JP2018104576A - Silicone resin composition and optical semiconductor device - Google Patents
Silicone resin composition and optical semiconductor device Download PDFInfo
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- JP2018104576A JP2018104576A JP2016253192A JP2016253192A JP2018104576A JP 2018104576 A JP2018104576 A JP 2018104576A JP 2016253192 A JP2016253192 A JP 2016253192A JP 2016253192 A JP2016253192 A JP 2016253192A JP 2018104576 A JP2018104576 A JP 2018104576A
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- resin composition
- silicone resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 47
- 230000003287 optical effect Effects 0.000 title claims abstract description 22
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 54
- -1 diphenylsiloxane units Chemical group 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- 125000001931 aliphatic group Chemical group 0.000 claims description 36
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 125000002723 alicyclic group Chemical group 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 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 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 11
- 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 11
- 150000003961 organosilicon compounds Chemical class 0.000 description 11
- 229920000647 polyepoxide Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000004756 silanes Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 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
- 230000000737 periodic effect Effects 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 5
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 5
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- QXBYUPMEYVDXIQ-UHFFFAOYSA-N 4-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound CC1CCCC2C(=O)OC(=O)C12 QXBYUPMEYVDXIQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004954 Polyphthalamide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006375 polyphtalamide Polymers 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- UJPWWRPNIRRCPJ-UHFFFAOYSA-L strontium;dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Sr+2] UJPWWRPNIRRCPJ-UHFFFAOYSA-L 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Led Device Packages (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ジフェニルシロキサン単位を多く含みながらも耐熱性、耐光性に優れるシリコーン樹脂組成物及びそのシリコーン樹脂組成物の硬化物で封止してなる光半導体装置に関する。 The present invention relates to a silicone resin composition excellent in heat resistance and light resistance while containing many diphenylsiloxane units, and an optical semiconductor device formed by sealing with a cured product of the silicone resin composition.
接着性や機械的強度に優れるビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂或いは脂環式エポキシ樹脂のようなＵＶ吸収の無いエポキシ樹脂、硬化剤、及び硬化触媒を含む組成物が光半導体素子用封止樹脂組成物として多用されている。しかし、ＬＥＤ素子の輝度及び出力が高くなるに従い、ＬＥＤ素子からの光及び熱等により、これらの樹脂組成物から得られる硬化物は変色及びクラックを起こす問題がある。 A composition containing an epoxy resin having no UV absorption, such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin or an alicyclic epoxy resin having excellent adhesion and mechanical strength, a curing agent, and a curing catalyst is an optical semiconductor. It is frequently used as a sealing resin composition for elements. However, as the luminance and output of the LED element increase, the cured product obtained from these resin compositions has a problem of causing discoloration and cracking due to light and heat from the LED element.
ＵＶ吸収がなく、且つ可撓性のある硬化物を与える樹脂として、シリコーン樹脂にエポキシ基を導入した樹脂が知られている。例えば、特開２０１４−３１５２２号公報（特許文献１）には、グリシジル基、脂環式エポキシ基等の環状エーテル含有基を１個以上有するアルコキシシランと、両末端シラノール基及び／又はアルコキシ基を有するポリオルガノシロキサンとの反応生成物が記載されている。しかし、このようなシリコーン樹脂は、エポキシ樹脂に比べてガス透過性が非常に高い。そのため、シリコーン含有量が増えるにつれて、低ガス透過性が必要な用途に用いることは困難になる。 As a resin that does not absorb UV and gives a flexible cured product, a resin in which an epoxy group is introduced into a silicone resin is known. For example, JP 2014-31522 A (Patent Document 1) includes an alkoxysilane having one or more cyclic ether-containing groups such as a glycidyl group and an alicyclic epoxy group, a silanol group and / or an alkoxy group at both ends. The reaction product with the polyorganosiloxane is described. However, such a silicone resin has a very high gas permeability compared to an epoxy resin. Therefore, as the silicone content increases, it becomes difficult to use in applications that require low gas permeability.
特開２０１２−９２１７２号公報（特許文献２）には、低ガス透過性を向上させる為に、ポリオルガノシロキサン中にフェニル基を導入することが記載されている。詳細には、エポキシ基を有し、ジフェニルシロキサン単位を所定量有するオルガノポリシロキサンを含有する組成物が、耐熱性及び耐透湿性に優れた封止材となると記載している。上記特許文献２に記載のオルガノポリシロキサンは、ジフェニルジメトキシシラン、ジフェニルシランジオール、ジメチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン等の有機ケイ素化合物と、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とを反応させて製造される。該オルガノポリシロキサンは、脂環式エポキシ基をＴ単位シロキサン構造上に有する。このようなオルガノポリシロキサンにおいて、低ガス透過性を得るためにジフェニルシロキサン単位の量を増やすと、耐光性が低下する。 Japanese Patent Application Laid-Open No. 2012-92172 (Patent Document 2) describes that a phenyl group is introduced into polyorganosiloxane in order to improve low gas permeability. Specifically, it describes that a composition containing an organopolysiloxane having an epoxy group and a predetermined amount of diphenylsiloxane units is a sealing material excellent in heat resistance and moisture permeability resistance. The organopolysiloxane described in Patent Document 2 includes an organosilicon compound such as diphenyldimethoxysilane, diphenylsilanediol, dimethyldimethoxysilane, cyclohexylmethyldimethoxysilane, and 2- (3′4′-epoxycyclohexyl) ethyltrimethoxysilane. It is manufactured by reacting with The organopolysiloxane has an alicyclic epoxy group on the T unit siloxane structure. In such an organopolysiloxane, when the amount of diphenylsiloxane units is increased in order to obtain low gas permeability, the light resistance decreases.
そこで、耐光性を向上させる手段として、ヒンダードアミンの添加が挙げられる。中でも２，２，６，６−テトラメチルピペリジン骨格を有するヒンダードアミン系光安定剤（ＨＡＬＳ）があり、例えば、特開平５−１３２５８０号公報（特許文献３）には、屋外暴露用途における長期耐光性に優れるヒンダードアミン系光安定剤（ＨＡＬＳ）が報告されている。しかしながら、上記のＨＡＬＳを添加することで、耐光性は向上するが、添加に伴い、耐熱性が低下してしまう。そこで、耐熱性、耐光性に優れるヒンダードアミン系光安定剤（ＨＡＬＳ）を含むシリコーン樹脂組成物の開発が望まれている。 Then, addition of a hindered amine is mentioned as a means to improve light resistance. Among them, there is a hindered amine light stabilizer (HALS) having a 2,2,6,6-tetramethylpiperidine skeleton. For example, JP-A-5-132580 (Patent Document 3) discloses long-term light resistance in outdoor exposure applications. Hindered amine light stabilizers (HALS) which are excellent in water resistance have been reported. However, although the light resistance is improved by adding the above-mentioned HALS, the heat resistance is lowered with the addition. Then, development of the silicone resin composition containing the hindered amine light stabilizer (HALS) excellent in heat resistance and light resistance is desired.
本発明は、上記事情に鑑み、ジフェニルシロキサン単位を多く含みながらも、耐熱性、耐光性に優れるシリコーン樹脂組成物及びそのシリコーン樹脂組成物で封止してなる光半導体装置を提供することを目的とする。 In view of the above circumstances, the present invention aims to provide a silicone resin composition excellent in heat resistance and light resistance while containing many diphenylsiloxane units, and an optical semiconductor device sealed with the silicone resin composition. And
本発明者は、上記課題を解決すべく鋭意検討した結果、下記式（２）のヒンダードアミン骨格を有する新規オルガノポリシロキサンを用いることにより、ジフェニルシロキサン単位の量が多くても、耐熱性、耐光性に優れる組成物が得られることを見出し、本発明をなすに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor uses a novel organopolysiloxane having a hindered amine skeleton represented by the following formula (2), so that even if the amount of diphenylsiloxane units is large, heat resistance and light resistance The inventors have found that a composition excellent in the above can be obtained, and have made the present invention.
従って、本発明は、下記シリコーン樹脂組成物及び光半導体装置を提供する。
〔１〕
（Ａ−１）下記式（１）で表されるオルガノポリシロキサン、
（Ａ−２）エポキシ当量が１００以上であるケイ素原子を含まないエポキシ基含有有機化合物、
（Ｂ）酸無水物系硬化剤 （Ａ）成分中のエポキシ基１個に対する（Ｂ）成分中の酸無水物基の個数が０．３〜１．０個となる量、
（Ｃ）硬化触媒、
（Ｄ）下記一般式（２）
で示される基であり、Ｒ4は下記式（４）
で示される基であり、ｎは１〜１０の整数であり、ｍは０〜１０の整数であり、ｍ及びｎで括られたシロキサン単位は、ブロックであってもランダムであってもよい。〕
で示されるヒンダードアミン骨格含有分岐状オルガノポリシロキサン
を含有するシリコーン樹脂組成物。
〔２〕
式（２）のオルガノポリシロキサンにおいて、Ｒ1がフェニル基、ベンジル基、２−フェニルエチル基及び２−フェニルプロピル基から選ばれる基である〔１〕に記載のシリコーン樹脂組成物。
〔３〕
式（２）のオルガノポリシロキサンにおいて、ｎが１又は２である〔１〕又は〔２〕に記載のシリコーン樹脂組成物。
〔４〕
式（１）のオルガノポリシロキサンにおいて、１価脂環式エポキシ基（Ｒ13）が、下記式（５）で表される、〔１〕〜〔３〕のいずれかに記載のシリコーン樹脂組成物。
〔５〕
（Ｂ）成分の酸無水物系硬化剤が、２種以上の酸無水物を併用する、〔１〕〜〔４〕のいずれかに記載のシリコーン樹脂組成物。
〔６〕
さらに、（Ｅ）酸化防止剤を含む〔１〕〜〔５〕のいずれかに記載のシリコーン樹脂組成物。
〔７〕
さらに、（Ｆ）シランカップリング剤を含む〔１〕〜〔６〕のいずれかに記載のシリコーン樹脂組成物。
〔８〕
さらに、（Ｅ）成分の酸化防止剤がフェノール系酸化防止剤とリン系酸化防止剤とを併用する〔１〕〜〔７〕のいずれかに記載のシリコーン樹脂組成物。
〔９〕
光半導体素子封止用である、〔１〕〜〔８〕のいずれかに記載のシリコーン樹脂組成物。
〔１０〕
〔９〕に記載のシリコーン樹脂組成物の硬化物で封止してなる光半導体装置。
Accordingly, the present invention provides the following silicone resin composition and optical semiconductor device.
[1]
(A-1) an organopolysiloxane represented by the following formula (1),
(A-2) an epoxy group-containing organic compound containing no silicon atom and having an epoxy equivalent of 100 or more,
(B) Acid anhydride-based curing agent (A) The amount that the number of acid anhydride groups in the component (B) is 0.3 to 1.0 with respect to one epoxy group in the component,
(C) a curing catalyst,
(D) The following general formula (2)
R 4 is a group represented by the following formula (4):
Wherein n is an integer of 1 to 10, m is an integer of 0 to 10, and the siloxane unit enclosed by m and n may be a block or random. ]
The silicone resin composition containing the hindered amine frame containing branched organopolysiloxane shown by these.
[2]
The silicone resin composition according to [1], wherein in the organopolysiloxane of the formula (2), R 1 is a group selected from a phenyl group, a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group.
[3]
The silicone resin composition according to [1] or [2], wherein n is 1 or 2 in the organopolysiloxane of formula (2).
[4]
In the organopolysiloxane of the formula (1), the monovalent alicyclic epoxy group (R 13 ) is represented by the following formula (5), and the silicone resin composition according to any one of [1] to [3] .
[5]
The silicone resin composition according to any one of [1] to [4], wherein the acid anhydride curing agent as the component (B) uses two or more acid anhydrides in combination.
[6]
Furthermore, (E) The silicone resin composition in any one of [1]-[5] containing antioxidant.
[7]
Furthermore, (F) The silicone resin composition in any one of [1]-[6] containing a silane coupling agent.
[8]
Furthermore, the silicone resin composition in any one of [1]-[7] in which antioxidant of (E) component uses a phenolic antioxidant and phosphorus antioxidant together.
[9]
The silicone resin composition according to any one of [1] to [8], which is used for sealing an optical semiconductor element.
[10]
An optical semiconductor device formed by sealing with a cured product of the silicone resin composition according to [9].
本発明のシリコーン樹脂組成物の硬化物は、耐熱性及び耐光性にも優れる。従って、光半導体素子封止用の樹脂組成物として好適に使用することができる。 The cured product of the silicone resin composition of the present invention is also excellent in heat resistance and light resistance. Therefore, it can be suitably used as a resin composition for sealing an optical semiconductor element.
以下、本発明のシリコーン樹脂組成物について、詳細に説明する。
（Ａ−１）オルガノポリシロキサン
（Ａ−１）成分は、下記式（１）で表されるオルガノポリシロキサンである。
（Ａ−１）下記式（１）で表されるオルガノポリシロキサン
(A-1) The organopolysiloxane (A-1) component is an organopolysiloxane represented by the following formula (1).
(A-1) Organopolysiloxane represented by the following formula (1)
上記式（１）において、Ｒ11は炭素数６〜１２、好ましくは炭素数６〜９の１価芳香族炭化水素基である。１価芳香族炭化水素基としては、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基や、ベンジル基、２−フェニルエチル基、２−フェニルプロピル基等のアラルキル基が挙げられる。中でも、好ましくはフェニル基、ベンジル基、２−フェニルエチル基、及び２−フェニルプロピル基であり、更に好ましくはフェニル基である。 In the above formula (1), R 11 is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms. Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group, and aralkyl groups such as benzyl group, 2-phenylethyl group and 2-phenylpropyl group. Among these, a phenyl group, a benzyl group, a 2-phenylethyl group, and a 2-phenylpropyl group are preferable, and a phenyl group is more preferable.
上記式（１）において、Ｒ12は炭素数１〜１２、好ましくは炭素数１〜６の１価脂肪族炭化水素基である。１価脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ヘプチル基、２−エチルヘキシル基、ヘプチル基、オクチル基等のアルキル基などの飽和１価脂肪族炭化水素基、ビニル基、アリル基、イソプロペニル基、ブテニル基、２−（３−シクロヘキセニル）エチル基、等の不飽和１価脂肪族炭化水素基などが挙げられる。中でも、好ましくは飽和１価脂肪族炭化水素基であり、特にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、及びヘプチル基が好ましく、更に好ましくはメチル基である。 In the above formula (1), R 12 is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Examples of monovalent aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, heptyl, 2-ethylhexyl, heptyl, octyl and the like. And unsaturated monovalent aliphatic hydrocarbon groups such as a saturated monovalent aliphatic hydrocarbon group such as a vinyl group, vinyl group, allyl group, isopropenyl group, butenyl group, and 2- (3-cyclohexenyl) ethyl group. It is done. Among them, a saturated monovalent aliphatic hydrocarbon group is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a heptyl group are particularly preferable. It is a methyl group.
上記式（１）において、Ｒ13は炭素数７〜５０、好ましくは炭素数７〜４０、さらに好ましくは炭素数７〜３０の１価脂環式エポキシ基である。１価脂環式エポキシ基は、例えば、下記構造で表される。
中でも、下記式（５）で表される１価脂環式エポキシ基が好ましい。
特に好ましくは、下記構造の脂環式エポキシ基〔β−（３，４−エポキシシクロへキシル）エチル基〕である。
Particularly preferred is an alicyclic epoxy group [β- (3,4-epoxycyclohexyl) ethyl group] having the following structure.
上記式（１）において、Ｒは、上記Ｒ11、Ｒ12、及びＲ13から選ばれる基である。 In the above formula (1), R is a group selected from R 11 , R 12 and R 13 .
上記式（１）は組成式であり、ａ、ｂ、ｃ、ｄ及びｅは、各シロキサン単位の個数比（モル比）を示す。０≦ａ＜０．５、０．１≦ｂ≦０．５、０≦ｃ＜０．８、０＜ｄ≦０．５、０≦ｅ＜０．６であり、ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１である。但し、ａ及びｃは同時に０でない。上記括弧内にある各シロキサン単位の結合順序は制限されない。 The above formula (1) is a composition formula, and a, b, c, d, and e indicate the number ratio (molar ratio) of each siloxane unit. 0 ≦ a <0.5, 0.1 ≦ b ≦ 0.5, 0 ≦ c <0.8, 0 <d ≦ 0.5, 0 ≦ e <0.6, and a + b + c + d + e = 1. However, a and c are not 0 at the same time. The bonding order of the siloxane units in the parentheses is not limited.
ｄは脂環式エポキシ基含有Ｔ単位（即ち、（Ｒ13ＳｉＯ3/2）単位）の含有量（モル比）を示す。好ましくは０．０３≦ｄ≦０．５であり、さらに好ましくは０．０５≦ｄ≦０．５であり、特に好ましくは０．０５≦ｄ≦０．４である。 d represents the content (molar ratio) of the alicyclic epoxy group-containing T unit (that is, (R 13 SiO 3/2 ) unit). Preferably 0.03 ≦ d ≦ 0.5, more preferably 0.05 ≦ d ≦ 0.5, and particularly preferably 0.05 ≦ d ≦ 0.4.
ｃはＲ11Ｒ12ＳｉＯ2/2単位の含有量（モル比）を示す。ｃの好ましい範囲は０＜ｃ≦０．７、さらに好ましくは０．５≦ｃ≦０．７８、特には０．６≦ｃ≦０．７である。 c represents the content (molar ratio) of R 11 R 12 SiO 2/2 units. The preferable range of c is 0 <c ≦ 0.7, more preferably 0.5 ≦ c ≦ 0.78, and particularly 0.6 ≦ c ≦ 0.7.
ａはＲ12 2ＳｉＯ2/2単位の含有量（モル比）を示す。ａの好ましい範囲は０＜ａ≦０．４５、さらに好ましくは０．１≦ａ≦０．３８、特には０．２≦ａ≦０．３５である。 a represents the content (molar ratio) of R 12 2 SiO 2/2 units. The preferable range of a is 0 <a ≦ 0.45, more preferably 0.1 ≦ a ≦ 0.38, and particularly 0.2 ≦ a ≦ 0.35.
ｂはＲ11 2ＳｉＯ2/2単位の含有量（モル比）を示す。ｂの好ましい範囲は０．３≦ｂ≦０．５、さらに好ましくは０．３５≦ｂ≦０．４８、特には０．３８≦ｂ≦０．４５である。 b represents the content (molar ratio) of R 11 2 SiO 2/2 units. The preferable range of b is 0.3 ≦ b ≦ 0.5, more preferably 0.35 ≦ b ≦ 0.48, and particularly 0.38 ≦ b ≦ 0.45.
上記において、ｅで示す単位はＴ単位（即ち、（ＲＳｉＯ3/2）単位）の含有量（モル比）を示す。ｅの値は、好ましくは０≦ｅ≦０．５であり、さらに好ましくは０≦ｅ≦０．３、特に好ましくは０≦ｅ≦０．１である。 In the above, the unit represented by e represents the content (molar ratio) of T unit (that is, (RSiO 3/2 ) unit). The value of e is preferably 0 ≦ e ≦ 0.5, more preferably 0 ≦ e ≦ 0.3, and particularly preferably 0 ≦ e ≦ 0.1.
上記オルガノポリシロキサンは末端が−Ｏ1/2Ｘで封鎖されている。Ｘは水素原子又は炭素数１〜１０、好ましくは炭素数１〜３のアルキル基である。ｆは１分子中に含まれる−Ｏ1/2Ｘの個数を意味する。ｅ＝０のときｆは２であり、ｅ≠０のときｆは（ＲＳｉＯ3/2）単位の個数＋２である。Ｘは好ましくは水素原子又はメチル基であり、特にはメチル基である。 The organopolysiloxane is blocked with —O 1/2 X at the ends. X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. f means the number of —O 1/2 X contained in one molecule. When e = 0, f is 2. When e ≠ 0, f is the number of (RSiO 3/2 ) units + 2. X is preferably a hydrogen atom or a methyl group, particularly a methyl group.
上記オルガノポリシロキサンにおいて、１価芳香族炭化水素基（Ｒ11）の個数は、Ｒ、Ｒ11、Ｒ12、及びＲ13の合計個数のうち４０モル％以上９５モル％以下であるのが好ましく、さらに好ましくは４５モル％以上７５モル％以下であり、特に好ましくは５０モル％以上６５モル％以下である。当該範囲内であることにより、低ガス透過性をより向上させることができる。１価芳香族炭化水素基（Ｒ11）の含有量が、上記上限値より大きいと組成物の粘度が非常に高く、作業性が悪くなり、上記下限値より小さいと、十分な低ガス透過性を有する硬化物が形成できない。上記１価芳香族炭化水素基（Ｒ11）は、好ましくはフェニル基である。 In the organopolysiloxane, the number of monovalent aromatic hydrocarbon groups (R 11 ) is preferably 40 mol% or more and 95 mol% or less of the total number of R, R 11 , R 12 , and R 13. More preferably, it is 45 mol% or more and 75 mol% or less, and particularly preferably 50 mol% or more and 65 mol% or less. By being in the said range, low gas permeability can be improved more. When the content of the monovalent aromatic hydrocarbon group (R 11 ) is larger than the above upper limit, the viscosity of the composition is very high and workability is deteriorated. When the content is smaller than the above lower limit, sufficient low gas permeability is obtained. A cured product having no can not be formed. The monovalent aromatic hydrocarbon group (R 11 ) is preferably a phenyl group.
上記オルガノポリシロキサンは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算での重量平均分子量（Ｍｗ）２，０００以上１０，０００以下が好ましく、より好ましくは２，５００以上６，０００以下である。重量平均分子量（Ｍｗ）が上記範囲内であれば作業性が良好な組成物となり、光半導体素子を封止する際に取り扱いやすい。また、当該組成物から得られる硬化物は光半導体封止材として十分な機械的特性を有する。 The organopolysiloxane preferably has a weight average molecular weight (Mw) of 2,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography (GPC), more preferably 2,500 to 6,000. . When the weight average molecular weight (Mw) is within the above range, the composition has good workability and is easy to handle when sealing an optical semiconductor element. Moreover, the hardened | cured material obtained from the said composition has sufficient mechanical characteristics as an optical semiconductor sealing material.
上記式（１）で表されるオルガノポリシロキサンとしては、例えば、下記式で示される構造が挙げられる。
上記式（１）で示されるオルガノポリシロキサンの製造方法は特に制限されるものではない。（Ｒ12 2ＳｉＯ2/2）単位、（Ｒ11 2ＳｉＯ2/2）単位、（Ｒ11Ｒ12ＳｉＯ2/2）単位、（Ｒ13ＳｉＯ3/2）単位、（ＲＳｉＯ3/2）単位の原料となる、シラノール基又はアルコキシシリル基を１分子中に少なくとも２個有する有機ケイ素化合物の１種以上を、触媒存在下、縮合反応させることによって得られる。Ｒ11、Ｒ12、Ｒ13、及びＲは上記の通りである。原料化合物の反応比率は、各シロキサン単位のモル比が上記した範囲となるように適宜調整されればよい。 The method for producing the organopolysiloxane represented by the above formula (1) is not particularly limited. (R 12 2 SiO 2/2 ) unit, (R 11 2 SiO 2/2 ) unit, (R 11 R 12 SiO 2/2 ) unit, (R 13 SiO 3/2 ) unit, (RSiO 3/2 ) unit It can be obtained by subjecting at least one organosilicon compound having at least two silanol groups or alkoxysilyl groups in a molecule to a condensation reaction in the presence of a catalyst. R 11 , R 12 , R 13 , and R are as described above. The reaction ratio of the raw material compounds may be appropriately adjusted so that the molar ratio of each siloxane unit falls within the above-described range.
（Ｒ11 2ＳｉＯ2/2）単位の原料となる有機ケイ素化合物としては、例えば、下記式で示すジフェニルシランジオールが挙げられる。
（Ｒ13ＳｉＯ3/2）単位の原料となる有機ケイ素化合物としては、例えば、下記式で示す脂環式エポキシ基含有シラン化合物が挙げられる。
（Ｒ11Ｒ12ＳｉＯ2/2）単位の原料となる有機ケイ素化合物としては、例えば、下記式（６）で示すオルガノ（ポリ）シロキサンが挙げられる。
上記式（６）で表されるシラン化合物としては、下記式で示すメチルジアルコキシシランが挙げられる。好ましくはジメトキシシランである。
上記式（６）で表されるオルガノポリシロキサンとしては、繰返し単位数２〜１０を有する、下記式で示すジアルコキシシランのオリゴマーが挙げられる。
（ＲＳｉＯ3/2）単位の原料となる有機ケイ素化合物としては、例えば、下記式（７）で示すオルガノ（ポリ）シロキサンが挙げられる。
上記式（７）で表されるシラン化合物としては、下記式で示すトリアルコキシシランが挙げられる。好ましくはトリメトキシシランである。
上記式（７）で表されるオルガノポリシロキサンとしては、１分子中に加水分解性基を３つ以上有し、繰返し単位数２〜５を有する、下記に示すトリアルコキシシランのオリゴマーが挙げられる。
上記オリゴマーの中でも、反応性、作業性、低ガス透過性の観点から、ジメトキシシランのオリゴマーが特に好適である。 Among the above oligomers, dimethoxysilane oligomers are particularly preferred from the viewpoints of reactivity, workability, and low gas permeability.
上記縮合反応は、従来公知の触媒を使用して行えばよい。例えば、フェニル基を含有する両末端シラノール基及び／又はアルコキシ基を有するオルガノ（ポリ）シロキサンと、脂環式エポキシ基等の置換基を有するアルコキシシラン化合物との縮合反応として、水酸化ナトリウム、水酸化カリウム、及びテトラメチルアンモニア水酸化物、ジアザビシクロウンデセン、１，４−ジアザビシクロ［２，２，２］オクタンなど強塩基類を用いる方法がある。しかし、当該方法は、縮合反応中にシロキサン結合（Ｓｉ−Ｏ−Ｓｉ）の切断及び再配列を起こすおそれがある。また、当該製造方法では、フェニル基を有する環状シロキサンが大量に生成するという問題もある。 The condensation reaction may be performed using a conventionally known catalyst. For example, as a condensation reaction between an organo (poly) siloxane having a phenyl group-containing silanol group and / or an alkoxy group and an alkoxysilane compound having a substituent such as an alicyclic epoxy group, sodium hydroxide, water There are methods using strong bases such as potassium oxide, tetramethylammonium hydroxide, diazabicycloundecene, 1,4-diazabicyclo [2,2,2] octane. However, this method may cause cleavage and rearrangement of siloxane bonds (Si—O—Si) during the condensation reaction. In addition, the production method has a problem that a large amount of cyclic siloxane having a phenyl group is generated.
本発明のオルガノポリシロキサンの製造方法としては、オルガノポリシロキサン鎖の再配列を最小限に留め、構造を制御できる方法が望ましい。従って、例えば、下記特許公報に記載されるような特定の触媒を使用するのが好ましい。
特開平２−２３５９３３号公報
特開平３−１９７４８６号公報
特表２００６−５０８２１６号公報
特開２０１４−５５２３４号公報
As a method for producing the organopolysiloxane of the present invention, a method capable of controlling the structure while minimizing the rearrangement of the organopolysiloxane chain is desirable. Therefore, for example, it is preferable to use a specific catalyst as described in the following patent publication.
JP-A-2-235933 JP-A-3-197486 JP-T-2006-508216 JP-A-2014-55234
例えば、特開平２−２３５９３３号公報には、ナトリウム又はカリウムのホウ酸塩又はリン酸塩を触媒として用いる、オルガノシリコーン縮合生成物の製造方法が記載されている。特開平３−１９７４８６号公報には、アルカリ金属又はアルカリ土類金属の水酸化物、塩化物、酸化物あるいは塩基性金属塩から選ばれる少なくとも１種の触媒を用いる、ポリオルガノシロキサンの製造方法が記載されている。特表２００６−５０８２１６号公報には、プロトン性溶媒の存在下で；マグネシウム及びカルシウムの水酸化物を触媒として、シラノール基含有シロキサンとアルコキシシランの縮合反応を行うことが記載されている。特開２０１４−５５２３４号公報には、周期表第２族元素の水酸化物、前記水酸化物の水和物、及び周期表第２族元素の酸化物からなる群より選ばれる少なくとも１種をシランカップリング剤で表面処理して得られたものを触媒として使用する、オルガノシリコーン縮合物の製造方法が記載されている。これらの製造方法を使用することにより、オルガノポリシロキサン鎖の構造を好適に制御することができる。 For example, JP-A-2-235933 discloses a method for producing an organosilicone condensation product using sodium or potassium borate or phosphate as a catalyst. JP-A-3-197486 discloses a process for producing a polyorganosiloxane using at least one catalyst selected from hydroxides, chlorides, oxides or basic metal salts of alkali metals or alkaline earth metals. Have been described. JP-T-2006-508216 describes that a condensation reaction between a silanol group-containing siloxane and an alkoxysilane is carried out in the presence of a protic solvent; magnesium and calcium hydroxide as catalysts. JP-A-2014-55234 discloses at least one selected from the group consisting of a hydroxide of Group 2 element of the periodic table, a hydrate of the hydroxide, and an oxide of Group 2 element of the periodic table. A method for producing an organosilicone condensate is described in which a product obtained by surface treatment with a silane coupling agent is used as a catalyst. By using these production methods, the structure of the organopolysiloxane chain can be suitably controlled.
上記特許公報に記載される触媒は固体であるため、得られるオルガノポリシロキサン組成物から触媒を濾過により容易に除去することができる。当該利点は、例えば、光学材料や電子材料など、使用する材料に精密な制御を必要とする分野や残留不純物が許容されない分野において有利なことである。従って、当該方法で製造されるオルガノポリシロキサンは光半導体素子封止用樹脂組成物に好適に使用できる。 Since the catalyst described in the above patent publication is solid, the catalyst can be easily removed from the resulting organopolysiloxane composition by filtration. The advantage is advantageous in a field that requires precise control of a material to be used, such as an optical material or an electronic material, or a field in which residual impurities are not allowed. Therefore, the organopolysiloxane produced by the method can be suitably used for a resin composition for sealing an optical semiconductor element.
本発明のオルガノポリシロキサンを製造するための特に好ましい触媒としては、周期表第２族元素の水酸化物、周期表第２族元素の水酸化物の水和物、及び周期表第２族元素の酸化物からなる群より選ばれる少なくとも１種（以下、第２族元素の化合物と称す）が挙げられる。第２族元素の化合物は、シラノール基（−ＳｉＯＨ）及び／又はアルコキシシリル基（−ＳｉＯＲ）を有する有機ケイ素化合物の縮合反応を進行することができる触媒機能を有する化合物であればよい。例えば、水酸化ラジウム、水酸化バリウム、水酸化ストロンチウム、水酸化カルシウム、水酸化マグネシウム、水酸化ベリリウム、水酸化バリウム八水和物、水酸化バリウム一水和物、水酸化ストロンチウム八水和物、酸化バリウム、酸化ストロンチウム、酸化カルシウム、酸化マグネシウム、酸化ベリリウムなどが挙げられる。中でも、水酸化バリウム八水和物、水酸化バリウム一水和物、水酸化バリウム、酸化バリウム、水酸化カルシウム、水酸化ストロンチウム、及び水酸化ストロンチウム八水和物が好ましく、特には、水酸化バリウム、及び水酸化ストロンチウムが好ましい。 As a particularly preferred catalyst for producing the organopolysiloxane of the present invention, a hydroxide of a Group 2 element of the periodic table, a hydroxide hydrate of a Group 2 element of the periodic table, and a Group 2 element of the periodic table And at least one selected from the group consisting of these oxides (hereinafter referred to as Group 2 element compounds). The group 2 element compound may be a compound having a catalytic function capable of proceeding a condensation reaction of an organosilicon compound having a silanol group (—SiOH) and / or an alkoxysilyl group (—SiOR). For example, radium hydroxide, barium hydroxide, strontium hydroxide, calcium hydroxide, magnesium hydroxide, beryllium hydroxide, barium hydroxide octahydrate, barium hydroxide monohydrate, strontium hydroxide octahydrate, Examples thereof include barium oxide, strontium oxide, calcium oxide, magnesium oxide, and beryllium oxide. Among these, barium hydroxide octahydrate, barium hydroxide monohydrate, barium hydroxide, barium oxide, calcium hydroxide, strontium hydroxide, and strontium hydroxide octahydrate are preferable, and in particular, barium hydroxide And strontium hydroxide are preferred.
触媒の配合量は、縮合反応に供する原料有機ケイ素化合物の合計モル量に対する触媒のモル量が、０．０００１〜２０ｍｏｌ％となる量、好ましくは０．０１〜１０ｍｏｌ％となる量、より好ましくは０．１〜１ｍｏｌ％となる量がよい。触媒の配合量が上記範囲内であれば、縮合反応において十分な触媒効果を得ることができ、また、反応後に濾過により触媒を除去する工程において、濾紙が目詰まりすることなく、目的の化合物を効率良く得ることができる。 The compounding amount of the catalyst is such that the molar amount of the catalyst is 0.0001 to 20 mol%, preferably 0.01 to 10 mol%, more preferably, relative to the total molar amount of the raw material organosilicon compound subjected to the condensation reaction. An amount of 0.1 to 1 mol% is good. If the amount of the catalyst is within the above range, a sufficient catalytic effect can be obtained in the condensation reaction, and the target compound can be obtained without clogging the filter paper in the step of removing the catalyst by filtration after the reaction. It can be obtained efficiently.
（Ａ−２）エポキシ当量が１００以上であるケイ素原子を含まないエポキシ基含有有機化合物
（Ａ−２）成分は、エポキシ当量が１００以上であるケイ素原子を含まないエポキシ基含有有機化合物である。エポキシ樹脂としては、グリシジル基を有するエポキシ樹脂と脂環式エポキシ基を有するエポキシ樹脂が挙げられるが、耐熱性、耐ＵＶ性、高Ｔｇ化という観点から脂環式エポキシ基を有するエポキシ樹脂が望ましい。具体的には（３，３’，４，４’−ジエポキシ）ビシクロヘキシル、１，２−ビス（３，４−エポキシシクロヘキシル）エタン、１−（エポキシエチル）−３，４−エポキシシクロヘキサン、３’，４’−エポキシシクロヘキシルメチル３，４−エポキシシクロヘキサンカルボキシレートなどが挙げられる。好ましくは、下記式（８）で示される３’，４’−エポキシシクロヘキシルメチル３，４−エポキシシクロヘキサンカルボキシレートが使用される。
(A-2) The epoxy group-containing organic compound not containing a silicon atom having an epoxy equivalent of 100 or more (A-2) is an epoxy group-containing organic compound not containing a silicon atom having an epoxy equivalent of 100 or more. Examples of the epoxy resin include an epoxy resin having a glycidyl group and an epoxy resin having an alicyclic epoxy group, and an epoxy resin having an alicyclic epoxy group is desirable from the viewpoint of heat resistance, UV resistance, and high Tg. . Specifically, (3,3 ′, 4,4′-diepoxy) bicyclohexyl, 1,2-bis (3,4-epoxycyclohexyl) ethane, 1- (epoxyethyl) -3,4-epoxycyclohexane, 3 Examples include ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. Preferably, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate represented by the following formula (8) is used.
（Ａ−２）成分のエポキシ基含有有機化合物の配合量は、（Ａ−１）成分１００質量部に対して、１０〜１００質量部、好ましくは２０〜８０質量部である。（Ａ−２）成分の配合量が、前記下限値未満では、十分なＴｇが得られず、一方、前記上限値を超えては、耐熱性、耐ＵＶ性が低下する。
なお、（Ａ−１）成分と（Ａ−２）成分とを併せて（Ａ）成分とする。
(A-2) The compounding quantity of the epoxy group containing organic compound of a component is 10-100 mass parts with respect to 100 mass parts of (A-1) component, Preferably it is 20-80 mass parts. When the blending amount of the component (A-2) is less than the lower limit, sufficient Tg cannot be obtained. On the other hand, when the amount exceeds the upper limit, heat resistance and UV resistance are lowered.
In addition, (A-1) component and (A-2) component are combined and made into (A) component.
（Ｂ）酸無水物系硬化剤
（Ｂ）成分の硬化剤には、エポキシ基との反応性を有する酸無水物系硬化剤を使用する。なお、酸無水物系硬化剤における酸無水物基は−ＣＯ−Ｏ−ＣＯ−で表される。
(B) Acid anhydride curing agent (B) An acid anhydride curing agent having reactivity with an epoxy group is used as the curing agent of the component (B). The acid anhydride group in the acid anhydride curing agent is represented by -CO-O-CO-.
酸無水物系硬化剤としては、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水ピロメリット酸、ヘキサヒドロ無水フタル酸、３−メチル−ヘキサヒドロ無水フタル酸、４−メチル−ヘキサヒドロ無水フタル酸、３−メチル−ヘキサヒドロ無水フタル酸と４−メチル−ヘキサヒドロ無水フタル酸との混合物、テトラヒドロ無水フタル酸、無水ナジック酸、無水メチルナジック酸、ノルボルナン−２，３−ジカルボン酸無水物、メチルノルボルナン−２，３−ジカルボン酸無水物、２，４−ジエチルグルタル酸無水物、シクロヘキサン−１，２，４−トリカルボン酸−１，２−無水物などを挙げることができる。中でも、脂環式炭化水素構造を有する酸無水物が好ましく、２種以上の酸無水物を併用することがより好ましく、４−メチル−ヘキサヒドロ無水フタル酸及びその誘導体、特には４−メチル−ヘキサヒドロ無水フタル酸及びシクロヘキサン−１，２，４−トリカルボン酸−１，２−無水物を併用することがさらに好ましい。 Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, A mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2 , 3-dicarboxylic acid anhydride, 2,4-diethylglutaric acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and the like. Among them, an acid anhydride having an alicyclic hydrocarbon structure is preferable, and two or more acid anhydrides are more preferably used in combination, and 4-methyl-hexahydrophthalic anhydride and derivatives thereof, particularly 4-methyl-hexahydro. More preferably, phthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride are used in combination.
（Ｂ）成分の酸無水物系硬化剤の配合量は、（Ａ）成分中のエポキシ基の合計数に対する（Ｂ）成分中の酸無水物基の個数の比が０．３〜１．０となる量、好ましくは０．４〜０．８となる量である。（Ｂ）成分の配合量が、上記下限値以上であれば、硬化物の耐熱性及び透明性が向上し、また、上記上限値以下であれば、硬化物の機械特性が向上する。 The blending amount of the acid anhydride curing agent (B) is such that the ratio of the number of acid anhydride groups in the component (B) to the total number of epoxy groups in the component (A) is 0.3 to 1.0. Is an amount that is preferably 0.4 to 0.8. If the compounding quantity of (B) component is more than the said lower limit, the heat resistance and transparency of hardened | cured material will improve, and if it is below the said upper limit, the mechanical characteristic of hardened | cured material will improve.
（Ｃ）硬化触媒
（Ｃ）成分の硬化触媒は、特に制限されるものでなく、シリコーン樹脂組成物に従来使用されている硬化触媒から選択すればよい。例えば、テトラブチルホスホニウム−ｏ，ｏ−ジエチルホスホロジチオエート、テトラフェニルホスホニウムテトラフェニルボレートなどの第四級ホスホニウム塩、トリフェニルフォスフィン、ジフェニルフォスフィン等の有機フォスフィン系硬化触媒、１，８−ジアザビシクロ［５．４．０］ウンデセン−７、トリエタノールアミン、ベンジルジメチルアミン等の三級アミン系硬化触媒、１，８−ジアザビシクロ［５．４．０］ウンデセン−７ フェノール塩、１，８−ジアザビシクロ［５．４．０］ウンデセン−７ オクチル酸塩、１，８−ジアザビシクロ［５．４．０］ウンデセン−７ ｐ−トルエンスルホン酸塩、１，８−ジアザビシクロ［５．４．０］ウンデセン−７ ギ酸塩等の第四級アンモニウム塩、オクチル酸亜鉛、ナフチル酸亜鉛等の有機カルボン酸塩、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート、アルミニウムエチルアセトアセテート・ジイソプロピレート等のアルミキレート化合物、２−メチルイミダゾール、２−フェニル−４−メチルイミダゾールなどのイミダゾール類などが挙げられる。中でも第四級ホスホニウム塩、及び第四級アンモニウム塩が好ましい。
(C) Curing catalyst The curing catalyst of the component (C) is not particularly limited, and may be selected from curing catalysts conventionally used for silicone resin compositions. For example, quaternary phosphonium salts such as tetrabutylphosphonium-o, o-diethyl phosphorodithioate, tetraphenylphosphonium tetraphenylborate, organic phosphine-based curing catalysts such as triphenylphosphine, diphenylphosphine, 1,8- Tertiary amine-based curing catalyst such as diazabicyclo [5.4.0] undecene-7, triethanolamine, benzyldimethylamine, 1,8-diazabicyclo [5.4.0] undecene-7 phenol salt, 1,8- Diazabicyclo [5.4.0] undecene-7 octylate, 1,8-diazabicyclo [5.4.0] undecene-7 p-toluenesulfonate, 1,8-diazabicyclo [5.4.0] undecene -7 Quaternary ammonium salts such as formate, zinc octylate, naphthylic acid Organic carboxylates such as lead, aluminum chelate compounds such as aluminum bisethyl acetoacetate monoacetylacetonate, aluminum ethyl acetoacetate diisopropylate, and imidazoles such as 2-methylimidazole and 2-phenyl-4-methylimidazole Etc. Of these, quaternary phosphonium salts and quaternary ammonium salts are preferred.
（Ｃ）成分の硬化触媒の配合量は、特に制限されず、（Ａ）成分と（Ｂ）成分との反応を促進する有効量（触媒量）であればよい。（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、０．０１〜３質量部、好ましくは０．０５〜１．５質量部であるのがよい。硬化触媒の配合量が、前記下限値より少ないと、エポキシ樹脂と硬化剤との反応を促進させる効果が十分得られないおそれがあり、また、前記上限値より多いと、硬化時やリフロー試験時の変色の原因となるおそれがある。 The blending amount of the (C) component curing catalyst is not particularly limited as long as it is an effective amount (catalytic amount) that promotes the reaction between the (A) component and the (B) component. It is good that it is 0.01-3 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 0.05-1.5 mass part. If the blending amount of the curing catalyst is less than the lower limit value, the effect of promoting the reaction between the epoxy resin and the curing agent may not be sufficiently obtained. If the blending amount is greater than the upper limit value, the curing time or the reflow test may occur. May cause discoloration.
（Ｄ）ヒンダードアミン骨格含有分岐状オルガノポリシロキサン
（Ｄ）成分は、下記式（２）で表される新規なオルガノポリシロキサンである。
で示される基であり、Ｒ4は下記式（４）
で示される基であり、ｎは１〜１０の整数であり、ｍは０〜１０の整数であり、ｍ及びｎで括られたシロキサン単位は、ブロックであってもランダムであってもよい。〕
(D) The hindered amine skeleton-containing branched organopolysiloxane (D) component is a novel organopolysiloxane represented by the following formula (2).
R 4 is a group represented by the following formula (4):
Wherein n is an integer of 1 to 10, m is an integer of 0 to 10, and the siloxane unit enclosed by m and n may be a block or random. ]
ここで、Ｒ1は独立に炭素数１〜１２の１価脂肪族炭化水素基又は炭素数６〜１２の１価芳香族炭化水素基から選ばれる基である。炭素数１〜１２の１価脂肪族炭化水素基の例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基等のアルキル基などの飽和１価脂肪族炭化水素基、ビニル基、アリル基、イソプロペニル基、ブテニル基等のアルケニル基などの不飽和１価脂肪族炭化水素基などが挙げられ、好ましくはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ヘプチル基であり、更に好ましくはメチル基である。炭素数６〜１２の１価芳香族炭化水素基の例としては、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基や、ベンジル基、２−フェニルエチル基、２−フェニルプロピル基等のアラルキル基であり、好ましくはフェニル基、ベンジル基、２−フェニルエチル基、２−フェニルプロピル基であり、更に好ましくはフェニル基である。 Here, R 1 is a group independently selected from a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, 2- Saturated monovalent aliphatic hydrocarbon groups such as alkyl groups such as ethylhexyl group, heptyl group and octyl group, and unsaturated monovalent aliphatic hydrocarbon groups such as alkenyl groups such as vinyl group, allyl group, isopropenyl group and butenyl group And preferably include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a heptyl group, and more preferably a methyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, 2-phenylethyl group, 2-phenylpropyl group, etc. An aralkyl group, preferably a phenyl group, a benzyl group, a 2-phenylethyl group, or a 2-phenylpropyl group, and more preferably a phenyl group.
Ｒ2は独立に炭素数１〜１２の１価脂肪族炭化水素基であり、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基等のアルキル基などの飽和１価脂肪族炭化水素基、ビニル基、アリル基、イソプロペニル基、ブテニル基等のアルケニル基などの不飽和１価脂肪族炭化水素基などが挙げられ、好ましくはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ヘプチル基であり、更に好ましくはメチル基である。 R 2 is independently a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, Saturated monovalent aliphatic hydrocarbon groups such as alkyl groups such as pentyl group, hexyl group, 2-ethylhexyl group, heptyl group and octyl group, and alkenyl groups such as vinyl group, allyl group, isopropenyl group and butenyl group. Examples thereof include a saturated monovalent aliphatic hydrocarbon group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and a heptyl group, and more preferably a methyl group. is there.
Ｒ3は独立に炭素数１〜１２の１価脂肪族炭化水素基であり、炭素数１〜１２の１価脂肪族炭化水素基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基等のアルキル基などの飽和１価脂肪族炭化水素基、ビニル基、アリル基、イソプロペニル基、ブテニル基等のアルケニル基などの不飽和１価脂肪族炭化水素基などが挙げられ、好ましくはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ヘプチル基であり、更に好ましくはメチル基である。 R 3 is independently a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms. Specific examples of the monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. Saturated monovalent aliphatic hydrocarbon groups such as alkyl groups such as isopropyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, vinyl group, allyl group And unsaturated monovalent aliphatic hydrocarbon groups such as alkenyl groups such as isopropenyl group and butenyl group, preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t- A butyl group and a heptyl group, more preferably a methyl group.
Ｑは、互いに独立に、炭素数１〜１０のアルキレン基である。具体的には、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基等が挙げられるが、好ましくはメチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ペンチレン基、ヘキシレン基、さらに好ましくはエチレン基である。 Q is independently an alkylene group having 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and the like, preferably a methylene group, an ethylene group, and a propylene group. Group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, more preferably ethylene group.
Ｘ1は下記式（３）
Ｒ4は下記式（４）
式（２）中、ｍは０〜１０の整数であり、好ましくは０〜５の整数であり、ｎは１〜１０の整数、好ましくは１〜５の整数、更に好ましくは１又は２である。また、式（４）中、ｒは０〜１０の整数であり、好ましくは０〜５の整数である。 In the formula (2), m is an integer of 0 to 10, preferably an integer of 0 to 5, and n is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1 or 2. . Moreover, in Formula (4), r is an integer of 0-10, Preferably it is an integer of 0-5.
本発明の新規なオルガノポリシロキサンの具体的な例としては、下記式（９）で示されるポリシロキサンが挙げられる。
本発明の新規なオルガノポリシロキサンは、例えば、下記一般式（１０）
で示される基である。〕
で示される分子中の全ての末端にＳｉＨ基を有する有機ケイ素化合物の１種以上と、下記式（１２）
で示されるヒンダードアミン骨格及び末端ビニル基を有する化合物とを、白金触媒存在下、ヒドロシリル化反応させることによって製造することができる。
The novel organopolysiloxane of the present invention includes, for example, the following general formula (10)
It is group shown by these. ]
At least one organosilicon compound having a SiH group at all terminals in the molecule represented by the following formula (12):
And a compound having a hindered amine skeleton and a terminal vinyl group can be produced by a hydrosilylation reaction in the presence of a platinum catalyst.
この場合、末端にＳｉＨ基を有する有機ケイ素化合物とヒンダードアミン骨格及び末端ビニル基を有する化合物との反応割合としては、ヒンダードアミン骨格及び末端ビニル基を有する化合物中のアルケニル基１個に対して末端にＳｉＨ基を有する有機ケイ素化合物中のＳｉＨ基が０．２５〜１．０個、特に０．５〜０．８個となる割合で反応させることが好ましい。なお、ヒドロシリル化反応は、従来公知の方法に従えばよい。 In this case, the reaction ratio between the organosilicon compound having a SiH group at the terminal and the compound having a hindered amine skeleton and a terminal vinyl group is defined as SiH at the terminal with respect to one alkenyl group in the compound having a hindered amine skeleton and a terminal vinyl group. It is preferable to react at a ratio of 0.25 to 1.0, particularly 0.5 to 0.8 SiH groups in the organosilicon compound having a group. The hydrosilylation reaction may be performed according to a conventionally known method.
上記式（１２）で示されるヒンダードアミン骨格及び末端ビニル基を有する化合物
は、下記式（１３）
で示されるビニル基を有するクロロシランと、下記式（１４）
で表されるアルコール性ＯＨ基を有する４−ヒドロキシ−２，２，６，６−テトラメチルピペリジンとを脱塩酸反応させることで製造することができる。
The compound having a hindered amine skeleton and a terminal vinyl group represented by the above formula (12) is represented by the following formula (13).
And a chlorosilane having a vinyl group represented by the following formula (14):
It can manufacture by carrying out dehydrochlorination reaction with 4-hydroxy-2,2,6,6-tetramethylpiperidine which has alcoholic OH group represented by these.
得られるオルガノポリシロキサンの重量平均分子量（Ｍｗ）としては、好ましくは５００〜１０，０００、より好ましくは５００〜５，０００、更に好ましくは５００〜２，０００である。なお、ここで言及する重量平均分子量とは、下記条件で測定したゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレンを標準物質とした重量平均分子量を指すこととする。
［測定条件］
展開溶媒：テトラヒドロフラン（ＴＨＦ）
流量：０．６ｍＬ／ｍｉｎ
検出器：示差屈折率検出器（ＲＩ）
カラム：ＴＳＫ Ｇｕａｒｄｃｏｌｏｍｎ ＳｕｐｅｒＨ−Ｌ
ＴＳＫｇｅｌ ＳｕｐｅｒＨ４０００（６．０ｍｍＩ．Ｄ．×１５ｃｍ×１）
ＴＳＫｇｅｌ ＳｕｐｅｒＨ３０００（６．０ｍｍＩ．Ｄ．×１５ｃｍ×１）
ＴＳＫｇｅｌ ＳｕｐｅｒＨ２０００（６．０ｍｍＩ．Ｄ．×１５ｃｍ×２）
（いずれも東ソー社製）
カラム温度：４０℃
試料注入量：２０μＬ（濃度０．５重量％のＴＨＦ溶液）
The weight average molecular weight (Mw) of the resulting organopolysiloxane is preferably 500 to 10,000, more preferably 500 to 5,000, and still more preferably 500 to 2,000. The weight average molecular weight referred to here refers to a weight average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.6mL / min
Detector: Differential refractive index detector (RI)
Column: TSK Guardcolom SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H3000 (6.0 mm ID × 15 cm × 1)
TSKgel SuperH2000 (6.0 mm ID × 15 cm × 2)
(Both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (0.5% by weight THF solution)
（Ｄ）成分のヒンダードアミン骨格含有分岐状オルガノポリシロキサンの配合量は、（Ａ）成分１００質量部に対して、０．１〜０．５質量部、好ましくは０．２〜０．４質量部である。（Ｄ）成分の配合量が、上記上限値を超えると、耐熱性が低下するおそれがあり、また、上記下限値未満では、耐光性が低下するおそれがある。 The blending amount of the hindered amine skeleton-containing branched organopolysiloxane as component (D) is 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight, per 100 parts by weight of component (A). It is. When the blending amount of the component (D) exceeds the above upper limit value, the heat resistance may decrease, and when it is less than the above lower limit value, the light resistance may decrease.
（Ｅ）酸化防止剤
本発明のシリコーン樹脂組成物には、さらに（Ｅ）成分の酸化防止剤を配合するのが好ましい。酸化防止剤としては、亜リン酸化合物、ヒンダードフェノール系酸化防止剤等が挙げられる。特には、ヒンダードフェノール系酸化防止剤が好ましい。ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリスリトールテトラキス［３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオナート、Ｎ，Ｎ’−プロパン−１，３−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオナミド］、チオジエチレンビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、６，６’−ジ−ｔｅｒｔ−ブチル−２，２’−チオジ−ｐ−クレゾール、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオンアミド）］、ベンゼンプロパン酸，３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシ，Ｃ７−Ｃ９側鎖アルキルエステル、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスホネート、２，２’−エチリデンビス［４，６−ジ−ｔｅｒｔ−ブチルフェノール］、３，３’，３”，５，５’，５”−ヘキサ−ｔｅｒｔ−ブチル−ａ，ａ’，ａ”−（メシチレン−２，４，６−トリイル）トリ−ｐ−クレゾール、カルシウムジエチルビス［［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスホネート］、４，６−ビス（オクチルチオメチル）−ｏ−クレゾール、４，６−ビス（ドデシルチオメチル）−ｏ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔｅｒｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］、ヘキサメチレン ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６−トリオン、１，３，５−トリス［（４−ｔｅｒｔ−ブチル−３−ヒドロキシ−２，６−キシリル）メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、６，６’−ジ−ｔｅｒｔ−ブチル−４，４’−チオジ−ｍ−クレゾール、ジフェニルアミン、Ｎ−フェニルベンゼンアミンと２，４，４−トリメチルペンテンの反応生成物、２，６−ジ−ｔｅｒｔ−ブチル−４−（４，６−ビス（オクチルチオ）−１，３，５−トリアジン−２−イルアミノ）フェノール、３，４−ジヒドロ−２，５，７，８−テトラメチル−２−（４，８，１２−トリメチルトリデシル）−２Ｈ−１−ベンゾピラン−６−オール、２’，３−ビス［［３−［３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル］プロピオニル］］プロピオノヒドラジド、ジドデシル３，３’−チオジプロピオネート、ジオクタデシル３，３’−チオジプロピオネートが例示される。中でもフェノール系酸化防止剤やリン系酸化防止剤が好ましく、これらを併用して用いることが更に好ましい。
(E) Antioxidant It is preferable that the silicone resin composition of the present invention further contains an antioxidant as the component (E). Examples of the antioxidant include phosphorous acid compounds and hindered phenol antioxidants. In particular, a hindered phenol antioxidant is preferable. Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, N, N′-propane-1,3- Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 6,6′-di-tert-butyl-2,2′-thiodi-p-cresol, N, N′-hexane-1 , 6-Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,2 '-Ethylidenebis [4,6-di-tert-butylphenol], 3,3', 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(mesitylene-2 , 4,6-triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octyl) Thiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -M-tolyl) propionate], hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) -1,3,5-triazine-2,4,6-trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl]- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 6,6′-di-tert-butyl-4,4′-thiodi-m-cresol, diphenylamine, N-phenyl Reaction product of benzeneamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) F Nord, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) -2H-1-benzopyran-6-ol, 2 ', 3-bis [ [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, didodecyl 3,3′-thiodipropionate, dioctadecyl 3,3′-thiodipropionate Is done. Of these, phenolic antioxidants and phosphorus antioxidants are preferable, and it is more preferable to use these in combination.
（Ｅ）成分の酸化防止剤の配合量は、（Ａ）成分１００質量部に対して、０．１〜０．５質量部が好ましく、さらに好ましくは０．１〜０．３質量部である。酸化防止剤の配合量が、上記上限値を超えると、残存する酸化防止剤が硬化後の樹脂の表面に析出するおそれがあり、また、上記下限値未満では、得られる硬化物の耐熱性及び透明性が低下するおそれがある。 (E) As for the compounding quantity of antioxidant of a component, 0.1-0.5 mass part is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-0.3 mass part. . If the blending amount of the antioxidant exceeds the above upper limit, the remaining antioxidant may be deposited on the surface of the cured resin, and if it is less than the above lower limit, the heat resistance of the resulting cured product and Transparency may be reduced.
（Ｆ）シランカップリング剤
本発明には、基材との接着性等の点から、シランカップリング剤を配合することが好ましい。シランカップリング剤としては、エポキシ基含有シラン、ビニル基含有シラン、メタクリロキシ基含有シラン、アミノ基含有シラン、メルカプト基含有シラン化合物等があり、これらのうちエポキシ基含有シランもしくはメルカプト基含有シランが好ましい。
(F) Silane coupling agent It is preferable to mix | blend a silane coupling agent with this invention from points, such as adhesiveness with a base material. Examples of silane coupling agents include epoxy group-containing silanes, vinyl group-containing silanes, methacryloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silane compounds, etc. Among these, epoxy group-containing silanes or mercapto group-containing silanes are preferred. .
（Ｆ）成分のシランカップリング剤の配合量は、（Ａ）成分１００質量部に対して、０．１〜０．５質量部、好ましくは０．２〜０．３質量部である。シランカップリング剤の配合量が、上記上限値を超えると、組成物の耐熱性が低下するおそれがあり、また、上記下限値未満では、基材との接着性が不十分になるおそれがある。 (F) The compounding quantity of the silane coupling agent of a component is 0.1-0.5 mass part with respect to 100 mass parts of (A) component, Preferably it is 0.2-0.3 mass part. If the amount of the silane coupling agent exceeds the above upper limit, the heat resistance of the composition may be lowered, and if it is less than the lower limit, the adhesion to the substrate may be insufficient. .
本発明のシリコーン樹脂組成物は、上記成分（Ａ）〜（Ｆ）の他に、従来公知の添加剤、例えば、紫外線吸収剤、光又は熱劣化防止剤、蛍光体、熱可塑剤、及び希釈剤などを含有してもよい。紫外線吸収剤としては、例えば、ヒンダードアミン系紫外線吸収剤が好適に使用できる。蛍光体は、シリコーン樹脂組成物の硬化物により封止される光半導体素子が発する光の波長を変更するために添加される。該蛍光体としては、例えば、ＬＥＤに広く利用されている、ＹＡＧ（イットリウム、アルミニウム、ガーネット）系蛍光体、ＺｎＳ系蛍光体、Ｙ2Ｏ2Ｓ系蛍光体、赤色発光蛍光体、青色発光蛍光体、及び緑色発光蛍光体等が挙げられる。これら添加剤の配合量は、従来公知の技術に従い、本発明の効果を損ねない範囲で適宜選択することができる。 In addition to the above components (A) to (F), the silicone resin composition of the present invention includes conventionally known additives such as ultraviolet absorbers, light or thermal deterioration inhibitors, phosphors, thermoplastics, and dilutions. An agent or the like may be contained. As the ultraviolet absorber, for example, a hindered amine ultraviolet absorber can be suitably used. A fluorescent substance is added in order to change the wavelength of the light which the optical semiconductor element sealed with the hardened | cured material of a silicone resin composition emits. Examples of the phosphor include a YAG (yttrium, aluminum, garnet) phosphor, a ZnS phosphor, a Y 2 O 2 S phosphor, a red light emitting phosphor, and a blue light emitting phosphor widely used in LEDs. And green light emitting phosphors. The blending amount of these additives can be appropriately selected according to a conventionally known technique as long as the effects of the present invention are not impaired.
本発明のシリコーン樹脂組成物は、上記各成分及び必要により各種の添加剤を溶解又は溶融混合することで製造することができる。溶融混合は、公知の方法で行えばよい。例えば、上記各成分をリアクターに仕込み、バッチ式にて溶融混合してもよい。また、上記各成分をニーダーや熱三本ロールなどの混練機に投入して、連続的に溶融混合することもできる。特には、（Ｃ）成分の硬化触媒は（Ｂ）成分の硬化剤に予め加熱溶解混合し、混合の最終段階で（Ａ）成分のオルガノポリシロキサン及び（Ｅ）成分の酸化防止剤等と分散混合することが好ましい。 The silicone resin composition of this invention can be manufactured by melt | dissolving or melt-mixing each said component and various additives as needed. The melt mixing may be performed by a known method. For example, the above components may be charged into a reactor and melt mixed in a batch system. Moreover, each said component can also be thrown into kneading machines, such as a kneader and a heat | fever three roll, and can also be continuously melt-mixed. In particular, the curing catalyst for component (C) is pre-heated, dissolved and mixed in the curing agent for component (B), and dispersed with the organopolysiloxane for component (A) and the antioxidant for component (E) at the final stage of mixing. It is preferable to mix.
本発明のシリコーン樹脂組成物の硬化条件は、目的とする装置に応じて適宜設定すればよい。例えば、シリコーン樹脂組成物を用いて光半導体素子を封止する場合は、通常、１００℃で１〜２時間程度加熱（プレキュア）し、さらに１５０〜２００℃で０．１〜２時間加熱（アフターキュア）するのがよい。 What is necessary is just to set suitably the hardening conditions of the silicone resin composition of this invention according to the target apparatus. For example, when sealing an optical semiconductor element using a silicone resin composition, it is usually heated (precured) at 100 ° C. for about 1 to 2 hours, and further heated at 150 to 200 ° C. for 0.1 to 2 hours (after-sales). Cure).
本発明のシリコーン樹脂組成物は、耐熱性、耐光性に優れ、且つ、低ガス透過性に優れた硬化物を与えることができる。そのため、本発明のシリコーン樹脂組成物は、光半導体素子封止用の樹脂組成物として好適に使用でき、信頼性に優れた光半導体装置を提供することができる。光半導体装置の製造方法は、光半導体素子の種類に応じて公知の方法を採用すればよい。 The silicone resin composition of the present invention can give a cured product excellent in heat resistance and light resistance and excellent in low gas permeability. Therefore, the silicone resin composition of the present invention can be suitably used as a resin composition for sealing an optical semiconductor element, and can provide an optical semiconductor device having excellent reliability. As a method for manufacturing the optical semiconductor device, a known method may be adopted depending on the type of the optical semiconductor element.
以下、実施例及び比較例を示し、本発明をより詳細に説明するが、本発明は下記の実施例に制限されるものではない。ここで、「部」は質量部を意味し、Ｍｅはメチル基を、Ｐｈはフェニル基を表す。また、重量平均分子量（Ｍｗ）は、前述の通り、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって測定した値を指す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. Here, “part” means part by mass, Me represents a methyl group, and Ph represents a phenyl group. The weight average molecular weight (Mw) indicates a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance as described above.
［合成例１］
［オルガノポリシロキサン１の合成］
２Ｌのセパラブルフラスコにジフェニルシランジオール２１６ｇ、ＸＯ−（ＭｅＰｈＳｉＯ）a−Ｘ（Ｘは水素原子又はメチル基であり、ａは３〜１０の整数であり平均７である）４８６ｇ、β−（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２４６ｇを入れ、攪拌した後、内温を８０℃まで上昇させた。その後、触媒として水酸化ストロンチウム２．４ｇを加え、８０℃でメタノールを留去しながら４時間反応させた。反応終了後、トルエン９００ｇを加え、攪拌した後、０．８μｍのフィルターを用いて加圧ろ過を行い、触媒を除去した。その後、得られた反応溶液を熱水で水洗した後、共沸脱水し、トルエンを減圧下で溜去することで、下記式（１５）で表される、直鎖状のオルガノポリシロキサン１を得た。
[Synthesis of Organopolysiloxane 1]
In a 2 L separable flask, 216 g of diphenylsilanediol, XO- (MePhSiO) a -X (X is a hydrogen atom or a methyl group, a is an integer of 3 to 10 and an average of 7), 486 g, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (246 g) was added and stirred, and the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the obtained reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled off under reduced pressure, whereby linear organopolysiloxane 1 represented by the following formula (15) was obtained. Obtained.
［合成例２］
［オルガノポリシロキサン２の合成］
２Ｌのセパラブルフラスコにジフェニルシランジオール２８１ｇ、ＸＯ−（Ｍｅ2ＳｉＯ）a−Ｘ（Ｘは水素原子又はメチル基であり、ａは２〜５の整数であり平均は３．５である）５５ｇ、β−（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２４６ｇを攪拌した後、内温を８０℃まで上昇させた。その後、触媒として水酸化ストロンチウム２．４ｇを加え、８０℃でメタノールを留去しながら４時間反応させた。反応終了後、トルエン９００ｇを加え、攪拌した後、０．８μｍのフィルターを用いて加圧ろ過を行い、触媒を除去した。その後、得られた反応溶液を熱水で水洗した後、共沸脱水し、トルエンを減圧下で溜去することで、下記式（１６）で表される、直鎖状のオルガノポリシロキサン２を得た。
[Synthesis of Organopolysiloxane 2]
In a 2 L separable flask, 281 g of diphenylsilanediol, XO- (Me 2 SiO) a -X (X is a hydrogen atom or a methyl group, a is an integer of 2 to 5, and the average is 3.5) 55 g After stirring 246 g of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, the internal temperature was raised to 80 ° C. Thereafter, 2.4 g of strontium hydroxide was added as a catalyst, and the mixture was reacted at 80 ° C. for 4 hours while distilling off methanol. After completion of the reaction, 900 g of toluene was added and stirred, followed by pressure filtration using a 0.8 μm filter to remove the catalyst. Thereafter, the resulting reaction solution was washed with hot water, then azeotropically dehydrated, and toluene was distilled off under reduced pressure, whereby linear organopolysiloxane 2 represented by the following formula (16) was obtained. Obtained.
［合成例３］
［ＳｉＨ基を有するオルガノポリシロキサンの合成］
フェニルトリメトキシシラン（１．０ｍоｌ、１９８．４４ｇ）、アセトニトリル３０ｇを混合し、内温を１０℃以下に冷却した。そして、硫酸１６ｇを３０分かけて滴下し、その後、水８１ｇを１時間かけて滴下した。次に１，１，３，３−テトラメチル−１，３−ジシロキサン（１．５ｍоｌ、２０１．４８ｇ）を３０分かけて滴下し、終夜攪拌した。廃酸分離した後、トルエン５００ｇを添加し、熱水で３回、熱純水で２回洗浄した。得られたトルエン溶液を減圧蒸留することにより、下記式（１７）で示される化合物を主成分とするオルガノポリシロキサンを得た。
[Synthesis of organopolysiloxane having SiH group]
Phenyltrimethoxysilane (1.0 mol, 198.44 g) and 30 g of acetonitrile were mixed, and the internal temperature was cooled to 10 ° C. or lower. Then, 16 g of sulfuric acid was dropped over 30 minutes, and then 81 g of water was dropped over 1 hour. Next, 1,1,3,3-tetramethyl-1,3-disiloxane (1.5 mol, 201.48 g) was added dropwise over 30 minutes and stirred overnight. After separation of the waste acid, 500 g of toluene was added and washed 3 times with hot water and 2 times with hot pure water. The obtained toluene solution was distilled under reduced pressure to obtain an organopolysiloxane containing a compound represented by the following formula (17) as a main component.
［合成例４］
［ビニル基およびヒンダードアミン骨格を有する化合物１の合成］
４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン（１．２ｍоｌ、２０５．５ｇ）、トリエチルアミン（１．２ｍоｌ、１２１．４ｇ）、トルエン４００ｇを混ぜて溶解させた後、内温を１０℃以下に冷却した。次にジメチルビニルクロロシラン（１ｍоｌ、１２０．７ｇ）を３０分かけて滴下し、室温で２時間攪拌した。生成した塩をろ過で除去した後、熱水で２回、熱純水で２回洗浄した。得られたトルエン溶液を減圧蒸留することで、下記式（１８）で示される化合物１を得た。
[Synthesis of Compound 1 Having Vinyl Group and Hindered Amine Skeleton]
4-Hydroxy-2,2,6,6-tetramethylpiperidine (1.2 mol, 205.5 g), triethylamine (1.2 mol, 121.4 g) and 400 g of toluene were mixed and dissolved, and the internal temperature was 10 Cooled below ℃. Next, dimethylvinylchlorosilane (1 mol, 120.7 g) was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 hours. The produced salt was removed by filtration, and then washed twice with hot water and twice with hot pure water. The resulting toluene solution was distilled under reduced pressure to obtain Compound 1 represented by the following formula (18).
［合成例５］
［ヒンダードアミン骨格含有分岐状オルガノポリシロキサンの合成］
１Ｌのセパラブルフラスコに０．５質量％塩化白金酸トルエン溶液０．４５ｇ、トルエン２００ｇ、化合物１（０．３２ｍоｌ、８０．４７ｇ）を入れ、攪拌した後、内温を８０℃まで上昇させた。その後、上記で得られたオルガノポリシロキサン１（０．１ｍоｌ、３３．０７ｇ）を３０分かけて滴下し、１００℃で３時間反応させた。反応終了後、熱水で２回、熱純水で２回洗浄した。得られたトルエン溶液を減圧蒸留することで下記式（１９）に示される化合物を主成分とするオルガノポリシロキサンを得た。
[Synthesis of branched organopolysiloxane containing hindered amine skeleton]
Into a 1 L separable flask, 0.45 g of 0.5 mass% chloroplatinic acid toluene solution, 200 g of toluene and compound 1 (0.32 mol, 80.47 g) were added and stirred, and then the internal temperature was raised to 80 ° C. . Thereafter, the organopolysiloxane 1 (0.1 mol, 33.07 g) obtained above was added dropwise over 30 minutes and reacted at 100 ° C. for 3 hours. After completion of the reaction, washing was performed twice with hot water and twice with hot pure water. The obtained toluene solution was distilled under reduced pressure to obtain an organopolysiloxane having a compound represented by the following formula (19) as a main component.
［実施例１〜４、比較例１〜３］
下記表１に示す組成及び配合（質量部）でシリコーン樹脂組成物を調製した。表１に記載の各成分は以下の通りである。また、表中、空欄は「０」を意味する。
（Ａ−２）エポキシ樹脂：３’，４’−エポキシシクロヘキシルメチル３，４−エポキシシクロヘキサンカルボキシレート（ダイセル化学工業株式会社製、セロキサイド２０２１Ｐ）
（Ｂ）硬化剤１：４−メチルヘキサヒドロ無水フタル酸
（新日本理化株式会社製、リカシッドＭＨ）
硬化剤２：シクロヘキサン−１，２，４−トリカルボン酸−１，２−無水物
（三菱ガス化学株式会社製、Ｈ−ＴＭＡｎ）
（Ｃ）硬化触媒：第四級ホスホニウム塩（サンアプロ株式会社製、Ｕ−ＣＡＴ５００３）
（Ｄ）光安定剤１：化合物名：ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート（株式会社ＡＤＥＫＡ社製、アデカスタブＬＡ−７２）
光安定剤２：化合物名：ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート（株式会社ＡＤＥＫＡ社製、アデカスタブＬＡ−７７）
（Ｅ）酸化防止剤１：フェノール系酸化防止剤、化合物名：ペンタエリスリトールテトラキス［３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオナート］（株式会社ＡＤＥＫＡ社製、アデカスタブＡＯ−６０）
酸化防止剤２：リン系酸化防止剤、化合物名：イソデシルジフェニルホスファイト（株式会社ＡＤＥＫＡ社製、アデカスタブＡＯ−１３５Ａ）
（Ｆ）シランカップリング剤：３−グリシドキシプロピルトリメトキシシラン（信越化学工業株式会社製、ＫＢＭ−４０３）
[Examples 1-4, Comparative Examples 1-3]
A silicone resin composition was prepared with the composition and formulation (parts by mass) shown in Table 1 below. Each component described in Table 1 is as follows. In the table, a blank column means “0”.
(A-2) Epoxy resin: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Chemical Industries, Celoxide 2021P)
(B) Curing agent 1: 4-methylhexahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd., Ricacid MH)
Curing agent 2: Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (Mitsubishi Gas Chemical Co., Ltd., H-TMAn)
(C) Curing catalyst: quaternary phosphonium salt (manufactured by Sun Apro, U-CAT5003)
(D) Light stabilizer 1: Compound name: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (manufactured by ADEKA Corporation, ADK STAB LA-72)
Light stabilizer 2: Compound name: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (manufactured by ADEKA Corporation, ADK STAB LA-77)
(E) Antioxidant 1: Phenol antioxidant, Compound name: Pentaerythritol tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation) , ADK STAB AO-60)
Antioxidant 2: Phosphorous antioxidant, Compound name: Isodecyl diphenyl phosphite (manufactured by ADEKA Corporation, Adeka Stub AO-135A)
(F) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
［評価試験］
下記の評価に用いた硬化物の調製は、該組成物を、１００℃で１時間加熱し、次いで１５０℃で４時間加熱して行った。各組成物及び各硬化物を以下の方法で評価した。
（１）耐光性
３．５ｍｍ×２．８ｍｍ×１．４ｍｍｔ（封止部０．６ｍｍｔ）の底面に銀メッキを施した銅製電極を具備するＰＰＡ（ポリフタルアミド）製表面実装型ＬＥＤパッケージに発光波長４５０ｎｍを持つ発光素子を搭載し金ワイヤーを用いて電極と発光素子を接続した表面実装型ＬＥＤに、未硬化の組成物をシリンジに充填し精密吐出装置を使用して、開口部が平面になるように注型し、硬化した。封止した各パッケージに８５℃、１００ｍＡの条件で連続通電試験を行い、初期（Ｌ0）と通電後（２００ｈｒ）の全光束値（Ｌ1）をオーシャンフォトニクス社製全光束（Φ１００ｍｍ）測定システム（品番：ＯＰ−ＦＬＵＸ）を用いて温度２５℃、電流１００ｍＡ、待機時間２０秒の条件で測定した。Ｌ1／Ｌ0（％）の値を表１に示す。
（２）耐熱性
上記方法により、各組成物を硬化して１ｍｍ厚のシート状硬化物を作製した。該硬化物の波長４５０ｎｍにおける光透過率（Ｔ0）を分光光度計Ｕ−４１００（日立ハイテック社製）にて測定した。次いで、該硬化物を１５０℃×４００時間加熱した。加熱後の各硬化物の光透過率（Ｔ1）をＴ0と同じ方法で測定した。Ｔ1／Ｔ0（％）の値を表１に示す。
[Evaluation test]
The cured product used for the following evaluation was prepared by heating the composition at 100 ° C. for 1 hour and then at 150 ° C. for 4 hours. Each composition and each cured product were evaluated by the following methods.
(1) Light resistance A surface mount LED package made of PPA (polyphthalamide) having a copper electrode with a silver plating on the bottom of 3.5 mm × 2.8 mm × 1.4 mmt (sealing portion 0.6 mmt). A surface-mounted LED that has a light-emitting element with an emission wavelength of 450 nm and is connected to an electrode and a light-emitting element using a gold wire is filled with an uncured composition in a syringe, and the opening is flat using a precision dispensing device. Was cast and cured. Each encapsulated package is subjected to a continuous energization test under conditions of 85 ° C. and 100 mA, and the total luminous flux value (L 1 ) of the initial (L 0 ) and after energization (200 hr) is measured by a total luminous flux (Φ100 mm) manufactured by Ocean Photonics. (Product number: OP-FLUX) was measured under the conditions of a temperature of 25 ° C., a current of 100 mA, and a standby time of 20 seconds. The value of L 1 / L 0 (%) is shown in Table 1.
(2) Heat resistance Each composition was cured by the above method to produce a 1 mm thick sheet-like cured product. The light transmittance (T 0 ) at a wavelength of 450 nm of the cured product was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech). The cured product was then heated at 150 ° C. for 400 hours. The light transmittance (T 1 ) of each cured product after heating was measured by the same method as T 0 . The value of T 1 / T 0 (%) is shown in Table 1.
比較例１のシリコーン樹脂組成物は、（Ｄ）成分の光安定剤を含んでおらず、耐熱性は優れているが、耐光性が悪い。
比較例２及び３のシリコーン樹脂組成物は、（Ｄ）成分を含んでいるが、オルガノポリシロキサン成分を有していないため、耐光性は優れているが、耐熱性が悪い。
これらに対し、本発明のシリコーン樹脂組成物は、耐熱性、耐光性に優れる。
The silicone resin composition of Comparative Example 1 does not contain the light stabilizer of component (D) and has excellent heat resistance but poor light resistance.
Although the silicone resin compositions of Comparative Examples 2 and 3 contain the component (D), they do not have an organopolysiloxane component, so they have excellent light resistance but poor heat resistance.
On the other hand, the silicone resin composition of the present invention is excellent in heat resistance and light resistance.
本発明のシリコーン樹脂組成物は、耐熱性及び耐光性に優れ、かつ低ガス透過性に優れた硬化物を与え、光半導体素子を封止するための樹脂組成物として好適に使用することができるので、その工業的価値は大である。 The silicone resin composition of the present invention provides a cured product excellent in heat resistance and light resistance and excellent in low gas permeability, and can be suitably used as a resin composition for sealing an optical semiconductor element. So its industrial value is great.
Claims (10)
（Ａ−２）エポキシ当量が１００以上であるケイ素原子を含まないエポキシ基含有有機化合物、
（Ｂ）酸無水物系硬化剤 （Ａ）成分中のエポキシ基１個に対する（Ｂ）成分中の酸無水物基の個数が０．３〜１．０個となる量、
（Ｃ）硬化触媒、
（Ｄ）下記一般式（２）
で示される基であり、Ｒ4は下記式（４）
で示される基であり、ｎは１〜１０の整数であり、ｍは０〜１０の整数であり、ｍ及びｎで括られたシロキサン単位は、ブロックであってもランダムであってもよい。〕
で示されるヒンダードアミン骨格含有分岐状オルガノポリシロキサン
を含有するシリコーン樹脂組成物。 (A-1) an organopolysiloxane represented by the following formula (1),
(A-2) an epoxy group-containing organic compound containing no silicon atom and having an epoxy equivalent of 100 or more,
(B) Acid anhydride-based curing agent (A) The amount that the number of acid anhydride groups in the component (B) is 0.3 to 1.0 with respect to one epoxy group in the component,
(C) a curing catalyst,
(D) The following general formula (2)
R 4 is a group represented by the following formula (4):
Wherein n is an integer of 1 to 10, m is an integer of 0 to 10, and the siloxane unit enclosed by m and n may be a block or random. ]
The silicone resin composition containing the hindered amine frame containing branched organopolysiloxane shown by these.
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