" [component (G)], a compound represented by the following formula, manufactured by Shikoku Kasei Kogyo Co., Ltd.
イソシアヌレート化合物（ＭＡ－ＤＧＩＣ）：商品名「ＭＡ－ＤＧＩＣ」［（Ｇ）成分］、四国化成工業（株）製、下記式で表される化合物
Isocyanurate compound (MA-DGIC): trade name "MA-DGIC" [component (G)], a compound represented by the following formula, manufactured by Shikoku Kasei Kogyo Co., Ltd.
イソシアヌレート化合物（ＴＥＰＩＣ）：商品名「ＴＥＰＩＣ」［（Ｇ）成分］、日産化学工業（株）製、下記式で表される化合物
Isocyanurate compound (TEPIC): trade name "TEPIC" [(G) component], manufactured by Nissan Chemical Industries, Ltd., a compound represented by the following formula
オクチル酸亜鉛（ニッカオクチックス亜鉛）：商品名「ニッカオクチックス亜鉛」［２－エチルヘキサン酸亜鉛］、日本化学産業（株）製
シランカップリング剤（ＯＦＳ－６０４０）：商品名「ＸＩＡＭＥＴＥＲ ＯＦＳ－６０４０」［３－グリシドキシプロピルトリメトキシシラン、（Ｈ）成分］、ダウコーニング社製 Octylic acid zinc (Nikkotics zinc): Brand name “Nikkotics zinc” [Zinc 2-ethylhexanoate], Nippon Chemical Industrial Co., Ltd. Silane coupling agent (OFS-6040): Brand name “XIAMETER OFS- 6040 "[3-glycidoxypropyltrimethoxysilane, (H) component], manufactured by Dow Corning
シランカップリング剤（ＯＦＳ－６０４０）：商品名「ＸＩＡＭＥＴＥＲ ＯＦＳ－６０４０」［３－グリシドキシプロピルトリメトキシシラン、（Ｈ）成分］、ダウコーニング社製 Octylic acid zinc (Nikkotics zinc): Brand name “Nikkotics zinc” [Zinc 2-ethylhexanoate], Nippon Chemical Industrial Co., Ltd. Silane coupling agent (OFS-6040): Brand name “XIAMETER OFS- 6040 "[3-glycidoxypropyltrimethoxysilane, (H) component], manufactured by Dow Corning
（Ｂ剤）
ポリオルガノシロキサン（ＧＳ５１４５Ｂ）：商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ｂ」［シリコーン樹脂、（Ｂ）成分及び（Ｄ）成分を含む］、長興材料工業製
ポリオルガノシロキサン（ＯＥ－６６３０Ｂ）：商品名「ＯＥ－６６３０Ｂ」［シリコーン樹脂、（Ｂ）成分及び（Ｄ）成分を含む］、東レ・ダウコーニング（株）製 (B agent)
Polyorganosiloxane (GS5145B): trade name "ETERLED GS5145B" (including silicone resin, (B) component and (D) component), polyorganosiloxane (OE-6630B) manufactured by Choxing Materials Co., Ltd .: trade name "OE-6630B" [Including silicone resin, (B) component and (D) component], Toray Dow Corning Co., Ltd.
ポリオルガノシロキサン（ＧＳ５１４５Ｂ）：商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ｂ」［シリコーン樹脂、（Ｂ）成分及び（Ｄ）成分を含む］、長興材料工業製
ポリオルガノシロキサン（ＯＥ－６６３０Ｂ）：商品名「ＯＥ－６６３０Ｂ」［シリコーン樹脂、（Ｂ）成分及び（Ｄ）成分を含む］、東レ・ダウコーニング（株）製 (B agent)
Polyorganosiloxane (GS5145B): trade name "ETERLED GS5145B" (including silicone resin, (B) component and (D) component), polyorganosiloxane (OE-6630B) manufactured by Choxing Materials Co., Ltd .: trade name "OE-6630B" [Including silicone resin, (B) component and (D) component], Toray Dow Corning Co., Ltd.
実施例１
［硬化性シリコーン樹脂組成物の製造］
まず、表１に示すように、商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ａ」２０重量部及び商品名「ＴＥＰＩＣ－ＶＬ」（０．１重量部）を混合し、４０℃で２時間撹拌して、Ａ剤を調製した。
次に、上記で得たＡ剤２０．１重量部に対して、Ｂ剤として商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ｂ」８０重量部を混合し、自公転式撹拌装置（商品名「あわとり練太郎」、（株）シンキー製、型番：ＡＲＥ－３１０）を用いて撹拌５分、脱泡２分で混練し、均一な液体である硬化性シリコーン樹脂組成物を製造した。 Example 1
[Production of a curable silicone resin composition]
First, as shown in Table 1, 20 parts by weight of trade name "ETERLED GS5145A" and a trade name "TEPIC-VL" (0.1 parts by weight) are mixed and stirred at 40 ° C for 2 hours to prepare agent A. did.
Next, 80 parts by weight of trade name "ETERLED GS5145B" as agent B is mixed with 20.1 parts by weight of agent A obtained above, and a self-revolution stirring device (brand name "Awatori Neritaro", ( Kneader Co., Ltd., Model No .: ARE-310) was used for kneading for 5 minutes with stirring and 2 minutes of defoaming to produce a curable silicone resin composition which is a uniform liquid.
［硬化性シリコーン樹脂組成物の製造］
まず、表１に示すように、商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ａ」２０重量部及び商品名「ＴＥＰＩＣ－ＶＬ」（０．１重量部）を混合し、４０℃で２時間撹拌して、Ａ剤を調製した。
次に、上記で得たＡ剤２０．１重量部に対して、Ｂ剤として商品名「ＥＴＥＲＬＥＤ ＧＳ５１４５Ｂ」８０重量部を混合し、自公転式撹拌装置（商品名「あわとり練太郎」、（株）シンキー製、型番：ＡＲＥ－３１０）を用いて撹拌５分、脱泡２分で混練し、均一な液体である硬化性シリコーン樹脂組成物を製造した。 Example 1
[Production of a curable silicone resin composition]
First, as shown in Table 1, 20 parts by weight of trade name "ETERLED GS5145A" and a trade name "TEPIC-VL" (0.1 parts by weight) are mixed and stirred at 40 ° C for 2 hours to prepare agent A. did.
Next, 80 parts by weight of trade name "ETERLED GS5145B" as agent B is mixed with 20.1 parts by weight of agent A obtained above, and a self-revolution stirring device (brand name "Awatori Neritaro", ( Kneader Co., Ltd., Model No .: ARE-310) was used for kneading for 5 minutes with stirring and 2 minutes of defoaming to produce a curable silicone resin composition which is a uniform liquid.
［光半導体装置の製造］
図１に示す態様のＬＥＤパッケージ（ＩｎＧａＮ素子、３．０ｍｍ×３．０ｍｍ）に、上記で得られた硬化性シリコーン樹脂組成物を注入し、６０℃で１時間、続いて８０℃で１時間、さらに１５０℃で４時間加熱することで、上記硬化性シリコーン樹脂組成物の硬化物により光半導体素子が封止された光半導体装置を製造した。 [Manufacturing of optical semiconductor devices]
The curable silicone resin composition obtained above is injected into the LED package (InGaN device, 3.0 mm × 3.0 mm) of the embodiment shown in FIG. 1, and the solution is heated at 60 ° C. for 1 hour, then at 80 ° C. for 1 hour Furthermore, by heating at 150 ° C. for 4 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable silicone resin composition was manufactured.
図１に示す態様のＬＥＤパッケージ（ＩｎＧａＮ素子、３．０ｍｍ×３．０ｍｍ）に、上記で得られた硬化性シリコーン樹脂組成物を注入し、６０℃で１時間、続いて８０℃で１時間、さらに１５０℃で４時間加熱することで、上記硬化性シリコーン樹脂組成物の硬化物により光半導体素子が封止された光半導体装置を製造した。 [Manufacturing of optical semiconductor devices]
The curable silicone resin composition obtained above is injected into the LED package (InGaN device, 3.0 mm × 3.0 mm) of the embodiment shown in FIG. 1, and the solution is heated at 60 ° C. for 1 hour, then at 80 ° C. for 1 hour Furthermore, by heating at 150 ° C. for 4 hours, an optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the curable silicone resin composition was manufactured.
実施例２～１０、比較例１～５
硬化性シリコーン樹脂組成物の組成を表１に示すように変更したこと以外は実施例１と同様にして、硬化性シリコーン樹脂組成物及び光半導体装置を製造した。 Examples 2 to 10, Comparative Examples 1 to 5
A curable silicone resin composition and an optical semiconductor device were produced in the same manner as in Example 1 except that the composition of the curable silicone resin composition was changed as shown in Table 1.
硬化性シリコーン樹脂組成物の組成を表１に示すように変更したこと以外は実施例１と同様にして、硬化性シリコーン樹脂組成物及び光半導体装置を製造した。 Examples 2 to 10, Comparative Examples 1 to 5
A curable silicone resin composition and an optical semiconductor device were produced in the same manner as in Example 1 except that the composition of the curable silicone resin composition was changed as shown in Table 1.
（評価）
上記で得られた硬化性シリコーン樹脂組成物及び光半導体装置について、以下の評価を行った。評価結果を表１に示す。なお、比較例３については、商品名「ＴＥＰＩＣ」が硬化性シリコーン樹脂組成物中で溶解しなかったため、評価は行わなかった。 (Evaluation)
The following evaluation was performed about the curable silicone resin composition and optical semiconductor device which were obtained above. The evaluation results are shown in Table 1. In Comparative Example 3, evaluation was not performed because the trade name "TEPIC" did not dissolve in the curable silicone resin composition.
上記で得られた硬化性シリコーン樹脂組成物及び光半導体装置について、以下の評価を行った。評価結果を表１に示す。なお、比較例３については、商品名「ＴＥＰＩＣ」が硬化性シリコーン樹脂組成物中で溶解しなかったため、評価は行わなかった。 (Evaluation)
The following evaluation was performed about the curable silicone resin composition and optical semiconductor device which were obtained above. The evaluation results are shown in Table 1. In Comparative Example 3, evaluation was not performed because the trade name "TEPIC" did not dissolve in the curable silicone resin composition.
［硫黄腐食性試験］
上記で製造した光半導体装置を試料として用いた。
まず、上記試料について、全光束測定機（オプトロニックラボラトリーズ社製、マルチ分光放射測定システム「ＯＬ７７１」）を用いて、２０ｍＡの電流を流した際の全光束（単位：ｌｍ）を測定し、これを「ＳＯX腐食性試験前の全光束」とした。
次に、上記試料と硫黄粉末（キシダ化学（株）製）０．３ｇとを４５０ｍｌのガラス瓶に入れ、さらに上記ガラス瓶をアルミ製の箱の中に入れた。続いて、上記アルミ製の箱を８０℃のオーブン（ヤマト科学（株）製、型番：ＤＮ－６４）に入れ、１日後に取り出した。加熱後の試料について上記と同様に全光束を測定し、これを「ＳＯX腐食性試験後の全光束」とした。そして、ＳＯX腐食性試験前後における全光束の維持率（％）［＝１００×（ＳＯX腐食性試験後の全光束（ｌｍ））／（ＳＯX腐食性試験前の全光束（ｌｍ））］を算出した。
光度維持率が高いほど、硬化物（封止材）がＳＯX腐食性ガスに対するバリア性に優れることを示す。なお、硬化性シリコーン樹脂組成物ごとに（各実施例・比較例ごとに）１０個の光半導体装置について光度維持率を測定・算出し、表１にはこれらの光度維持率の平均値（Ｎ＝１０）を示した。結果を表１に示す。 [Sulfur corrosive test]
The optical semiconductor device manufactured above was used as a sample.
First, the total luminous flux (unit: lm) at a current of 20 mA was measured for the above sample using a total luminous flux measuring machine (Multispectral Emission Measurement System “OL 771” manufactured by Optoronic Laboratories, Inc.). “Total flux before SO X corrosion test”.
Next, the sample and 0.3 g of sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was placed in an aluminum box. Subsequently, the aluminum box was placed in an oven at 80 ° C. (manufactured by Yamato Scientific Co., Ltd., model number: DN-64), and taken out one day later. The total luminous flux of the sample after heating was measured in the same manner as described above, and this was taken as the "total luminous flux after the SO X corrosion test". And the maintenance rate (%) of total luminous flux before and after SO X corrosion test [= 100 × (total luminous flux after SO X corrosion test (lm)) / (total luminous flux (lm) before SO X corrosion test) ] Was calculated.
Higher luminous intensity retention rate is high, the cured product (sealant) is the better the barrier properties against SO X corrosive gases. The luminous intensity maintenance rate was measured and calculated for each of the curable silicone resin compositions (for each example and comparative example) for each of the ten optical semiconductor devices. Table 1 shows the average value of these luminous intensity maintenance rates (N = 10). The results are shown in Table 1.
上記で製造した光半導体装置を試料として用いた。
まず、上記試料について、全光束測定機（オプトロニックラボラトリーズ社製、マルチ分光放射測定システム「ＯＬ７７１」）を用いて、２０ｍＡの電流を流した際の全光束（単位：ｌｍ）を測定し、これを「ＳＯX腐食性試験前の全光束」とした。
次に、上記試料と硫黄粉末（キシダ化学（株）製）０．３ｇとを４５０ｍｌのガラス瓶に入れ、さらに上記ガラス瓶をアルミ製の箱の中に入れた。続いて、上記アルミ製の箱を８０℃のオーブン（ヤマト科学（株）製、型番：ＤＮ－６４）に入れ、１日後に取り出した。加熱後の試料について上記と同様に全光束を測定し、これを「ＳＯX腐食性試験後の全光束」とした。そして、ＳＯX腐食性試験前後における全光束の維持率（％）［＝１００×（ＳＯX腐食性試験後の全光束（ｌｍ））／（ＳＯX腐食性試験前の全光束（ｌｍ））］を算出した。
光度維持率が高いほど、硬化物（封止材）がＳＯX腐食性ガスに対するバリア性に優れることを示す。なお、硬化性シリコーン樹脂組成物ごとに（各実施例・比較例ごとに）１０個の光半導体装置について光度維持率を測定・算出し、表１にはこれらの光度維持率の平均値（Ｎ＝１０）を示した。結果を表１に示す。 [Sulfur corrosive test]
The optical semiconductor device manufactured above was used as a sample.
First, the total luminous flux (unit: lm) at a current of 20 mA was measured for the above sample using a total luminous flux measuring machine (Multispectral Emission Measurement System “OL 771” manufactured by Optoronic Laboratories, Inc.). “Total flux before SO X corrosion test”.
Next, the sample and 0.3 g of sulfur powder (manufactured by Kishida Chemical Co., Ltd.) were placed in a 450 ml glass bottle, and the glass bottle was placed in an aluminum box. Subsequently, the aluminum box was placed in an oven at 80 ° C. (manufactured by Yamato Scientific Co., Ltd., model number: DN-64), and taken out one day later. The total luminous flux of the sample after heating was measured in the same manner as described above, and this was taken as the "total luminous flux after the SO X corrosion test". And the maintenance rate (%) of total luminous flux before and after SO X corrosion test [= 100 × (total luminous flux after SO X corrosion test (lm)) / (total luminous flux (lm) before SO X corrosion test) ] Was calculated.
Higher luminous intensity retention rate is high, the cured product (sealant) is the better the barrier properties against SO X corrosive gases. The luminous intensity maintenance rate was measured and calculated for each of the curable silicone resin compositions (for each example and comparative example) for each of the ten optical semiconductor devices. Table 1 shows the average value of these luminous intensity maintenance rates (N = 10). The results are shown in Table 1.
［熱衝撃性試験］
上記で製造した光半導体装置を試料として用いた。試料は、硬化性シリコーン樹脂組成物ごとに１０個ずつ用いた。なお、試料は、試験前に２０ｍＡの電流を通電した時に点灯するものであることを確認した上で用いた。
上記試料について、熱衝撃試験機（エスペック（株）製、型番：ＴＳＢ－２１）を用いて、温度－４０℃で５分間、続いて温度１００℃で５分間曝露することを１サイクルとした熱衝撃付与を、１０００サイクル実施した。その後、１０００サイクルの熱衝撃を付与した後の試料について、２０ｍＡの電流を通電し、点灯しなかった試料の数を計測した。そして、点灯しなかった試料の数が０個である場合を○（耐熱衝撃性が良好である）、点灯しなかった試料の数が１個以上である場合を×（耐熱衝撃性が不良である）と評価した。結果を表１に示す。 [Thermal shock test]
The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable silicone resin composition. In addition, the sample was used after confirming that it lights up, when an electric current of 20 mA is supplied before a test.
About the above sample, using a thermal shock tester (manufactured by ESPEC Co., Ltd., model number: TSB-21), the thermal cycle is a cycle of exposing for 5 minutes at a temperature of -40 ° C and then for 5 minutes at a temperature of 100 ° C. Shock application was performed for 1000 cycles. Thereafter, a current of 20 mA was applied to the sample after the thermal shock of 1000 cycles was applied, and the number of samples which did not light was counted. And, when the number of samples not lit is 0, ○ (good heat shock resistance), when the number of samples not lit is 1 or more, x (heat shock resistance is poor) Yes). The results are shown in Table 1.
上記で製造した光半導体装置を試料として用いた。試料は、硬化性シリコーン樹脂組成物ごとに１０個ずつ用いた。なお、試料は、試験前に２０ｍＡの電流を通電した時に点灯するものであることを確認した上で用いた。
上記試料について、熱衝撃試験機（エスペック（株）製、型番：ＴＳＢ－２１）を用いて、温度－４０℃で５分間、続いて温度１００℃で５分間曝露することを１サイクルとした熱衝撃付与を、１０００サイクル実施した。その後、１０００サイクルの熱衝撃を付与した後の試料について、２０ｍＡの電流を通電し、点灯しなかった試料の数を計測した。そして、点灯しなかった試料の数が０個である場合を○（耐熱衝撃性が良好である）、点灯しなかった試料の数が１個以上である場合を×（耐熱衝撃性が不良である）と評価した。結果を表１に示す。 [Thermal shock test]
The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable silicone resin composition. In addition, the sample was used after confirming that it lights up, when an electric current of 20 mA is supplied before a test.
About the above sample, using a thermal shock tester (manufactured by ESPEC Co., Ltd., model number: TSB-21), the thermal cycle is a cycle of exposing for 5 minutes at a temperature of -40 ° C and then for 5 minutes at a temperature of 100 ° C. Shock application was performed for 1000 cycles. Thereafter, a current of 20 mA was applied to the sample after the thermal shock of 1000 cycles was applied, and the number of samples which did not light was counted. And, when the number of samples not lit is 0, ○ (good heat shock resistance), when the number of samples not lit is 1 or more, x (heat shock resistance is poor) Yes). The results are shown in Table 1.
［吸湿リフロー試験］
上記で製造した光半導体装置を試料として用いた。試料は、硬化性シリコーン樹脂組成物ごとに１０個ずつ用いた。なお、試料は、試験前に２０ｍＡの電流を通電した時に点灯するものであることを確認した上で用いた。
上記試料を３０℃、６０％ＲＨに調整した恒温恒湿槽（エスペック（株）製、型番「ＳＨ－６４１」）に入れ、１９２時間後に取り出した。続いて、上記各試料について、リフロー炉（ＡＮＴＯＭ（株）製、型番「ＵＮＩ－５０１６Ｆ」）を用いて、２６０℃で１０秒間の加熱処理を２回施した。その後、リフロー炉による２回の加熱処理を施した後の試料について、２０ｍＡの電流を通電し、点灯しなかった試料の数を計測した。そして、点灯しなかった試料の数が０個である場合を○（吸湿リフロー性が良好である）、点灯しなかった試料の数が１個以上である場合を×（吸湿リフロー性が不良である）と評価した。結果を表１に示す。 Moisture absorption reflow test
The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable silicone resin composition. In addition, the sample was used after confirming that it lights up, when an electric current of 20 mA is supplied before a test.
The above sample was placed in a constant temperature and humidity chamber (manufactured by Espec Corp., model number “SH-641”) adjusted to 30 ° C. and 60% RH, and taken out after 192 hours. Subsequently, heat treatment was performed twice at 260 ° C. for 10 seconds using each of the above samples using a reflow furnace (manufactured by ANTOM Co., Ltd., model number “UNI-5016F”). Thereafter, a current of 20 mA was applied to the sample after the two heat treatments by the reflow furnace, and the number of samples which did not light was measured. And, when the number of samples which were not lighted is 0, ((good in moisture absorption reflowability), when the number of samples which were not lighted is 1 or more, x (hygroscopic reflow property is not good Yes). The results are shown in Table 1.
上記で製造した光半導体装置を試料として用いた。試料は、硬化性シリコーン樹脂組成物ごとに１０個ずつ用いた。なお、試料は、試験前に２０ｍＡの電流を通電した時に点灯するものであることを確認した上で用いた。
上記試料を３０℃、６０％ＲＨに調整した恒温恒湿槽（エスペック（株）製、型番「ＳＨ－６４１」）に入れ、１９２時間後に取り出した。続いて、上記各試料について、リフロー炉（ＡＮＴＯＭ（株）製、型番「ＵＮＩ－５０１６Ｆ」）を用いて、２６０℃で１０秒間の加熱処理を２回施した。その後、リフロー炉による２回の加熱処理を施した後の試料について、２０ｍＡの電流を通電し、点灯しなかった試料の数を計測した。そして、点灯しなかった試料の数が０個である場合を○（吸湿リフロー性が良好である）、点灯しなかった試料の数が１個以上である場合を×（吸湿リフロー性が不良である）と評価した。結果を表１に示す。 Moisture absorption reflow test
The optical semiconductor device manufactured above was used as a sample. Ten samples were used for each curable silicone resin composition. In addition, the sample was used after confirming that it lights up, when an electric current of 20 mA is supplied before a test.
The above sample was placed in a constant temperature and humidity chamber (manufactured by Espec Corp., model number “SH-641”) adjusted to 30 ° C. and 60% RH, and taken out after 192 hours. Subsequently, heat treatment was performed twice at 260 ° C. for 10 seconds using each of the above samples using a reflow furnace (manufactured by ANTOM Co., Ltd., model number “UNI-5016F”). Thereafter, a current of 20 mA was applied to the sample after the two heat treatments by the reflow furnace, and the number of samples which did not light was measured. And, when the number of samples which were not lighted is 0, ((good in moisture absorption reflowability), when the number of samples which were not lighted is 1 or more, x (hygroscopic reflow property is not good Yes). The results are shown in Table 1.
［総合判定］
実施例及び比較例で得られた硬化性シリコーン樹脂組成物について、ＳＯX腐食性試験、熱衝撃性試験、及び吸湿リフロー試験の３項目の評価結果に基づき、以下の基準で総合判定を行った。
○（良好である）：ＳＯX腐食性試験の評価結果が８０％以上であり、熱衝撃性試験の評価結果が○であり、吸湿リフロー試験の評価結果が○である。
×（不良である）：ＳＯX腐食性試験の評価結果が８０％以上であること、熱衝撃性試験の評価結果が○であること、及び吸湿リフロー試験の評価結果が○であることのうちの１つでも満たさないもの [Comprehensive judgment]
About the curable silicone resin composition obtained by the Example and the comparative example, based on the evaluation result of three items, a SO X corrosion test, a thermal shock test, and a moisture absorption reflow test, comprehensive judgment was performed on the following criteria .
○ (Good): The evaluation result of the SO X corrosion test is 80% or more, the evaluation result of the thermal shock test is ○, and the evaluation result of the moisture absorption reflow test is ○.
X (defective): out of the evaluation results of the SO X corrosion test being 80% or more, the evaluation results of the thermal shock test being 、, and the evaluation results of the moisture absorption reflow test being ○ What does not satisfy even one of
実施例及び比較例で得られた硬化性シリコーン樹脂組成物について、ＳＯX腐食性試験、熱衝撃性試験、及び吸湿リフロー試験の３項目の評価結果に基づき、以下の基準で総合判定を行った。
○（良好である）：ＳＯX腐食性試験の評価結果が８０％以上であり、熱衝撃性試験の評価結果が○であり、吸湿リフロー試験の評価結果が○である。
×（不良である）：ＳＯX腐食性試験の評価結果が８０％以上であること、熱衝撃性試験の評価結果が○であること、及び吸湿リフロー試験の評価結果が○であることのうちの１つでも満たさないもの [Comprehensive judgment]
About the curable silicone resin composition obtained by the Example and the comparative example, based on the evaluation result of three items, a SO X corrosion test, a thermal shock test, and a moisture absorption reflow test, comprehensive judgment was performed on the following criteria .
○ (Good): The evaluation result of the SO X corrosion test is 80% or more, the evaluation result of the thermal shock test is ○, and the evaluation result of the moisture absorption reflow test is ○.
X (defective): out of the evaluation results of the SO X corrosion test being 80% or more, the evaluation results of the thermal shock test being 、, and the evaluation results of the moisture absorption reflow test being ○ What does not satisfy even one of
上記で説明した本発明のバリエーションを以下に付記する。
［１］下記の（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を含むことを特徴とする硬化性シリコーン樹脂組成物。
（Ａ）：分子内に２個以上のアルケニル基（好ましくはビニル基）及び１個以上のアリール基（好ましくはフェニル基）を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基（好ましくはビニル基）及び１個以上のアリール基（好ましくはフェニル基）を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上（好ましくは２個以上、より好ましくは２～５０個）のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
［式（１）中、Ｒa、Ｒb、及びＲcは、同一又は異なって、式（１ａ）で表される基、式（１ｂ）で表される基、水素原子、又はアルキル基を示す。但し、Ｒa、Ｒb、及びＲcのうち少なくとも１個（好ましくは２又は３個、より好ましくは３個）は、式（１ａ）で表される基である。
［式（１ａ）中、Ｒdは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（好ましくは水素原子）を示す。ｓは２～１０（好ましくは２～８、より好ましくは２～６、さらに好ましくは２～４）の整数を示す。］
［式（１ｂ）中、Ｒeは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（好ましくは水素原子）を示す。ｔは１～１０（好ましくは１～６）の整数を示す。］］
（Ｄ）：分子内に１個以上（好ましくは２個以上、より好ましくは２～５０個）のアルケニル基（好ましくはビニル基）を有する分岐鎖状のポリオルガノシロキサン
［２］前記ポリオルガノシロキサン（Ａ１）が、アルケニル基及びアリール基以外に、アルキル基（好ましくはメチル基）を有する、前記［１］に記載の硬化性シリコーン樹脂組成物。
［３］前記ポリオルガノシロキサン（Ａ１）が、下記平均単位式：
（Ｒ1aＳｉＯ3/2）a1（Ｒ1a 2ＳｉＯ2/2）a2（Ｒ1a 3ＳｉＯ1/2）a3（ＳｉＯ4/2）a4（Ｘ1aＯ1/2）a5
［平均単位式中、Ｒ1aは、同一又は異なって、一価の置換又は無置換炭化水素基である。Ｒ1aの一部はアルケニル基（好ましくはビニル基）であり、その割合は、分子内に２個以上である。Ｒ1aの一部はアリール基（好ましくはフェニル基）であり、その割合は、分子内に１個以上である。Ｘ1は、水素原子又はアルキル基（好ましくはメチル基）である。ａ１は０又は正数、ａ２は０又は正数、ａ３は０又は正数、ａ４は０又は正数、ａ５は０又は正数であり、かつ、（ａ１＋ａ２＋ａ３）は正数である。］
で表されるポリオルガノシロキサンである、前記［１］又は［２］に記載の硬化性シリコーン樹脂組成物。
［４］Ｒ1aの全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［３］に記載の硬化性シリコーン樹脂組成物。
［５］Ｒ1aの全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、３０～７０モル％である、前記［３］又は［４］に記載の硬化性シリコーン樹脂組成物。
［６］アルケニル基、アリール基以外のＲ1aが、アルキル基（好ましくはメチル基）である、前記［３］～［５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 The variations of the present invention described above are additionally described below.
[1] A curable silicone resin composition comprising the following components (A), (B), (C) and (D).
(A): Polyorganosiloxane (A1) having two or more alkenyl groups (preferably vinyl group) and one or more aryl groups (preferably phenyl group) in the molecule and two or more alkenyl groups in the molecule Polysiloxane (B) which is at least one member selected from the group consisting of polyorganosiloxysil alkylene (A2) having (preferably a vinyl group) and one or more aryl groups (preferably a phenyl group): Polyorganosiloxane having one or more (preferably 2 or more, more preferably 2 to 50) hydrosilyl groups and having no aliphatic unsaturated group (C): Isocyanate represented by the following formula (1) Nurate compound
[In Formula (1), R a , R b , and R c are the same or different and each represents a group represented by Formula (1a), a group represented by Formula (1b), a hydrogen atom, or an alkyl group Show. However, at least one (preferably 2 or 3 and more preferably 3) of R a , R b and R c is a group represented by Formula (1a).
In formula (1a), R d represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom). s represents an integer of 2 to 10 (preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4). ]
[In the formula (1b), R e represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom). t represents an integer of 1 to 10 (preferably 1 to 6). ]]
(D): A branched polyorganosiloxane having one or more (preferably 2 or more, more preferably 2 to 50) alkenyl groups (preferably vinyl groups) in the molecule [2] the polyorganosiloxane The curable silicone resin composition as described in said [1] in which (A1) has an alkyl group (preferably methyl group) other than an alkenyl group and an aryl group.
[3] The polyorganosiloxane (A1) has the following average unit formula:
(R 1a SiO 3/2 ) a1 (R 1a 2 SiO 2/2 ) a2 (R 1a 3 SiO 1/2 ) a3 (SiO 4/2 ) a4 (X 1a O 1/2 ) a5
[In the unit formula, R 1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R 1a is an alkenyl group (preferably a vinyl group), and the ratio is 2 or more in the molecule. A part of R 1a is an aryl group (preferably a phenyl group), and the proportion is at least one in the molecule. X 1 is a hydrogen atom or an alkyl group (preferably a methyl group). a1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1 + a2 + a3) is a positive number. ]
The curable silicone resin composition as described in said [1] or [2] which is a polyorganosiloxane represented by these.
[4] The curable silicone resin composition as described in [3] above, wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of R 1a is 0.1 to 40 mol%.
[5] The curable silicone resin composition according to the above [3] or [4], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of R 1a is 30 to 70 mol%. .
[6] The curable silicone resin composition according to any one of the above [3] to [5], wherein R 1a other than an alkenyl group and an aryl group is an alkyl group (preferably a methyl group).
［１］下記の（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を含むことを特徴とする硬化性シリコーン樹脂組成物。
（Ａ）：分子内に２個以上のアルケニル基（好ましくはビニル基）及び１個以上のアリール基（好ましくはフェニル基）を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基（好ましくはビニル基）及び１個以上のアリール基（好ましくはフェニル基）を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上（好ましくは２個以上、より好ましくは２～５０個）のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
（Ｄ）：分子内に１個以上（好ましくは２個以上、より好ましくは２～５０個）のアルケニル基（好ましくはビニル基）を有する分岐鎖状のポリオルガノシロキサン
［２］前記ポリオルガノシロキサン（Ａ１）が、アルケニル基及びアリール基以外に、アルキル基（好ましくはメチル基）を有する、前記［１］に記載の硬化性シリコーン樹脂組成物。
［３］前記ポリオルガノシロキサン（Ａ１）が、下記平均単位式：
（Ｒ1aＳｉＯ3/2）a1（Ｒ1a 2ＳｉＯ2/2）a2（Ｒ1a 3ＳｉＯ1/2）a3（ＳｉＯ4/2）a4（Ｘ1aＯ1/2）a5
［平均単位式中、Ｒ1aは、同一又は異なって、一価の置換又は無置換炭化水素基である。Ｒ1aの一部はアルケニル基（好ましくはビニル基）であり、その割合は、分子内に２個以上である。Ｒ1aの一部はアリール基（好ましくはフェニル基）であり、その割合は、分子内に１個以上である。Ｘ1は、水素原子又はアルキル基（好ましくはメチル基）である。ａ１は０又は正数、ａ２は０又は正数、ａ３は０又は正数、ａ４は０又は正数、ａ５は０又は正数であり、かつ、（ａ１＋ａ２＋ａ３）は正数である。］
で表されるポリオルガノシロキサンである、前記［１］又は［２］に記載の硬化性シリコーン樹脂組成物。
［４］Ｒ1aの全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［３］に記載の硬化性シリコーン樹脂組成物。
［５］Ｒ1aの全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、３０～７０モル％である、前記［３］又は［４］に記載の硬化性シリコーン樹脂組成物。
［６］アルケニル基、アリール基以外のＲ1aが、アルキル基（好ましくはメチル基）である、前記［３］～［５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 The variations of the present invention described above are additionally described below.
[1] A curable silicone resin composition comprising the following components (A), (B), (C) and (D).
(A): Polyorganosiloxane (A1) having two or more alkenyl groups (preferably vinyl group) and one or more aryl groups (preferably phenyl group) in the molecule and two or more alkenyl groups in the molecule Polysiloxane (B) which is at least one member selected from the group consisting of polyorganosiloxysil alkylene (A2) having (preferably a vinyl group) and one or more aryl groups (preferably a phenyl group): Polyorganosiloxane having one or more (preferably 2 or more, more preferably 2 to 50) hydrosilyl groups and having no aliphatic unsaturated group (C): Isocyanate represented by the following formula (1) Nurate compound
(D): A branched polyorganosiloxane having one or more (preferably 2 or more, more preferably 2 to 50) alkenyl groups (preferably vinyl groups) in the molecule [2] the polyorganosiloxane The curable silicone resin composition as described in said [1] in which (A1) has an alkyl group (preferably methyl group) other than an alkenyl group and an aryl group.
[3] The polyorganosiloxane (A1) has the following average unit formula:
(R 1a SiO 3/2 ) a1 (R 1a 2 SiO 2/2 ) a2 (R 1a 3 SiO 1/2 ) a3 (SiO 4/2 ) a4 (X 1a O 1/2 ) a5
[In the unit formula, R 1a is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R 1a is an alkenyl group (preferably a vinyl group), and the ratio is 2 or more in the molecule. A part of R 1a is an aryl group (preferably a phenyl group), and the proportion is at least one in the molecule. X 1 is a hydrogen atom or an alkyl group (preferably a methyl group). a1 is 0 or a positive number, a2 is 0 or a positive number, a3 is 0 or a positive number, a4 is 0 or a positive number, a5 is 0 or a positive number, and (a1 + a2 + a3) is a positive number. ]
The curable silicone resin composition as described in said [1] or [2] which is a polyorganosiloxane represented by these.
[4] The curable silicone resin composition as described in [3] above, wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of R 1a is 0.1 to 40 mol%.
[5] The curable silicone resin composition according to the above [3] or [4], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of R 1a is 30 to 70 mol%. .
[6] The curable silicone resin composition according to any one of the above [3] to [5], wherein R 1a other than an alkenyl group and an aryl group is an alkyl group (preferably a methyl group).
［７］前記ポリオルガノシロキサン（Ａ１）が、分子内に２個以上のアルケニル基（好ましくはビニル基）及び１個以上のアリール基（好ましくはフェニル基）を有する直鎖状ポリオルガノシロキサンである、前記［１］～［６］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［８］前記ポリオルガノシロキサン（Ａ１）が、さらに、アルキル基（好ましくはメチル基）を有する、前記［７］に記載の硬化性シリコーン樹脂組成物。
［９］ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［７］又は［８］に記載の硬化性シリコーン樹脂組成物。
［１０］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、４０～６０モル％（好ましくは５０モル％以上、より好ましくは５５～６０モル％）である、前記［８］又は［９］に記載の硬化性シリコーン樹脂組成物。
［１１］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、３０～７０モル％（好ましくは４０モル％以上、より好ましくは４５～７０モル％）である、前記［７］～［１０］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［１２］前記ポリオルガノシロキサン（Ａ１）が、下記式（Ｉ－１）で表される、前記［１］～［１１］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［上記式中、Ｒ11は、同一又は異なって、一価の置換又は無置換の炭化水素基である。但し、Ｒ11の少なくとも２個はアルケニル基（好ましくはビニル基）であり、少なくとも１個はアリール基（好ましくはフェニル基）である。ｍ１は、５～１０００の整数である］
[7] The polyorganosiloxane (A1) is a linear polyorganosiloxane having two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) in the molecule. The curable silicone resin composition according to any one of the above [1] to [6].
[8] The curable silicone resin composition as described in [7] above, wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).
[9] The compound according to the above [7] or [8], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 0.1 to 40 mol% Curable silicone resin composition.
[10] The proportion of the alkyl group (preferably methyl group) is 40 to 60 mol% (preferably 50 mol% or more, more preferably 55 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition as described in said [8] or [9] which is it.
[11] The proportion of aryl group (preferably phenyl group) is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to any one of the above [7] to [10], which is
[12] The curable silicone resin composition according to any one of the above [1] to [11], wherein the polyorganosiloxane (A1) is represented by the following formula (I-1).
[In the above formula, R 11 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 11 are alkenyl groups (preferably vinyl groups), and at least one is an aryl group (preferably phenyl group). m1 is an integer of 5 to 1000]
［８］前記ポリオルガノシロキサン（Ａ１）が、さらに、アルキル基（好ましくはメチル基）を有する、前記［７］に記載の硬化性シリコーン樹脂組成物。
［９］ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［７］又は［８］に記載の硬化性シリコーン樹脂組成物。
［１０］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、４０～６０モル％（好ましくは５０モル％以上、より好ましくは５５～６０モル％）である、前記［８］又は［９］に記載の硬化性シリコーン樹脂組成物。
［１１］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、３０～７０モル％（好ましくは４０モル％以上、より好ましくは４５～７０モル％）である、前記［７］～［１０］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［１２］前記ポリオルガノシロキサン（Ａ１）が、下記式（Ｉ－１）で表される、前記［１］～［１１］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
[8] The curable silicone resin composition as described in [7] above, wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).
[9] The compound according to the above [7] or [8], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 0.1 to 40 mol% Curable silicone resin composition.
[10] The proportion of the alkyl group (preferably methyl group) is 40 to 60 mol% (preferably 50 mol% or more, more preferably 55 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition as described in said [8] or [9] which is it.
[11] The proportion of aryl group (preferably phenyl group) is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to any one of the above [7] to [10], which is
[12] The curable silicone resin composition according to any one of the above [1] to [11], wherein the polyorganosiloxane (A1) is represented by the following formula (I-1).
［１３］前記ポリオルガノシロキサン（Ａ１）が、分子内に２個以上のアルケニル基（好ましくはビニル基）及び１個以上のアリール基（好ましくはフェニル基）を有し、ＲaＳｉＯ3/2［Ｒaは、一価の置換又は無置換炭化水素基である。］で表されるシロキサン単位（Ｔ単位）を有する分岐鎖状ポリオルガノシロキサンである、前記［１］～［１２］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［１４］前記ポリオルガノシロキサン（Ａ１）が、さらに、アルキル基（好ましくはメチル基）を有する、前記［１３］に記載の硬化性シリコーン樹脂組成物。
［１５］ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［１３］又は［１４］に記載の硬化性シリコーン樹脂組成物。
［１６］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、４０～６０モル％（好ましくは５０モル％以上、より好ましくは５５～６０モル％）である、前記［１４］又は［１５］に記載の硬化性シリコーン樹脂組成物。
［１７］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、３０～７０モル％（好ましくは４０モル％以上、より好ましくは４５～７０モル％）である、前記［１３］～［１６］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [13] The polyorganosiloxane (A1) has two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) in the molecule, and R a SiO 3/2 [ Ra is a monovalent substituted or unsubstituted hydrocarbon group. The curable silicone resin composition according to any one of the above [1] to [12], which is a branched polyorganosiloxane having a siloxane unit (T unit) represented by the formula:
[14] The curable silicone resin composition as described in [13] above, wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).
[15] The compound according to the above [13] or [14], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 0.1 to 40 mol% Curable silicone resin composition.
[16] The proportion of the alkyl group (preferably methyl group) is 40 to 60 mol% (preferably 50 mol% or more, more preferably 55 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition as described in said [14] or [15] which is it.
[17] The proportion of aryl groups (preferably phenyl groups) is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to any one of the above [13] to [16], which is
［１４］前記ポリオルガノシロキサン（Ａ１）が、さらに、アルキル基（好ましくはメチル基）を有する、前記［１３］に記載の硬化性シリコーン樹脂組成物。
［１５］ケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［１３］又は［１４］に記載の硬化性シリコーン樹脂組成物。
［１６］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、４０～６０モル％（好ましくは５０モル％以上、より好ましくは５５～６０モル％）である、前記［１４］又は［１５］に記載の硬化性シリコーン樹脂組成物。
［１７］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、３０～７０モル％（好ましくは４０モル％以上、より好ましくは４５～７０モル％）である、前記［１３］～［１６］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [13] The polyorganosiloxane (A1) has two or more alkenyl groups (preferably vinyl groups) and one or more aryl groups (preferably phenyl groups) in the molecule, and R a SiO 3/2 [ Ra is a monovalent substituted or unsubstituted hydrocarbon group. The curable silicone resin composition according to any one of the above [1] to [12], which is a branched polyorganosiloxane having a siloxane unit (T unit) represented by the formula:
[14] The curable silicone resin composition as described in [13] above, wherein the polyorganosiloxane (A1) further has an alkyl group (preferably a methyl group).
[15] The compound according to the above [13] or [14], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom is 0.1 to 40 mol% Curable silicone resin composition.
[16] The proportion of the alkyl group (preferably methyl group) is 40 to 60 mol% (preferably 50 mol% or more, more preferably 55 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition as described in said [14] or [15] which is it.
[17] The proportion of aryl groups (preferably phenyl groups) is 30 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 70 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to any one of the above [13] to [16], which is
［１８］前記ポリオルガノシロキシシルアルキレン（Ａ２）が分子内に有するシルアルキレン結合におけるアルキレン基が、直鎖又は分岐鎖状のＣ1-12アルキレン基（好ましくはＣ2-4アルキレン基、より好ましくはエチレン基）である、前記［１］～［１７］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［１９］前記ポリオルガノシロキシシルアルキレン（Ａ２）が、さらに、アルキル基（好ましくはメチル基）を有する、前記［１］～［１８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［２０］前記ポリオルガノシロキシシルアルキレン（Ａ２）が、下記平均単位式：
（Ｒ1b 2ＳｉＯ2/2）b1（Ｒ1b 3ＳｉＯ1/2）b2（Ｒ1bＳｉＯ3/2）b3（ＳｉＯ4/2）b4（ＲA）b5（Ｘ1bＯ）b6
［平均単位式中、Ｒ1bは、同一又は異なって、一価の置換又は無置換炭化水素基である。Ｒ1bの一部はアルケニル基（好ましくはビニル基）であり、その割合は、分子内に２個以上である。Ｒ1bの一部はアリール基（好ましくはフェニル基）であり、その割合は、分子内に１個以上である。ＲAは、アルキレン基（好ましくはエチレン基）である。Ｘ1bは、水素原子又はアルキル基（好ましくはメチル基）である。ｂ１は正数（好ましくは１～２００）、ｂ２は正数（好ましくは１～２００）、ｂ３は０又は正数（好ましくは０～１０）、ｂ４は０又は正数（好ましくは０～５）、ｂ５は正数（好ましくは１～１００）、ｂ６は０又は正数である。］
で表されるポリオルガノシロキシシルアルキレンである、前記［１］～［１９］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［２１］Ｒ1bの全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［２０］に記載の硬化性シリコーン樹脂組成物。
［２２］Ｒ1bの全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、１０～５０モル％である、前記［２０］又は［２１］に記載の硬化性シリコーン樹脂組成物。 [18] The alkylene group in the silalkylene bond which the polyorganosiloxysil alkylene (A2) has in the molecule is a linear or branched C 1-12 alkylene group (preferably a C 2-4 alkylene group, more preferably Is an ethylene group). The curable silicone resin composition according to any one of the above [1] to [17].
[19] The curable silicone resin composition according to any one of the above [1] to [18], wherein the polyorganosiloxycyl alkylene (A2) further has an alkyl group (preferably a methyl group).
[20] The polyorganosiloxycyl alkylene (A2) has the following average unit formula:
(R 1 b 2 SiO 2/2 ) b 1 (R 1 b 3 SiO 1/2 ) b 2 (R 1 b SiO 3/2 ) b 3 (SiO 4/2 ) b 4 (R A ) b 5 (X 1 b O) b 6
[In the unit formula, R 1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R 1b is an alkenyl group (preferably a vinyl group), and the ratio is 2 or more in the molecule. A part of R 1b is an aryl group (preferably a phenyl group), and the proportion is at least one in the molecule. R A is an alkylene group (preferably an ethylene group).X 1 b is a hydrogen atom or an alkyl group (preferably a methyl group). b1 is a positive number (preferably 1 to 200), b2 is a positive number (preferably 1 to 200), b3 is 0 or a positive number (preferably 0 to 10), b4 is 0 or a positive number (preferably 0 to 5) B5 is a positive number (preferably 1 to 100), and b6 is 0 or a positive number. ]
The curable silicone resin composition according to any one of the above [1] to [19], which is a polyorganosiloxycyl alkylene represented by
[21] The curable silicone resin composition as described in [20] above, wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of R 1b is 0.1 to 40 mol%.
[22] The curable silicone resin composition according to the above [20] or [21], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of R 1b is 10 to 50 mol% .
［１９］前記ポリオルガノシロキシシルアルキレン（Ａ２）が、さらに、アルキル基（好ましくはメチル基）を有する、前記［１］～［１８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［２０］前記ポリオルガノシロキシシルアルキレン（Ａ２）が、下記平均単位式：
（Ｒ1b 2ＳｉＯ2/2）b1（Ｒ1b 3ＳｉＯ1/2）b2（Ｒ1bＳｉＯ3/2）b3（ＳｉＯ4/2）b4（ＲA）b5（Ｘ1bＯ）b6
［平均単位式中、Ｒ1bは、同一又は異なって、一価の置換又は無置換炭化水素基である。Ｒ1bの一部はアルケニル基（好ましくはビニル基）であり、その割合は、分子内に２個以上である。Ｒ1bの一部はアリール基（好ましくはフェニル基）であり、その割合は、分子内に１個以上である。ＲAは、アルキレン基（好ましくはエチレン基）である。Ｘ1bは、水素原子又はアルキル基（好ましくはメチル基）である。ｂ１は正数（好ましくは１～２００）、ｂ２は正数（好ましくは１～２００）、ｂ３は０又は正数（好ましくは０～１０）、ｂ４は０又は正数（好ましくは０～５）、ｂ５は正数（好ましくは１～１００）、ｂ６は０又は正数である。］
で表されるポリオルガノシロキシシルアルキレンである、前記［１］～［１９］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［２１］Ｒ1bの全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［２０］に記載の硬化性シリコーン樹脂組成物。
［２２］Ｒ1bの全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、１０～５０モル％である、前記［２０］又は［２１］に記載の硬化性シリコーン樹脂組成物。 [18] The alkylene group in the silalkylene bond which the polyorganosiloxysil alkylene (A2) has in the molecule is a linear or branched C 1-12 alkylene group (preferably a C 2-4 alkylene group, more preferably Is an ethylene group). The curable silicone resin composition according to any one of the above [1] to [17].
[19] The curable silicone resin composition according to any one of the above [1] to [18], wherein the polyorganosiloxycyl alkylene (A2) further has an alkyl group (preferably a methyl group).
[20] The polyorganosiloxycyl alkylene (A2) has the following average unit formula:
(
[In the unit formula, R 1b is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. A part of R 1b is an alkenyl group (preferably a vinyl group), and the ratio is 2 or more in the molecule. A part of R 1b is an aryl group (preferably a phenyl group), and the proportion is at least one in the molecule. R A is an alkylene group (preferably an ethylene group).
The curable silicone resin composition according to any one of the above [1] to [19], which is a polyorganosiloxycyl alkylene represented by
[21] The curable silicone resin composition as described in [20] above, wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of R 1b is 0.1 to 40 mol%.
[22] The curable silicone resin composition according to the above [20] or [21], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of R 1b is 10 to 50 mol% .
［２３］前記ポリオルガノシロキシシルアルキレン（Ａ２）が、下記式（Ｉ－２）で表される構造を有するポリオルガノシロキシシルアルキレンである、前記［１］～［２２］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［式（Ｉ－２）中、Ｒ12は、同一又は異なって、水素原子、又は一価の置換若しくは無置換炭化水素基である。但し、Ｒ12の少なくとも２個はアルケニル基（好ましくはビニル基）であり、Ｒ12の少なくとも１個はアリール基（好ましくはフェニル基）である。ＲAは、アルキレン基（好ましくはＣ2-4アルキレン基、より好ましくはエチレン基）である。ｒ１は１以上の整数（好ましくは１～１００）を示す。ｒ２は１以上の整数（好ましくは１～４００）を示す。ｒ３は０又は１以上の整数（好ましくは０～５０）を示す。ｒ４は０又は１以上の整数（好ましくは０～５０）を示す。ｒ５は０又は１以上の整数（好ましくは０～５０）を示す。］
［２４］アルケニル基及びアリール基以外のＲ12が、アルキル基（好ましくはメチル基）である、前記［２３］に記載の硬化性シリコーン樹脂組成物。
［２５］前記（Ａ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．１～６０重量％（好ましくは０．１～５５重量％、より好ましくは０．１～５０重量％）である、前記［１］～［２４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [23] In any one of the above-mentioned [1] to [22], wherein the polyorganosiloxycyl alkylene (A2) is a polyorganosiloxycyl alkylene having a structure represented by the following formula (I-2) Curable silicone resin composition as described.
[In Formula (I-2), R 12 is the same or different and is a hydrogen atom, or a monovalent substituted or unsubstituted hydrocarbon group. However, at least two of R 12 are an alkenyl group (preferably a vinyl group), and at least one of R 12 is an aryl group (preferably a phenyl group). R A is an alkylene group (preferably a C 2-4 alkylene group, more preferably an ethylene group). r1 represents an integer of 1 or more (preferably 1 to 100). r2 represents an integer of 1 or more (preferably 1 to 400). r3 represents 0 or an integer of 1 or more (preferably 0 to 50). r4 represents 0 or an integer of 1 or more (preferably 0 to 50). r5 represents 0 or an integer of 1 or more (preferably 0 to 50). ]
[24] The curable silicone resin composition as described in [23] above, wherein R 12 other than an alkenyl group and an aryl group is an alkyl group (preferably a methyl group).
[25] The content (blending amount) of the component (A) is 0.1 to 60% by weight (preferably 0.1 to 55% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to any one of the above [1] to [24], which is more preferably 0.1 to 50% by weight.
［２４］アルケニル基及びアリール基以外のＲ12が、アルキル基（好ましくはメチル基）である、前記［２３］に記載の硬化性シリコーン樹脂組成物。
［２５］前記（Ａ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．１～６０重量％（好ましくは０．１～５５重量％、より好ましくは０．１～５０重量％）である、前記［１］～［２４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [23] In any one of the above-mentioned [1] to [22], wherein the polyorganosiloxycyl alkylene (A2) is a polyorganosiloxycyl alkylene having a structure represented by the following formula (I-2) Curable silicone resin composition as described.
[24] The curable silicone resin composition as described in [23] above, wherein R 12 other than an alkenyl group and an aryl group is an alkyl group (preferably a methyl group).
[25] The content (blending amount) of the component (A) is 0.1 to 60% by weight (preferably 0.1 to 55% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to any one of the above [1] to [24], which is more preferably 0.1 to 50% by weight.
［２６］前記ポリオルガノシロキサン（Ｂ１）が、下記平均単位式：
（Ｒ2ＳｉＯ3/2）c1（Ｒ2 2ＳｉＯ2/2）c2（Ｒ2 3ＳｉＯ1/2）c3（ＳｉＯ4/2）c4（Ｘ2Ｏ1/2）c5
［上記平均単位式中、Ｒ2は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）である。但し、Ｒ2の一部は水素原子（ヒドロシリル基を構成する水素原子）であり、その割合は、ヒドロシリル基が分子内に１個以上（好ましくは２個以上）である。Ｘ2は、水素原子又はアルキル基（好ましくはメチル基）である。ｃ１は０又は正数、ｃ２は０又は正数、ｃ３は０又は正数、ｃ４は０又は正数、ｃ５は０又は正数であり、かつ、（ｃ１＋ｃ２＋ｃ３）は正数である。］
で表されるポリオルガノシロキサンである、前記［１］～［２５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［２７］Ｒ2の全量（１００モル％）に対する水素原子の割合が、０．１～４０モル％である、前記［２６］に記載の硬化性シリコーン樹脂組成物。
［２８］水素原子以外のＲ2が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［２６］又は［２７］に記載の硬化性シリコーン樹脂組成物。 [26] The polyorganosiloxane (B1) has the following average unit formula:
(R 2 SiO 3/2 ) c 1 (R 2 2 SiO 2/2 ) c 2 (R 2 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (X 2 O 1/2 ) c 5
[In the above average unit formula, R 2 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, aliphatic unsaturated groups are excluded). However, a part of R 2 is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the proportion thereof is that the hydrosilyl group is one or more (preferably two or more) in the molecule. X 2 is a hydrogen atom or an alkyl group (preferably a methyl group). c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1 + c2 + c3) is a positive number. ]
The curable silicone resin composition according to any one of the above [1] to [25], which is a polyorganosiloxane represented by
[27] The curable silicone resin composition as described in [26] above, wherein the ratio of hydrogen atoms to the total amount (100 mol%) of R 2 is 0.1 to 40 mol%.
[28] to the above [26] or [27], wherein R 2 other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
（Ｒ2ＳｉＯ3/2）c1（Ｒ2 2ＳｉＯ2/2）c2（Ｒ2 3ＳｉＯ1/2）c3（ＳｉＯ4/2）c4（Ｘ2Ｏ1/2）c5
［上記平均単位式中、Ｒ2は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）である。但し、Ｒ2の一部は水素原子（ヒドロシリル基を構成する水素原子）であり、その割合は、ヒドロシリル基が分子内に１個以上（好ましくは２個以上）である。Ｘ2は、水素原子又はアルキル基（好ましくはメチル基）である。ｃ１は０又は正数、ｃ２は０又は正数、ｃ３は０又は正数、ｃ４は０又は正数、ｃ５は０又は正数であり、かつ、（ｃ１＋ｃ２＋ｃ３）は正数である。］
で表されるポリオルガノシロキサンである、前記［１］～［２５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［２７］Ｒ2の全量（１００モル％）に対する水素原子の割合が、０．１～４０モル％である、前記［２６］に記載の硬化性シリコーン樹脂組成物。
［２８］水素原子以外のＲ2が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［２６］又は［２７］に記載の硬化性シリコーン樹脂組成物。 [26] The polyorganosiloxane (B1) has the following average unit formula:
(R 2 SiO 3/2 ) c 1 (R 2 2 SiO 2/2 ) c 2 (R 2 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (X 2 O 1/2 ) c 5
[In the above average unit formula, R 2 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (however, aliphatic unsaturated groups are excluded). However, a part of R 2 is a hydrogen atom (a hydrogen atom constituting a hydrosilyl group), and the proportion thereof is that the hydrosilyl group is one or more (preferably two or more) in the molecule. X 2 is a hydrogen atom or an alkyl group (preferably a methyl group). c1 is 0 or a positive number, c2 is 0 or a positive number, c3 is 0 or a positive number, c4 is 0 or a positive number, c5 is 0 or a positive number, and (c1 + c2 + c3) is a positive number. ]
The curable silicone resin composition according to any one of the above [1] to [25], which is a polyorganosiloxane represented by
[27] The curable silicone resin composition as described in [26] above, wherein the ratio of hydrogen atoms to the total amount (100 mol%) of R 2 is 0.1 to 40 mol%.
[28] to the above [26] or [27], wherein R 2 other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
［２９］前記ポリオルガノシロキサン（Ｂ１）が、分子内に１個以上（好ましくは２個以上）のヒドロシリル基を有する直鎖状ポリオルガノシロキサンである、前記［１］～［２８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［３０］水素原子以外のケイ素原子に結合した基が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［２９］に記載の硬化性シリコーン樹脂組成物。
［３１］ケイ素原子に結合した基の全量（１００モル％）に対する水素原子（ケイ素原子に結合した水素原子）の割合が、０．１～４０モル％である、前記［２９］又は［３０］に記載の硬化性シリコーン樹脂組成物。
［３２］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、２０～９９モル％（好ましくは９０モル％以上、より好ましくは９５～９９モル％）である、前記［３０］又は［３１］に記載の硬化性シリコーン樹脂組成物。
［３３］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、１０～５０モル％（好ましくは２０～５０モル％）である、前記［３０］～［３２］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［３４］前記ポリオルガノシロキサン（Ｂ１）が、下記式（ＩＩ－１）で表される、前記［１］～［３３］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［上記式中、Ｒ21は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）である。但し、Ｒ21の少なくとも１個（好ましくは少なくとも２個）は水素原子である。ｍ２は、５～１０００の整数である。］
[29] Any of the above-mentioned [1] to [28], wherein the polyorganosiloxane (B1) is a linear polyorganosiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule. The curable silicone resin composition as described in one.
[30] In the above-mentioned [29], the group bonded to a silicon atom other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
[31] The above [29] or [30], wherein the ratio of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount (100 mol%) of groups bonded to silicon atoms is 0.1 to 40 mol%. The curable silicone resin composition as described in 4.
[32] The proportion of alkyl group (preferably methyl group) is 20 to 99 mol% (preferably 90 mol% or more, more preferably 95 to 99 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition as described in said [30] or [31] which is it.
[33] The ratio of an aryl group (preferably a phenyl group) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 to 50 mol% (preferably 20 to 50 mol%) [30] The curable silicone resin composition according to any one of [32].
[34] The curable silicone resin composition according to any one of the above [1] to [33], wherein the polyorganosiloxane (B1) is represented by the following formula (II-1):
[In the above-mentioned formula, R 21 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups). However, at least one (preferably at least two) of R 21 is a hydrogen atom. m2 is an integer of 5 to 1000. ]
［３０］水素原子以外のケイ素原子に結合した基が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［２９］に記載の硬化性シリコーン樹脂組成物。
［３１］ケイ素原子に結合した基の全量（１００モル％）に対する水素原子（ケイ素原子に結合した水素原子）の割合が、０．１～４０モル％である、前記［２９］又は［３０］に記載の硬化性シリコーン樹脂組成物。
［３２］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、２０～９９モル％（好ましくは９０モル％以上、より好ましくは９５～９９モル％）である、前記［３０］又は［３１］に記載の硬化性シリコーン樹脂組成物。
［３３］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、１０～５０モル％（好ましくは２０～５０モル％）である、前記［３０］～［３２］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［３４］前記ポリオルガノシロキサン（Ｂ１）が、下記式（ＩＩ－１）で表される、前記［１］～［３３］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
[30] In the above-mentioned [29], the group bonded to a silicon atom other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
[31] The above [29] or [30], wherein the ratio of hydrogen atoms (hydrogen atoms bonded to silicon atoms) to the total amount (100 mol%) of groups bonded to silicon atoms is 0.1 to 40 mol%. The curable silicone resin composition as described in 4.
[32] The proportion of alkyl group (preferably methyl group) is 20 to 99 mol% (preferably 90 mol% or more, more preferably 95 to 99 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition as described in said [30] or [31] which is it.
[33] The ratio of an aryl group (preferably a phenyl group) to the total amount (100 mol%) of groups bonded to silicon atoms is 10 to 50 mol% (preferably 20 to 50 mol%) [30] The curable silicone resin composition according to any one of [32].
[34] The curable silicone resin composition according to any one of the above [1] to [33], wherein the polyorganosiloxane (B1) is represented by the following formula (II-1):
［３５］前記ポリオルガノシロキサン（Ｂ１）が、分子内に１個以上（好ましくは２個以上）のヒドロシリル基を有し、ＲbＳｉＯ3/2［Ｒbは、水素原子、又は、一価の置換若しくは無置換炭化水素基（但し、脂肪族不飽和基は除かれる）である。］で表されるシロキサン単位（Ｔ単位）を有する分岐鎖状ポリオルガノシロキサンである、前記［１］～［３４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［３６］水素原子以外のケイ素原子に結合した基が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［３５］に記載の硬化性シリコーン樹脂組成物。
［３７］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、７０～９５モル％（好ましくは５０モル％以上、より好ましくは５０～９０モル％）である、前記［３６］に記載の硬化性シリコーン樹脂組成物。
［３８］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、１０～７０モル％である、前記［３６］又は［３７］に記載の硬化性シリコーン樹脂組成物。
［３９］前記（Ｂ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、１～６０重量％（好ましくは５～５５重量％、より好ましくは１０～５０重量％）である、前記［１］～［３８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [35] The polyorganosiloxane (B1) has one or more (preferably two or more) hydrosilyl groups in the molecule, R b SiO 3/2 [R b is a hydrogen atom or a monovalent atom. Or a substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups). The curable silicone resin composition according to any one of the above [1] to [34], which is a branched polyorganosiloxane having a siloxane unit (T unit) represented by the formula:
[36] In the above [35], the group bonded to a silicon atom other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
[37] The ratio of the alkyl group (preferably methyl group) to the total amount (100 mol%) of groups bonded to silicon atoms is 70 to 95 mol% (preferably 50 mol% or more, more preferably 50 to 90 mol%) The curable silicone resin composition according to the above [36], which is
[38] The curability according to the above [36] or [37], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 10 to 70 mol% Silicone resin composition.
[39] The content (blending amount) of the component (B) is 1 to 60% by weight (preferably 5 to 55% by weight, more preferably 10) to the curable silicone resin composition (100% by weight). The curable silicone resin composition according to any one of the above [1] to [38], which is ̃50% by weight).
［３６］水素原子以外のケイ素原子に結合した基が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［３５］に記載の硬化性シリコーン樹脂組成物。
［３７］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、７０～９５モル％（好ましくは５０モル％以上、より好ましくは５０～９０モル％）である、前記［３６］に記載の硬化性シリコーン樹脂組成物。
［３８］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、１０～７０モル％である、前記［３６］又は［３７］に記載の硬化性シリコーン樹脂組成物。
［３９］前記（Ｂ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、１～６０重量％（好ましくは５～５５重量％、より好ましくは１０～５０重量％）である、前記［１］～［３８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [35] The polyorganosiloxane (B1) has one or more (preferably two or more) hydrosilyl groups in the molecule, R b SiO 3/2 [R b is a hydrogen atom or a monovalent atom. Or a substituted or unsubstituted hydrocarbon group (with the exception of aliphatic unsaturated groups). The curable silicone resin composition according to any one of the above [1] to [34], which is a branched polyorganosiloxane having a siloxane unit (T unit) represented by the formula:
[36] In the above [35], the group bonded to a silicon atom other than a hydrogen atom is at least one selected from the group consisting of an alkyl group (preferably methyl group) and an aryl group (preferably phenyl group) Curable silicone resin composition as described.
[37] The ratio of the alkyl group (preferably methyl group) to the total amount (100 mol%) of groups bonded to silicon atoms is 70 to 95 mol% (preferably 50 mol% or more, more preferably 50 to 90 mol%) The curable silicone resin composition according to the above [36], which is
[38] The curability according to the above [36] or [37], wherein the ratio of the aryl group (preferably phenyl group) to the total amount (100 mol%) of the groups bonded to silicon atoms is 10 to 70 mol% Silicone resin composition.
[39] The content (blending amount) of the component (B) is 1 to 60% by weight (preferably 5 to 55% by weight, more preferably 10) to the curable silicone resin composition (100% by weight). The curable silicone resin composition according to any one of the above [1] to [38], which is ̃50% by weight).
［４０］前記（Ｃ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～１０重量％（好ましくは０．０３～５重量％、より好ましくは０．０５～３重量％、さらに好ましくは０．１～２重量％）である、前記［１］～［３９］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
[40] The content (blending amount) of the component (C) is 0.01 to 10% by weight (preferably 0.03 to 5% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to any one of the above [1] to [39], which is more preferably 0.05 to 3% by weight, still more preferably 0.1 to 2% by weight.
［４１］前記（Ｄ）成分が、下記平均単位式：
（Ｒ8ＳｉＯ3/2）d1（Ｒ8 2ＳｉＯ2/2）d2（Ｒ8 3ＳｉＯ1/2）d3（ＳｉＯ4/2）d4（Ｘ3Ｏ1/2）d5
［上記平均単位式中、Ｒ8は、同一又は異なって、一価の置換又は無置換炭化水素基である。但し、Ｒ8の一部はアルケニル基（好ましくはビニル基）であり、その割合は、分子内に１個以上（好ましくは２個以上）である。Ｘ3は、水素原子又はアルキル基（好ましくはメチル基）である。ｄ１は０又は正数、ｄ２は０又は正数、ｄ３は０又は正数、ｄ４は０又は正数、ｄ５は０又は正数であり、かつ、（ｄ１＋ｄ２＋ｄ３）及び（ｄ１＋ｄ４）がそれぞれ正数である。］
で表されるポリオルガノシロキサンである、前記［１］～［４０］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４２］前記（Ｄ）成分におけるアルケニル基以外のケイ素原子に結合した基が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［１］～［４１］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４３］前記（Ｄ）成分におけるケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［１］～［４２］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４４］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、２０～６０モル％（好ましくは３０モル％以上、より好ましくは３５～６０モル％）である、前記［４２］又は［４３］に記載の硬化性シリコーン樹脂組成物。
［４５］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、５～７０モル％（好ましくは４０モル％以上、より好ましくは４５～６０モル％）である、前記［４２］～［４４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４６］前記（Ｄ）成分の含有量（配合量）が、前記（Ａ）成分及び前記（Ｂ）成分の合計１００重量部に対して、５０～２００重量部（好ましくは７５～１７５重量部、より好ましくは１００～１５０重量部）である、前記［１］～［４５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [41] The component (D) has the following average unit formula:
(R 8 SiO 3/2) d1 ( R 8 2 SiO 2/2) d2 (R 8 3SiO 1/2) d3 (SiO 4/2) d4 (X 3 O 1/2) d5
[In the above average unit formula, R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, a part of R 8 is an alkenyl group (preferably a vinyl group), and the ratio is 1 or more (preferably 2 or more) in the molecule. X 3 is a hydrogen atom or an alkyl group (preferably a methyl group). d1 is 0 or a positive number, d2 is 0 or a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is 0 or a positive number, and (d1 + d2 + d3) and (d1 + d4) are each a positive number It is. ]
The curable silicone resin composition according to any one of the above [1] to [40], which is a polyorganosiloxane represented by
[42] The group bonded to a silicon atom other than an alkenyl group in the component (D) is at least one selected from the group consisting of an alkyl group (preferably a methyl group) and an aryl group (preferably a phenyl group) The curable silicone resin composition according to any one of the above [1] to [41].
[43] The above [1] to [1], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom in the component (D) is 0.1 to 40 mol% The curable silicone resin composition as described in any one of [42].
[44] The proportion of alkyl group (preferably methyl group) is 20 to 60 mol% (preferably 30 mol% or more, more preferably 35 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to the above [42] or [43], which is
[45] The proportion of the aryl group (preferably phenyl group) is 5 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to any one of the above [42] to [44], which is
[46] The content (blending amount) of the component (D) is 50 to 200 parts by weight (preferably 75 to 175 parts by weight) based on 100 parts by weight of the total of the components (A) and (B). The curable silicone resin composition according to any one of the above [1] to [45], which is more preferably 100 to 150 parts by weight.
（Ｒ8ＳｉＯ3/2）d1（Ｒ8 2ＳｉＯ2/2）d2（Ｒ8 3ＳｉＯ1/2）d3（ＳｉＯ4/2）d4（Ｘ3Ｏ1/2）d5
［上記平均単位式中、Ｒ8は、同一又は異なって、一価の置換又は無置換炭化水素基である。但し、Ｒ8の一部はアルケニル基（好ましくはビニル基）であり、その割合は、分子内に１個以上（好ましくは２個以上）である。Ｘ3は、水素原子又はアルキル基（好ましくはメチル基）である。ｄ１は０又は正数、ｄ２は０又は正数、ｄ３は０又は正数、ｄ４は０又は正数、ｄ５は０又は正数であり、かつ、（ｄ１＋ｄ２＋ｄ３）及び（ｄ１＋ｄ４）がそれぞれ正数である。］
で表されるポリオルガノシロキサンである、前記［１］～［４０］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４２］前記（Ｄ）成分におけるアルケニル基以外のケイ素原子に結合した基が、アルキル基（好ましくはメチル基）、及びアリール基（好ましくはフェニル基）からなる群から選ばれる少なくとも１種である、前記［１］～［４１］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４３］前記（Ｄ）成分におけるケイ素原子に結合した基の全量（１００モル％）に対するアルケニル基（好ましくはビニル基）の割合が、０．１～４０モル％である、前記［１］～［４２］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４４］ケイ素原子に結合した基の全量（１００モル％）に対するアルキル基（好ましくはメチル基）の割合が、２０～６０モル％（好ましくは３０モル％以上、より好ましくは３５～６０モル％）である、前記［４２］又は［４３］に記載の硬化性シリコーン樹脂組成物。
［４５］ケイ素原子に結合した基の全量（１００モル％）に対するアリール基（好ましくはフェニル基）の割合が、５～７０モル％（好ましくは４０モル％以上、より好ましくは４５～６０モル％）である、前記［４２］～［４４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［４６］前記（Ｄ）成分の含有量（配合量）が、前記（Ａ）成分及び前記（Ｂ）成分の合計１００重量部に対して、５０～２００重量部（好ましくは７５～１７５重量部、より好ましくは１００～１５０重量部）である、前記［１］～［４５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [41] The component (D) has the following average unit formula:
(R 8 SiO 3/2) d1 ( R 8 2 SiO 2/2) d2 (R 8 3
[In the above average unit formula, R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group. However, a part of R 8 is an alkenyl group (preferably a vinyl group), and the ratio is 1 or more (preferably 2 or more) in the molecule. X 3 is a hydrogen atom or an alkyl group (preferably a methyl group). d1 is 0 or a positive number, d2 is 0 or a positive number, d3 is 0 or a positive number, d4 is 0 or a positive number, d5 is 0 or a positive number, and (d1 + d2 + d3) and (d1 + d4) are each a positive number It is. ]
The curable silicone resin composition according to any one of the above [1] to [40], which is a polyorganosiloxane represented by
[42] The group bonded to a silicon atom other than an alkenyl group in the component (D) is at least one selected from the group consisting of an alkyl group (preferably a methyl group) and an aryl group (preferably a phenyl group) The curable silicone resin composition according to any one of the above [1] to [41].
[43] The above [1] to [1], wherein the ratio of the alkenyl group (preferably vinyl group) to the total amount (100 mol%) of the groups bonded to the silicon atom in the component (D) is 0.1 to 40 mol% The curable silicone resin composition as described in any one of [42].
[44] The proportion of alkyl group (preferably methyl group) is 20 to 60 mol% (preferably 30 mol% or more, more preferably 35 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to the above [42] or [43], which is
[45] The proportion of the aryl group (preferably phenyl group) is 5 to 70 mol% (preferably 40 mol% or more, more preferably 45 to 60 mol%) based on the total amount (100 mol%) of groups bonded to silicon atoms The curable silicone resin composition according to any one of the above [42] to [44], which is
[46] The content (blending amount) of the component (D) is 50 to 200 parts by weight (preferably 75 to 175 parts by weight) based on 100 parts by weight of the total of the components (A) and (B). The curable silicone resin composition according to any one of the above [1] to [45], which is more preferably 100 to 150 parts by weight.
［４６］下記の（Ｅ）成分を含む、前記［１］～［４５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
（Ｅ）：白金族金属を含むヒドロシリル化触媒
［４７］前記（Ｅ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物に含まれるアルケニル基の全量１モル（１モル当たり）に対して、１×１０-8～１×１０-2モル（好ましくは１．０×１０-6～１．０×１０-3モル）である、前記［４６］に記載の硬化性シリコーン樹脂組成物。
［４８］前記（Ｅ）成分の含有量（配合量）が、ヒドロシリル化触媒中の白金族金属が重量単位で、０．０１～１０００ｐｐｍの範囲内となる量（好ましくは０．１～５００ｐｐｍの範囲内となる量）である、前記［４６］又は［４７］に記載の硬化性シリコーン樹脂組成物。 [46] The curable silicone resin composition as described in any one of the above [1] to [45], which comprises the following component (E).
(E): Hydrosilylation catalyst containing platinum group metal [47] The content (blending amount) of the component (E) is the total amount (per mole) of alkenyl groups contained in the curable silicone resin composition. On the other hand, the curable silicone resin composition according to the above [46], which is 1 × 10 −8 to 1 × 10 −2 mole (preferably 1.0 × 10 −6 to 1.0 × 10 −3 mole) object.
[48] The content (blending amount) of the component (E) is such that the weight of the platinum group metal in the hydrosilylation catalyst is in the range of 0.01 to 1000 ppm (preferably 0.1 to 500 ppm) The curable silicone resin composition according to the above [46] or [47], wherein the amount is within the range.
（Ｅ）：白金族金属を含むヒドロシリル化触媒
［４７］前記（Ｅ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物に含まれるアルケニル基の全量１モル（１モル当たり）に対して、１×１０-8～１×１０-2モル（好ましくは１．０×１０-6～１．０×１０-3モル）である、前記［４６］に記載の硬化性シリコーン樹脂組成物。
［４８］前記（Ｅ）成分の含有量（配合量）が、ヒドロシリル化触媒中の白金族金属が重量単位で、０．０１～１０００ｐｐｍの範囲内となる量（好ましくは０．１～５００ｐｐｍの範囲内となる量）である、前記［４６］又は［４７］に記載の硬化性シリコーン樹脂組成物。 [46] The curable silicone resin composition as described in any one of the above [1] to [45], which comprises the following component (E).
(E): Hydrosilylation catalyst containing platinum group metal [47] The content (blending amount) of the component (E) is the total amount (per mole) of alkenyl groups contained in the curable silicone resin composition. On the other hand, the curable silicone resin composition according to the above [46], which is 1 × 10 −8 to 1 × 10 −2 mole (preferably 1.0 × 10 −6 to 1.0 × 10 −3 mole) object.
[48] The content (blending amount) of the component (E) is such that the weight of the platinum group metal in the hydrosilylation catalyst is in the range of 0.01 to 1000 ppm (preferably 0.1 to 500 ppm) The curable silicone resin composition according to the above [46] or [47], wherein the amount is within the range.
［４９］下記の（Ｇ）成分を含む、前記［１］～［４８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
（Ｇ）：下記式（２）で表されるイソシアヌレート化合物
［式（２）中、Ｒf、Ｒg、及びＲhは、同一又は異なって、式（２ａ）で表される基、又は式（２ｂ）で表される基を示す。但し、Ｒf、Ｒg、及びＲhのうち少なくとも１個は、式（２ｂ）で表される基である。］
［式（２ａ）中、Ｒiは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（好ましくは水素原子）を示す。］
［式（２ｂ）中、Ｒjは、水素原子又は炭素数１～８の直鎖若しくは分岐鎖状のアルキル基（好ましくは水素原子）を示す。］］
［５０］前記（Ｇ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～６重量％（好ましくは０．０５～４重量％、より好ましくは０．１～３重量％）である、前記［４９］に記載の硬化性シリコーン樹脂組成物。
［５１］前記（Ｃ）成分と前記（Ｇ）成分の含有量の合計（合計含有量）が、硬化性シリコーン樹脂組成物に対して、０．０１～１５重量％（好ましくは０．１～１０重量％、より好ましくは０．２～３重量％、さらに好ましくは０．４～２重量％）である、前記［４９］又は［５０］に記載の硬化性シリコーン樹脂組成物。 [49] The curable silicone resin composition according to any one of the above [1] to [48], which comprises the following component (G):
(G): isocyanurate compound represented by the following formula (2)
[In Formula (2), R f , R g , and R h are the same or different and each represents a group represented by Formula (2a) or a group represented by Formula (2b). However, at least one of R f , R g and R h is a group represented by formula (2b). ]
[In the formula (2a), R i represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom). ]
[In the formula (2b), R j represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms (preferably a hydrogen atom). ]]
[50] The content (blending amount) of the component (G) is 0.01 to 6% by weight (preferably 0.05 to 4% by weight) based on 100% by weight of the curable silicone resin composition, The curable silicone resin composition according to the above [49], which is more preferably 0.1 to 3% by weight).
[51] The total (total content) of the content of the component (C) and the component (G) is 0.01 to 15% by weight (preferably 0.1 to 15% by weight) based on the curable silicone resin composition. The curable silicone resin composition according to the above [49] or [50], which is 10% by weight, more preferably 0.2 to 3% by weight, still more preferably 0.4 to 2% by weight.
（Ｇ）：下記式（２）で表されるイソシアヌレート化合物
［５０］前記（Ｇ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～６重量％（好ましくは０．０５～４重量％、より好ましくは０．１～３重量％）である、前記［４９］に記載の硬化性シリコーン樹脂組成物。
［５１］前記（Ｃ）成分と前記（Ｇ）成分の含有量の合計（合計含有量）が、硬化性シリコーン樹脂組成物に対して、０．０１～１５重量％（好ましくは０．１～１０重量％、より好ましくは０．２～３重量％、さらに好ましくは０．４～２重量％）である、前記［４９］又は［５０］に記載の硬化性シリコーン樹脂組成物。 [49] The curable silicone resin composition according to any one of the above [1] to [48], which comprises the following component (G):
(G): isocyanurate compound represented by the following formula (2)
[50] The content (blending amount) of the component (G) is 0.01 to 6% by weight (preferably 0.05 to 4% by weight) based on 100% by weight of the curable silicone resin composition, The curable silicone resin composition according to the above [49], which is more preferably 0.1 to 3% by weight).
[51] The total (total content) of the content of the component (C) and the component (G) is 0.01 to 15% by weight (preferably 0.1 to 15% by weight) based on the curable silicone resin composition. The curable silicone resin composition according to the above [49] or [50], which is 10% by weight, more preferably 0.2 to 3% by weight, still more preferably 0.4 to 2% by weight.
［５２］下記の（Ｆ）成分を含む、前記［１］～［５１］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
（Ｆ）：分子内に１個以上（好ましくは２個以上）のアルケニル基（好ましくはビニル基）を有するラダー型ポリオルガノシルセスキオキサン
［５３］前記（Ｆ）成分が、分子内に２個以上のアルケニル基（好ましくはビニル基）を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサン（「ラダー型ポリオルガノシルセスキオキサン（ａ）」と称する場合がある）である、前記［５２］に記載の硬化性シリコーン樹脂組成物。
［５４］前記ラダー型ポリオルガノシルセスキオキサン（ａ）のゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量（Ｍｎ）が、５５０～１４５０（好ましくは６００～１４００）である、前記［５３］に記載の硬化性シリコーン樹脂組成物。
［５５］前記ラダー型ポリオルガノシルセスキオキサン（ａ）のゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の分子量分散度（Ｍｗ／Ｍｎ）が、１．０５～１．３５（好ましくは１．１０～１．３０）である、前記［５３］又は［５４］に記載の硬化性シリコーン樹脂組成物。
［５６］前記ラダー型ポリオルガノシルセスキオキサン（ａ）が、下記式（ＩＩＩ－２）で表され、かつ分子内に２個以上のアルケニル基を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量（Ｍｎ）が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサンである、前記［５３］～［５５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［上記式（ＩＩＩ－２）中、Ｒ42は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基である。Ｒ43は、同一又は異なって、水素原子、アルキル基、下記式（ＩＩＩ－２－１）で表される一価の基、下記式（ＩＩＩ－２－２）で表される一価の基、又は、下記式（ＩＩＩ－２－３）で表される一価の基を示す。ｎは０以上の整数（好ましくは２以上の偶数）を示す。
［上記式（ＩＩＩ－２－１）中、Ｒ44は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（好ましくはアルキル基）である。Ｒ45は、同一又は異なって、一価の置換又は無置換炭化水素基（好ましくはアルキル基）である。ｎ１は、０以上（好ましくは０～５、より好ましくは０～３、さらに好ましくは０）の整数を示す。］
［上記式（ＩＩＩ－２－２）中、Ｒ44は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（好ましくはアルキル基）である。Ｒ45は、同一又は異なって、一価の置換又は無置換炭化水素基（好ましくはアルキル基）である。Ｒ46はアルケニル基（好ましくはビニル基）である。ｎ２は、０以上（好ましくは０～５、より好ましくは０～３、さらに好ましくは０）の整数を示す。］
［上記式（ＩＩＩ－２－３）中、Ｒ44は、同一又は異なって、水素原子、又は、一価の置換若しくは無置換炭化水素基（好ましくはアルキル基）である。Ｒ47は、同一又は異なって、一価の飽和脂肪族炭化水素基（好ましくはアルキル基、より好ましくはメチル基）である。ｎ３は、０以上（好ましくは０～５、より好ましくは０～３、さらに好ましくは０）の整数を示す。］］
［５７］前記（Ｆ）成分の含有量（配合量）が、前記（Ａ）成分及び前記（Ｂ）成分の合計１００重量部に対して、０．０１～５０重量部（好ましくは０．０１～４５重量部、より好ましくは０．０１～４０重量部）である、前記［５２］～［５６］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [52] The curable silicone resin composition according to any one of the above [1] to [51], which comprises the following component (F):
(F): Ladder-type polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups (preferably vinyl groups) in the molecule [53] The component (F) has two in the molecule. Have a maximum number of alkenyl groups (preferably vinyl), and have a number average molecular weight of 500 to 1,500 and a molecular weight distribution (Mw / Mn) of 1.00 to 1.40, as determined by gel permeation chromatography, as standard polystyrene equivalent. The curable silicone resin composition as described in the above [52], which is a certain ladder-type polyorganosilsesquioxane (sometimes referred to as "ladder-type polyorganosilsesquioxane (a)").
[54] The gel permeation chromatography of ladder-type polyorganosilsesquioxane (a) has a polystyrene-equivalent number average molecular weight (Mn) of 550 to 1450 (preferably 600 to 1400), [53] ] The curable silicone resin composition as described in.
[55] The molecular weight dispersion degree (Mw / Mn) in terms of standard polystyrene equivalent by gel permeation chromatography of the ladder type polyorganosilsesquioxane (a) is 1.05 to 1.35 (preferably 1.10 to The curable silicone resin composition as described in said [53] or [54] which is 1.30).
[56] The ladder-type polyorganosilsesquioxane (a) is represented by the following formula (III-2) and has two or more alkenyl groups in the molecule, and is a standard polystyrene by gel permeation chromatography [53] to [55], which is a ladder-type polyorganosilsesquioxane having a converted number average molecular weight (Mn) of 500 to 1,500 and a molecular weight dispersion degree (Mw / Mn) of 1.00 to 1.40. The curable silicone resin composition as described in any one of the above.
[In the above formula (III-2), R 42 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group. R 43 is the same or different, and is a hydrogen atom, an alkyl group, a monovalent group represented by the following formula (III-2-1), a monovalent group represented by the following formula (III-2-2) Or a monovalent group represented by the following formula (III-2-3): n is an integer of 0 or more (preferably an even number of 2 or more).
[In the above formula (III-2-1), R 44 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R 45 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). n1 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, further preferably 0). ]
[In the above formula (III-2-2), R 44 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R 45 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R 46 is an alkenyl group (preferably a vinyl group). n2 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, further preferably 0). ]
[In the above formula (III-2-3), R 44 's are the same or different and are a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group (preferably an alkyl group). R 47 is the same or different and is a monovalent saturated aliphatic hydrocarbon group (preferably an alkyl group, more preferably a methyl group). n3 represents an integer of 0 or more (preferably 0 to 5, more preferably 0 to 3, further preferably 0). ]]
[57] The content (blending amount) of the component (F) is preferably 0.01 to 50 parts by weight (preferably 0.01) to 100 parts by weight in total of the components (A) and (B). The curable silicone resin composition according to any one of the above [52] to [56], which is ̃45 parts by weight, more preferably 0.01 to 40 parts by weight.
（Ｆ）：分子内に１個以上（好ましくは２個以上）のアルケニル基（好ましくはビニル基）を有するラダー型ポリオルガノシルセスキオキサン
［５３］前記（Ｆ）成分が、分子内に２個以上のアルケニル基（好ましくはビニル基）を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサン（「ラダー型ポリオルガノシルセスキオキサン（ａ）」と称する場合がある）である、前記［５２］に記載の硬化性シリコーン樹脂組成物。
［５４］前記ラダー型ポリオルガノシルセスキオキサン（ａ）のゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量（Ｍｎ）が、５５０～１４５０（好ましくは６００～１４００）である、前記［５３］に記載の硬化性シリコーン樹脂組成物。
［５５］前記ラダー型ポリオルガノシルセスキオキサン（ａ）のゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の分子量分散度（Ｍｗ／Ｍｎ）が、１．０５～１．３５（好ましくは１．１０～１．３０）である、前記［５３］又は［５４］に記載の硬化性シリコーン樹脂組成物。
［５６］前記ラダー型ポリオルガノシルセスキオキサン（ａ）が、下記式（ＩＩＩ－２）で表され、かつ分子内に２個以上のアルケニル基を有し、ゲルパーミエーションクロマトグラフィーによる標準ポリスチレン換算の数平均分子量（Ｍｎ）が５００～１５００、分子量分散度（Ｍｗ／Ｍｎ）が１．００～１．４０であるラダー型ポリオルガノシルセスキオキサンである、前記［５３］～［５５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［５７］前記（Ｆ）成分の含有量（配合量）が、前記（Ａ）成分及び前記（Ｂ）成分の合計１００重量部に対して、０．０１～５０重量部（好ましくは０．０１～４５重量部、より好ましくは０．０１～４０重量部）である、前記［５２］～［５６］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [52] The curable silicone resin composition according to any one of the above [1] to [51], which comprises the following component (F):
(F): Ladder-type polyorganosilsesquioxane having one or more (preferably two or more) alkenyl groups (preferably vinyl groups) in the molecule [53] The component (F) has two in the molecule. Have a maximum number of alkenyl groups (preferably vinyl), and have a number average molecular weight of 500 to 1,500 and a molecular weight distribution (Mw / Mn) of 1.00 to 1.40, as determined by gel permeation chromatography, as standard polystyrene equivalent. The curable silicone resin composition as described in the above [52], which is a certain ladder-type polyorganosilsesquioxane (sometimes referred to as "ladder-type polyorganosilsesquioxane (a)").
[54] The gel permeation chromatography of ladder-type polyorganosilsesquioxane (a) has a polystyrene-equivalent number average molecular weight (Mn) of 550 to 1450 (preferably 600 to 1400), [53] ] The curable silicone resin composition as described in.
[55] The molecular weight dispersion degree (Mw / Mn) in terms of standard polystyrene equivalent by gel permeation chromatography of the ladder type polyorganosilsesquioxane (a) is 1.05 to 1.35 (preferably 1.10 to The curable silicone resin composition as described in said [53] or [54] which is 1.30).
[56] The ladder-type polyorganosilsesquioxane (a) is represented by the following formula (III-2) and has two or more alkenyl groups in the molecule, and is a standard polystyrene by gel permeation chromatography [53] to [55], which is a ladder-type polyorganosilsesquioxane having a converted number average molecular weight (Mn) of 500 to 1,500 and a molecular weight dispersion degree (Mw / Mn) of 1.00 to 1.40. The curable silicone resin composition as described in any one of the above.
[57] The content (blending amount) of the component (F) is preferably 0.01 to 50 parts by weight (preferably 0.01) to 100 parts by weight in total of the components (A) and (B). The curable silicone resin composition according to any one of the above [52] to [56], which is ̃45 parts by weight, more preferably 0.01 to 40 parts by weight.
［５８］下記の（Ｈ）成分を含む、前記［１］～［５７］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
（Ｈ）：シランカップリング剤
［５９］前記（Ｈ）成分が、エポキシ基含有シランカップリング剤（好ましくは、３－グリシドキシプロピルトリメトキシシラン）である、前記［５８］に記載の硬化性シリコーン樹脂組成物。
［６０］前記（Ｈ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～１５重量％（好ましくは０．１～１０重量％、より好ましくは０．４～５重量％）である、前記［５８］又は［５９］に記載の硬化性シリコーン樹脂組成物。 [58] The curable silicone resin composition as described in any one of the above [1] to [57], which comprises the following (H) component:
(H): Silane coupling agent [59] The curing as described in the above [58], wherein the (H) component is an epoxy group-containing silane coupling agent (preferably 3-glycidoxypropyltrimethoxysilane) Silicone resin composition.
[60] The content (blending amount) of the component (H) is 0.01 to 15% by weight (preferably 0.1 to 10% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to the above [58] or [59], which is more preferably 0.4 to 5% by weight).
（Ｈ）：シランカップリング剤
［５９］前記（Ｈ）成分が、エポキシ基含有シランカップリング剤（好ましくは、３－グリシドキシプロピルトリメトキシシラン）である、前記［５８］に記載の硬化性シリコーン樹脂組成物。
［６０］前記（Ｈ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～１５重量％（好ましくは０．１～１０重量％、より好ましくは０．４～５重量％）である、前記［５８］又は［５９］に記載の硬化性シリコーン樹脂組成物。 [58] The curable silicone resin composition as described in any one of the above [1] to [57], which comprises the following (H) component:
(H): Silane coupling agent [59] The curing as described in the above [58], wherein the (H) component is an epoxy group-containing silane coupling agent (preferably 3-glycidoxypropyltrimethoxysilane) Silicone resin composition.
[60] The content (blending amount) of the component (H) is 0.01 to 15% by weight (preferably 0.1 to 10% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to the above [58] or [59], which is more preferably 0.4 to 5% by weight).
［６１］下記の（Ｉ）成分を含む、前記［１］～［６０］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
（Ｉ）：カルボン酸亜鉛、及び下記式（３）で表される亜鉛錯体又は亜鉛塩（但し、亜鉛ビスアセチルアセトナートを除く）からなる群から選ばれる少なくとも１種の亜鉛化合物
［Ｚｎ（Ｌ１）（Ｌ２）］ （３）
［式中、Ｌ１及びＬ２は、同一又は異なって、下記式（３ａ）
Ｒ31ＣＯＣＨＲ32ＣＯＲ33 （３ａ）
［式（３ａ）中、Ｒ31は、置換若しくは無置換のＣ1-30アルキル基（好ましくは分岐鎖を有するＣ3-10アルキル基）を示す。Ｒ32は、水素原子、又は置換若しくは無置換のＣ1-30アルキル基（好ましくは水素原子）を示す。Ｒ33は、置換若しくは無置換のＣ1-30アルキル基、置換若しくは無置換の芳香族複素環式基、又は－ＯＲ34基を示す。Ｒ34は、置換若しくは無置換のＣ1-30アルキル基を示す。Ｒ31及びＲ32は、互いに結合して環を形成してもよく、上記Ｒ32及びＲ33は、互いに結合して環を形成してもよい。］
で表される、β－ジケトン又はβ－ケトエステルのアニオン若しくはエノラートアニオンを示す。］
［６２］カルボン酸亜鉛が、ナフテン酸亜鉛、オクチル酸亜鉛、アセト酢酸亜鉛、亜鉛(メタ)アクリレート、及び亜鉛ネオデカネートからなる群から選ばれる少なくとも１種（好ましくはナフテン酸亜鉛、及びオクチル酸亜鉛からなる群から選ばれる少なくとも１種、より好ましくはオクチル酸亜鉛）である、前記［６１］に記載の硬化性シリコーン樹脂組成物。
［６３］前記（Ｉ）成分が、式（３’）で表される化合物である、前記［６１］又は［６２］に記載の硬化性シリコーン樹脂組成物。
［式（３’）中、Ｒ35は、置換若しくは無置換のＣ1-30アルキル基（好ましくは分岐鎖を有するＣ3-10アルキル基）を示し、Ｒ36は、水素原子、又は置換若しくは無置換のＣ1-30アルキル基（好ましくは水素原子）を示し、Ｒ37は、置換若しくは無置換のＣ1-30アルキル基、置換若しくは無置換の芳香族複素環式基、又は－ＯＲ38基を示す。Ｒ38は、置換若しくは無置換のＣ1-30アルキル基を示す。Ｒ35及びＲ36は、互いに結合して環を形成してもよく、Ｒ36及びＲ37は、互いに結合して環を形成してもよい］
［６４］前記（Ｉ）成分が、亜鉛ビス（２，２，７－トリメチル－３，５－オクタンジオナート）、及び亜鉛ビスジピバロイルメタンからなる群から選ばれる少なくとも１種である、前記［６１］～［６３］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［６５］前記（Ｉ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～５重量％（好ましくは０．０５～３重量％、より好ましくは０．１～２重量％、さらに好ましくは０．１～１．５重量％）である、前記［６１］～［６４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［６６］前記（Ｉ）成分の含有量（配合量）が、前記（Ａ）成分１００重量部に対して、０．０２～１０重量部（好ましくは０．０５～６重量部、より好ましくは０．１～４重量部、さらに好ましくは０．１～３重量部）である、前記［６１］～［６５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [61] The curable silicone resin composition as described in any one of the above [1] to [60], which comprises the following component (I):
(I): at least one zinc compound selected from the group consisting of zinc carboxylate and a zinc complex or zinc salt represented by the following formula (3) (with the exception of zinc bisacetylacetonate) [Zn (L 1) ) (L2)] (3)
[Wherein,L 1 and L 2 are the same or different and the following formula (3a)
R 31 COCHR 32 COR 33 (3a)
[In formula (3a), R 31 represents a substituted or unsubstituted C 1-30 alkyl group (preferably a C 3-10 alkyl group having a branched chain). R 32 represents a hydrogen atom or a substituted or unsubstituted C 1-30 alkyl group (preferably a hydrogen atom). R 33 represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 34 group. R 34 represents a substituted or unsubstituted C 1-30 alkyl group. R 31 and R 32 may be bonded to each other to form a ring, and the R 32 and R 33 may be bonded to each other to form a ring. ]
The anion or enolate anion of β-diketone or β-ketoester represented by ]
[62] At least one member selected from the group consisting of zinc naphthenate, zinc octylate, zinc acetoacetate, zinc (meth) acrylate, and zinc neodecanate (preferably zinc naphthenate and zinc octylate) The curable silicone resin composition according to the above [61], which is at least one selected from the group consisting of
[63] The curable silicone resin composition according to the above [61] or [62], wherein the component (I) is a compound represented by the formula (3 ′).
[In formula (3 ′), R 35 represents a substituted or unsubstituted C 1-30 alkyl group (preferably a C 3-10 alkyl group having a branched chain), and R 36 represents a hydrogen atom, or a substitution or unsubstituted C 1-30 alkyl group (preferably a hydrogen atom) indicates, R 37 is a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or -OR 38 Indicates a group. R 38 represents a substituted or unsubstituted C 1-30 alkyl group. R 35 and R 36 may be bonded to each other to form a ring, and R 36 and R 37 may be bonded to each other to form a ring]
[64] The component (I) is at least one member selected from the group consisting of zinc bis (2,2,7-trimethyl-3,5-octanedionate) and zinc bisdipivaloylmethane, The curable silicone resin composition according to any one of the above [61] to [63].
[65] The content (blending amount) of the component (I) is 0.01 to 5% by weight (preferably 0.05 to 3% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to any one of the above [61] to [64], which is more preferably 0.1 to 2% by weight, still more preferably 0.1 to 1.5% by weight.
[66] The content (blending amount) of the component (I) is preferably 0.02 to 10 parts by weight (preferably 0.05 to 6 parts by weight, more preferably 100 parts by weight of the component (A)). The curable silicone resin composition according to any one of the above [61] to [65], which is 0.1 to 4 parts by weight, more preferably 0.1 to 3 parts by weight.
（Ｉ）：カルボン酸亜鉛、及び下記式（３）で表される亜鉛錯体又は亜鉛塩（但し、亜鉛ビスアセチルアセトナートを除く）からなる群から選ばれる少なくとも１種の亜鉛化合物
［Ｚｎ（Ｌ１）（Ｌ２）］ （３）
［式中、Ｌ１及びＬ２は、同一又は異なって、下記式（３ａ）
Ｒ31ＣＯＣＨＲ32ＣＯＲ33 （３ａ）
［式（３ａ）中、Ｒ31は、置換若しくは無置換のＣ1-30アルキル基（好ましくは分岐鎖を有するＣ3-10アルキル基）を示す。Ｒ32は、水素原子、又は置換若しくは無置換のＣ1-30アルキル基（好ましくは水素原子）を示す。Ｒ33は、置換若しくは無置換のＣ1-30アルキル基、置換若しくは無置換の芳香族複素環式基、又は－ＯＲ34基を示す。Ｒ34は、置換若しくは無置換のＣ1-30アルキル基を示す。Ｒ31及びＲ32は、互いに結合して環を形成してもよく、上記Ｒ32及びＲ33は、互いに結合して環を形成してもよい。］
で表される、β－ジケトン又はβ－ケトエステルのアニオン若しくはエノラートアニオンを示す。］
［６２］カルボン酸亜鉛が、ナフテン酸亜鉛、オクチル酸亜鉛、アセト酢酸亜鉛、亜鉛(メタ)アクリレート、及び亜鉛ネオデカネートからなる群から選ばれる少なくとも１種（好ましくはナフテン酸亜鉛、及びオクチル酸亜鉛からなる群から選ばれる少なくとも１種、より好ましくはオクチル酸亜鉛）である、前記［６１］に記載の硬化性シリコーン樹脂組成物。
［６３］前記（Ｉ）成分が、式（３’）で表される化合物である、前記［６１］又は［６２］に記載の硬化性シリコーン樹脂組成物。
［６４］前記（Ｉ）成分が、亜鉛ビス（２，２，７－トリメチル－３，５－オクタンジオナート）、及び亜鉛ビスジピバロイルメタンからなる群から選ばれる少なくとも１種である、前記［６１］～［６３］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［６５］前記（Ｉ）成分の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～５重量％（好ましくは０．０５～３重量％、より好ましくは０．１～２重量％、さらに好ましくは０．１～１．５重量％）である、前記［６１］～［６４］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［６６］前記（Ｉ）成分の含有量（配合量）が、前記（Ａ）成分１００重量部に対して、０．０２～１０重量部（好ましくは０．０５～６重量部、より好ましくは０．１～４重量部、さらに好ましくは０．１～３重量部）である、前記［６１］～［６５］のいずれか１つに記載の硬化性シリコーン樹脂組成物。 [61] The curable silicone resin composition as described in any one of the above [1] to [60], which comprises the following component (I):
(I): at least one zinc compound selected from the group consisting of zinc carboxylate and a zinc complex or zinc salt represented by the following formula (3) (with the exception of zinc bisacetylacetonate) [Zn (L 1) ) (L2)] (3)
[Wherein,
R 31 COCHR 32 COR 33 (3a)
[In formula (3a), R 31 represents a substituted or unsubstituted C 1-30 alkyl group (preferably a C 3-10 alkyl group having a branched chain). R 32 represents a hydrogen atom or a substituted or unsubstituted C 1-30 alkyl group (preferably a hydrogen atom). R 33 represents a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted aromatic heterocyclic group, or an —OR 34 group. R 34 represents a substituted or unsubstituted C 1-30 alkyl group. R 31 and R 32 may be bonded to each other to form a ring, and the R 32 and R 33 may be bonded to each other to form a ring. ]
The anion or enolate anion of β-diketone or β-ketoester represented by ]
[62] At least one member selected from the group consisting of zinc naphthenate, zinc octylate, zinc acetoacetate, zinc (meth) acrylate, and zinc neodecanate (preferably zinc naphthenate and zinc octylate) The curable silicone resin composition according to the above [61], which is at least one selected from the group consisting of
[63] The curable silicone resin composition according to the above [61] or [62], wherein the component (I) is a compound represented by the formula (3 ′).
[64] The component (I) is at least one member selected from the group consisting of zinc bis (2,2,7-trimethyl-3,5-octanedionate) and zinc bisdipivaloylmethane, The curable silicone resin composition according to any one of the above [61] to [63].
[65] The content (blending amount) of the component (I) is 0.01 to 5% by weight (preferably 0.05 to 3% by weight) with respect to the curable silicone resin composition (100% by weight), The curable silicone resin composition according to any one of the above [61] to [64], which is more preferably 0.1 to 2% by weight, still more preferably 0.1 to 1.5% by weight.
[66] The content (blending amount) of the component (I) is preferably 0.02 to 10 parts by weight (preferably 0.05 to 6 parts by weight, more preferably 100 parts by weight of the component (A)). The curable silicone resin composition according to any one of the above [61] to [65], which is 0.1 to 4 parts by weight, more preferably 0.1 to 3 parts by weight.
［６７］さらに蛍光体を含む、前記［１］～［６６］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［６８］前記蛍光体の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～２０重量％（好ましくは０．５～１０重量％）である、前記［６７］に記載の硬化性シリコーン樹脂組成物。 [67] The curable silicone resin composition according to any one of the above [1] to [66], further comprising a phosphor.
[68] The content (blending amount) of the phosphor is 0.01 to 20% by weight (preferably 0.5 to 10% by weight) based on 100% by weight of the curable silicone resin composition. The curable silicone resin composition according to [67].
［６８］前記蛍光体の含有量（配合量）が、硬化性シリコーン樹脂組成物（１００重量％）に対して、０．０１～２０重量％（好ましくは０．５～１０重量％）である、前記［６７］に記載の硬化性シリコーン樹脂組成物。 [67] The curable silicone resin composition according to any one of the above [1] to [66], further comprising a phosphor.
[68] The content (blending amount) of the phosphor is 0.01 to 20% by weight (preferably 0.5 to 10% by weight) based on 100% by weight of the curable silicone resin composition. The curable silicone resin composition according to [67].
［６９］前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物の硬化物。
［７０］半導体封止用樹脂組成物である、前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［７１］前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物の半導体封止用樹脂組成物としての使用。
［７２］光半導体用レンズの形成用樹脂組成物である、前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［７３］前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物の光半導体用レンズの形成用樹脂組成物としての使用。
［７４］光半導体素子と、該光半導体素子を封止する封止材とを含み、前記封止材が前記［７０］に記載の硬化性シリコーン樹脂組成物の硬化物であることを特徴とする光半導体装置。
［７５］光半導体素子とレンズとを含み、前記レンズが前記［７２］に記載の硬化性シリコーン樹脂組成物の硬化物であることを特徴とする光半導体装置。 [69] A cured product of the curable silicone resin composition as described in any one of the above [1] to [68].
[70] The curable silicone resin composition according to any one of the above [1] to [68], which is a resin composition for semiconductor encapsulation.
[71] Use of the curable silicone resin composition as described in any one of the above [1] to [68] as a resin composition for semiconductor encapsulation.
[72] The curable silicone resin composition according to any one of the above [1] to [68], which is a resin composition for forming a lens for an optical semiconductor.
[73] Use of the curable silicone resin composition according to any one of the above [1] to [68] as a resin composition for forming a lens for an optical semiconductor.
[74] A photosemiconductor element, and a sealing material for sealing the photosemiconductor element, wherein the sealing material is a cured product of the curable silicone resin composition according to the above [70]. Optical semiconductor device.
[75] An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable silicone resin composition according to [72].
［７０］半導体封止用樹脂組成物である、前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［７１］前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物の半導体封止用樹脂組成物としての使用。
［７２］光半導体用レンズの形成用樹脂組成物である、前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物。
［７３］前記［１］～［６８］のいずれか１つに記載の硬化性シリコーン樹脂組成物の光半導体用レンズの形成用樹脂組成物としての使用。
［７４］光半導体素子と、該光半導体素子を封止する封止材とを含み、前記封止材が前記［７０］に記載の硬化性シリコーン樹脂組成物の硬化物であることを特徴とする光半導体装置。
［７５］光半導体素子とレンズとを含み、前記レンズが前記［７２］に記載の硬化性シリコーン樹脂組成物の硬化物であることを特徴とする光半導体装置。 [69] A cured product of the curable silicone resin composition as described in any one of the above [1] to [68].
[70] The curable silicone resin composition according to any one of the above [1] to [68], which is a resin composition for semiconductor encapsulation.
[71] Use of the curable silicone resin composition as described in any one of the above [1] to [68] as a resin composition for semiconductor encapsulation.
[72] The curable silicone resin composition according to any one of the above [1] to [68], which is a resin composition for forming a lens for an optical semiconductor.
[73] Use of the curable silicone resin composition according to any one of the above [1] to [68] as a resin composition for forming a lens for an optical semiconductor.
[74] A photosemiconductor element, and a sealing material for sealing the photosemiconductor element, wherein the sealing material is a cured product of the curable silicone resin composition according to the above [70]. Optical semiconductor device.
[75] An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable silicone resin composition according to [72].
本発明の硬化性シリコーン樹脂組成物は、特に光半導体装置における光半導体素子（ＬＥＤ素子）の封止材や光学レンズを形成するための材料（封止剤、レンズ形成用樹脂組成物）として好ましく使用することができる。
The curable silicone resin composition of the present invention is particularly preferable as a sealing material for an optical semiconductor element (LED element) in an optical semiconductor device or a material for forming an optical lens (sealing agent, resin composition for forming a lens) It can be used.
１００：リフレクター（光反射用樹脂組成物）
１０１：金属配線（電極）
１０２：光半導体素子
１０３：ボンディングワイヤ
１０４：硬化物（封止材） 100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor device 103: Bonding wire 104: Cured product (sealing material)
１０１：金属配線（電極）
１０２：光半導体素子
１０３：ボンディングワイヤ
１０４：硬化物（封止材） 100: Reflector (resin composition for light reflection)
101: Metal wiring (electrode)
102: Optical semiconductor device 103: Bonding wire 104: Cured product (sealing material)
Claims (11)
- 下記の（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を含むことを特徴とする硬化性シリコーン樹脂組成物。
（Ａ）：分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキサン（Ａ１）及び分子内に２個以上のアルケニル基及び１個以上のアリール基を有するポリオルガノシロキシシルアルキレン（Ａ２）からなる群より選択される少なくとも１種であるポリシロキサン
（Ｂ）：分子内に１個以上のヒドロシリル基を有し、脂肪族不飽和基を有しないポリオルガノシロキサン
（Ｃ）：下記式（１）で表されるイソシアヌレート化合物
（Ｄ）：分子内に１個以上のアルケニル基を有する分岐鎖状のポリオルガノシロキサン A curable silicone resin composition comprising the following components (A), (B), (C) and (D).
(A): Polyorganosiloxane (A1) having two or more alkenyl groups and one or more aryl groups in the molecule and polyorganosiloxy having two or more alkenyl groups and one or more aryl groups in the molecule Polysiloxane (B) which is at least one selected from the group consisting of silalkylene (A2): polyorganosiloxane having one or more hydrosilyl groups in the molecule and having no aliphatic unsaturated group (C) : Isocyanurate compound represented by the following formula (1)
(D): branched polyorganosiloxane having one or more alkenyl groups in the molecule - 下記の（Ｅ）成分を含む請求項１に記載の硬化性シリコーン樹脂組成物。
（Ｅ）：白金族金属を含むヒドロシリル化触媒 The curable silicone resin composition according to claim 1, comprising the following component (E).
(E): hydrosilylation catalyst containing platinum group metal - 下記の（Ｇ）成分を含む請求項１又は２に記載の硬化性シリコーン樹脂組成物。
（Ｇ）：下記式（２）で表されるイソシアヌレート化合物
(G): isocyanurate compound represented by the following formula (2)
- 下記の（Ｆ）成分を含む請求項１～３のいずれか１項に記載の硬化性シリコーン樹脂組成物。
（Ｆ）：分子内に１個以上のアルケニル基を有するラダー型ポリオルガノシルセスキオキサン The curable silicone resin composition according to any one of claims 1 to 3, which comprises the following component (F).
(F): Ladder-type polyorganosilsesquioxane having one or more alkenyl groups in the molecule - 下記の（Ｈ）成分を含む請求項１～４のいずれか１項に記載の硬化性シリコーン樹脂組成物。
（Ｈ）：シランカップリング剤 The curable silicone resin composition according to any one of claims 1 to 4, which comprises the following component (H).
(H): Silane coupling agent - さらに蛍光体を含む請求項１～５のいずれか１項に記載の硬化性シリコーン樹脂組成物。 The curable silicone resin composition according to any one of claims 1 to 5, further comprising a phosphor.
- 請求項１～６のいずれか１項に記載の硬化性シリコーン樹脂組成物の硬化物。 A cured product of the curable silicone resin composition according to any one of claims 1 to 6.
- 光半導体封止用樹脂組成物である請求項１～６のいずれか１項に記載の硬化性シリコーン樹脂組成物。 The curable silicone resin composition according to any one of claims 1 to 6, which is a resin composition for encapsulating an optical semiconductor.
- 光半導体用レンズの形成用樹脂組成物である請求項１～６のいずれか１項に記載の硬化性シリコーン樹脂組成物。 The curable silicone resin composition according to any one of claims 1 to 6, which is a resin composition for forming a lens for an optical semiconductor.
- 光半導体素子と、該光半導体素子を封止する封止材とを含み、前記封止材が請求項８に記載の硬化性シリコーン樹脂組成物の硬化物であることを特徴とする光半導体装置。 An optical semiconductor device comprising: an optical semiconductor element; and a sealing material for sealing the optical semiconductor element, wherein the sealing material is a cured product of the curable silicone resin composition according to claim 8. .
- 光半導体素子とレンズとを含み、前記レンズが請求項９に記載の硬化性シリコーン樹脂組成物の硬化物であることを特徴とする光半導体装置。 An optical semiconductor device comprising an optical semiconductor element and a lens, wherein the lens is a cured product of the curable silicone resin composition according to claim 9.
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| US20220064382A1 (en) * | 2020-04-14 | 2022-03-03 | Shin-Etsu Chemical Co., Ltd. | Silylated isocyanurate compound, metal corrosion inhibitor, curable organosilicon resin composition, and semiconductor apparatus |
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| TW201906933A (en) | 2019-02-16 |
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