JP2009167390A - Thermosetting resin composition and use thereof - Google Patents
Thermosetting resin composition and use thereof Download PDFInfo
- Publication number
- JP2009167390A JP2009167390A JP2008297132A JP2008297132A JP2009167390A JP 2009167390 A JP2009167390 A JP 2009167390A JP 2008297132 A JP2008297132 A JP 2008297132A JP 2008297132 A JP2008297132 A JP 2008297132A JP 2009167390 A JP2009167390 A JP 2009167390A
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- JP
- Japan
- Prior art keywords
- anhydride
- thermosetting resin
- resin composition
- carbon atoms
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 51
- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 17
- 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 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- -1 oxiranylene Chemical group 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 7
- RDKHLJOYZLSXEZ-UHFFFAOYSA-N 6-methyl-2-oxaspiro[3.5]nonane-1,3-dione Chemical compound C1C(C)CCCC21C(=O)OC2=O RDKHLJOYZLSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- OYUPBTZWEJJCCG-UHFFFAOYSA-N 7-methyl-2-oxaspiro[3.5]nonane-1,3-dione Chemical compound C1CC(C)CCC21C(=O)OC2=O OYUPBTZWEJJCCG-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 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 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 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 claims description 3
- 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 claims description 3
- 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 claims description 3
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003566 oxetanyl group Chemical group 0.000 claims description 3
- 125000000466 oxiranyl group Chemical group 0.000 claims description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- NRIMHVFWRMABGJ-UHFFFAOYSA-N bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylic acid Chemical compound C1C2C(C(=O)O)=C(C(O)=O)C1C=C2 NRIMHVFWRMABGJ-UHFFFAOYSA-N 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 7
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 22
- 239000002966 varnish Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005452 bending Methods 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
- 238000009835 boiling Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 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 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- OZEHOHQZIRILDX-UHFFFAOYSA-N ctk1b7797 Chemical compound O=C1OC(=O)C2C1C1(C)CC2CC1 OZEHOHQZIRILDX-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002921 oxetanes Chemical class 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QRVASEIATBVCRN-UHFFFAOYSA-N (2,4-ditert-butyl-4-methylcyclohexa-1,5-dien-1-yl) dihydrogen phosphite Chemical compound P(O)(O)OC1=C(CC(C=C1)(C)C(C)(C)C)C(C)(C)C QRVASEIATBVCRN-UHFFFAOYSA-N 0.000 description 1
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-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
- STHGLRYNMROMHZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-11-methyl-3-(8-methylnonyl)dodecane-1,3-diol Chemical compound C(CCCCCCC(C)C)C(O)(C(CO)(CO)CO)CCCCCCCC(C)C STHGLRYNMROMHZ-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- MCRZWYDXIGCFKO-UHFFFAOYSA-N 2-butylpropanedioic acid Chemical compound CCCCC(C(O)=O)C(O)=O MCRZWYDXIGCFKO-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- MGVDSBGNZUMFRD-UHFFFAOYSA-N 3-benzoylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 MGVDSBGNZUMFRD-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- ACTKQYFQQDFDAM-UHFFFAOYSA-N 4-methylcyclohexane-1,1-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)(C(O)=O)CC1 ACTKQYFQQDFDAM-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ONTIGGPRJSEVGB-UHFFFAOYSA-N 6-decoxybenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound C1=CC=C2P(OCCCCCCCCCC)(=O)OC3=CC=CC=C3C2=C1 ONTIGGPRJSEVGB-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004956 Amodel Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
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- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
Abstract
【課題】本発明はＬＥＤ等の樹脂封止に用いられている従来のエポキシ樹脂−酸無水物硬化系の封止剤の問題点である耐熱性や透明性を改善すること。
【解決手段】式（１）で示されるシルセスキオキサン誘導体、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物およびその他の酸無水物を含有する熱硬化性樹脂組成物による。
【選択図】なしAn object of the present invention is to improve heat resistance and transparency, which are problems of a conventional epoxy resin-anhydride curing sealant used for resin sealing of LEDs and the like.
According to a thermosetting resin composition containing a silsesquioxane derivative represented by the formula (1), cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and other acid anhydrides. .
[Selection figure] None
Description
本発明は、コーティング材、光学材料、電気絶縁材料などの用途に有用な熱硬化性樹脂組成物及びこれを熱硬化させた硬化物に関する。 The present invention relates to a thermosetting resin composition useful for applications such as a coating material, an optical material, and an electrical insulating material, and a cured product obtained by thermosetting the same.
近年、種々の表示板、画像読み取り用光源、交通信号、大型ディスプレイ用ユニット、携帯電話のバックライト等に実用化されている発光ダイオード（ＬＥＤ）等の発光装置は、芳香族エポキシ樹脂に硬化剤として脂環式酸無水物を用いたもので樹脂封止して製造されているのが一般的である。しかし、この樹脂系は酸無水物が酸で変色しやすいことや、硬化に長時間を要することが知られている。また、硬化した封止樹脂が屋外に放置される場合や、紫外線を発生する光源に曝される場合に、封止樹脂が黄変するという問題点を有している。 In recent years, light-emitting devices such as light-emitting diodes (LEDs) that have been put to practical use in various display boards, light sources for image reading, traffic signals, large display units, and backlights for mobile phones are hardened with aromatic epoxy resins. In general, the resin is sealed with a resin using an alicyclic acid anhydride. However, it is known that in this resin system, an acid anhydride is easily discolored by an acid, and a long time is required for curing. Further, when the cured sealing resin is left outdoors or exposed to a light source that generates ultraviolet rays, there is a problem that the sealing resin turns yellow.
このような問題点を解消するために、脂環式エポキシ樹脂またはアクリル樹脂を用い、カチオン重合開始剤によってＬＥＤ等の樹脂封止を行なう方法が試みられている（特許文献１および２を参照）。しかし、上記カチオン重合した硬化樹脂は非常に脆いため、冷熱サイクルにより亀裂破壊を生じやすく、また、従来の芳香族エポキシ樹脂−酸無水物硬化系に比べ、硬化後の封止樹脂の着色が著しいという重大な欠点を有している。そのため、この硬化樹脂は、無色透明性を要求される用途、特に耐熱性と透明性が要求されるＬＥＤの封止用途には不向きである。 In order to solve such problems, an attempt has been made to perform resin sealing of an LED or the like with a cationic polymerization initiator using an alicyclic epoxy resin or an acrylic resin (see Patent Documents 1 and 2). . However, the cation-polymerized cured resin is very brittle, so that it is liable to be cracked by a thermal cycle, and the sealing resin after curing is significantly colored compared to the conventional aromatic epoxy resin-acid anhydride curing system. It has a serious drawback. Therefore, this cured resin is not suitable for applications requiring colorless transparency, particularly for LED sealing applications requiring heat resistance and transparency.
そこで、冷熱サイクルによるクラックの発生が改良され、耐光性に優れたＬＥＤ封止材用樹脂組成物が特許文献３に開示されている。ここに示された樹脂組成物は、水素化エポキシ樹脂や脂環式エポキシ樹脂をマトリックス成分とするものではあるが、未だ硬化後の着色が大きく更なる変色に対する改善が望まれている。 Then, generation | occurrence | production of the crack by a cold-heat cycle is improved, and the resin composition for LED sealing materials excellent in light resistance is disclosed by patent document 3. FIG. Although the resin composition shown here uses a hydrogenated epoxy resin or an alicyclic epoxy resin as a matrix component, the coloration after curing is still large, and an improvement for further discoloration is desired.
一方、特許文献４には、低粘度化剤として脂環式エポキシ樹脂やオキセタン樹脂を用いた配線基板の電子部品と基板との隙間を埋めるための埋込樹脂組成物が記載されている。しかし、この樹脂組成物は、多量の無機フィラーを含有するために、透明性を必要とする分野には適用できない。また、特許文献５には、変性オキセタン樹脂を活性エネルギー線硬化性樹脂とするアルカリ水溶液に可溶な樹脂組成物が示されているが、ここに示されたものは、アルカリ可溶性樹脂とすることを目的としており、また、変性オキセタン樹脂や多官能オキセタン樹脂は不飽和結合を有するため熱履歴による変色は避けられないものであった。なお、特許文献６〜１０には、かご型ケイ素化合物およびその重合体が開示されているが、本発明の熱硬化性樹脂組成物は開示されていない。 On the other hand, Patent Document 4 describes an embedded resin composition for filling a gap between an electronic component of a wiring board and a board using an alicyclic epoxy resin or oxetane resin as a viscosity reducing agent. However, since this resin composition contains a large amount of an inorganic filler, it cannot be applied to fields that require transparency. Patent Document 5 discloses a resin composition that is soluble in an alkaline aqueous solution using a modified oxetane resin as an active energy ray-curable resin, and the one shown here should be an alkali-soluble resin. Moreover, since the modified oxetane resin and the polyfunctional oxetane resin have an unsaturated bond, discoloration due to heat history is inevitable. Patent Documents 6 to 10 disclose a cage-type silicon compound and a polymer thereof, but do not disclose the thermosetting resin composition of the present invention.
本発明は、耐熱性と透明性が良好な硬化物を得ることができる熱硬化性樹脂組成物を提供することを課題の一つとし、また、この熱硬化性樹脂組成物からなる硬化物、成形体を提供することを課題の一つとする。 An object of the present invention is to provide a thermosetting resin composition capable of obtaining a cured product having good heat resistance and transparency, and a cured product comprising the thermosetting resin composition, An object is to provide a molded body.
本発明者は、上記課題を解決すべく鋭意検討を行った。その結果、例えば絶縁性、透明性、耐光性、耐熱性などに優れた熱硬化性樹脂組成物を見出し、本発明を完成するに至った。
即ち、本発明は下記の構成を有する。
The present inventor has intensively studied to solve the above problems. As a result, for example, a thermosetting resin composition excellent in insulation, transparency, light resistance, heat resistance and the like was found, and the present invention was completed.
That is, the present invention has the following configuration.
［１］式（１）で示されるシルセスキオキサン誘導体、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物およびその他の酸無水物を含有してなる熱硬化性樹脂組成物。
式（１）において、Ｒは炭素数１〜４５のアルキル、炭素数４〜８のシクロアルキル、炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキルから独立して選択される基であり；炭素数１〜４５のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は、−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールおよびアリールアルキル中のベンゼン環において、任意の水素はハロゲンまたは炭素数１〜１０のアルキルで置き換えられてもよく、この炭素数１〜１０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールアルキル中のアルキレンの炭素数は１〜１０であり、そして隣接しない任意の−ＣＨ２−は−Ｏ−で置き換えられてもよく；Ｒ１およびＲ２は、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから独立して選択される基であり；そして、Ｘ1はオキシラニル、オキシラニレン、３，４−エポキシシクロヘキシル、オキセタニルまたはオキセタニレンのいずれか１つを有する基である。
［２］ Ｒが、シクロヘキシルまたはフェニルである、前記［１］項記載の熱硬化性樹脂組成物。
［３］ Ｒが、フェニルである、前記［１］項記載の熱硬化性樹脂組成物。
［４］ Ｘ１が式（２）、式（３）、式（４）および式（５）のいずれか１つで示される基である、前記［１］〜［３］のいずれか１項記載の熱硬化性樹脂組成物。
［７］ さらに、ケイ素を分子内に含有しないエポキシ樹脂、ケイ素を分子内に含有しないオキセタン樹脂または有機溶媒を含有する前記［１］〜［６］のいずれか１項記載の熱硬化性樹脂組成物。
［８］ さらに、紫外線吸収剤、硬化促進剤または酸化防止剤を含有する前記［１］〜［７］のいずれか１項記載の熱硬化性樹脂組成物。
［９］ 前記［１］〜［８］のいずれか１項記載の熱硬化性樹脂組成物を熱硬化させてなる硬化物。
［１０］ 前記［９］項記載の硬化物からなる成形体。
[1] A thermosetting resin composition comprising a silsesquioxane derivative represented by the formula (1), cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and other acid anhydrides .
In the formula (1), R is a group independently selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms. Yes; in alkyl of 1 to 45 carbon atoms, any hydrogen may be replaced with fluorine, and any non-adjacent —CH 2 — may be replaced with —O— or —CH═CH—; In the benzene ring in aryl and arylalkyl, any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms, and in this alkyl having 1 to 10 carbon atoms, any hydrogen may be replaced by fluorine. Well, and any non-adjacent —CH 2 — may be replaced by —O— or —CH═CH—; the number of alkylene carbons in the arylalkyl Are 1 to 10 and any non-adjacent —CH 2 — may be replaced by —O—; R 1 and R 2 are independently of C 1 -C 4 alkyl, cyclopentyl, cyclohexyl and phenyl; And X 1 is a group having any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl or oxetanylene.
[2] The thermosetting resin composition according to [1], wherein R is cyclohexyl or phenyl.
[3] The thermosetting resin composition according to the above [1], wherein R is phenyl.
[4] Any one of [1] to [3], wherein X 1 is a group represented by any one of formula (2), formula (3), formula (4), and formula (5). The thermosetting resin composition as described.
[7] The thermosetting resin composition according to any one of [1] to [6], further comprising an epoxy resin not containing silicon in the molecule, an oxetane resin not containing silicon in the molecule, or an organic solvent. object.
[8] The thermosetting resin composition according to any one of [1] to [7], further comprising an ultraviolet absorber, a curing accelerator, or an antioxidant.
[9] A cured product obtained by thermosetting the thermosetting resin composition according to any one of [1] to [8].
[10] A molded article made of the cured product according to [9].
本発明の熱硬化性樹脂組成物の硬化物は、例えば、絶縁性、透明性、耐光性、耐熱性などに優れている。そのため、硬化物からなる成形体は、半導体の封止材、光半導体の封止材、絶縁膜、シール剤、光学レンズなどの用途に好適に用いることができる。また、本発明の熱硬化性樹脂組成物は、熱硬化の特性を利用して、例えば、接着剤に用いることができる。 The cured product of the thermosetting resin composition of the present invention is excellent in, for example, insulation, transparency, light resistance, heat resistance, and the like. Therefore, the molded body made of a cured product can be suitably used for applications such as a semiconductor sealing material, an optical semiconductor sealing material, an insulating film, a sealing agent, and an optical lens. Moreover, the thermosetting resin composition of this invention can be used for an adhesive agent, for example using the characteristic of thermosetting.
本発明で用いる用語について説明する。式（１）で表わされる化合物を化合物（１）と表記することがある。他の式で表される化合物についても同様に簡略化して称することがある。本発明において「任意の」は位置だけではなく個数についても任意であることを意味する。そして、「任意のＡはＢまたはＣで置き換えられてもよい」という表現は、少なくとも１つのＡがＢで置き換えられる場合と少なくとも１つのＡがＣで置き換えられる場合とに加えて、少なくとも１つのＡがＢで置き換えられると同時にその他のＡの少なくとも１つがＣで置き換えられる場合も含まれることを意味する。なお、アルキルまたはアルキレンにおける任意の−ＣＨ２−が−Ｏ−で置き換えられてもよいという設定には、連続する複数の−ＣＨ２−のすべてが−Ｏ−で置き換えられることは含まれない。実施例においては、電子天秤の表示データを質量単位であるｇ（グラム）を用いて示した。重量％や重量比はこのような数値に基づくデータである。 Terms used in the present invention will be described. A compound represented by the formula (1) may be referred to as a compound (1). Similarly, compounds represented by other formulas may be referred to in a simplified manner. In the present invention, “arbitrary” means that not only the position but also the number is arbitrary. And the expression “any A may be replaced by B or C” means that at least one A is replaced by B and at least one A is replaced by C, at least one This means that the case where A is replaced by B and at least one of the other A is replaced by C is also included. Note that the setting that any —CH 2 — in alkyl or alkylene may be replaced by —O— does not include the replacement of all of a plurality of consecutive —CH 2 — with —O—. In the examples, the display data of the electronic balance is shown using g (gram) which is a mass unit. Weight% and weight ratio are data based on such numerical values.
本発明の熱硬化性樹脂組成物として式（１）で示されるシルセスキオキサン誘導体が必要である。以下の説明においては、式（１）におけるシルセスキオキサン骨格の形状をダブルデッカータイプと表現することがある。
式（１）において、Ｒは炭素数１〜４５のアルキル、炭素数４〜８のシクロアルキル、炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキルから独立して選択される基である。この炭素数１〜４５のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は、−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよい。アリールおよびアリールアルキル中のベンゼン環において、任意の水素はハロゲンまたは炭素数１〜１０のアルキルで置き換えられてもよい。この炭素数１〜１０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよい。アリールアルキル中のアルキレンの炭素数は１〜１０であり、そして隣接しない任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。 In the formula (1), R is a group independently selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms. is there. In the alkyl having 1 to 45 carbon atoms, any hydrogen may be replaced by fluorine, and any non-adjacent —CH 2 — may be replaced by —O— or —CH═CH—. In the benzene ring in aryl and arylalkyl, any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons. In the alkyl having 1 to 10 carbon atoms, any hydrogen may be replaced with fluorine, and any non-adjacent —CH 2 — may be replaced with —O— or —CH═CH—. The number of carbon atoms of alkylene in arylalkyl is 1 to 10, and any non-adjacent —CH 2 — may be replaced by —O—.
Ｒはシクロペンチル、シクロヘキシル、フェニルおよび素数１〜１０のアルキルから独立して選択される基であることが好ましい。この炭素数１〜１０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は−Ｏ−で置き換えられてもよい。また、フェニルにおいて、任意の水素はフッ素等のハロゲンもしくは炭素数１〜１０のアルキルで置き換えられてもよい。
Ｒはシクロペンチル、シクロヘキシル、または任意の水素が塩素、フッ素、メチル、メトキシまたはトリフルオロメチルで置き換えられてもよいフェニルであることがより好ましく、シクロヘキシルまたはフェニルであることが更に好ましく、そしてフェニルであることが最も好ましい。
R is preferably a group independently selected from cyclopentyl, cyclohexyl, phenyl, and alkyl having 1 to 10 primes. In the alkyl having 1 to 10 carbon atoms, any hydrogen may be replaced with fluorine, and any non-adjacent —CH 2 — may be replaced with —O—. In the phenyl, arbitrary hydrogen may be replaced by halogen such as fluorine or alkyl having 1 to 10 carbon atoms.
R is more preferably cyclopentyl, cyclohexyl, or phenyl where any hydrogen may be replaced by chlorine, fluorine, methyl, methoxy or trifluoromethyl, more preferably cyclohexyl or phenyl, and is phenyl Most preferred.
Ｒ１およびＲ２は、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから独立して選択される基である。炭素数１〜４のアルキルの例は、メチル、エチル、プロピル、２−メチルエチル、ブチルおよびｔ−ブチルである。Ｒ１またはＲ２の好ましい例はメチルおよびフェニルである。Ｒ１およびＲ２は同じ基であることが好ましい。 R 1 and R 2 are groups independently selected from alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl and phenyl. Examples of alkyl having 1 to 4 carbon atoms are methyl, ethyl, propyl, 2-methylethyl, butyl and t-butyl. Preferred examples of R 1 or R 2 are methyl and phenyl. R 1 and R 2 are preferably the same group.
Ｘ1はオキシラニル、オキシラニレン、３，４−エポキシシクロヘキシル、オキセタニルおよびオキセタニレンのいずれか１つを有する基である。
このようなＸ1の好ましい例を次に示す。
Preferred examples of such X 1 are as follows.
Ｘ１の特に好ましい例は、式（２）、式（３）、式（４）および式（５）のそれぞれで示される基である。
本発明において、化合物（１）の他に分子内にケイ素原子を含有しないエポキシ樹脂やケイ素を分子内に含有しないオキセタン樹脂を用いることができる。前記エポキシ樹脂の具体例としては、ビスフェノール−Ａ型、ビスフェノール−Ｆ型、ビスフェノール−Ｓ型、水素化されたビスフェノール−Ａ型などのエポキシ樹脂、ダイセル化学工業（株）製のセロキサイド（商品名） ２０２１ Ｐ、セロキサイド（商品名） ３０００、セロキサイド（商品名） ２０８１などの脂環式エポキシ樹脂が挙げられる。また、オキセタン樹脂の具体例としては、東亞合成（株）製アロンオキセタン（登録商標）などのオキセタン樹脂が挙げられる。脂環式エポキシ樹脂は耐熱性の向上、耐熱黄変性に優れており特に好ましい。 In the present invention, in addition to the compound (1), an epoxy resin not containing a silicon atom in the molecule or an oxetane resin not containing silicon in the molecule can be used. Specific examples of the epoxy resin include epoxy resins such as bisphenol-A type, bisphenol-F type, bisphenol-S type, and hydrogenated bisphenol-A type, Celoxide (trade name) manufactured by Daicel Chemical Industries, Ltd. Examples include alicyclic epoxy resins such as 2021, P, Celoxide (trade name) 3000, and Celoxide (trade name) 2081. Further, specific examples of the oxetane resin include oxetane resins such as Aron Oxetane (registered trademark) manufactured by Toagosei Co., Ltd. The alicyclic epoxy resin is particularly preferable because it is excellent in heat resistance and heat yellowing.
このような分子内にケイ素原子を含有しないオキセタン樹脂あるいは分子内にケイ素原子を含有しないエポキシ樹脂を用いるとき、その好ましい配合割合は、熱硬化性樹脂組成物の合計量を基準として５〜９５重量％である。この割合のより好ましい範囲は２５〜７５重量％である。 When such an oxetane resin that does not contain a silicon atom in the molecule or an epoxy resin that does not contain a silicon atom in the molecule is used, the preferred blending ratio is 5 to 95 weights based on the total amount of the thermosetting resin composition. %. A more preferable range of this ratio is 25 to 75% by weight.
本発明においては、化合物（１）、酸無水物であるシクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物（三菱瓦斯化学(株)製Ｈ−ＴＭＡｎ）及びその他の酸無水物を反応させることで、硬化促進剤を用いなくても反応させることができるが、硬化促進剤を用いてもよい。 In the present invention, compound (1), acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd.) and other acid anhydrides The reaction can be carried out without using a curing accelerator, but a curing accelerator may be used.
その他の酸無水物としては、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−シクロヘキサンジカルボン酸無水物、４−メチル−シクロヘキサンジカルボン酸無水物、３−メチル−シクロヘキサンジカルボン酸無水物と４−メチル−シクロヘキサンジカルボン酸無水物の混合物、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、およびメチルノルボルナン−２，３−ジカルボン酸無水物が利用できる。 Other acid anhydrides include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-cyclohexanedicarboxylic anhydride, 4-methyl-cyclohexanedicarboxylic anhydride A mixture of 3-methyl-cyclohexanedicarboxylic anhydride and 4-methyl-cyclohexanedicarboxylic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, and methyl Norbornane-2,3-dicarboxylic acid anhydride can be used.
熱硬化性樹脂組成物中の酸無水物の好ましい使用割合は、使用する熱硬化性樹脂中のエポキシ基と酸無水物のモル比が３：７〜７：３であることが好ましく、４：６〜６：４であることがより好ましく、１：１であることが更に好ましい。 The preferred use ratio of the acid anhydride in the thermosetting resin composition is preferably such that the molar ratio of the epoxy group to the acid anhydride in the thermosetting resin to be used is 3: 7 to 7: 3. 6 to 6: 4 is more preferable, and 1: 1 is still more preferable.
熱硬化性樹脂組成物中のシクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物（以下、Ｈ−ＴＭＡｎと略すことがある。）とその他の酸無水物とのモル比は、１：１００〜１００：１であればよく、１：５〜５：１が好ましく、１：２〜２：１が特に好ましい。酸無水物として新日本理化（株）製リカシッド（商品名） ＭＨ−７００Ｇを用いた場合には、Ｈ−ＴＭＡｎ：ＭＨ−７００Ｇ＝１：２で混合して用いることが耐熱性、耐黄変性の点から好ましい。 The molar ratio of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride (hereinafter sometimes abbreviated as H-TMAn) in the thermosetting resin composition to other acid anhydrides is as follows: The ratio may be 1: 100 to 100: 1, preferably 1: 5 to 5: 1, and particularly preferably 1: 2 to 2: 1. When Rikacid (trade name) MH-700G manufactured by Shin Nippon Rika Co., Ltd. is used as the acid anhydride, it is heat-resistant and yellowing-resistant to be used by mixing with H-TMAn: MH-700G = 1: 2. From the point of view, it is preferable.
硬化促進剤としては、テトラフェニルホスホニウムブロミド、テトラブチルホスホニウムブロミド、メチルトリフェニルホスホニウムブロミド、エチルトリフェニルホスホニウムブロミド、ｎ−ブチルトリフェニルホスホニウムブロミドなどの４級ホスホニウム塩；３級アミン；４級アンモニウム塩；１，８−ジアザビシクロ（５，４，０）ウンデセン−７などの双環式アミジン類とその誘導体；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。しかしながら、硬化性がよく、着色がなければ、特に限定されない。これらの硬化促進剤は、単独で用いても２種以上を併用してもよい。１，８−ジアザビシクロ（５，４，０）ウンデセン−７などの双環式アミジン類、およびイミダゾール類は、少量の添加量でも熱硬化性樹脂組成物に対して高い活性を示し、比較的低い硬化温度でも短時間、例えば、１５０℃程度でも９０秒位で硬化することができるのでより好ましい。市販品としては、日本化学産業（株）製ニッカオクチックス亜鉛（商品名）やサンアプロ（株）製Ｕ−ＣＡＴ５００３（商品名）などが好ましく利用できる。 Examples of the curing accelerator include tetraphenylphosphonium bromide, tetrabutylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, and the like; tertiary amine; quaternary ammonium salt Bicyclic amidines such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; imidazoles such as 2-methylimidazole and 2-phenyl-4-methylimidazole; However, there is no particular limitation as long as the curability is good and there is no coloring. These curing accelerators may be used alone or in combination of two or more. Bicyclic amidines such as 1,8-diazabicyclo (5,4,0) undecene-7, and imidazoles exhibit high activity against thermosetting resin compositions even with a small addition amount, and are relatively low. It is more preferable because it can be cured at a curing temperature for a short time, for example, about 150 ° C. in about 90 seconds. As commercially available products, Nikka Octix zinc (trade name) manufactured by Nippon Chemical Industry Co., Ltd., U-CAT5003 (trade name) manufactured by San Apro Co., Ltd., etc. can be preferably used.
このような硬化促進剤を用いるとき、その好ましい使用割合は、熱硬化性樹脂組成物の合計量に対する重量比で０．００３〜０．０４であり、より好ましくは０．００４〜０．０２である。この範囲であれば、充分な硬化促進効果が得られ、硬化物の物性低下や着色を引き起こすことがない。 When such a curing accelerator is used, the preferred use ratio is 0.003 to 0.04, more preferably 0.004 to 0.02, by weight ratio to the total amount of the thermosetting resin composition. is there. If it is this range, sufficient hardening promotion effect will be acquired and it will not cause the physical-property fall and coloring of hardened | cured material.
本発明の熱硬化性樹脂組成物には、酸化防止剤を添加してもよい。酸化防止剤を添加することにより、加熱時の酸化劣化を防止し着色の少ない硬化物とすることができる。酸化防止剤の例はフェノール系、硫黄系、およびリン系の酸化防止剤である。酸化防止剤を使用するときの好ましい配合割合は、熱硬化性樹脂組成物全量を基準とする重量比で０．０００１〜０．１である。 An antioxidant may be added to the thermosetting resin composition of the present invention. By adding an antioxidant, it is possible to prevent oxidative deterioration during heating and to obtain a cured product with little coloring. Examples of antioxidants are phenolic, sulfur and phosphorus antioxidants. A preferable blending ratio when using the antioxidant is 0.0001 to 0.1 in a weight ratio based on the total amount of the thermosetting resin composition.
酸化防止剤の具体例は、モノフェノール類（２，６−ジ−ｔ−ブチル−ｐ−クレゾール、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−ｐ−エチルフェノール、ステアリル−β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートなど）、ビスフェノール類（２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、３，９−ビス［１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル］２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンなど）、高分子型フェノール類（１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、テトラキス−［メチレン−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］メタン、ビス［３，３’−ビス−（４’−ヒドロキシ−３’−ｔ−ブチルフェニル）ブチリックアシッド］グリコールエステル、１，３，５−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）−Ｓ−トリアジンー２，４，６−（１Ｈ，３Ｈ，５Ｈ）トリオン、トコフェノールなど）、硫黄系酸化防止剤（ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリルル−３，３’−チオジプロピオネートなど）、ホスファイト類（リフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、トリス（ノニルフェニル）ホスファイト、ジイソデシルペンタエリスリトールホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビス（オクタデシル）ホスファイト、サイクリックネオペンタンテトライルビ（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、サイクリックネオペンタンテトライルビ（２，４−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、ビス［２−ｔ−ブチル−６−メチル−４−｛２−（オクタデシルオキシカルボニル）エチル｝フェニル］ヒドロゲンホスファイトなど）、およびオキサホスファフェナントレンオキサイド類（９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−デシロキシ−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイドなど）である。これらの酸化防止剤はそれぞれ単独で使用できるが、フェノール系／硫黄系またはフェノール系／リン系と組み合わせて使用することが特に好ましい。市販のフェノール系の酸化防止剤としては、チバ・ジャパン（株）製ＩＲＧＡＮＯＸ １０１０（商品名）やＩＲＧＡＦＯＳ １６８（商品名）をそれぞれ単独で利用することができ、また、これらを混合して利用することもできる。 Specific examples of the antioxidant include monophenols (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), bisphenols (2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxy Saspiro [5,5] undecane, etc.), polymer type phenols (1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2) , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-) t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, etc.), sulfur-based antioxidants (dilauryl-3,3′-thiodipropio) , Dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate), phosphites (riphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (Nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2 , 4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl- 4- {2- (octadecyloxy Rubonyl) ethyl} phenyl] hydrogen phosphite), and oxaphosphaphenanthrene oxides (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-) t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide etc.). These antioxidants can be used alone, but it is particularly preferable to use them in combination with phenol / sulfur or phenol / phosphorus. As commercially available phenolic antioxidants, IRGANOX 1010 (trade name) and IRGAFOS 168 (trade name) manufactured by Ciba Japan Co., Ltd. can be used singly or in combination. You can also
本発明の熱硬化性樹脂組成物には、耐光性を向上させるために紫外線吸収剤を配合してもよい。紫外線吸収剤としては、一般のプラスチック用紫外線吸収剤を使用でき、その好ましい配合割合は、熱硬化性樹脂組成物全量を基準とする重量比で０．０００１〜０．１である。 The thermosetting resin composition of the present invention may contain an ultraviolet absorber in order to improve light resistance. As the ultraviolet absorber, a general ultraviolet absorber for plastics can be used, and a preferable blending ratio thereof is 0.0001 to 0.1 in terms of a weight ratio based on the total amount of the thermosetting resin composition.
紫外線吸収剤の具体例は、フェニルサリシレート、ｐ−ｔ−ブチルフェニルサリシレート、ｐ−オクチルフェニルサリシレート等のサリチル酸類、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−ヒドロキシ−４−ドデシルオキシベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−５−スルホベンゾフェノン等のベンゾフェノン類、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジｔｅｒｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジｔｅｒｔ−アミルフェニル）ベンゾトリアゾール、２−｛（２’−ヒドロキシ−３’，３’’，４’’，５’’，６’’−テトラヒドロフタルイミドメチル）−５’−メチルフェニル｝ベンゾトリアゾール等のベンゾトリアゾール類、およびビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［｛３，５−ビス（１，１−ジメチルエチル）−４−ヒドリキシフェニル｝メチル］ブチルマロネート等のヒンダートアミン類である。 Specific examples of the ultraviolet absorber include salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy- Benzophenones such as 5-sulfobenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ' 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′) , 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3) Benzotriazoles such as', 3 '', 4 '', 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, and bis (2,2,6,6-tetramethyl -4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Ntamechiru 4-piperidyl) is [{3,5-bis (1,1-dimethylethyl) -4-hydrido hydroxyphenyl} methyl] hindered amines such as butyl malonate.
本発明の熱硬化性樹脂組成物には、更に下記成分を配合してもよい。
（１）粉末状の補強剤や充填剤、例えば、酸化アルミニウム、酸化マグネシウムなどの金属酸化物、微粉末シリカ、溶融シリカ、結晶シリカなどのケイ素化合物、ガラスビーズ等の透明フィラー、水酸化アルミニウムなどの金属水酸化物、その他、カオリン、マイカ、石英粉末、グラファイト、二硫化モリブデン等。これらは、本発明の熱硬化性樹脂組成物の透明性を損なわない範囲で配合される。これらを配合するときの好ましい割合は、本発明の熱硬化性樹脂組成物全量に対する重量比で、０．１０〜１．０の範囲である。
The thermosetting resin composition of the present invention may further contain the following components.
(1) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, aluminum hydroxide, etc. Metal hydroxide, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc. These are mix | blended in the range which does not impair the transparency of the thermosetting resin composition of this invention. A desirable ratio when blending these is a weight ratio with respect to the total amount of the thermosetting resin composition of the present invention and is in the range of 0.10 to 1.0.
（２）着色剤または顔料、例えば、二酸化チタン、モリブデン赤、紺青、群青、カドミウム黄、カドミウム赤および有機色素等。
（３）難燃剤、例えば、三酸化アンチモン、ブロム化合物およびリン化合物等。
（４）イオン吸着体。
これらの成分を配合するときの好ましい割合は、熱硬化性樹脂組成物全量に対する重量比で０．０００１〜０．３０である。
（５）シランカップリング剤。
（６）ジルコニア、チタニア、アルミナ、シリカなどの金属酸化物のナノ粒子分散液。
これら（１）〜（６）の成分を配合するときの好ましい割合は、熱硬化性樹脂組成物全量に対する重量比で０．０１〜０．５０である。
(2) Colorants or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes.
(3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
(4) Ion adsorbent.
A desirable ratio when blending these components is 0.0001 to 0.30 in a weight ratio with respect to the total amount of the thermosetting resin composition.
(5) Silane coupling agent.
(6) A nanoparticle dispersion of a metal oxide such as zirconia, titania, alumina, or silica.
A desirable ratio when blending these components (1) to (6) is 0.01 to 0.50 in a weight ratio with respect to the total amount of the thermosetting resin composition.
硬化物は、例えば、以下の方法で作製できる。式（１）または式（１−１）で示されるシルセスキオキサン誘導体、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物およびその他の酸無水物を混合する。次に酸化防止剤を入れて攪拌し混合した後、減圧して脱泡する。そしてこの混合物を型に流し込み、１００℃で１時間加熱し、次に１２５℃で１時間加熱し、最後に１５０℃で２〜３時間加熱することで硬化させることができる。 The cured product can be produced, for example, by the following method. A silsesquioxane derivative represented by formula (1) or formula (1-1), cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and other acid anhydrides are mixed. Next, after adding antioxidant and stirring and mixing, it depressurizes and defoams. The mixture can then be poured into a mold, heated at 100 ° C. for 1 hour, then heated at 125 ° C. for 1 hour, and finally heated at 150 ° C. for 2-3 hours to be cured.
本発明の熱硬化性樹脂組成物中に硬化促進剤、酸化防止剤、紫外線吸収剤等の添加剤を混合してもよい。 You may mix additives, such as a hardening accelerator, antioxidant, and an ultraviolet absorber, in the thermosetting resin composition of this invention.
硬化物の透明性は、耐熱試験前後の硬化物の透過率を紫外可視分光光度計で測定し、ＪＩＳ Ｋ７３６３に従って計算される黄色度（ＹＩ値）及び光線透過率の保持率により評価し、それぞれ１０前後、７０％以上であることが好ましい。これらの範囲内にそれぞれの値が入る場合には、硬化物は、無色で透明性が高いことを示しており、透明性が要求されるような光半導体封止剤などの分野に特に好ましく利用できる。 The transparency of the cured product is determined by measuring the transmittance of the cured product before and after the heat resistance test with an ultraviolet-visible spectrophotometer, and evaluating the yellowness (YI value) calculated according to JIS K7363 and the retention of light transmittance, It is preferably around 10 and 70% or more. When each value falls within these ranges, it indicates that the cured product is colorless and highly transparent, and is particularly preferably used in fields such as optical semiconductor encapsulants that require transparency. it can.
本発明の熱硬化性樹脂組成物を熱硬化させてなる硬化物を成形し、成形体とすることで、様々な用途に用いることができる。用途としては、光半導体封止材、半導体封止材、絶縁膜、シール材、接着剤、光学レンズなどが挙げられる。 By molding a cured product obtained by thermosetting the thermosetting resin composition of the present invention to form a molded product, it can be used for various applications. Applications include optical semiconductor sealing materials, semiconductor sealing materials, insulating films, sealing materials, adhesives, optical lenses, and the like.
本発明を実施例に基づいて更に詳細に説明する。なお、本発明は以下の実施例によって限定されない。
〔合成例１〕
＜化合物（１−１）の製造＞
下記の経路により化合物（１−１）を製造した。
[Synthesis Example 1]
<Production of Compound (1-1)>
Compound (1-1) was produced by the following route.
窒素雰囲気下、温度計、滴下ロートおよび還流冷却器を備えた内容積２００ミリリットルの反応容器に、国際公開ＷＯ２００４／０２４７４１パンフレットに開示されている方法により合成した化合物（ａ）（２１．０ｇ）、乾燥トルエン（２０ｇ）を仕込み、乾燥窒素でシールした。マグネチックスターラーで攪拌しながら反応温度が６０℃になるように加熱した。マイクロシリンジを用いてＰｔ触媒（２１μＬ）を添加し、滴下ロートからダイセル化学工業（株）製セロキサイド（商品名）２０００（製品名 ＣＥＬ２０００）（１０ｇ）をゆっくりと滴下し、３時間攪拌した。反応容器の内容物をエバポレータに移し、濃縮し粗結晶を得た。得られた粗結晶にアセトンを加え２０重量％溶液とした。さらに粗結晶に対して３重量％の活性炭を加えて１時間攪拌した。その後、活性炭をろ過し粗結晶の１０倍量のヘキサンを加えて、２５℃で２時間攪拌した。その後、ろ過を行い、ろ液をエバポレータで濃縮した。得られた粗結晶の１．２５倍量のヘキサンを加えて、６０℃に加熱して溶解した後、２５℃で再結晶を行った。得られた結晶（収量２２ｇ、収率７６％）は、ＮＭＲの測定の結果、化合物（１−１）であることがわかった。 Compound (a) (21.0 g) synthesized by a method disclosed in International Publication WO 2004/024741 in a reaction vessel having an internal volume of 200 ml equipped with a thermometer, a dropping funnel and a reflux condenser in a nitrogen atmosphere, Dry toluene (20 g) was charged and sealed with dry nitrogen. While stirring with a magnetic stirrer, the reaction temperature was heated to 60 ° C. Pt catalyst (21 μL) was added using a microsyringe, and Celoxide (trade name) 2000 (product name) CEL2000 (product name) manufactured by Daicel Chemical Industries, Ltd. was slowly dropped from the dropping funnel and stirred for 3 hours. The contents of the reaction vessel were transferred to an evaporator and concentrated to obtain crude crystals. Acetone was added to the obtained crude crystals to make a 20 wt% solution. Further, 3% by weight of activated carbon was added to the crude crystals and stirred for 1 hour. Thereafter, the activated carbon was filtered, 10 times the amount of hexane as crude crystals was added, and the mixture was stirred at 25 ° C. for 2 hours. Thereafter, filtration was performed, and the filtrate was concentrated with an evaporator. 1.25 times as much hexane as the obtained crude crystals was added and dissolved by heating to 60 ° C., followed by recrystallization at 25 ° C. As a result of NMR measurement, the obtained crystal (yield 22 g, yield 76%) was found to be compound (1-1).
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ（ｐｐｍ）；０．０１（ｓ，２４Ｈ），０．４０−０．４６（ｍ，８Ｈ），０．５８−０．６３（ｍ，２Ｈ），０．８３−０．８７（ｍ，４Ｈ），０．９５−１．２６（ｍ，１８Ｈ），１．４５−１．４９（ｍ，２Ｈ），１．５９−１．８１（ｍ，６Ｈ），１．９８（ｄｄ，４Ｈ），２．９１−３．０３（ｍ，８Ｈ），７．１４（ｔ，８Ｈ），７．２５（ｔ，８Ｈ），７．３３（ｔ，４Ｈ），７．３８−７．４３（ｍ，１２Ｈ），７．４５（ｄ，８Ｈ）．
２９Ｓｉ−ＮＭＲ（ＣＤＣｌ３）：δ（ｐｐｍ）；−１０６．９２，−７９．４１，−７９．１８，１１．２６，１１．２８，１１．３４，１１．３６．
1 H-NMR (CDCl 3 ): δ (ppm); 0.01 (s, 24H), 0.40-0.46 (m, 8H), 0.58-0.63 (m, 2H), 0 .83-0.87 (m, 4H), 0.95-1.26 (m, 18H), 1.45-1.49 (m, 2H), 1.59-1.81 (m, 6H) 1.98 (dd, 4H), 2.91-3.03 (m, 8H), 7.14 (t, 8H), 7.25 (t, 8H), 7.33 (t, 4H), 7.38-7.43 (m, 12H), 7.45 (d, 8H).
29 Si-NMR (CDCl 3 ): δ (ppm); −106.92, −79.41, −79.18, 11.26, 11.28, 11.34, 11.36.
実施例において使用した主な材料
・シルセスキオキサン誘導体：合成例で製造した化合物（１−１）
・シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物：三菱瓦斯化学(株)製酸無水物Ｈ−ＴＭＡｎ
・ヘキサヒドロフタル酸無水物：新日本理化(株)製リガシッド（商品名） ＭＨ−７００Ｇ
・エポキシ樹脂：ダイセル化学工業(株)製セロキサイド（商品名）２０２１ Ｐ（製品名ＣＥＬ２０２１Ｐ）
・酸化防止剤：チバ・ジャパン（株）製ＩＲＧＡＮＯＸ１０１０（商品名）
・硬化促進剤：サンアプロ（株）製Ｕ−ＣＡＴ５００３（商品名）
Main materials used in Examples: Silsesquioxane derivative: Compound (1-1) produced in Synthesis Example
Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride: acid anhydride H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd.
・ Hexahydrophthalic anhydride: Rigashid (trade name) MH-700G manufactured by Shin Nippon Rika Co., Ltd.
Epoxy resin: Daicel Chemical Industries, Ltd. Celoxide (Product Name) 2021 P (Product Name CEL2021P)
Antioxidant: IRGANOX 1010 (trade name) manufactured by Ciba Japan Co., Ltd.
Curing accelerator: U-CAT5003 (trade name) manufactured by San Apro Co., Ltd.
実施例１
スクリュー管１にＨ−ＴＭＡｎ（０．９１ｇ）、ＭＨ−７００Ｇ（２．０ｇ）を仕込み攪拌して溶解した。スクリュー管２にＭＨ−７００Ｇ（０．７５ｇ）、ＣＥＬ２０２１Ｐ（２．０ｇ）、および化合物（１−１）（４．０ｇ）を仕込み、４５℃に温めながら攪拌して溶解した。溶解後、ＩＲＧＡＮＯＸ１０１０（商品名）（１０ｍｇ）を加え、攪拌して溶解した。
スクリュー管２の溶液をスクリュー管１の溶液に注ぎ込み、充分に攪拌してワニスを調製した。ワニスをデシケーター中で攪拌しながら減圧し脱泡した後、このうちの約７ｇを気泡が入らないようにフロン工業（株）製テフロン（登録商標）ＰＦＡペトリー皿に流し込んだ。そして１００℃に予め温めておいたオーブン中に、直接熱風が当たらないように置き、加熱して硬化した。加熱は、１００℃で１時間、１２５℃で１時間、１５０℃で３時間の順に行った。
Example 1
H-TMAn (0.91 g) and MH-700G (2.0 g) were charged into the screw tube 1 and dissolved by stirring. MH-700G (0.75 g), CEL2021P (2.0 g), and compound (1-1) (4.0 g) were charged into the screw tube 2 and dissolved by stirring while warming to 45 ° C. After dissolution, IRGANOX 1010 (trade name) (10 mg) was added and dissolved by stirring.
The solution in the screw tube 2 was poured into the solution in the screw tube 1 and stirred sufficiently to prepare a varnish. After the varnish was depressurized while being stirred in a desiccator, about 7 g of the varnish was poured into a Teflon (registered trademark) PFA Petri dish manufactured by Freon Industries Co., Ltd. so as not to contain bubbles. Then, it was placed in an oven preheated to 100 ° C. so that it was not directly exposed to hot air, and was cured by heating. Heating was performed in order of 100 ° C. for 1 hour, 125 ° C. for 1 hour, and 150 ° C. for 3 hours.
実施例２
スクリュー管３にＨ−ＴＭＡｎ（０．２７ｇ）、ＭＨ−７００Ｇ（２．０ｇ）を仕込み、攪拌して溶解した。スクリュー管４にＭＨ−７００Ｇ（１．７５ｇ）、ＣＥＬ２０２１Ｐ（２．０ｇ）、および化合物（１−１）（４．０ｇ）を入れ、４５℃に温めながら攪拌し溶解した。溶解後、ＩＲＧＡＮＯＸ１０１０（商品名）（１０ｍｇ）を加え、攪拌し溶解した。
スクリュー管４の溶液をスクリュー管３の溶液に注ぎ込み、充分に攪拌してワニスを調製した。ワニスをデシケーター中で攪拌しながら減圧し脱泡した後、このうちの約７ｇを気泡が入らないようにフロン工業（株）製テフロン（登録商標）ＰＦＡペトリー皿に流し込んだ。そして予め１００℃に温めておいたオーブン中に、直接熱風が当たらないように置き、加熱して硬化した。加熱は、１００℃で１時間、１２５℃で１時間、１５０℃で３時間の順に行った。
Example 2
H-TMAn (0.27 g) and MH-700G (2.0 g) were charged into the screw tube 3 and dissolved by stirring. MH-700G (1.75 g), CEL2021P (2.0 g), and compound (1-1) (4.0 g) were placed in the screw tube 4 and stirred and dissolved while warming to 45 ° C. After dissolution, IRGANOX 1010 (trade name) (10 mg) was added and dissolved by stirring.
The solution in the screw tube 4 was poured into the solution in the screw tube 3 and sufficiently stirred to prepare a varnish. After the varnish was depressurized while being stirred in a desiccator, about 7 g of the varnish was poured into a Teflon (registered trademark) PFA Petri dish manufactured by Freon Industries Co., Ltd. so as not to contain bubbles. Then, it was placed in an oven preheated to 100 ° C. so that it was not directly exposed to hot air, and was cured by heating. Heating was performed in order of 100 ° C. for 1 hour, 125 ° C. for 1 hour, and 150 ° C. for 3 hours.
比較例１
スクリュー管５にＭＨ−７００Ｇ（４．１７ｇ）、ＣＥＬ２０２１Ｐ（２．０ｇ）、及び化合物（１−１）（４．０ｇ）を入れ、４５℃に温めながら攪拌し溶解した。溶解後、ＩＲＧＡＮＯＸ１０１０（商品名）（１０ｍｇ）を加え、攪拌し溶解した。次に、ニッカオクチックス亜鉛（商品名）８％（１２ｍｇ）を加え、攪拌し溶解した。そしてエチレングリコール（４０ｍｇ）を加え、攪拌し溶解しワニスを調製した。ワニスをデシケーター中で攪拌しながら減圧し脱泡した後、このうちの約７ｇを気泡が入らないようにフロン工業（株）製テフロン（登録商標）ＰＦＡペトリー皿に流し込んだ。そして予め１００℃に温めておいたオーブン中に、直接熱風が当たらないように置き、加熱して硬化した。加熱は、１００℃で１時間、１２５℃で１時間、１５０℃で３時間の順に行った。
Comparative Example 1
MH-700G (4.17g), CEL2021P (2.0g), and compound (1-1) (4.0g) were put into the screw tube 5, and it stirred and melt | dissolved, warming to 45 degreeC. After dissolution, IRGANOX 1010 (trade name) (10 mg) was added and dissolved by stirring. Next, 8% (12 mg) of Nikka Octix zinc (trade name) was added and stirred to dissolve. And ethylene glycol (40 mg) was added, and it stirred and melt | dissolved and prepared the varnish. After the varnish was depressurized while being stirred in a desiccator, about 7 g of the varnish was poured into a Teflon (registered trademark) PFA Petri dish manufactured by Freon Industries Co., Ltd. so as not to contain bubbles. Then, it was placed in an oven preheated to 100 ° C. so that it was not directly exposed to hot air, and was cured by heating. Heating was performed in order of 100 ° C. for 1 hour, 125 ° C. for 1 hour, and 150 ° C. for 3 hours.
比較例２
スクリュー管６にＵ−ＣＡＴ５００３（１２ｍｇ）、ＭＨ−７００Ｇ（３．０ｇ）を入れ、攪拌し溶解した。スクリュー管７にＭＨ−７００Ｇ（１．１７ｇ）、ＣＥＬ２０２１Ｐ（２．０ｇ）、および化合物（１−１）（４．０ｇ）を入れ、４５℃に温めながら攪拌し溶解した。溶解後、ＩＲＧＡＮＯＸ１０１０（商品名）（１０ｍｇ）を加え、攪拌し溶解した。
スクリュー管６の溶液をスクリュー管７の溶液に注ぎ込み、充分に攪拌してワニスを調製した。ワニスをデシケーター中で攪拌しながら減圧し脱泡した後、このうちの約７ｇをフロン工業（株）製テフロン（登録商標）ＰＦＡペトリー皿に気泡が入らないように流し込んだ。そして予め１００℃に温めておいたオーブン中に、直接熱風が当たらないように置き、加熱して硬化した。加熱は、１００℃で１時間、１２５℃で１時間、１５０℃で３時間の順に行った。
Comparative Example 2
U-CAT5003 (12 mg) and MH-700G (3.0 g) were placed in the screw tube 6 and dissolved by stirring. MH-700G (1.17 g), CEL2021P (2.0 g), and compound (1-1) (4.0 g) were placed in the screw tube 7 and stirred and dissolved while warming to 45 ° C. After dissolution, IRGANOX 1010 (trade name) (10 mg) was added and dissolved by stirring.
The solution in the screw tube 6 was poured into the solution in the screw tube 7 and sufficiently stirred to prepare a varnish. The varnish was depressurized while stirring in a desiccator, and about 7 g of the varnish was poured into a Teflon (registered trademark) PFA Petri dish manufactured by Freon Industries Co., Ltd. so that no bubbles would enter. Then, it was placed in an oven preheated to 100 ° C. so that it was not directly exposed to hot air, and was cured by heating. Heating was performed in order of 100 ° C. for 1 hour, 125 ° C. for 1 hour, and 150 ° C. for 3 hours.
＜耐熱試験＞
実施例１〜２、比較例１〜２で得られた硬化物の４００ｎｍでの透過率を測定するため、研磨機（ムサシノ電子株式会社製ＭＡ−２００Ｄ）で硬化物の両面を研磨し、表面が平滑に研磨された厚さ３ｍｍの試験片を得た。
得られた硬化物を半分に切断し、一つは、熱処理を行なわず、もう一つは、内温１５０℃に調整したオーブン（送風定温乾燥機：アドバンテック東洋（株）製ＤＲＭ４２０ＤＡ）に入れ、１６８時間放置した。
<Heat resistance test>
In order to measure the transmittance at 400 nm of the cured products obtained in Examples 1-2 and Comparative Examples 1-2, both surfaces of the cured product were polished with a polishing machine (MA-200D manufactured by Musashino Electronics Co., Ltd.) A test piece having a thickness of 3 mm was obtained.
The obtained cured product was cut in half, one was not heat-treated, and the other was placed in an oven adjusted to an internal temperature of 150 ° C. (blower constant temperature dryer: DRM420DA manufactured by Advantech Toyo Co., Ltd.) Left for 168 hours.
＜耐熱性の評価＞
硬化物の耐熱性は、耐熱試験前後の硬化物の光線透過率を紫外可視分光光度計（日本分光（株）製、Ｖ−６６０）で測定し、黄色度（ＹＩ値）、波長４００ｎｍの透過率の保持率を式１に従って計算し評価した。
（耐熱試験後の透過率／初期透過率）×１００ …（式１）
<Evaluation of heat resistance>
The heat resistance of the cured product is determined by measuring the light transmittance of the cured product before and after the heat resistance test with an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, V-660), and transmitting the yellowness (YI value) at a wavelength of 400 nm. The rate retention was calculated and evaluated according to Equation 1.
(Transmittance after heat test / initial transmittance) × 100 (Formula 1)
＜試験結果＞
表１に上記試験の結果を示す。
<Test results>
Table 1 shows the results of the above test.
実施例３
スクリュー管８にＨ−ＴＭＡｎ（８．５７ｇ）、ＭＨ−７００Ｇ（２５．９８ｇ）を仕
Example 3
H-TMAn (8.57 g) and MH-700G (25.98 g) are prepared on the screw tube 8.
込み、攪拌しながら溶解した。溶解後、ＩＲＧＡＮＯＸ１０１０（商品名）（７０．６ｍｇ）を加え、攪拌し溶解した。スクリュー管９にＣＥＬ２０２１Ｐ（２７．０ｇ）、化合物（１−１）（９．０ｇ）を仕込み、４５℃に温めながら攪拌し溶解した。スクリュー管９の溶液をスクリュー管８の溶液に注ぎ込み、充分に撹拌してワニスを調製した。ワニスをデシケーター中で攪拌しながら減圧し脱泡した。 And dissolved with stirring. After dissolution, IRGANOX 1010 (trade name) (70.6 mg) was added and dissolved by stirring. CEL2021P (27.0 g) and compound (1-1) (9.0 g) were charged into the screw tube 9 and dissolved by stirring while warming to 45 ° C. The solution in the screw tube 9 was poured into the solution in the screw tube 8 and sufficiently stirred to prepare a varnish. The varnish was defoamed under reduced pressure while stirring in a desiccator.
＜硬化物の作製＞
ワニスを熱硬化させて、硬化物とするためにの容器は次の方法で組み立てた。片側表面にフッ素樹脂シート（フロン工業（株）製テフロン（登録商標）ＦＥＰ粘着シートフィルム）を貼り付けた一辺の長さが約２００ｍｍの正方形のステンレス製の板（以下ＳＵＳ板と表記する）を２枚用意した。１枚のＳＵＳ板には３辺の縁にフッ素樹脂パッキン（ニチアス（株）製ナフロン（登録商標）ＳＰパッキン５．６ｍｍφ）を置き、もう１枚のＳＵＳ板でフッ素樹脂シートが向かい合うようにしてこのパッキンを挟んだ。 そして、２枚のＳＵＳ板を固定して容器とした。ここで、フッ素樹脂パッキンで囲われた空間の隙間は一辺の長さが約１００ｍｍで、厚さが４．２〜４．５ｍｍであった。そしてパッキンを挟んでいない縁から容器の中に、ワニスを流し込んだ。そして１２５℃に予め温めておいたオーブンの中に、ワニス入りの容器を置き、１２５℃で１時間、１５０℃で３時間加熱して硬化させて、硬化物（大きさ約１００×１００ｍｍ、厚さ４．２から４．５ｍｍ）を得た。得られた硬化物をバンドソーで切断後、マルチプレップ形サンプルポリッシャー（Allied社製Item NO.15-2000）で研磨した。
<Production of cured product>
A container for thermally curing the varnish to obtain a cured product was assembled by the following method. A square stainless steel plate (hereinafter referred to as a SUS plate) with a side length of about 200 mm with a fluororesin sheet (Teflon (registered trademark) FEP adhesive sheet film manufactured by Freon Industries Co., Ltd.) attached to one surface. Two sheets were prepared. Place one side of the SUS plate with fluororesin packing (Naflon (registered trademark) SP packing 5.6 mmφ manufactured by Nichias Corp.) on the edges of the three sides, so that the fluororesin sheet faces the other SUS plate. I sandwiched this packing. And two SUS boards were fixed and it was set as the container. Here, the gap between the spaces surrounded by the fluororesin packing had a side length of about 100 mm and a thickness of 4.2 to 4.5 mm. And the varnish was poured into the container from the edge without the packing. Then, a container with varnish is placed in an oven preheated to 125 ° C. and cured by heating at 125 ° C. for 1 hour and at 150 ° C. for 3 hours to obtain a cured product (size: about 100 × 100 mm, thickness 4.2 to 4.5 mm). The obtained cured product was cut with a band saw and polished with a multi-prep sample polisher (Item No. 15-2000 manufactured by Allied).
実施例４〜８および比較例３
Ｈ−ＴＭＡｎ、ＭＨ−７００Ｇ、ＣＥＬ２０２１Ｐ、および化合物（１−１）を表２の割合で仕込んだ以外は実施例３と同様にワニスを調製して硬化物を作製した。このようにして得られた試験片を用いて以下の評価を実施した。表２に硬化物の組成を示す。また、表３に実施例３〜８と比較例３で得られた試験片の評価結果を示す。
Examples 4 to 8 and Comparative Example 3
A varnish was prepared in the same manner as in Example 3 except that H-TMAn, MH-700G, CEL2021P, and compound (1-1) were charged in the proportions shown in Table 2, and a cured product was produced. The following evaluation was performed using the test piece thus obtained. Table 2 shows the composition of the cured product. Table 3 shows the evaluation results of the test pieces obtained in Examples 3 to 8 and Comparative Example 3.
＜全光線透過率・濁度測定＞
試験片は両面を平滑に研磨し厚さを３ｍｍに揃えた硬化物を用いて、ヘーズメータ（日本電色工業（株）製ＮＨＤ５０００）により全光線透過率、拡散透過率と濁度を測定した。
＜屈折率＞
試験片は硬化物をバンドソーにて切断し、ＪＩＳ Ｋ７１４２に従って試験片を作製した。この試験片を用いて、アッベ屈折計（（株）アタゴ製ＮＡＲ−２Ｔ）によりナトリウムランプのＤ線（５８６ｎｍ）を用いて屈折率を測定した。中間液はヨウ化メチレンを用いた。
＜曲げ強度試験＞
試験片は、硬化物から、ＪＩＳ Ｋ７１７１に従って切り出し作製した。曲げ弾性率・曲げ破壊強度は、引張圧縮試験機（（株）東洋精機製作所製ストログラフＶ１０−Ｃ）により５ｋＮのロードセルを用いて測定した。
＜ショア硬度＞
試験片は、硬化物からＪＩＳ Ｂ７７２７に従って成形して作製した。硬度の測定は、ショア硬さ試験器（（株）ミツトヨ製ＡＳＨ−Ｄ）により測定した。
＜煮沸試験＞
試験片は両面を平滑に研磨し厚さを３ｍｍに揃えた硬化物を用いて、沸騰水中で１６８時間煮沸を行い、得られた試験片の表面を目視にて観察するとともに、紫外可視分光光度計を用いて波長４００ｎｍの光線透過率の保持率で評価を行なった。
＜曲げ接着強さ試験＞
試験片は、基材としてポリフタルアミド樹脂（ソルベイアドバンスドポリマーズ（株）製アモデル（商品名）Ａ−４１２２ＮＬＷＨ９０５）を厚さ２ｍｍの板状に成形し、ＪＩＳ Ｋ６８５６に従って寸法を調整して作製した。接着試験は引張圧縮試験機（（株）東洋精機製作所製ストログラフＶ１０−Ｃ）により５ｋＮのロードセルを用いて測定した。
<Total light transmittance / turbidity measurement>
The test piece was measured for total light transmittance, diffuse transmittance, and turbidity with a haze meter (NHD5000 manufactured by Nippon Denshoku Industries Co., Ltd.) using a cured product having both surfaces polished smoothly and having a thickness of 3 mm.
<Refractive index>
The test piece cut the hardened | cured material with the band saw, and produced the test piece according to JISK7142. Using this test piece, the refractive index was measured with an Abbe refractometer (NAR-2T manufactured by Atago Co., Ltd.) using a D line (586 nm) of a sodium lamp. The intermediate solution was methylene iodide.
<Bending strength test>
The test piece was cut out from the cured product according to JIS K7171. The flexural modulus and bending fracture strength were measured using a 5 kN load cell with a tensile and compression tester (Strograph V10-C manufactured by Toyo Seiki Seisakusho Co., Ltd.).
<Shore hardness>
The test piece was produced from the cured product according to JIS B7727. The hardness was measured with a Shore hardness tester (ASH-D manufactured by Mitutoyo Corporation).
<Boiling test>
The test piece was boiled in boiling water for 168 hours using a cured product having both surfaces polished smoothly and having a thickness of 3 mm, and the surface of the obtained test piece was visually observed, and ultraviolet-visible spectrophotometry was obtained. Evaluation was performed by using a meter to maintain the light transmittance at a wavelength of 400 nm.
<Bending bond strength test>
The test piece was prepared by forming a polyphthalamide resin (Amodel (trade name) A-4122NLWH905 manufactured by Solvay Advanced Polymers Co., Ltd.) as a substrate into a 2 mm thick plate and adjusting the dimensions according to JIS K6856. The adhesion test was measured using a 5 kN load cell with a tensile and compression tester (Strograph V10-C manufactured by Toyo Seiki Seisakusho Co., Ltd.).
実施例、比較例の結果から、本発明の熱硬化性樹脂組成物を用いて得られた硬化物は、透明で屈折率が高く、耐熱黄変性、耐沸騰水性に優れ、耐熱性の優れた特性を損なうことなくエポキシ樹脂に柔軟性を与えることができた。また、この硬化物はダブルデッカー型のシルセスキオキサンの骨格を有することから、絶縁性に優れることがわかる。
このことから、これらの硬化物は、半導体封止材、光半導体封止材、絶縁膜、シール剤、接着剤、光学レンズなどに利用できることがわかった。
From the results of Examples and Comparative Examples, the cured product obtained using the thermosetting resin composition of the present invention is transparent and has a high refractive index, excellent heat-resistant yellowing resistance, boiling water resistance, and excellent heat resistance. The flexibility could be given to the epoxy resin without impairing the properties. Moreover, since this hardened | cured material has frame | skeleton of a double decker type silsesquioxane, it turns out that it is excellent in insulation.
From this, it was found that these cured products can be used for semiconductor encapsulants, optical semiconductor encapsulants, insulating films, sealants, adhesives, optical lenses, and the like.
Claims (10)
式（１）において、Ｒは炭素数１〜４５のアルキル、炭素数４〜８のシクロアルキル、炭素数６〜１４のアリールおよび炭素数７〜２４のアリールアルキルから独立して選択される基であり；炭素数１〜４５のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は、−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールおよびアリールアルキル中のベンゼン環において、任意の水素はハロゲンまたは炭素数１〜１０のアルキルで置き換えられてもよく、この炭素数１〜１０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、そして隣接しない任意の−ＣＨ２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールアルキル中のアルキレンの炭素数は１〜１０であり、そして隣接しない任意の−ＣＨ２−は−Ｏ−で置き換えられてもよく；Ｒ１およびＲ２は、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシルおよびフェニルから独立して選択される基であり；そして、Ｘ1はオキシラニル、オキシラニレン、３，４−エポキシシクロヘキシル、オキセタニルまたはオキセタニレンのいずれか１つを有する基である。 A thermosetting resin composition comprising a silsesquioxane derivative represented by the formula (1), cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and other acid anhydrides.
In the formula (1), R is a group independently selected from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 14 carbon atoms and arylalkyl having 7 to 24 carbon atoms. Yes; in alkyl of 1 to 45 carbon atoms, any hydrogen may be replaced with fluorine, and any non-adjacent —CH 2 — may be replaced with —O— or —CH═CH—; In the benzene ring in aryl and arylalkyl, any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms, and in this alkyl having 1 to 10 carbon atoms, any hydrogen may be replaced by fluorine. Well, and any non-adjacent —CH 2 — may be replaced by —O— or —CH═CH—; the number of alkylene carbons in the arylalkyl Are 1 to 10 and any non-adjacent —CH 2 — may be replaced by —O—; R 1 and R 2 are independently of C 1 -C 4 alkyl, cyclopentyl, cyclohexyl and phenyl; And X 1 is a group having any one of oxiranyl, oxiranylene, 3,4-epoxycyclohexyl, oxetanyl or oxetanylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010119903A1 (en) | 2009-04-14 | 2010-10-21 | チッソ株式会社 | Glass fiber-silsesquioxane composite molded article and method for producing same |
| JP2011063799A (en) * | 2009-08-21 | 2011-03-31 | Jsr Corp | Sealing composition for optical semiconductor |
| JP2011088947A (en) * | 2009-10-20 | 2011-05-06 | Sumitomo Metal Mining Co Ltd | Epoxy group-containing adhesive resin composition and adhesive for optical semiconductor prepared by using the same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004024741A1 (en) * | 2002-09-13 | 2004-03-25 | Chisso Corporation | Silsesquioxane derivative and process for producing the same |
| JP2004331647A (en) * | 2003-03-13 | 2004-11-25 | Chisso Corp | Polymer and compound having silsesquioxane skeleton |
| JP2004359933A (en) * | 2003-05-14 | 2004-12-24 | Nagase Chemtex Corp | Sealing material for optical element |
| JP2007169406A (en) * | 2005-12-21 | 2007-07-05 | Jsr Corp | Composition for optical semiconductor encapsulation, method for producing the same, and optical semiconductor encapsulant |
| JP2007326988A (en) * | 2006-06-09 | 2007-12-20 | Chisso Corp | Epoxy resin composition |
-
2008
- 2008-11-20 JP JP2008297132A patent/JP5013127B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004024741A1 (en) * | 2002-09-13 | 2004-03-25 | Chisso Corporation | Silsesquioxane derivative and process for producing the same |
| JP2004331647A (en) * | 2003-03-13 | 2004-11-25 | Chisso Corp | Polymer and compound having silsesquioxane skeleton |
| JP2004359933A (en) * | 2003-05-14 | 2004-12-24 | Nagase Chemtex Corp | Sealing material for optical element |
| JP2007169406A (en) * | 2005-12-21 | 2007-07-05 | Jsr Corp | Composition for optical semiconductor encapsulation, method for producing the same, and optical semiconductor encapsulant |
| JP2007326988A (en) * | 2006-06-09 | 2007-12-20 | Chisso Corp | Epoxy resin composition |
Cited By (14)
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| WO2010119903A1 (en) | 2009-04-14 | 2010-10-21 | チッソ株式会社 | Glass fiber-silsesquioxane composite molded article and method for producing same |
| JP2011063799A (en) * | 2009-08-21 | 2011-03-31 | Jsr Corp | Sealing composition for optical semiconductor |
| JP2011088947A (en) * | 2009-10-20 | 2011-05-06 | Sumitomo Metal Mining Co Ltd | Epoxy group-containing adhesive resin composition and adhesive for optical semiconductor prepared by using the same |
| JP2011111550A (en) * | 2009-11-27 | 2011-06-09 | Sumitomo Metal Mining Co Ltd | Epoxy resin adhesive composition and adhesive for optical semiconductor using the same |
| WO2011105192A1 (en) * | 2010-02-25 | 2011-09-01 | ダイセル化学工業株式会社 | Resin composition for sealing an optical semiconductor and optical semiconductor device using said resin composition |
| JP2011174023A (en) * | 2010-02-25 | 2011-09-08 | Daicel Chemical Industries Ltd | Resin composition for optical semiconductor sealing and optical semiconductor device produced by using the same |
| JPWO2011145638A1 (en) * | 2010-05-18 | 2013-07-22 | Jnc株式会社 | Novel organosilicon compound, thermosetting resin composition containing the organosilicon compound, cured resin, and sealing material for optical semiconductor |
| DE112011101961T5 (en) | 2010-06-08 | 2013-03-21 | Dic Corporation | Sealing material, solar cell module and LED |
| JP2013035880A (en) * | 2011-08-03 | 2013-02-21 | Adeka Corp | Curing agent for epoxy resin, and epoxy resin composition containing the curing agent for epoxy resin |
| US10988616B2 (en) | 2013-07-25 | 2021-04-27 | Jnc Corporation | Thermosetting resin composition, cured film, substrate with cured film, and electronic component |
| JP2016160420A (en) * | 2015-03-05 | 2016-09-05 | Jnc株式会社 | Thermosetting composition, cured film, substrate with cured film, electronic component, and display device |
| WO2018037565A1 (en) * | 2016-08-26 | 2018-03-01 | Jnc株式会社 | Epoxy resin composition and cured resin film with low curing shrinkage and excellent adhesion |
| JPWO2018037565A1 (en) * | 2016-08-26 | 2019-06-20 | Jnc株式会社 | Epoxy resin composition and low cure shrinkable resin cured film excellent in adhesion |
| US12305004B2 (en) | 2020-03-30 | 2025-05-20 | Jnc Corporation | Cationically polymerizable composition |
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