JPS6154327B2 - - Google Patents
Info
- Publication number
- JPS6154327B2 JPS6154327B2 JP14663081A JP14663081A JPS6154327B2 JP S6154327 B2 JPS6154327 B2 JP S6154327B2 JP 14663081 A JP14663081 A JP 14663081A JP 14663081 A JP14663081 A JP 14663081A JP S6154327 B2 JPS6154327 B2 JP S6154327B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- epoxy
- aluminum
- groups
- 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.)
- Expired
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920003986 novolac Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920002050 silicone resin Polymers 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- -1 aluminum compound Chemical class 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000012778 molding material Substances 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 150000004645 aluminates Chemical class 0.000 description 7
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CSJKPFQJIDMSGF-UHFFFAOYSA-K aluminum;tribenzoate Chemical compound [Al+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 CSJKPFQJIDMSGF-UHFFFAOYSA-K 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 125000005372 silanol group Chemical group 0.000 description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 239000004593 Epoxy Chemical class 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- YKPAABNCNAGAAJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)propane Chemical compound C=1C=C(O)C=CC=1C(CC)C1=CC=C(O)C=C1 YKPAABNCNAGAAJ-UHFFFAOYSA-N 0.000 description 2
- MQXNNWDXHFBFEB-UHFFFAOYSA-N 2,2-bis(2-hydroxyphenyl)propane Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1O MQXNNWDXHFBFEB-UHFFFAOYSA-N 0.000 description 2
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 2
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- 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
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- DMGNPLVEZUUCBT-UHFFFAOYSA-K aluminum;propanoate Chemical compound [Al+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O DMGNPLVEZUUCBT-UHFFFAOYSA-K 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 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
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000001287 2,4-xylenyl group Chemical group [H]C1=C(O*)C(=C([H])C(=C1[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JHOPNNNTBHXSHY-UHFFFAOYSA-N 2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1O JHOPNNNTBHXSHY-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000286819 Malo Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- JZUPEYITGSJFNX-UHFFFAOYSA-K aluminum octadecanoate diacetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JZUPEYITGSJFNX-UHFFFAOYSA-K 0.000 description 1
- SUXQAUVHBJPFFS-UHFFFAOYSA-K aluminum;3-methylbenzoate Chemical compound [Al+3].CC1=CC=CC(C([O-])=O)=C1.CC1=CC=CC(C([O-])=O)=C1.CC1=CC=CC(C([O-])=O)=C1 SUXQAUVHBJPFFS-UHFFFAOYSA-K 0.000 description 1
- ACAXTBGMSDIPQV-UHFFFAOYSA-K aluminum;diacetate;benzoate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.[O-]C(=O)C1=CC=CC=C1 ACAXTBGMSDIPQV-UHFFFAOYSA-K 0.000 description 1
- TZPOMCMYQHNEJQ-UHFFFAOYSA-L aluminum;propan-2-olate;dibenzoate Chemical compound [Al+3].CC(C)[O-].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 TZPOMCMYQHNEJQ-UHFFFAOYSA-L 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- BSBSDQUZDZXGFN-UHFFFAOYSA-N cythioate Chemical compound COP(=S)(OC)OC1=CC=C(S(N)(=O)=O)C=C1 BSBSDQUZDZXGFN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WPCPXPTZTOMGRF-UHFFFAOYSA-K di(butanoyloxy)alumanyl butanoate Chemical compound [Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WPCPXPTZTOMGRF-UHFFFAOYSA-K 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 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 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- HXPLDADFOLJSKO-UHFFFAOYSA-N hydroxy-dimethoxy-methylsilane Chemical compound CO[Si](C)(O)OC HXPLDADFOLJSKO-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical class CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- CMEVTVGFRCKPGC-UHFFFAOYSA-N trihexadecoxyalumane Chemical compound [Al+3].CCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCC[O-] CMEVTVGFRCKPGC-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- ZFYVMCFENKKDFG-UHFFFAOYSA-N trioctoxyalumane Chemical compound [Al+3].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] ZFYVMCFENKKDFG-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Organic Insulating Materials (AREA)
Description
本発明は新規なエポキシ―シリコーン樹脂組成
物に関し、特には電気特性、耐熱性及び耐湿性等
が良好な成形品等を与える樹脂組成物を提供しよ
うとするものである。
従来、エポキシ―シリコーン樹脂組成物として
は、例えば〓Si―OH含有オルガノシリコーン化
合物、エポキシ化合物、アルミニウム化合物及び
The present invention relates to a novel epoxy-silicone resin composition, and in particular, it is an object of the present invention to provide a resin composition that provides molded articles with good electrical properties, heat resistance, moisture resistance, etc. Conventionally, epoxy-silicone resin compositions include, for example, Si-OH-containing organosilicone compounds, epoxy compounds, aluminum compounds, and
【式】含有オルガノシリコン化合物からな
る組成物（特公昭53―29720号公報参照）あるい
は[Formula] A composition comprising an organosilicon compound (see Japanese Patent Publication No. 53-29720) or
【式】含有有機けい素化合物、エポキシ
化合物及びある特定の数種のアルミニウム化合物
から選択されるアルミニウム化合物からなる組成
物（特開昭51―118728号公報参照）等が知られて
いる。
しかしながら、これらの組成物から得られる硬
化物はいずれも膨張係数が大きく、しかも硬化用
触媒としてアルミニウム化合物を用いていること
から有機基（フエニル基）とけい素原子との結合
の切断やシロキサン結合のクラツキング等により
加熱減量が大きくなつて長期の耐熱寸法安定性に
乏しいものになるという不利があり、又エポキシ
樹脂のみから得られる硬化物に比較して透湿性に
劣るようになる（即ち透湿率が大きくなる）とい
う欠点がある。
本発明は上記したような従来の不利及び欠点を
除去した新規なエポキシ―シリコーン樹脂組成物
を提供しようとするものであつて、これは
(A) １分子中にエポキシ基を２個以上有するエポ
キシ樹脂 20〜95重量部
(B) 式
（式中、Ａはフエノール性水酸基を有する化
合物からフエノール性水酸基を除いた残基、
R1はC1〜C10の二価炭化水素基、R2及びR3は一
価有機基、ａは０、１又は２、ｌは０又は正の
整数、ｍは１〜70の整数、ｎは０〜10の整数）
で示されるシリコーン変性フエノール系プレポ
リマー 80〜５重量部、
(C) 上記(A)及び(B)成分の合計量100重量部に対し
て０〜1000重量部の無機質充填剤、及び
(D) 硬化用触媒
からなるものである。
以下、本発明に係るエポキシ―シリコーン樹脂
組成物について詳細に説明する。
まず、本発明における(A)成分としてのエポキシ
樹脂は、１分子中にエポキシ基を２個以上有する
ことが必須とされ、これには例えばビスフエノー
ルＡ、ハロゲン化ビスフエノールＡ、カテコー
ル、レゾルシノール等の多価フエノール類又はグ
リセリン等の多価アルコール類とエピクロルヒド
リンとを塩基性触媒の存在下で反応させることに
より得られるポリグリシジルエーテルあるいはポ
リグリシジルエステル、ノボラツク型フエノール
樹脂とエピクロルヒドリンとを縮合させることに
より得られるエポキシ化ノボラツク、過酸化法に
よりエポキシ化してなるエポキシ化オレフイン、
エポキシ化ポリブタジエン、エポキシ化植物
油、、ビニルシクロヘキセンジオキサイド、ジペ
ンテンジオキサイド、２，２―ビス（３，４―エ
ポキシシクロヘキシル）プロバン、ビス（２，３
―エポキシシクロペンチル）エーテル、ジシクロ
ペンタジエンオキサイド等のシクロヘキサン誘導
体等をあげることができる。
しかしながら、これらはあくまでも(A)成分を具
体的に例示したものであつてこれらに限定される
ものではなく現在知られている種々のものを使用
することができるが、硬化性を考慮した場合には
脂環式エポキシ樹脂又はノボラツク樹脂が好適と
される。
つぎに、本発明で使用する(B)成分としてのシリ
コーン変性フエノール系プレポリマーは上記した
式(i)で示されるものであつて、上記式(i)中のＡで
示されるフエノール性水酸基を有する化合物から
フエノール性水酸基を除いた基としては、例えば
カテコール、レゾルシノール、ハイドロキノンあ
るいはフロログルシノール等のフエノール誘導
体、２，２―ビス（２―ヒドロキシフエニル）プ
ロパン、２，4′―ジヒドロキシジフエニルメタ
ン、２，２―ビス（４―ヒドロキシフエニル）プ
ロパン、１，１―ビス（４―ヒドロキシフエニ
ル）エタン、１，１―ビス（４―ヒドロキシフエ
ニル）プロパン、２，２―ビス（４―ヒドロキシ
フエニル）ペンタン、４，4′―ジヒドロキシビフ
エニル、４，4′―ジヒドロキシベンゾフエノン、
４，4′―ジヒドロキシジフエニルスルホン、４，
4′―ジヒドロキシフエニルスルフイド等の二価フ
エノール類、フエノールノボラツク樹脂、レゾー
ル型フエノール樹脂、イソプロペニルフエノール
のオリゴマーあるいはポリパラビニルフエノール
類等のフエノール性水酸基含有化合物から該水酸
基を除いた基があげられる。
以下に、該残基のいくつかを例示する。Compositions comprising an organosilicon compound containing the formula [formula], an epoxy compound, and an aluminum compound selected from several specific types of aluminum compounds (see Japanese Patent Laid-Open No. 118728/1983) are known. However, the cured products obtained from these compositions all have large expansion coefficients, and because aluminum compounds are used as curing catalysts, it is difficult to break the bonds between organic groups (phenyl groups) and silicon atoms and to break the siloxane bonds. There is a disadvantage that the loss on heating increases due to cracking, etc., resulting in poor long-term heat-resistant dimensional stability, and the moisture permeability is inferior compared to a cured product obtained only from epoxy resin (i.e., moisture permeability). has the disadvantage that it becomes large). The present invention aims to provide a novel epoxy-silicone resin composition which eliminates the conventional disadvantages and disadvantages as described above, and which consists of (A) an epoxy silicone resin composition having two or more epoxy groups in one molecule; Resin 20-95 parts by weight (B) Formula (In the formula, A is a residue obtained by removing a phenolic hydroxyl group from a compound having a phenolic hydroxyl group,
R 1 is a C 1 to C 10 divalent hydrocarbon group, R 2 and R 3 are monovalent organic groups, a is 0, 1 or 2, l is 0 or a positive integer, m is an integer from 1 to 70, n is an integer from 0 to 10)
80 to 5 parts by weight of a silicone-modified phenolic prepolymer represented by (C) 0 to 1000 parts by weight of an inorganic filler per 100 parts by weight of the total amount of components (A) and (B) above, and (D) It consists of a curing catalyst. Hereinafter, the epoxy-silicone resin composition according to the present invention will be explained in detail. First, it is essential that the epoxy resin as component (A) in the present invention has two or more epoxy groups in one molecule, such as bisphenol A, halogenated bisphenol A, catechol, resorcinol, etc. Polyglycidyl ether or polyglycidyl ester obtained by reacting polyhydric phenols or polyhydric alcohols such as glycerin with epichlorohydrin in the presence of a basic catalyst, and by condensing a novolac type phenolic resin with epichlorohydrin. The obtained epoxidized novolak, the epoxidized olefin obtained by epoxidizing it by the peroxidation method,
Epoxidized polybutadiene, epoxidized vegetable oil, vinylcyclohexene dioxide, dipentene dioxide, 2,2-bis(3,4-epoxycyclohexyl)proban, bis(2,3
-epoxycyclopentyl) ether, cyclohexane derivatives such as dicyclopentadiene oxide, etc. However, these are just concrete examples of component (A), and the present invention is not limited to these. Various currently known components can be used; however, when taking curability into consideration, A cycloaliphatic epoxy resin or a novolak resin is preferred. Next, the silicone-modified phenolic prepolymer as component (B) used in the present invention is represented by the above formula (i), and has a phenolic hydroxyl group represented by A in the above formula (i). Examples of groups obtained by removing the phenolic hydroxyl group from the compound include phenol derivatives such as catechol, resorcinol, hydroquinone or phloroglucinol, 2,2-bis(2-hydroxyphenyl)propane, and 2,4'-dihydroxydiphenyl. Methane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxyphenyl)pentane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenyl sulfone, 4,
Divalent phenols such as 4'-dihydroxyphenyl sulfide, phenolic novolac resins, resol type phenolic resins, isopropenylphenol oligomers, or groups obtained by removing the hydroxyl group from phenolic hydroxyl group-containing compounds such as polyparavinylphenols. can be given. Some of these residues are illustrated below.
【式】【formula】
【式】【formula】
【式】（R′；Ｈ、CH3、C2H5
など）、
R1で示されるC1〜C10の二価炭化水素基として
は、メチレン基、エチレン基あるいはプロピレン
基等のアルキレン基、フエニレン基等のアリーレ
ン基、１，４―キシリレン基、フエネチレン基あ
るいは[Formula] (R′; H, CH 3 , C 2 H 5 , etc.), The C 1 to C 10 divalent hydrocarbon group represented by R 1 includes a methylene group, an alkylene group such as an ethylene group or a propylene group, an arylene group such as a phenylene group, a 1,4-xylylene group, a phenethylene group, or
【式】等が例示され、ま
たR2，R3で示される有機基としては、メチル
基、エチル基、プロピル基、ブチル基、ペンチル
基、ヘキシル基あるいはオクチル基等の低級アル
キル基、ビニル基、アリル基あるいは１―プロペ
ニル基等の低級アルケニル基、フエニル基、キシ
リル基、トリル基、ナフチル基あるいはベンジル
基等の単核および二核アリール基、シクロブチル
基、シクロヘプチル基、あるいはシクロヘキシル
基等のシクロアルキル基、シアノエチル基、シア
ノプロピル基あるいはシアノブチル基等のシアノ
基置換低級アルキル基、クロロメチル基、クロロ
プロピル基あるいはクロロフエニル基等の塩素原
子置換アルキル基あるいはアリール基、フエニル
エチル基等のアリール基置換アルキル基、
（CF）3CFOCH2CH2CH2―（CF3）2CF
（CF3）2COCH2CH2CH2―あるいはCF3CH2CH2―
等のふつ素原子置換アルキル基、メトキシ基、エ
トキシ基あるいはブトキシ基等のアルコキシ基、
アセトキシ基等のアシロキシ基等があげられる。
なお、このR2およびR3は必ずしも同一である
必要はなく異種のものであつてもよいことはいう
までもない。
本発明で使用するプレポリマーは、分子中にフ
エノール系残基に結合する式
（R1，R2，R3、ａ及びｎは前述と同じ意味で
ある）で示される基を１個以上有することが必須
とされるが、該プレポリマーはその分子中にフエ
ノール性水酸基を有していてもよいことはいうま
でもない。
上記した式(i)で示されるシリコーン変性フエノ
ール系プレポリマーとしては具体的には下記に示
すようなものをあげることができる。
（ｍはいずれも正の整数である）。
このようなシリコーン変性フエノール系プレポ
リマーは、フエノール系化合物とオルガノシラン
またはオルガノシロキサンとを反応させることに
より合成することができ、例えばフエノールノボ
ラツク樹脂を始発原料とした場合の反応を反応式
で示すと下記のとおりである。
なお、上記反応に従つて得られる生成物が加水
分解可能な基を有している場合には、これを加水
分解することにより目的生成物を得ることができ
る（下記反応式参照）。
（上記各式中、R1，R2，R3，ａ，ｍ及びｎは
前記と同じ意味であり、Ｘはハロゲン原子、Ｙは
加水分解可能な基、ｂは０，１，２又は３であ
る）。
上記した反応において始発原料として使用する
反応によつてフエノール系残基（式(i)中のＡに相
当）に変換し得る化合物としては、１分子中にフ
エノール系水酸基を有するものが望ましく、これ
には、例えばカテコール、レゾルシノール、ハイ
ドロキノンあるいはフロログルシノール等のフエ
ノール誘導体、２，２―ビス（２―ヒドロキシフ
エニル）プロパン、２，4′―ジヒドロキシジフエ
ニルメタン、２，２―ビス（４―ヒドロキシフエ
ニル）プロパン、１，１―ビス（４―ヒドロキシ
フエニル）エタン、１，１―ビス（４―ヒドロキ
シフエニル）プロパン、２，２―ビス（４―ヒド
ロキシフエニル）ペンタン、４，4′―ジヒドロキ
シビフエニル、４，4′―ジヒドロキシベンゾフエ
ノン、４，4′―ジヒドロキシジフエニルスルホ
ン、４，4′―ジヒドロキシジフエニルスルフイド
等の二価フエノール類、フエノールノボラツク樹
脂、レゾール型フエノール樹脂、下記に示すよう
なイソプロペニルフエノールのオリゴマーあるい
はポリパラビニルフエノール類等があげられる。
なお、上記したプロピルフエノールなどの置換
フエノール類におけるプロピル基等の置換位置は
水酸基に対しｏ―，ｍ―あるいはｐ―位のいずれ
であつてもよい。又、フエノール樹脂を得る場合
における原料であるホルムアルデヒド類として
は、ホルムアルデヒド、パラホルムアルデヒドあ
るいはホルマリン等のホルムアルデヒドを供給す
ることができるものであればその種類に制限はな
く従来公知の種々のものが使用される。
他方、上記したフエノール化合物とともに始発
原料として使用するオルガノシラン又はオルガノ
シロキサンとしては、例えば式
（式中、R1，R2，R3，Ｘ，Ｙ，ａおよびｎは
前記と同じ意味である）で示される化合物をあげ
ることができ、具体的には下記に示すようなもの
をあげることができる。
ClCH2―Si（―OCH3）3、
ClCH2CH2CH2―Si（―OCH3）3、
なお、このようなオルガノシランもしくはオル
ガノシロキサンは、これをフエノール化合物と反
応させると前記した反応式(1)に従つて反応し、つ
いでこの反応生成物を加水分解するよとにより該
けい素原子に直結する加水分解可能な基が容易に
水酸基に変換する。
なお、加水分解が不十分であるため、生成物中
に加水分解可能な基が残存していても何ら影響を
うけるものではない。
本発明の実施に際しては、該シリコーン変性フ
エノール系プレポリマーは必ずしも１種類のみの
使用に制限されるものではなく、必要に応じて２
種以上を併用してもよいことはいうまでもない。
前記した(A)成分と(B)成分との使用割合は、(A)成
分20〜95重量部、好ましくは40〜70重量部に対し
て(B)成分を80〜５重量部、好ましくは60〜30重量
部とすることが必要とされる。
これは(A)成分と(B)成分との使用割合が上記範囲
外であると、硬化反応が全く進行しないかあるい
はたとえ反応したとしてもその速度がきわめて遅
く実用性に乏しくなる。
更に本発明で使用される(C)成分としての無機質
充てん剤としては、例えばけいそう土、フユーム
ドシリカ、石英等の無定形あるいは結晶形シリカ
系充填剤、けい酸アルミニウム、けい酸マグネシ
ウム、けい酸ジルコニウム、けい酸マグネシウム
等のけい酸塩類等で代表される非シリカ系充填
剤、ガラス繊維、ウオラストナイト、カーボン繊
維等の繊維状充填剤等をあげることができる。
この(C)成分の使用量は、前記した(A)及び(B)成分
の合計量100重量部に対して1000重量部以下とさ
れる。
また、(D)成分である硬化用触媒としては例えば
アルミニウムトリエトキシド、アルミニウムトリ
プロポキシド、アルミニウムトリブトキシド、ア
ルミニウムトリ―３―アミルオキシド、トリオク
トキシアルミニウム、トリデシルオキシアルミニ
ウム、トリヘキサデシルオキシアルミニウム及び
トリオクタデシルオキシアルミニウム等のアルミ
ニウムアルコラート類、例えばジ―イソプロポキ
シド―クレジルアルミネート及びアリールアルミ
ネート類、例えばトリ（Ｏ―クレジル）―アルミ
ネート、トリ（ｍ―クレジル）アルミネート、ト
リ（２，４―キシレニル）アルミネート、トリ
（ヘキシルフエニル）アルミネート、トリ（ノニ
ルフエニル）アルミネート、トリ（ジノニルフエ
ニル）アルミネート、トリ（ドデシルフエニル）
アルミネート、及びトリ（２―ナフチル）アルミ
ネート等のトリアルコキシド類、例えばアルミニ
ウムトリアセテート、アルミニウムトリプロピオ
ネート、アルミニウムトリベンゾエート、アルミ
ニウムトリステアレート、アルミニウムトリブチ
レート、アルミニウム―ジアセテート―モノステ
アレート及びアルミニウムトリ（３―メチルベン
ゾエート）等のアルミニウムトリアシレート類、
アルミニウムヒドロキシジステアレート、アルミ
ニウムモノイソプロポキシドジベンゾエート、ア
ルミニウムヒドロキシジアセテート、アルミニウ
ムジヒドロキシモノブチレート及びアルミニウム
エトキシドステアレート等のヒドロキシル化又は
アルコキシ化アルミニウムアシレート類、
ＨAl（OC3H7）3OCH2、ＨAl（OC4H9）4
及びＨAl（OC6H5）（OC3H7）3等のアルミニ
ウムトリアルコキシド類の塩、アルミニウムエト
オキシドのメチルジメトキシシラノールその反応
生成物、アルミニウムイソプロポキシドのジメチ
ルジアセトキシシランとの反応生成物、アルミニ
ウムヒドロキシジステアレートのトリメチルシラ
ノールとの反応生成物、アルミニウムジアセテー
トベンゾエートのHO〔（CH3）2SiO〕xＨ（正の整
数）との反応生成物、アルミニウムプロピオネー
トの３―クロロプロピルトリエトキシシラン化合
物との反応生成物等のアルミノ―シロキシ化合
物、アルミニウムアルコオキシド又はアシレート
類を窒素と、及び配位原子として酸素を含む硫黄
なしのキレート剤、例えばエチルアセトアセテー
ト、アセチルアセトン、ジエチルマロネート及び
高分子量アルコール類、例えばステアリルアルコ
ールのアセト酢酸エステル類と反応させることに
よつて形成されるアルミニウムキレート触媒等を
あげることができるが、これらの内でもアルミニ
ウムアセチルアセトン塩、安息香酸アルミニウ
ム、ステアリン酸アルミニウム等は特に好適であ
る。
この(D)成分は、本発明の組成物を硬化させるの
に必要な量、具体的には前記(A)及び(B)成分の合計
量100重量部に対し0.1〜10重量部の範囲で使用す
れば充分である。
更に本発明の組成物には必要に応じて顔料、可
撓性付与剤、離型性付与剤、難燃剤、難燃助剤、
劣化防止剤、樹脂成分と無機質充填剤との結合を
高めるための各種カーボンフアンクシヨナルシラ
ン等を添加配合することは何ら差支えない。
又、任意のシリコーンポリマー（ワニス、オイ
ル等）を添加することも必須成分である(B)成分が
シリコーン変性フエノール系プレポリマーである
ことから相溶性あるいは分散性の向上により大き
な効果を期待することができる。
本発明に係る樹脂組成物は、前記した(A)〜(D)成
分及びその他添加剤を種々の方法（例えば２本ロ
ール等）を採用して均一に混練することにより調
製することができ、このものは100℃以上、好ま
しくは150℃以上で短時間加熱することによつて
硬化する。
本発明に係る組成物は、その硬化に当つて硬化
用触媒としてたとえばアルミニウム化合物を選択
使用したとしても構成成分における分子の切断や
クラツキング等に伴う加熱減量はほとんどないし
全くみられず、又該樹脂組成物から得られる硬化
物は膨張係数及び透湿性が小さく、しかも長期耐
熱寸法安定性にすぐれ、更に電気特性が良好であ
るという特長を有する。
本発明の樹脂組成物は耐熱性が要求される絶縁
材料、注型用材料、含浸用材料、積層用材料ある
いは半導体封止用材料等をはじめとし種々の用途
に広く応用可能である。
つぎに本発明の実施例及び比較例をあげる。
実施例 １
エポキシ当量が120であるエポキシ化クレゾー
ルノボラツク樹脂（EOCN―102 日本化薬社
製）45.5重量部、脂環式エポキシ樹脂（CY―175
チバガイギー社製）９重量部、式
で示されるシラノール基含有オルガノシラン変性
フエノール系プレポリマー45.5重量部、溶融シリ
カ250重量部、シランカツプリング剤（KBM―
403 信越化学社製）１重量部、カーボンブラツ
ク１重量部、OP―ワツクス1.3重量部及び安息香
酸アルミニウム1.8重量部を熱二本ロールで十分
に混練して成形材料Ａを得た。
実施例 ２
エポキシ化クレゾールノボラツク樹脂の使用量
を50重量部、シラノール基含有オルガノシラン変
性フエノール系プレポリマーの使用量を50重量部
に変更したほかは実施例１と全く同じ組成からな
るものを同様に処理し成形材料Ｂを得た。
実施例 ３
エポキシ化クレゾールノボラツク樹脂の使用量
を60重量部、脂環式エポキシ樹脂の使用量を17重
量部、シラノール基含有オルガノシラン変性フエ
ノール系プレポリマーの使用量を23重量部に変更
したほかは実施例１と全く同じ組成物からなるも
のを同様に処理し成形材料Ｃを得た。
実施例 ４
エポキシ化クレゾールノボラツク樹脂の使用量
を42重量部、脂環式エポキシ樹脂の使用量を16重
量部、シラノール基含有オルガノシラン変性フエ
ノール系プレポリマーの使用量を42重量部に変更
したほかは実施例１と全く同じ組成からなるもの
を同様に処理し成形材料Ｄを得た。
比較例 １
実施例１で用いたエポキシ樹脂91重量部、脂環
式エポキシ樹脂９重量部、溶融シリカ250重量
部、シランカツプリング剤（KBM―403 信越化
学社製）１重量部、カーボンブラツク１重量部、
OP―ワツクス1.3重量部及び安息香酸アルミニウ
ム1.8重量部を均一に混練して成形材料Ｅを得
た。
しかしこの成形材料は下記成形条件では全く硬
化しなかつた。
比較例 ２
実施例１で用いたシラノール基含有オルガノシ
ラン変性フエノール樹脂100重量部、溶融シリカ
250重量部、シランカツプリング剤（KBM―403
信越化学社製）１重量部、カーボンブラツク１
重量部、OP―ワツクス1.3重量部及び安息香酸ア
ルミニウム1.8重量部を均一に混練して成形材料
Ｆを得た。
この成形材料は下記成形条件では全く硬化しな
かつた。
比較例 ３
実施例１で用いたエポキシ化クレゾールノボラ
ツク樹脂60重量部、C6H5SiO1.540モル％、
CH3SiO1.545モル％、（CH3）2SiO 15モル％より
なり、シラノール基含有量が５重量％のオルガノ
ポリシロキサン40重量部、溶融シリカ250重量
部、シランカツプリング剤（KBM―403 信越化
学社製）１重量部、カーボンブラツク１重量部、
OP―ワツクス1.3重量部及び安息香酸アルミニウ
ム1.8重量部を熱二本ロールで混練して成形材料
Ｇを得た。
成形方法
実施例１〜４及び比較例１〜３で得た成形材料
を成形温度175℃、成形圧力56Kg／cm2の成形条件
で成形することにより各種の試験片を得た。
なお、特性測定試験片はすべて180℃で４時間
ポストキユアしたものである。Examples of organic groups represented by R 2 and R 3 include lower alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, or octyl, and vinyl groups. , lower alkenyl groups such as allyl group or 1-propenyl group, mononuclear and dinuclear aryl groups such as phenyl group, xylyl group, tolyl group, naphthyl group or benzyl group, cyclobutyl group, cycloheptyl group, or cyclohexyl group, etc. Lower alkyl groups substituted with cyano groups such as cycloalkyl groups, cyanoethyl groups, cyanopropyl groups, or cyanobutyl groups, chlorine atom-substituted alkyl groups such as chloromethyl groups, chloropropyl groups, or chlorophenyl groups, or aryl groups substituted with aryl groups and phenylethyl groups. alkyl group,
(CF) 3 CFOCH 2 CH 2 CH 2 - (CF 3 ) 2 CF
(CF 3 ) 2 COCH 2 CH 2 CH 2 - or CF 3 CH 2 CH 2 -
fluorine atom-substituted alkyl groups such as, alkoxy groups such as methoxy groups, ethoxy groups or butoxy groups,
Examples include acyloxy groups such as acetoxy groups. It goes without saying that R 2 and R 3 do not necessarily have to be the same and may be different types. The prepolymer used in the present invention has a formula that binds to phenolic residues in the molecule. (R 1 , R 2 , R 3 , a and n have the same meanings as above) is essential, but the prepolymer must have a phenolic hydroxyl group in its molecule. Needless to say, it may be included. Specific examples of the silicone-modified phenolic prepolymer represented by the above formula (i) include those shown below. (All m are positive integers). Such a silicone-modified phenolic prepolymer can be synthesized by reacting a phenolic compound with an organosilane or an organosiloxane. and as follows. In addition, when the product obtained according to the above reaction has a hydrolyzable group, the desired product can be obtained by hydrolyzing this (see the reaction formula below). (In each of the above formulas, R 1 , R 2 , R 3 , a, m and n have the same meanings as above, X is a halogen atom, Y is a hydrolyzable group, and b is 0, 1, 2 or 3 ). As a compound that can be converted into a phenolic residue (corresponding to A in formula (i)) by the reaction and used as a starting material in the above reaction, it is desirable to have a phenolic hydroxyl group in one molecule; Examples include phenol derivatives such as catechol, resorcinol, hydroquinone or phloroglucinol, 2,2-bis(2-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, 2,2-bis(4- hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 4, Divalent phenols such as 4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, phenol novolak resin, Examples include resol type phenolic resins, oligomers of isopropenylphenol as shown below, and polyparavinylphenols. The substitution position of the propyl group in the above-mentioned substituted phenols such as propylphenol may be at the o-, m- or p-position with respect to the hydroxyl group. Further, as the formaldehyde which is a raw material for obtaining a phenol resin, there is no restriction on the type as long as it can supply formaldehyde such as formaldehyde, paraformaldehyde or formalin, and various conventionally known ones can be used. Ru. On the other hand, as the organosilane or organosiloxane used as a starting material together with the above-mentioned phenol compound, for example, (In the formula, R 1 , R 2 , R 3 , X, Y, a and n have the same meanings as above.) Specifically, the following compounds can be mentioned. be able to. ClCH 2 -Si(-OCH 3 ) 3 , ClCH 2 CH 2 CH 2 ―Si(―OCH 3 ) 3 , Note that when such an organosilane or organosiloxane is reacted with a phenol compound, it reacts according to the reaction formula (1) described above, and then this reaction product is hydrolyzed to form the silicon atoms. Directly linked hydrolyzable groups are easily converted to hydroxyl groups. Note that since the hydrolysis is insufficient, even if hydrolyzable groups remain in the product, there is no effect. When carrying out the present invention, the silicone-modified phenolic prepolymer is not necessarily limited to the use of only one type, but two types may be used as necessary.
It goes without saying that more than one species may be used in combination. The proportion of component (A) and component (B) used is 80 to 5 parts by weight, preferably 80 to 5 parts by weight of component (B) to 20 to 95 parts by weight, preferably 40 to 70 parts by weight, of component (A). 60-30 parts by weight is required. This is because if the ratio of components (A) and (B) used is outside the above range, the curing reaction will not proceed at all, or even if it does, the reaction rate will be extremely slow and impractical. Inorganic fillers as component (C) used in the present invention include, for example, amorphous or crystalline silica fillers such as diatomaceous earth, fumed silica, and quartz, aluminum silicate, magnesium silicate, and zirconium silicate. , non-silica fillers typified by silicates such as magnesium silicate, and fibrous fillers such as glass fiber, wollastonite, and carbon fiber. The amount of component (C) to be used is 1000 parts by weight or less per 100 parts by weight of the total amount of components (A) and (B). Examples of the curing catalyst as component (D) include aluminum triethoxide, aluminum tripropoxide, aluminum tributoxide, aluminum tri-3-amyl oxide, trioctoxyaluminum, tridecyloxyaluminum, trihexadecyloxy Aluminum and aluminum alcoholates such as triotadecyloxyaluminum, such as di-isopropoxide-cresyl aluminate and aryl aluminates, such as tri(O-cresyl)-aluminate, tri(m-cresyl)aluminate, tri- (2,4-xylenyl) aluminate, tri(hexyl phenyl) aluminate, tri(nonylphenyl) aluminate, tri(dinonylphenyl) aluminate, tri(dodecylphenyl)
aluminate, and trialkoxides such as tri(2-naphthyl)aluminate, such as aluminum triacetate, aluminum tripropionate, aluminum tribenzoate, aluminum tristearate, aluminum tributyrate, aluminum diacetate monostearate and Aluminum triacylates such as aluminum tri(3-methylbenzoate),
Hydroxylated or alkoxylated aluminum acylates such as aluminum hydroxy distearate, aluminum monoisopropoxide dibenzoate, aluminum hydroxy diacetate, aluminum dihydroxy monobutyrate and aluminum ethoxide stearate, HAl(OC 3 H 7 ) 3 OCH 2 , HAl( OC4H9 ) 4
and salts of aluminum trialkoxides such as HAl (OC 6 H 5 ) (OC 3 H 7 ) 3 , reaction products of aluminum ethoxide with methyldimethoxysilanol, and reaction products of aluminum isopropoxide with dimethyldiacetoxysilane. , reaction product of aluminum hydroxydistearate with trimethylsilanol, reaction product of aluminum diacetate benzoate with HO[(CH 3 ) 2 SiO] x H (positive integer), 3-chloro of aluminum propionate Alumino-siloxy compounds, aluminum alkoxides or acylates, such as reaction products with propyltriethoxysilane compounds, with nitrogen, and sulfur-free chelating agents containing oxygen as coordinating atom, such as ethyl acetoacetate, acetylacetone, diethyl malo Aluminum chelate catalysts formed by reacting stearyl alcohol with acetoacetate and high molecular weight alcohols, such as stearyl alcohol, include aluminum acetylacetone salt, aluminum benzoate, and stearic acid. Aluminum etc. are particularly suitable. Component (D) is added in an amount necessary for curing the composition of the present invention, specifically in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of components (A) and (B). It is sufficient to use it. Furthermore, the composition of the present invention may contain pigments, flexibility imparting agents, release properties imparting agents, flame retardants, flame retardant aids,
There is no problem in adding and blending a deterioration inhibitor, various carbon functional silanes, etc. to enhance the bond between the resin component and the inorganic filler. Additionally, addition of any silicone polymer (varnish, oil, etc.) is also an essential component.Since component (B) is a silicone-modified phenolic prepolymer, a greater effect can be expected in improving compatibility or dispersibility. I can do it. The resin composition according to the present invention can be prepared by uniformly kneading the components (A) to (D) and other additives described above using various methods (for example, using two rolls), This material is cured by heating at 100°C or higher, preferably 150°C or higher for a short period of time. In the composition of the present invention, even if, for example, an aluminum compound is selectively used as a curing catalyst during curing, there is little or no loss on heating due to molecular cleavage or cracking in the constituent components, and the resin The cured product obtained from the composition has a low coefficient of expansion and low moisture permeability, excellent long-term heat-resistant dimensional stability, and good electrical properties. The resin composition of the present invention can be widely applied to various uses including insulating materials, casting materials, impregnating materials, laminating materials, semiconductor sealing materials, etc. that require heat resistance. Next, examples of the present invention and comparative examples will be given. Example 1 45.5 parts by weight of epoxidized cresol novolac resin (EOCN-102 manufactured by Nippon Kayaku Co., Ltd.) with an epoxy equivalent of 120, alicyclic epoxy resin (CY-175)
(manufactured by Ciba Geigy) 9 parts by weight, formula 45.5 parts by weight of organosilane-modified phenolic prepolymer containing silanol group, 250 parts by weight of fused silica, silane coupling agent (KBM-
403 (manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part by weight of carbon black, 1.3 parts by weight of OP-wax, and 1.8 parts by weight of aluminum benzoate were thoroughly kneaded using two heated rolls to obtain molding material A. Example 2 A product having the same composition as Example 1 was used, except that the amount of epoxidized cresol novolac resin used was changed to 50 parts by weight, and the amount of silanol group-containing organosilane-modified phenolic prepolymer was changed to 50 parts by weight. Molding material B was obtained by processing in the same manner. Example 3 The amount of epoxidized cresol novolac resin used was changed to 60 parts by weight, the amount of alicyclic epoxy resin used was changed to 17 parts by weight, and the amount of silanol group-containing organosilane-modified phenolic prepolymer was changed to 23 parts by weight. A molding material C was obtained by treating the same composition as in Example 1 in the same manner as in Example 1. Example 4 The amount of epoxidized cresol novolak resin used was changed to 42 parts by weight, the amount of alicyclic epoxy resin used was changed to 16 parts by weight, and the amount of silanol group-containing organosilane-modified phenolic prepolymer was changed to 42 parts by weight. A molding material D having the same composition as in Example 1 was otherwise treated in the same manner as in Example 1 to obtain molding material D. Comparative Example 1 91 parts by weight of the epoxy resin used in Example 1, 9 parts by weight of alicyclic epoxy resin, 250 parts by weight of fused silica, 1 part by weight of silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part by weight of carbon black weight part,
Molding material E was obtained by uniformly kneading 1.3 parts by weight of OP-wax and 1.8 parts by weight of aluminum benzoate. However, this molding material did not harden at all under the following molding conditions. Comparative Example 2 100 parts by weight of the silanol group-containing organosilane-modified phenolic resin used in Example 1, fused silica
250 parts by weight, silane coupling agent (KBM-403
(manufactured by Shin-Etsu Chemical) 1 part by weight, 1 part carbon black
A molding material F was obtained by uniformly kneading 1.3 parts by weight of OP-wax and 1.8 parts by weight of aluminum benzoate. This molding material did not harden at all under the following molding conditions. Comparative Example 3 60 parts by weight of the epoxidized cresol novolak resin used in Example 1, 40 mol% of C 6 H 5 SiO 1.5 ,
40 parts by weight of an organopolysiloxane with a silanol group content of 5% by weight, 250 parts by weight of fused silica, and a silane coupling agent (KBM ) . -403 manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight, carbon black 1 part by weight,
Molding material G was obtained by kneading 1.3 parts by weight of OP-wax and 1.8 parts by weight of aluminum benzoate using two heated rolls. Molding method Various test pieces were obtained by molding the molding materials obtained in Examples 1 to 4 and Comparative Examples 1 to 3 under molding conditions of a molding temperature of 175° C. and a molding pressure of 56 kg/cm 2 . All test pieces for measuring characteristics were post-cured at 180°C for 4 hours.
【表】【table】
【表】【table】
Claims (1)
エポキシ樹脂 20〜95重量部 (B) 式 （式中Ａはフエノール性水酸基を有する化合
物からフエノール性水酸基を除いた残基、R1
はC1〜C10の二価炭化水素基、R2およびR3は一
価有機基、ａは０，１または２、ｌは０または
正の整数、ｍは１〜70の整数、ｎは０〜10の整
数）で示されるシリコーン変性フエノール系プ
レポリマー 80〜５重量部 (C) 上記(A)及び(B)成分の合計量100重量部に対し
て０〜1000重量部の無機質充填剤及び (D) 効果用触媒 からなるエポキシ―シリコーン樹脂組成物。 ２ シリコーン変性フエノール系プレポリマーに
おけるＡが、置換または非置換のフエノールノボ
ラツク化合物から誘導されるフエノー系残基であ
る特許請求の範囲第１項記載のエポキシ―シリコ
ーン樹脂組成物。 ３ エポキシ樹脂が、置換または非置換のエポキ
シ化ノボラツク樹脂である特許請求の範囲第１項
記載のエポキシ―シリコーン樹脂組成物。 ４ エポキシ樹脂が、脂環式エポキシ樹脂である
特許請求の範囲第１項記載のエポキシ―シリコー
ン樹脂組成物。 ５ エポキシ樹脂が、置換または非置換のエポキ
シ化ノボラツク樹脂と脂環式エポキシ樹脂との混
合物である特許請求の範囲第１項記載のエポキシ
―シリコーン樹脂組成物。[Claims] 1 (A) 20 to 95 parts by weight of an epoxy resin having two or more epoxy groups in one molecule (B) Formula (In the formula, A is a residue obtained by removing a phenolic hydroxyl group from a compound having a phenolic hydroxyl group, R 1
is a C 1 to C 10 divalent hydrocarbon group, R 2 and R 3 are monovalent organic groups, a is 0, 1 or 2, l is 0 or a positive integer, m is an integer from 1 to 70, n is 80 to 5 parts by weight of a silicone-modified phenolic prepolymer (an integer from 0 to 10) (C) 0 to 1000 parts by weight of an inorganic filler per 100 parts by weight of the total amount of components (A) and (B) above. and (D) an epoxy-silicone resin composition comprising an effect catalyst. 2. The epoxy-silicone resin composition according to claim 1, wherein A in the silicone-modified phenolic prepolymer is a phenolic residue derived from a substituted or unsubstituted phenolic novolak compound. 3. The epoxy-silicone resin composition according to claim 1, wherein the epoxy resin is a substituted or unsubstituted epoxidized novolak resin. 4. The epoxy-silicone resin composition according to claim 1, wherein the epoxy resin is an alicyclic epoxy resin. 5. The epoxy-silicone resin composition according to claim 1, wherein the epoxy resin is a mixture of a substituted or unsubstituted epoxidized novolak resin and an alicyclic epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14663081A JPS5847014A (en) | 1981-09-17 | 1981-09-17 | Epoxy-silicone resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14663081A JPS5847014A (en) | 1981-09-17 | 1981-09-17 | Epoxy-silicone resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5847014A JPS5847014A (en) | 1983-03-18 |
| JPS6154327B2 true JPS6154327B2 (en) | 1986-11-21 |
Family
ID=15412072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14663081A Granted JPS5847014A (en) | 1981-09-17 | 1981-09-17 | Epoxy-silicone resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5847014A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6322853A (en) * | 1987-02-13 | 1988-01-30 | Hitachi Ltd | Siliconephenolic compound composition and use thereof |
-
1981
- 1981-09-17 JP JP14663081A patent/JPS5847014A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5847014A (en) | 1983-03-18 |
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