JPH01268717A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH01268717A JPH01268717A JP9769188A JP9769188A JPH01268717A JP H01268717 A JPH01268717 A JP H01268717A JP 9769188 A JP9769188 A JP 9769188A JP 9769188 A JP9769188 A JP 9769188A JP H01268717 A JPH01268717 A JP H01268717A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- epoxy resin
- manufactured
- parts
- 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
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 43
- -1 polysiloxane Polymers 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 10
- 238000007259 addition reaction Methods 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract 2
- 229910000077 silane Inorganic materials 0.000 claims description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 14
- 238000010168 coupling process Methods 0.000 claims description 14
- 238000005859 coupling reaction Methods 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000005650 substituted phenylene group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 16
- 229920002050 silicone resin Polymers 0.000 abstract description 11
- 125000005372 silanol group Chemical group 0.000 abstract description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 abstract description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 14
- 238000003756 stirring Methods 0.000 description 10
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 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 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920003319 Araldite® Polymers 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UAWDZAKIFJNTHX-UHFFFAOYSA-N tert-butyl(oxo)tin Chemical compound CC(C)(C)[Sn]=O UAWDZAKIFJNTHX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- WGFZZGXKRATULP-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)aniline Chemical class NC1=CC=CC=C1OCC1OC1 WGFZZGXKRATULP-UHFFFAOYSA-N 0.000 description 1
- WTTLJKANHROXFH-UHFFFAOYSA-N 2-cyanoethyl triethyl silicate Chemical compound CCO[Si](OCC)(OCC)OCCC#N WTTLJKANHROXFH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CXIQRWSWJUPLFT-UHFFFAOYSA-N C(C)O[SiH3].C[Si](OC)(OC)OC Chemical compound C(C)O[SiH3].C[Si](OC)(OC)OC CXIQRWSWJUPLFT-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- CLYWMXVFAMGARU-UHFFFAOYSA-N n-benzyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC1=CC=CC=C1 CLYWMXVFAMGARU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はエポキシ樹脂組成物、更に詳しくは、エポキシ
樹脂マトリックス中に特定の分散安定剤を用いてシリコ
ーン樹脂粒子を安定分散させたことから成り、特にエポ
キシ樹脂に対し耐クラツク性や靭性を付与した新規なエ
ポキシ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention consists of an epoxy resin composition, more specifically, silicone resin particles are stably dispersed in an epoxy resin matrix using a specific dispersion stabilizer, and is particularly resistant to epoxy resins. This invention relates to a novel epoxy resin composition that has crack resistance and toughness.
周知の如く、エポキシ樹脂組成物は引張り強度、曲げ強
度等の機械的性質、誘電特性、体積抵抗率等の電気的性
質に優れ、このため接着剤材料、コーティング材料、各
種電機・電子機器用絶縁材料へと幅広く応用されている
。As is well known, epoxy resin compositions have excellent mechanical properties such as tensile strength and bending strength, and electrical properties such as dielectric properties and volume resistivity, and are therefore used as adhesive materials, coating materials, and insulation for various electrical and electronic devices. It is widely applied to materials.
しかし、主成分であるエポキシ樹脂は通常、耐クラツク
性や靭性に欠け、さらには硬化時の収縮によるストレス
の緩和が困難であるため、これら欠点を改良する必要が
あった。However, the main component, epoxy resin, usually lacks crack resistance and toughness, and furthermore, it is difficult to alleviate stress due to shrinkage during curing, so it was necessary to improve these drawbacks.
このため、かかるエポキシ樹脂の改質について研究開発
がなされつつあり、最近では、エポキシ樹脂に対して特
定割合の両末端シラノールオルガノポリシロキサンと、
１分子内に少なくとも２個のアルコキシシリル基を有す
るシランカップリング化合物とを加え、要すれば加温下
で撹拌混合することにより、両末端シラノールオルガノ
ポリシロキサンとシランカップリング化合物の架橋反応
生成物であるシリコーン樹脂粒子をエポキシ樹脂マトリ
ックス中に分散状態で存在せしめ、エポキシ樹脂の改質
を意図した組成物が案出されており、これについて既に
特許出願中である（特願昭６２−１７９６５３号参照）
。For this reason, research and development are being carried out on the modification of such epoxy resins, and recently, a specific proportion of both terminal silanol organopolysiloxane and
By adding a silane coupling compound having at least two alkoxysilyl groups in one molecule and stirring and mixing under heating if necessary, a crosslinking reaction product of the both-terminated silanol organopolysiloxane and the silane coupling compound is obtained. A composition intended for modifying epoxy resins by dispersing silicone resin particles in an epoxy resin matrix has been devised, and a patent application has already been filed for this composition (Japanese Patent Application No. 179653/1988). reference)
.
しかしながら、このシリコーン樹脂粒子はマトリックス
中で経時変化ｌこよって粒径が増大する傾向にあり、さ
らに組成物使用時の硬化条件によって、調製時（硬化前
）から硬化後昏こかけて分散粒径が変動し易く、特に高
温条件で硬化すると、粒径が大きく変動することがあり
、物性面での新たな問題が起る。However, the particle size of these silicone resin particles tends to increase due to changes over time in the matrix, and furthermore, depending on the curing conditions when the composition is used, the dispersed particle size increases from the time of preparation (before curing) to the time after curing. The particle size tends to fluctuate, and especially when hardened under high temperature conditions, the particle size can vary greatly, creating new problems in terms of physical properties.
そこで本発明者らは、上記経時変化や硬化条件による分
散粒径の変動を解消するため鋭意研究を進めた結果、シ
ランカップリング化合物醤こ特定の分散安定剤を併用す
れば、シリコーン樹脂粒子が極めて均一安定に分散し、
所期目的が達成しつることを見出して、本発明を完成さ
せるに至った。Therefore, the present inventors conducted intensive research to resolve the above-mentioned fluctuations in dispersed particle size due to changes over time and curing conditions, and found that if a silane coupling compound sauce and a specific dispersion stabilizer are used together, silicone resin particles can be Disperses extremely uniformly and stably,
The inventors have found that the intended purpose has been achieved and have completed the present invention.
発明の構成と効果
すなわち、本発明は、（Ａ）エポキシ樹脂１００部（重
量部、以下同様）、（Ｂ）両末端シラノールオルガノポ
リシロキサン５〜２００部、（ｃ）１分子内に少なくと
も２個のアルコキシシリル基を有するシランカップリン
グ化合物で、そのアルコキシ基と上記ポリシロキサン（
Ｂ）の水酸基とのモル比率が０．１〜１５、および（Ｄ
）分散安定剤として、式：
％式％
〔式中、Ｘ工はメチル基、またはエポキシ基、アミノ基
、水酸基、カルボキシル基またはカルボン酸エステル基
を含有する１個有機基（該１個有機基を構成する基とし
ては、メチレン、エチレン、プロピレン、ブチレンなど
のアルキレン基、クロルエチレン、フルオロエチレンな
どのハロゲン化アルキレン基、脂肪族環状体含有アルキ
レン基、フェニレン基、アルキレンアリーレン基、−Ｃ
６Ｈ４ＣＯ−１−ＣＯ−１−ＮＨＣＯ−１−ＣＨ２ｏＣ
Ｈ２ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２０ＣＨ２ＣＨ２−
１Ｈ３
−ＣＨ２ＣＨ２０−ＣＨ−ＣＨ２−１−（ＣＨ２背１庁
ＮＨＣＨ２ＣＨ２）□〜５等）、Ｙｏは−Ｒ−０＋Ｃ２
Ｈ４０ｆ＋Ｃ３Ｈ６０九Ｒ’（Ｒは炭素数１〜１０のア
ルキレン、Ｃ６Ｈ４、ＣＯまたはＮＨＣＯ％Ｒ′ はＨ
，１価炭化水素基（メチル、エチル、プロピル、ドデシ
ル、シクロヘキシル、フェニル、β−フェニルエチルな
ど）、アシル（アセチル、プロピオニル、ベンゾイルな
ど）または炭酸モノエステル基、ａおよびｂはそれぞれ
１〜５０で、ａ＋ｂは２〜１゜Ｏ）、ａはＯ〜１０００
、ｍおよびｎはそれぞれ１〜１００である〕
で示されるオルガノポリシロキサン、または式：％式％
〔式中、Ｘ２はＣＨ３、−Ｒ″−ＮＨ２、−Ｒ″−ＮＨ
−−Ｒ”−ＮＨ２、−Ｒ”−ＣＯＯＨマタハー〇ＲＩｖ
（Ｒ″ｉ−！−ＱＣ２Ｈ４−１炭素数１〜２０のアルキ
レン基、フェニレン基または置換フェニレン基、Ｒ″′
は炭素Ｖ
数１〜２０のアルキレン基、およびＲはＣＨ３またはＣ
２Ｈ３）、Ｘ３はＣＨ３、−Ｒ”−ＮＨ２、−Ｒ″−Ｎ
Ｈ−Ｒ” −Ｎ Ｈ２、−Ｒ”−３Ｈまたは−Ｒ″−
ＣＯＯＨ（Ｒ″ およびＲ″′は前記と同意義）である
〕のポリシロキサンと分子中に少なくとも１個のグリシ
ジル基を有する化合物の付加反応生成物０．０１〜５．
０部から成ることを特徴とするエポキシ樹脂組成物を提
供するものである。Structure and Effects of the Invention Namely, the present invention provides (A) 100 parts (by weight, the same applies hereinafter) of an epoxy resin, (B) 5 to 200 parts of both-terminated silanol organopolysiloxane, and (c) at least two silanols in one molecule. A silane coupling compound having an alkoxysilyl group of
The molar ratio of B) to the hydroxyl group is 0.1 to 15, and (D
) As a dispersion stabilizer, the formula: %Formula% [In the formula, Examples of the group constituting the group include alkylene groups such as methylene, ethylene, propylene, and butylene, halogenated alkylene groups such as chloroethylene and fluoroethylene, alkylene groups containing aliphatic rings, phenylene groups, alkylenearylene groups, -C
6H4CO-1-CO-1-NHCO-1-CH2oC
H2CH2CH2-, -CH2CH20CH2CH2-
1H3 -CH2CH20-CH-CH2-1- (CH2 back 1 agency NHCH2CH2) □~5 etc.), Yo is -R-0+C2
H40f+C3H609R' (R is alkylene having 1 to 10 carbon atoms, C6H4, CO or NHCO%R' is H
, monovalent hydrocarbon group (methyl, ethyl, propyl, dodecyl, cyclohexyl, phenyl, β-phenylethyl, etc.), acyl (acetyl, propionyl, benzoyl, etc.) or carbonate monoester group, a and b are each 1 to 50. , a+b is 2~1°O), a is O~1000
, m and n are each from 1 to 100] or an organopolysiloxane represented by the formula: % formula % [wherein,
--R"-NH2, -R"-COOHMatahar〇RIv
(R″i-!-QC2H4-1 alkylene group having 1 to 20 carbon atoms, phenylene group or substituted phenylene group, R″′
is an alkylene group having 1 to 20 carbon atoms, and R is CH3 or C
2H3), X3 is CH3, -R''-NH2, -R''-N
H-R"-N H2, -R"-3H or -R"-
An addition reaction product of a polysiloxane of COOH (R″ and R″′ have the same meanings as above) and a compound having at least one glycidyl group in the molecule, 0.01 to 5.
The present invention provides an epoxy resin composition characterized in that it consists of 0 parts.
本発明ｌこおけるエポキシ樹脂（Ａ）は通常のものが使
用されてよく、特（こ制限はない。具体例としては以下
のものが挙げられ、１種または２種以上の混合物を使用
に供する。The epoxy resin (A) used in the present invention may be any ordinary one, and is not particularly limited. Specific examples include the following, and one type or a mixture of two or more types may be used. .
（１）グリシジルアミン型エポキシ樹脂Ｎ、Ｎ−ジグリ
シジルアミノ基を少なくとも１個有するエポキシ樹脂で
、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラグリシジルアミノジフェ
ニルメタン、Ｎ、Ｎ−ジグリシジルメタ（またはパラ）
アミノフェノールグリシジルエーテルおよびそれらの縮
合物。これらはアラルダイトＭＹ７２０（チバガイギー
社製）、エボトートＹＨ４３４、ＹＨ１２０（東部化成
社製）として市販。(1) Glycidylamine type epoxy resin An epoxy resin having at least one N,N-diglycidylamino group, including N,N,N',N'-tetraglycidylaminodiphenylmethane, N,N-diglycidylmethane (or )
Aminophenol glycidyl ethers and their condensates. These are commercially available as Araldite MY720 (manufactured by Ciba Geigy), Evoto YH434, and YH120 (manufactured by Tobu Kasei).
（２）ノボラック型エポキシ樹脂
フェノールノボラック型エポキシ樹脂トしてエピコート
１５２．１５４（シェル化学社製）、ダウエポキシ樹脂
ＤＥＮ４３１．４３８．４３９ 。(2) Novolac type epoxy resin Phenol novolac type epoxy resin Epikote 152.154 (manufactured by Shell Chemical Co., Ltd.), Dowaepoxy resin DEN431.438.439.
４８５（ダウケミカル社製）、チバガイギーＥＰＮ１１
３８．１１３９（チバガイギー社製）等。485 (manufactured by Dow Chemical Company), Ciba Geigy EPN11
38.1139 (manufactured by Ciba Geigy), etc.
タレゾールノボラック型エポキシ樹脂としてチバガイギ
ーＥＣＮ１２３５．１２７３．１２８０．１２９９（チ
バガイギー社製）、ＥＯＣＮＩ Ｏ２，１０３，１０４
（日本化業社製）等。Ciba Geigy ECN1235.1273.1280.1299 (manufactured by Ciba Geigy), EOCNI O2, 103, 104 as Talesol novolac type epoxy resin
(manufactured by Nippon Kagyosha) etc.
（３）ビスフェノールＡ型エポキシ樹脂トしてエピコー
ト８２８．８３４．８２７．１００１．１００２．１０
０４．１００７．１００９（油化シェル社製）、ダウエ
ポキシＤＥＲ３３１，３３２゜６６２．６６３Ｕ、６６
２Ｕ（ダウケミカル社製）、アラルダイト６０７１．７
０７１．７０７２（チバガイギー社製）、エビクロン８
４０．８５０．８５５，８６０，１０５０．３０５０，
４０５０．７０５０（大日本インキ化学工業社製）等。(3) Bisphenol A epoxy resin and Epicoat 828.834.827.1001.1002.10
04.1007.1009 (manufactured by Yuka Shell Co., Ltd.), Dowepoxy DER331, 332°662.663U, 66
2U (manufactured by Dow Chemical Company), Araldite 6071.7
071.7072 (manufactured by Ciba Geigy), Ebicuron 8
40.850.855,860,1050.3050,
4050.7050 (manufactured by Dainippon Ink Chemical Industries, Ltd.), etc.
ウレタン変性ビスフェノールＡ型エポキシ樹脂としてア
デカレジンＥＰＶ−６、ＥＰＶ−９、ＥＰＶ−１５（旭
電化社製）等。Urethane-modified bisphenol A type epoxy resins include Adekal Resin EPV-6, EPV-9, and EPV-15 (manufactured by Asahi Denka Co., Ltd.).
臭素化ビスフェノールＡ型エポキシ樹脂としてアラルダ
イト８０１１（チバガイギー社製）、ダウエポキシ樹脂
ＤＥＲ５１１（ダウケミカル社製）等。Brominated bisphenol A type epoxy resins include Araldite 8011 (manufactured by Ciba Geigy), Dowe poxy resin DER511 (manufactured by Dow Chemical), and the like.
（４）脂環式エポキシ樹脂としてアラルダイトＣＹ−１
７９、ＣＹ−１７８、ＣＹ−１８２、ＣＹ−１８３（チ
バガイギー社製）等。(4) Araldite CY-1 as alicyclic epoxy resin
79, CY-178, CY-182, CY-183 (manufactured by Ciba Geigy), etc.
（５）その他：ビスフェノールＦ型、レゾルシン型、テ
トラヒドロキシフェニルエタン型、ポリアルコール、ポ
リグリコール型、グリセリントリエーテル型、ポリオレ
フィン型、エポキシ化大豆油、エステル型エポキシ樹脂
等も使用することができる。(5) Others: Bisphenol F type, resorcin type, tetrahydroxyphenylethane type, polyalcohol, polyglycol type, glycerin triether type, polyolefin type, epoxidized soybean oil, ester type epoxy resin, etc. can also be used.
なお、これらのエポキシ樹脂にあって、常温液状のもの
はそのまま使用できるが、常温固形のものについては、
その融点以上１こ加熱溶融するか、あるいは液状エポキ
シ樹脂を併用して液状化すればよい。Note that among these epoxy resins, those that are liquid at room temperature can be used as is, but those that are solid at room temperature are
It may be melted by heating above its melting point, or it may be liquefied using a liquid epoxy resin.
本発明における両末端シラノールオルガノポリシロキサ
ン（Ｂ）としては、式：
％式％［）
〔式中、Ｒ１はメチルまたはフェニル、Ｒ２はフェニル
、ｐは９〜５００．およびｑは０またはｐの６％以下で
ある〕
で示されるポリシロキサンが挙げられ、これらの群から
選ばれた１種または２種以上の混合物を使用量こ供する
。具体的には、たとえばチッソ（株）製の末端シラノー
ルポリジメチルシロキサン、末端シラノールジフェニル
シロキサン、末端シラノールポリジメチル−ジフェニル
シロキサン、ポリテトラメチル−ｐ−シルフェニレンシ
ロキサンが市販されている。使用量は、エポキシ樹脂（
Ａ） １００部に対して５〜２００部、好ましくは５〜
５０部の範囲で選定する。５部未満であると、改質効果
が得られず、また２００部を越えると、樹脂全体がゲル
化状態となる。The both-terminated silanol organopolysiloxane (B) in the present invention has the formula: %Formula%[) [In the formula, R1 is methyl or phenyl, R2 is phenyl, and p is 9 to 500. and q is 0 or 6% or less of p], and one type or a mixture of two or more types selected from these groups is provided in the amount used. Specifically, for example, terminal silanol polydimethylsiloxane, terminal silanol diphenylsiloxane, terminal silanol polydimethyl-diphenylsiloxane, and polytetramethyl-p-silphenylene siloxane manufactured by Chisso Corporation are commercially available. The amount used is epoxy resin (
A) 5 to 200 parts per 100 parts, preferably 5 to 200 parts
Select from a range of 50 copies. If it is less than 5 parts, no modification effect will be obtained, and if it exceeds 200 parts, the entire resin will be in a gelled state.
本発明におけるシランカップリング化合物（Ｃ）として
は、下記化合物群（１）〜（１ｖ〕のものが挙げられ、
これらから選ばれた１種または２種以上の混合物を使用
に供する。Examples of the silane coupling compound (C) in the present invention include the following compound groups (1) to (1v),
One type or a mixture of two or more types selected from these is used.
（１）式：
〔式中、Ｒ３は水素、フェニル、ベンジル、シクロヘキ
シル、ビニルベンジルまたはアリル、Ｒ４は−Ｃ２Ｈ４
−１−Ｃ３Ｈ６−または−Ｃ２Ｈ４５Ｃ２Ｈ４−１Ｒ５
およびＲ６は同一もしくは異なってメチルまたはエチル
、Ｒ７は−Ｃ２Ｈ４−１−Ｃ２Ｈ４Ｓ Ｃ２Ｈ４−、−
Ｃ２Ｈ４ＮＨＣ２Ｈ４−または−Ｃ−１Ｒ８は−Ｃ２Ｈ
４−または一〇３Ｈ６−、およびｒはＯまたは１である
〕
で示されるアミノシラン化合物、
（１１）式：
％式％（）
〔式中、Ｒ５，Ｒ６およびｒは前記と同意義、およびＲ
９は−Ｃ３Ｈ６−または−ＣＨ２−である〕で示すしる
メルカプトシラン化合物、
（ｉｌｌ）式：
％式％）
で示されるエポキシシラン化合物、および（１ｖ）式：
％式％（）
〔式中、Ｒ５，Ｒ６およびｒは前記と同意義、およびＲ
１□４；！−Ａ−または−Ｑ−ＮＨＣＯＸ−Ａ−（ここ
で、Ａはアルキレン基、好ましくは炭素数２以上、特に
３以上の低級アルキレンでたとえば−（ＣＨ２）２−１
− （ＣＨ２） ３−等、Ｑはジインシアネート残基、
たとえば２，４−もしくは２．６−）リレンジイソシア
ネート、４．４’−ジフェニルメタンジイソシアネート
などの芳香族ジイソシアネート残基またはへキサメチレ
ンジイソシアネート、リジンジイソシアネート、インホ
ロンジイソシアネート、水添ＭＤＩ、水添ＴＤＩなどの
脂肪族系ジイソシアネート残基、およびＸは−ＮＨ−１
−〇−または−３−）である〕
で示されるインシアネートシラン化合物。(1) Formula: [wherein R3 is hydrogen, phenyl, benzyl, cyclohexyl, vinylbenzyl or allyl, R4 is -C2H4
-1-C3H6- or -C2H45C2H4-1R5
and R6 are the same or different and are methyl or ethyl, R7 is -C2H4-1-C2H4S C2H4-, -
C2H4NHC2H4- or -C-1R8 is -C2H
4- or 103H6-, and r is O or 1] An aminosilane compound represented by formula (11): % formula % () [wherein R5, R6 and r have the same meanings as above, and R
9 is -C3H6- or -CH2-], an epoxysilane compound represented by the formula (ill): %formula%), and a formula (1v): %formula%() [in the formula , R5, R6 and r have the same meanings as above, and R
1□4;! -A- or -Q-NHCOX-A- (where A is an alkylene group, preferably lower alkylene having 2 or more carbon atoms, especially 3 or more carbon atoms, such as -(CH2)2-1
- (CH2) 3- etc., Q is a diincyanate residue,
For example, aromatic diisocyanate residues such as 2,4- or 2,6-) lylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or hexamethylene diisocyanate, lysine diisocyanate, inphorone diisocyanate, hydrogenated MDI, hydrogenated TDI, etc. aliphatic diisocyanate residue, and X is -NH-1
-〇- or -3-)] An incyanate silane compound represented by the following.
以下、式（Ｉ［３〜（ＶＩ）のシラン化合物の具体側番
ζついて、それぞれその構造式および化合御名を列挙す
る。Hereinafter, the structural formulas and compound names of the specific side numbers ζ of the silane compounds of formulas (I[3 to (VI)) will be listed.
式（ｎ）のアミノシラン化合物
Ｈ２Ｎ Ｃ３Ｈ６Ｓ ｉ （ＯＣ２Ｈ５）３ｒ−アミノ
プ口ピルトリエトキシシランＨ２ＮＣ２Ｈ４Ｓｉ （Ｏ
ＣＨ３）３
β−アミノエチルトリメトキシシラン
Ｈ２ＮＣ３Ｈ６Ｓｉ （ＯＣ２Ｈ５）２ＣＨ３
γ−アミ７ノプロピルジエトキシメチルシランＣＨ２＝
ＣＨＣＨ２ＮＨＯ２Ｈ６Ｓ ｉ（ＯＣＨ３）３γ−アリ
ルアミノプロピルトリメトキシシランＨ２ＮＣ２Ｈ４５
Ｃ２Ｈ４Ｓｉ （ＯＣ２Ｈ５）２■
ＣＨ３
β−（β−アミノエチルチオエチル）ジェトキシメチル
シラン
Ｈ２ＮＣ２Ｈ４５Ｃ２Ｈ４Ｓ ｉ （ＯＣ２Ｈ５）３β
−（β−アミノエチルチオエチル）トリエトキシシラン
β−フェニルアミノプロピルトリメト牛クジシラ
ン−シクロへキシルアミノプロピルトリメトキシシラン
γ−ベンジルアミノプロピルトリメトキシシラン
ｒ−（ビニルベンジルアミノプロピル）トリエトキシシ
ラン
Ｈ２ＮＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ （ＯＣＨ３）３Ｎ−
β−（アミノエチル）−ｒ−アミノプロピルトリメトキ
シシラン
Ｈ２Ｎ Ｃ２Ｈ４ＮＨＯ２Ｈ６Ｓ ｉ （ＯＣＨ３）２
ＣＨ３
Ｎ−β−（アミノエチル）−ｒ−アミノプロピルメチル
ジメトキシシラン
Ｈ２ＮＣ２Ｈ４ＮＨＣＨ２Ｓｉ （ＯＣＨ３）３β−ア
ミノエチルアミノメチルトリメトキシシラン
Ｈ２Ｎ Ｃ２Ｈ４ＮＨＯ２Ｈ４ＮＨＯ２Ｈ６Ｓ ｉ （
ＯＣＨ３）３γ−〔β−（β−アミノエチルアミノエチ
ルアミノ〕プロピル〕トリエトキシシラン
Ｈ２ＮＣＮＨ（ＣＨ２）３ Ｓｉ （ＯＣ２Ｈ５）３Ｎ
−（３−トリエト牛シシリルプロピル）ウレア
Ｈ５−ＣＨ２ＣＨ２ＣＨ２−５ｉ（−ＯＣＨ３）２ＣＨ
３
３−メルカプトプロピルメチルジメトキシシラン
Ｈ５−ＣＨ２ＣＨ２ＣＨ２−５ｉ ＋ＯＣ２Ｈ５）３３
−メルカプトプロピルトリエトキシシランＨＳ−ＣＨ２
−Ｓｉ＋０ＣＨ３）３
メルカプトメチルトリメトキシシラン
Ｈ３−ＣＨ２ＣＨ２ＣＨ２−Ｓｉ＋０ＣＨ３）３３−メ
ルカプトプロピルトリメトキシシラン式［Ｖ］ 、 Ｅ
Ｖ’ ）のエポキシシラン化合物Ｓ ｉ ＋ＯＣＨ３）
３
β−（３，４−エポキシシクロヘキシル〕エチルトリメ
トキシシラン
ＣＨ３−ＣＨ−ＣＨ２−５ｉ−ＣＨ３
Ｃ２Ｈ３
（２−（３，４−エポ牛シー４−メチルシクロへキシル
）プロピル〕メチルジェトキシシランＣＨ３０Ｃ２Ｈ５
（３−グリシドキシプロピル）メチルジェトキシシラン
３−グリシドキシプロピルトリメトキシシラン式［ＶＩ
）のインシアネートシラン化合物０ＣＮ−ＣＨ２ＣＨ２
ＣＨ２−３ｉ（−ＯＣ２Ｈ５）３ｒ−インシアネートプ
ロピルトリエトキシシラン
０ＣＮ−ＣＨ２ＣＨ２ＣＨ２−Ｓ ｉ＋０ｃＨ３）３γ
−インシアネートプロピルトリメトキシシラン
これらのシランカップリング化合物（Ｃ）はいずれも、
分散剤兼架橋剤として機能し、使用量はそれらのアルコ
キシ基と上記ポリシロキサン（Ｂ）の水酸基とのモル比
率：〔アルコキシ基）／［ＯＲ３が０．１〜１５となる
ように選定する。この比率が０．１未満であると、分散
安定効果が発揮されず、また１５を越えると、シリコー
ン樹脂粒子を分散して得られるエポキシ樹脂組成物の粘
度安定性が劣る。本発明では、エポキシ樹脂とシリコー
ン樹脂粒子界面の接着性も考慮しており、アルコキシ基
が水酸基（シラノール基）に対してかなり過剰のモル比
で使用することもある。Aminosilane compound of formula (n) H2N C3H6S i (OC2H5)3r-aminopyrtriethoxysilane H2NC2H4Si (O
CH3)3 β-aminoethyltrimethoxysilane H2NC3H6Si (OC2H5)2CH3 γ-aminopropyldiethoxymethylsilane CH2=
CHCH2NHO2H6S i(OCH3)3γ-allylaminopropyltrimethoxysilane H2NC2H45
C2H4Si (OC2H5)2■ CH3 β-(β-aminoethylthioethyl)jethoxymethylsilane H2NC2H45C2H4S i (OC2H5)3β
-(β-aminoethylthioethyl)triethoxysilane β-phenylaminopropyltrimethoxdisilane -cyclohexylaminopropyltrimethoxysilane γ-benzylaminopropyltrimethoxysilane r-(vinylbenzylaminopropyl)triethoxysilane H2NC2H4NHC3H6Si (OCH3)3N-
β-(aminoethyl)-r-aminopropyltrimethoxysilane H2N C2H4NHO2H6S i (OCH3)2
CH3 N-β-(aminoethyl)-r-aminopropylmethyldimethoxysilane H2NC2H4NHCH2Si (OCH3)3β-aminoethylaminomethyltrimethoxysilane H2N C2H4NHO2H4NHO2H6S i (
OCH3) 3γ-[β-(β-aminoethylaminoethylamino]propyl]triethoxysilane H2NCNH(CH2)3 Si (OC2H5)3N
-(3-trietocycilylpropyl)urea H5-CH2CH2CH2-5i(-OCH3)2CH
3 3-Mercaptopropylmethyldimethoxysilane H5-CH2CH2CH2-5i +OC2H5)33
-Mercaptopropyltriethoxysilane HS-CH2
-Si+0CH3)3 Mercaptomethyltrimethoxysilane H3-CH2CH2CH2-Si+0CH3)33-Mercaptopropyltrimethoxysilane Formula [V], E
V') epoxysilane compound S i +OCH3)
3 β-(3,4-epoxycyclohexyl]ethyltrimethoxysilane CH3-CH-CH2-5i-CH3 C2H3 (2-(3,4-epoxycyclohexyl)propyl)methyljethoxysilane CH30C2H5 ( 3-glycidoxypropyl) methyljethoxysilane 3-glycidoxypropyltrimethoxysilane Formula [VI
) incyanate silane compound 0CN-CH2CH2
CH2-3i(-OC2H5)3r-incyanatepropyltriethoxysilane0CN-CH2CH2CH2-S i+0cH3)3γ
- Incyanatepropyltrimethoxysilane Each of these silane coupling compounds (C) is
It functions as a dispersant and a crosslinking agent, and the amount used is selected so that the molar ratio of these alkoxy groups to the hydroxyl group of the polysiloxane (B): [alkoxy group)/[OR3] is 0.1 to 15. If this ratio is less than 0.1, the dispersion stabilizing effect will not be exhibited, and if it exceeds 15, the viscosity stability of the epoxy resin composition obtained by dispersing silicone resin particles will be poor. In the present invention, adhesion between the epoxy resin and the silicone resin particle interface is also considered, and the alkoxy group may be used in a considerably excessive molar ratio relative to the hydroxyl group (silanol group).
なお、これらのシランカップリング化合物に加えて、式
：
％式％
〔式中、Ｒ５は前記と同意義、Ｒ１２はメチルまたはエ
チル、Ｒ１３は＝ＣＨ２−１−Ｃ２Ｈ４−または−ｃ３
Ｈ６−１ＹはＣＨ２＝ＣＨ−１Ｃ６Ｈ５、ｃｏ／Ｆ２ｏ
、＋１（ｎ′＝１〜１゜） 、ＣＦ３Ｃ−０−１ＮＣ−
またはＮＣ（ＣＨ２）３ Ｓ−１およびＳは０．１また
は２、ｒはＳが２のとき０または１である〕
または式：
％式％
〔式中、Ｒ５，Ｒ□２は前記と同意義、Ｒ工。はＣｎ−
１Ｈ２ｎｑ＋１（ｎｑ：＝：１〜２０）、ＣＨ２＝ＣＨ
−またはＣ６Ｈ５、およびＳは０，１または２、ｒはＳ
が２のときＯまたは１である〕
で示される有機シラン化合物を使用してもよい。In addition to these silane coupling compounds, the formula: %Formula% [In the formula, R5 has the same meaning as above, R12 is methyl or ethyl, and R13 is =CH2-1-C2H4- or -c3
H6-1Y is CH2=CH-1C6H5, co/F2o
, +1 (n'=1~1°), CF3C-0-1NC-
or NC(CH2)3 S-1 and S are 0.1 or 2, r is 0 or 1 when S is 2] Or formula: % formula % [In the formula, R5, R□2 are the same as above Significance, R Eng. is Cn-
1H2nq+1 (nq:=:1~20), CH2=CH
- or C6H5, and S is 0, 1 or 2, r is S
is O or 1 when is 2] An organic silane compound represented by the following may be used.
この有機シラン化合物〔■〕、〔■〕の使用によって、
エポキシ樹脂を架橋させることなくシリコーン樹脂のみ
を架橋し粒子化できる。かかる有機シラン化合物の具体
例（構造式と化合御名）を以丁優ζ列挙する。By using this organic silane compound [■], [■],
Only the silicone resin can be crosslinked and made into particles without crosslinking the epoxy resin. Specific examples (structural formula and compound name) of such organic silane compounds are listed below.
（Ｃ２Ｈ５０％Ｓｉ
テトラエトキシシラン
ＣＨ２＝ＣＨＣＨ２Ｓ １ （ＯＣ２Ｒ５） ３アリル
トリエトキシシラン
ＣＨ２＝ＣＨＣＨ２５ｉ（ＯＣＨ３）３アリルトリメト
キシシラン
Ｃ５Ｈ工ＩＳｔ （ＯＣ２Ｈ５）３
アミルトリエトキシシラン
ベンジルトリエト牛ジシラン
Ｃ４Ｈｇ Ｓｉ （ＯＣＨ３）３
ｎ−ブチルトリメトキシシラン
Ｃ２Ｒ５Ｓ ｉ （ＯＣ２Ｒ５）３
エチルトリエトキシシラン
Ｃ２Ｈ５Ｓ ｉ （ＯＣＨ３）３
エチルトリメトキシシラン
ＣＨ３（ＣＨ２）５ Ｓｉ （ＯＣＨ３）３ｎ−ヘキシ
ルトリメトキシシラン
ＣＨ３５ｉ （ＯＣ２Ｈ５）３
メチルトリエトキシシラン
ＣＨ３Ｓ ｉ （ＯＣＨ３）３
メチルトリメトキシシラン
ＣＨ３（ＣＨ２）１７Ｓｉ （ＯＣ２Ｈ５）３ｎ−オク
タデシルトリエトキシシラン
フェニルトリエト牛ジシラン
フェニルトリメト牛ジシラン
ＣＨ３（ＣＨ２）２ Ｓ ｉ （ＯＣＨ３）３ｎ−プロ
ビルトリメトキシシラン
（ＣＨ３０）４ Ｓ ｉ
テトラメト牛ジシラン
ＣＨ２＝ＣＨ３ｉ （ＯＣ２Ｈ５）３
ヒニルトリエトキシシラン
ＣＨ２＝ＣＨ３ｌ （ＯＣＨ３）３
ヒニルトリメトキシシラン
ＮＣ（ＣＨ２）２Ｓｉ （ＯＣ２Ｈ５）３シアノエトキ
シトリエトキシシラン
ＮＣ（ＣＨ２）３Ｓ（ＣＨ２）３ＳＩ（ＯＣＨ３）２「
ＣＦ３
３−（３−シアノプロピルチオプロビル）ジメトキシメ
チルシラン
Ｃ３Ｆ１□ＣＨ２ＣＨ２Ｓｉ （ＯＣ２Ｈ５）３（ヘプ
タデカフルオロ−１，ｌ、 ２．２−テトラヒドロデシ
ル）トリエトキシシラン
Ｃ６Ｆ１３ＣＨ２ＣＨ２Ｓｉ （ＯＣ２Ｈ５）３（トリ
デカフルオロ−１，１，２，２−テトラヒドロオクチル
）トリエトキシシラン
（３，３，３−トリフルオロプロピル）メチルジメトキ
シシラン
ＣＦ３ ＣＨ２ＣＨ２Ｓ ｉ （ＯＣＨ３）３（３，３
，３−トリフルオロプロピル）トリメト牛ジシラン
ＣＦ３ Ｃ−０ＣＨ２ＣＨ２ＣＨ２Ｓ ｉ （ＯＣＨ３
）３３−トリフルオロアセトキシプロピルトリメトキシ
シラン
ＣＦ３ＣＨ２ＣＨ２５ｉ（ＯＣ２Ｈ５）３（３，３，３
−） リフルオロプロピル） ｌ−ＩＪエトキシシラン
本発明で分散安定促進剤（Ｄ）として用いる前記式〔Ｄ
１〕で示されるオルガノポリシロキサン、および式〔Ｄ
２〕のポリシロキサンと分子中に少なくとも１個のグリ
シジル基を有する化合物の付加反応生成物の具体例につ
いて、その構造式を以下に列挙する。(C2H50%Si Tetraethoxysilane CH2=CHCH2S 1 (OC2R5) 3 Allyltriethoxysilane CH2=CHCH25i (OCH3) 3 Allyltrimethoxysilane C5H Engineering ISt (OC2H5) 3 Amyltriethoxysilane Benzyltriethoxdisilane C4Hg Si (OCH3 )3 n-Butyltrimethoxysilane C2R5S i (OC2R5)3 Ethyltriethoxysilane C2H5S i (OCH3)3 Ethyltrimethoxysilane CH3(CH2)5 Si (OCH3)3 n-hexyltrimethoxysilane CH35i (OC2H5)3 Methyltrimethoxysilane Ethoxysilane CH3S i (OCH3)3 Methyltrimethoxysilane CH3(CH2)17Si (OC2H5)3n-Octadecyltriethoxysilane Phenyltrietho-Bovine disilane Phenyltrimetho-Bovine disilane CH3(CH2)2 S i (OCH3)3n-Provyl Trimethoxysilane (CH30)4 S i Tetramethoxysilane CH2=CH3i (OC2H5)3 Hinyltriethoxysilane CH2=CH3l (OCH3)3 Hinyltrimethoxysilane NC (CH2)2Si (OC2H5)3 Cyanoethoxytriethoxysilane NC ( CH2)3S(CH2)3SI(OCH3)2 CF3 3-(3-cyanopropylthioprobyl)dimethoxymethylsilane C3F1 CH2CH2Si (OC2H5)3 (heptadecafluoro-1,l, 2.2-tetrahydrodecyl) Triethoxysilane C6F13CH2CH2Si (OC2H5)3 (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (3,3,3-trifluoropropyl)methyldimethoxysilane CF3 CH2CH2S i (OCH3)3(3 ,3
, 3-trifluoropropyl)trimethoxdisilane CF3 C-0CH2CH2CH2S i (OCH3
)33-Trifluoroacetoxypropyltrimethoxysilane CF3CH2CH25i(OC2H5)3(3,3,3
-) l-IJ ethoxysilane The above formula [D] used as the dispersion stability promoter (D) in the present invention
1] and an organopolysiloxane represented by the formula [D
Structural formulas of specific examples of addition reaction products of polysiloxane (2) and compounds having at least one glycidyl group in the molecule are listed below.
ＣＨ３ＣＨ３ＣＨ３ＣＨ３ＣＨ３
ＣＨ３−５ｉ叶ＳｉＯ■ダＳｉＯ早ＳｉＯ堝Ｓ ｉ −
ＣＨ５ＩＩ Ｉ Ｉ
＋０ ０（−Ｃ２Ｈ４０７Ｃ３Ｈ６０％ＣＨ３Ｃ
Ｆ２
ＣＨ３ＣＨ３ＣＨ３ＣＨ３ＣＨ３
ＩＩ ｌ１１
ＣＨ３−３ｉ（）ｅ−５ｉ０７がＳ ｉＯ￥Ｓｔ Ｏｑ
Ｓ ＋ −ＣＨ３ＩＩ ｌ
ｌ １ＣＯＯＨ０ｅＣ２Ｈ４０％（Ｃ，Ｈ
６０７ω鴨ＣＨ３ＣＨ３ＣＨ３ＣＨ２ＣＨ３
ｉＩ ＩＩ＋
ＣＨ３−Ｓｉ Ｏ＋Ｓ ｉ Ｏ塙いＳｉＯ早ＳｉＯ旭５
ｉ−ＣＨ３ＩＩ ｌ ｌ
１なお、他の具体例として、アミ７基を有
するエーテル変性シリコーン：信越シリコーン（株）製
のｒＸ−２２−３９３９ＣＪ、ｒＸ−２２−３９３９Ｄ
Ｊ等、グリシジル基を有するエーテル変性シリコーン：
トーμ・シリコーン（株） 製のｒＳＦ−８４２１ＥＧ
Ｊ、ｒＢＹ１６−８４５Ｊ、ｒＢＸｌ６−８６６Ｊ等、
ＸｌがＣＨ３であるエーテル変性シｌ） コーン：信越
シリコーン（株）製のｒＫＦ−３５１（Ａ）」、ｒ Ｋ
Ｆ −３５３（Ａ） Ｊ、ｒＫＦ−３ｓ ｓ （Ａ）
Ｊ、ｒ Ｋ Ｆ −３５２（Ａ） Ｊ、ｒＫＦ−３ｓ
４ （Ａ） Ｊ、ｒ Ｋ Ｆ −６１５（Ａ） Ｊ、
トーμ・シリコーン（株）製のｒＳＦ−８４００Ｊ、ｒ
ＳＦ−８４１０Ｊ、ｒＳＨ−３７４９Ｊ等がある。CH3CH3CH3CH3CH3 CH3-5i Leaf SiO ■ da SiO early SiO basin Si −
CH5II I I
+0 0(-C2H407C3H60%CH3C
F2 CH3CH3CH3CH3CH3 II l11 CH3-3i()e-5i07 is S iO\St Oq
S + -CH3II l
l 1COOH0eC2H40% (C,H
607ω Kamo CH3CH3CH3CH2CH3 iI II+ CH3-Si O+S i O Hanawai SiO Early SiO Asahi 5
i-CH3II l l
1. Other specific examples include ether-modified silicones having 7 amino groups: rX-22-3939CJ and rX-22-3939D manufactured by Shin-Etsu Silicone Co., Ltd.
Ether-modified silicone having a glycidyl group, such as J:
rSF-8421EG manufactured by Tou Silicone Co., Ltd.
J, rBY16-845J, rBXl6-866J, etc.
(Ether-modified silicon in which Xl is CH3) Cone: rKF-351 (A) manufactured by Shin-Etsu Silicone Co., Ltd., rK
F-353 (A) J, rKF-3s s (A)
J,rKF-352(A) J,rKF-3s
4 (A) J, r K F -615 (A) J,
rSF-8400J, r manufactured by Tou Silicone Co., Ltd.
There are SF-8410J, rSH-3749J, etc.
生成物
両末端アミン変性シリコーンとしてチッソ（株）製のｒ
ＦＭ３３１１Ｊ、ｒＦＭ３３２１Ｊ、［ＦＭ ３３２５
Ｊ （Ｘ２”−Ｃ３Ｈ６−ＮＨ２）、ト−Ｌ／・シリ
コーン（株）製のｒＢＸｌ６−８５３Ｊ、ｒＢＸｌ ６
−８５３ Ｂ Ｊ （Ｘ２＝−Ｒ″−ＮＨ２） 、信
越化学（株）製のｒＸ−２２−１６１ＡＳＪ、ｒＸ−２
２−１６１Ａ、 Ｊ、ｒＸ−２２−１６１ＢＪ、「：］
−２２−１６１ ＣＪ （Ｘ２＝−Ｃ３Ｈ６−ＮＨ２）
、ＰＥＴＲＡＣ）ｌ ＳＹＳＴＥＭＳ社製の「ｐｓｓ
ｌＯＪ、ｒＰｓ５１３Ｊ等、側鎖アミノ変性シリコーン
（Ｘ２＝ＣＨ３、Ｘ３＝−Ｒ”−ＮＨ２、−Ｒ”−ＮＨ
−Ｒ”−ＮＨ２）としてトーμ・シリコーン（株）製の
ｒＳＦ８４１７」、ｒＢＹ１６−８２８Ｊ、ｒＢＸ１６
−８５９」、信越化学（株）製のｒＫＦ−３９３Ｊ、「
ＫＦ−８５９Ｊ、ｒＫＦ−８６０Ｊ、ｒＫＦ−８６１」
、ｒＫＦ−８６７Ｊ、ｌ’−Ｘ−２２−３８０Ｄ」、ｒ
ＫＦ−８６４Ｊ、ｒＫＦ−８６５Ｊ、「Ｘ−２２−３６
８０Ｊ、ｒＸ−２２−３８０１Ｃ」等、側鎖カルボキシ
変性シリコーンとしてトーμ・シリコーン（株）製のｒ
ＳＦ−８４１８Ｊ、信越化学（株）製（７）ｒＸ−２２
−３７０１ＥＪ、［Ｘ−２２−３７１０Ｊ、ｒＸ−２２
−３７１５Ｊ等、末端カルボキシ変性シリコーンとして
ＰＥＴＲＡＣＨＳＹＳＴＥＭＳ社製のｒＰＳ５６３ Ｊ
等、側鎖メルカプト変性シリコーンとしてトーμ・シリ
コーン（株）製のｒＢＸ１６−８３８ＡＪ、「ＢＹ１６
−８３８Ｊ、信越化学（株）製（７）ｒＸ−２２−９８
０Ｊ等がある。As a silicone modified with amines at both ends of the product, R manufactured by Chisso Co., Ltd.
FM3311J, rFM3321J, [FM 3325
J (X2''-C3H6-NH2), rBXl6-853J, rBXl 6 manufactured by To-L/Silicone Co., Ltd.
-853 B J (X2=-R''-NH2), rX-22-161ASJ, rX-2 manufactured by Shin-Etsu Chemical Co., Ltd.
2-161A, J, rX-22-161BJ, ":]
-22-161 CJ (X2=-C3H6-NH2)
, PETRAC) ``pss'' manufactured by SYSTEMS
side chain amino-modified silicone (X2=CH3, X3=-R"-NH2, -R"-NH
-R''-NH2) as rSF8417'' manufactured by Tou Silicone Co., Ltd., rBY16-828J, rBX16
-859", rKF-393J manufactured by Shin-Etsu Chemical Co., Ltd., "
KF-859J, rKF-860J, rKF-861"
, rKF-867J, l'-X-22-380D", r
KF-864J, rKF-865J, “X-22-36
80J, r
SF-8418J, Shin-Etsu Chemical Co., Ltd. (7) rX-22
-3701EJ, [X-22-3710J, rX-22
rPS563J manufactured by PETRACHSYSTEMS as a terminal carboxy-modified silicone such as -3715J, etc.
etc., as side chain mercapto-modified silicones such as rBX16-838AJ and “BY16” manufactured by TOμ Silicone Co., Ltd.
-838J, manufactured by Shin-Etsu Chemical Co., Ltd. (7) rX-22-98
There are 0J etc.
上記分子中に少なくとも１個のグリシジル基を有する化
合物としては、前記のエポキシ樹脂、その他グリシジル
基を有するブタジェンゴム、インプレンゴムまたはアク
リル樹脂などを用いることができる。特番こ、ポリシロ
キサン［Ｄ２］のグリシジル基との反応性官能茶番ζ対
して、該グリシジル基を有する化合物を過剰量に付加反
応する。通常、付加反応は常温乃至加熱下（４０〜１５
０℃）で行う。また、必要に応じて有機溶剤に溶解した
状態で付加反応を行い、予め付加反応生成物を調製して
もよいし、あるいはエポキシ樹脂中に分散して予め付加
反応を行った後に、更Ｉζ撹拌下昏こ（Ｂ）成分の両末
端シラノールオルガノポリシロキサンと（Ｃ）成分の１
分子内ζζ少なくとも２個のアルコキシシリル基を有す
るシランカップリング化合物を添加、反応させて本発明
のエポキシ樹脂組成物を得ることもできる。As the compound having at least one glycidyl group in the molecule, the above-mentioned epoxy resin, butadiene rubber, imprene rubber, acrylic resin, etc. having a glycidyl group can be used. In this special program, an excess amount of a compound having the glycidyl group is added to the reactive functional farce ζ of polysiloxane [D2] with the glycidyl group. Usually, the addition reaction is carried out at room temperature or under heating (40 to 15
0°C). Further, if necessary, the addition reaction product may be prepared in advance by performing the addition reaction while dissolved in an organic solvent, or the addition reaction product may be prepared in advance by dispersing it in an epoxy resin and then further stirred. Both terminal silanol organopolysiloxane of component (B) and 1 of component (C)
The epoxy resin composition of the present invention can also be obtained by adding and reacting a silane coupling compound having at least two alkoxysilyl groups in the molecule.
これら２群の分散安定促進剤（Ｄ）は、それぞれ単独に
使用することができ、使用量はエポキシ樹脂（Ａ） １
００部優こ対して０．０１〜５．０部、好ましくは０．
０５〜３部の範囲で選定する。０．０１部未満であると
、シリコーン樹脂の所望の分散安定効果が得られず、ま
た５、０部を越えても、分散安定効果はそれ以上増大し
ない傾向（こある。These two groups of dispersion stability promoters (D) can be used individually, and the amount used is 1 of the epoxy resin (A).
0.01 to 5.0 parts, preferably 0.00 parts.
Select from a range of 05 to 3 parts. If it is less than 0.01 part, the desired dispersion stabilizing effect of the silicone resin cannot be obtained, and even if it exceeds 5.0 parts, the dispersion stabilizing effect tends not to increase any further.
本発明に係るエポキシ樹脂組成物は、以下の各手法で製
造することができる。The epoxy resin composition according to the present invention can be manufactured by the following methods.
（１）上述のエポキシ樹脂（Ａ）、ポリシロキサン（Ｂ
）、シランカップリング化合物（Ｃ）、分散安定促進剤
（Ｄ）および要すれば有機シラン化合物〔■〕、〔■〕
を所定割合で配合し、これらを撹拌混合する方法。(1) The above-mentioned epoxy resin (A), polysiloxane (B)
), silane coupling compound (C), dispersion stability promoter (D), and if necessary, organic silane compound [■], [■]
A method in which the ingredients are mixed in a predetermined ratio and mixed by stirring.
（２）ポリシロキサン（Ｂ）にゲル化を生じさせない程
度にシランカップリング化合物（Ｃ）および分散安定促
進剤（Ｄ）および要すれば有機シラン化合物〔■〕、〔
■〕を反応せしめた後、これをエポキシ樹脂（Ａ）に添
加し、撹拌混合しつつ、さらにポリシロキサン（Ｂ）の
架橋に必要なシランカップリング化合物（Ｃ）および要
すれば有機シラン化合物〔■〕、〔■〕を添加する方法
。(2) Silane coupling compound (C) and dispersion stability promoter (D) and, if necessary, an organic silane compound [■], [
After reacting [2]], this is added to the epoxy resin (A), and while stirring and mixing, the silane coupling compound (C) necessary for crosslinking the polysiloxane (B) and, if necessary, the organic silane compound [ ■〕, method of adding [■].
（３）エポキシ樹脂（Ａ）１こシランカップリング化合
物（Ｃ）（エポキシシラン化合物（Ｖ）、（Ｖ’）を除
く）および分散安定促進剤（Ｄ）を反応せしめた後、ポ
リシロキサン（Ｂ）を加え、必要があればシランカップ
リング化合物（Ｃ）および要すれば有機シラン化合物〔
■〕、〔■〕を加え、撹拌混合する方法。(3) After reacting the epoxy resin (A) with the silane coupling compound (C) (excluding epoxy silane compounds (V) and (V')) and the dispersion stability promoter (D), the polysiloxane (B ), if necessary, add a silane coupling compound (C) and if necessary, an organic silane compound [
Method of adding [■] and [■] and stirring to mix.
かかる撹拌による架橋反応は、室温下で行ってもよいが
、要すれば適当温度に加熱したり、反応触媒（ｔ−ブチ
ル錫オキサイド、オクチル酸鉛、オクチル酸錫、第三級
アミノ化合物、水など）を添加したりして反応を促進す
ることができ、反応時間の短縮が図れる。また撹拌は、
高速回転で全体を均一化することが好ましく、撹拌効率
によって粒径が変化する。Such crosslinking reaction by stirring may be carried out at room temperature, but if necessary, it may be heated to an appropriate temperature or a reaction catalyst (t-butyltin oxide, lead octylate, tin octylate, tertiary amino compound, water etc.), the reaction can be accelerated and the reaction time can be shortened. Also, stirring is
It is preferable to homogenize the whole by high-speed rotation, and the particle size changes depending on the stirring efficiency.
形成したシリコーン樹脂粒子は、撹拌作用によってエポ
キシ樹脂マトリックス中に安定に分散することができ、
液体乃至固体の本発明組成物が得られる。The formed silicone resin particles can be stably dispersed in the epoxy resin matrix by stirring action,
A liquid or solid composition of the invention is obtained.
本発明組成物は、均一分散した特定のシリコーン樹脂粒
子を有することを特徴とし、これによってエポキシ樹脂
の熱時強度を下げることなく可撓性が向上し、所望の耐
クラツク性や靭性が付与される。本発明組成物は、通常
のエポキシ樹脂の硬化剤等の存在丁で硬化する。用途と
しては、たとえば誘電率が低いことからＩＣ用封止材、
良好な撥水性、耐衝撃性穴、可撓性大の点から各種コー
テイング材、塗料、接着剤、プリプレグなどへの適用が
考えられる。The composition of the present invention is characterized by having specific silicone resin particles uniformly dispersed, which improves the flexibility of the epoxy resin without reducing its strength when heated, and imparts the desired crack resistance and toughness. Ru. The composition of the present invention is cured in the presence of conventional epoxy resin curing agents. Applications include, for example, IC encapsulants due to their low dielectric constant,
Due to its good water repellency, impact-resistant holes, and high flexibility, it can be applied to various coating materials, paints, adhesives, prepregs, etc.
次に実施例を挙げて本発明をより具体的に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ビスフェノールＡ型エポキシ樹脂（油化シェル社製、エ
ピコート８２８）１００部−こｔ−ブチル錫オキサイド
０．５部を加え、８０℃で撹拌しながら、これ１こ末端
シラノールポリジメチルシロキサン［Ｉ：１（ｐ＝５０
〜６０、Ｒ，＝ＣＨ３、平均分子量４２００ ）２０部
、３−アミノプロピルトリエトキシシラン２．５部およ
び分散安定剤としてグリシジル基を有するエーテル変性
シリコーン（トーレ・シリコーン（株）製のｒＢＹ１６
−８４５Ｊ）１部を加え、さらに３時間加熱撹拌を続け
る。Example 1 100 parts of bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Ltd., Epicoat 828) and 0.5 part of tert-butyltin oxide were added, and while stirring at 80°C, this was mixed with 1-terminated silanol polydimethylsiloxane [ I:1 (p=50
~60, R,=CH3, average molecular weight 4200) 20 parts, 2.5 parts of 3-aminopropyltriethoxysilane, and an ether-modified silicone having a glycidyl group as a dispersion stabilizer (rBY16 manufactured by Toray Silicone Co., Ltd.)
-845J) was added, and heating and stirring was continued for an additional 3 hours.
反応混合物は乳白色の液体となり、反応終了後室温で放
置・冷却してエポキシ樹脂組成物を得る。分散樹脂粒子
の粒径変動の結果を表１に示す（粒径は、硬化前は光学
顕微鏡、硬化後は電子顕微鏡１こよる）。The reaction mixture becomes a milky white liquid, and after the reaction is completed, it is left to stand and cooled at room temperature to obtain an epoxy resin composition. The results of particle size variation of the dispersed resin particles are shown in Table 1 (particle size was measured using an optical microscope before curing and an electron microscope 1 after curing).
実施例２〜４
実施例ＩＩこおいて、下記製造例１〜３により製造した
分散安定剤１部を代用する以外は、同様な条件でエポキ
シ樹脂組成物を得る。Examples 2 to 4 In Example II, an epoxy resin composition is obtained under the same conditions except that 1 part of the dispersion stabilizer produced in Production Examples 1 to 3 below is used instead.
製造例１
式〔Ｄ２〕のボリンロキサンとしてアミノ変性シリコー
ン（トーレ・シリコーン（株）製、５Ｆ８４１７）１０
０部を、テトラヒドロフラン（ＴＨＦ月こ溶解（３０重
量％１こ）したエポキシ樹脂（油化シェル社製、エピコ
ート１００２）溶１１６７０部を５０℃、３６時間付加
反応して、分散安定剤を得る。なお、反応終了をＧＰＣ
により確認した。Production Example 1 Amino-modified silicone (manufactured by Toray Silicone Co., Ltd., 5F8417) 10 as borinloxane of formula [D2]
A dispersion stabilizer is obtained by adding 11,670 parts of an epoxy resin (Epicoat 1002 manufactured by Yuka Shell Co., Ltd.) dissolved in tetrahydrofuran (THF (30% by weight)) at 50° C. for 36 hours. In addition, the completion of the reaction was determined by GPC.
Confirmed by.
製造例２
式〔Ｄ２〕のポリシロキサンとして両末端アミノ変性シ
リコーン（チッソ社製、ＦＭ３３２１）１００部と、エ
ポキシ樹脂（油化シェル社製、エピコート８７１）の３
０重量％ＴＨＦ溶液１７０部を５０℃、３６時間付加反
応して分散安定剤を得る。ＧＰＣにより反応終了を確認
した。Production Example 2 As a polysiloxane of formula [D2], 100 parts of a silicone modified with amino at both ends (FM3321, manufactured by Chisso Corporation) and 3 parts of an epoxy resin (manufactured by Yuka Shell Co., Ltd., Epicoat 871) were used.
A dispersion stabilizer is obtained by addition-reacting 170 parts of a 0% by weight THF solution at 50° C. for 36 hours. Completion of the reaction was confirmed by GPC.
製造例３
式〔Ｄ２〕のポリシロキサンとしてカルボキシ変性シリ
コーン（ｉ越シリコーン社製、Ｘ−２２−３７１０）１
００部と、エポキシ樹脂３０重量％ＴＨＦ溶液９００部
を１２０℃、６時間付加反応して分散安定剤を得る。Production Example 3 Carboxy-modified silicone (manufactured by Ietsu Silicone Co., Ltd., X-22-3710) 1 as the polysiloxane of formula [D2]
00 parts of the epoxy resin and 900 parts of a 30% by weight THF solution of the epoxy resin were subjected to an addition reaction at 120° C. for 6 hours to obtain a dispersion stabilizer.
比較例１
実施例１１こおいて、分散安定剤を省略する以外は、同
様な条件でエポキシ樹脂組成物を得る。Comparative Example 1 An epoxy resin composition was obtained under the same conditions as in Example 11 except that the dispersion stabilizer was omitted.
表１
注■）実施例１〜４で得られたエポキシ樹脂組成物１０
０ハこ対し、ポリアミド硬化剤（富士化成社製、トーマ
イド２９０−Ｃ）３０ｐを混合し、常温３日間反応硬化
させた。Table 1 Note ■) Epoxy resin composition 10 obtained in Examples 1 to 4
30 parts of a polyamide curing agent (TOMIDE 290-C, manufactured by Fuji Kasei Co., Ltd.) was mixed with the 0 pieces, and the mixture was reacted and cured at room temperature for 3 days.
■）実施例１〜４で得られたエポキシ樹脂組成物１００
Ｉ！に対して、ジアミノジフェニルメタン２５！！を混
合し、３時間反応し硬化させた。■) Epoxy resin composition 100 obtained in Examples 1 to 4
I! For diaminodiphenylmethane 25! ! were mixed and reacted for 3 hours to cure.
Claims (1)
００重量部、 （Ｃ）１分子内に少なくとも２個のアルコキシシリル基
を有するシランカップリング化合物で、そのアルコキシ
基と上記ポリシロキサン（Ｂ）の水酸基とのモル比率が
０．１〜１５、および （Ｄ）分散安定剤として、式： ▲数式、化学式、表等があります▼ 〔式中、Ｘ＿１はメチル基、またはエポキシ基、アミノ
基、水酸基、カルボキシル基またはカルボン酸エステル
基を含有する１価有機基、Ｙ＿１は▲数式、化学式、表
等があります▼（Ｒは炭素数１ 〜１０のアルキレン、Ｃ＿６Ｈ＿４、ＣＯまたはＮＨＣ
Ｏ、Ｒ′はＨ、１価炭化水素基、アシルまたは炭酸モノ
エステル基、ａおよびｂはそれぞれ１〜５０）、ｌは０
〜１０００、ｍおよびｎはそれぞれ１〜１００である〕 で示されるオルガノポリシロキサン、または式：▲数式
、化学式、表等があります▼ 〔式中、Ｘ＿２はＣＨ＿３、−Ｒ″−ＮＨ＿２、−Ｒ″
−ＮＨ−−Ｒ″′−ＮＨ＿２、−Ｒ″−ＣＯＯＨまたは
−ＯＲ＾IV（Ｒ″ま−ＯＣ＿２Ｈ＿４−、炭素数１〜２
０のアルキレン基、フェニレン基または置換フェニレン
基、Ｒ″′は炭素数１〜２０のアルキレン基、およびＲ
＾IVはＣＨ＿３またはＣ＿２Ｈ＿５）、Ｘ＿３はＣＨ＿
３、−Ｒ″−ＮＨ＿２、−Ｒ″−ＮＨ−Ｒ″′−ＮＨ＿
２、−Ｒ″−ＳＨまたは−Ｒ″−ＣＯＯＨ（Ｒ″および
Ｒ″′は前記と同意義）である〕のポリシロキサンと分
子中に少なくとも１個のグリシジル基を有する化合物の
付加反応生成物０．０１〜５．０重量部 から成ることを特徴とするエポキシ樹脂組成物。[Claims] 1. (A) 100 parts by weight of epoxy resin, (B) silanol organopolysiloxane at both ends 5 to 2
00 parts by weight, (C) a silane coupling compound having at least two alkoxysilyl groups in one molecule, the molar ratio of the alkoxy groups to the hydroxyl groups of the polysiloxane (B) being 0.1 to 15, and (D) As a dispersion stabilizer, the formula: ▲Mathematical formula, chemical formula, table, etc.▼ [In the formula, The organic group Y_1 has ▲mathematical formula, chemical formula, table, etc.▼(R is alkylene with 1 to 10 carbon atoms, C_6H_4, CO or NHC
O, R' are H, monovalent hydrocarbon group, acyl or carbonate monoester group, a and b are each 1 to 50), l is 0
~1000, m and n are each 1 to 100] Organopolysiloxane or formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X_2 is CH_3, -R''-NH_2, -R ″
-NH--R"'-NH_2, -R"-COOH or -OR^IV (R"-OC_2H_4-, carbon number 1-2
0 alkylene group, phenylene group or substituted phenylene group, R″′ is an alkylene group having 1 to 20 carbon atoms, and R
^IV is CH_3 or C_2H_5), X_3 is CH_
3, -R''-NH_2, -R''-NH-R'''-NH_
2. -R''-SH or -R''-COOH (R'' and R''' have the same meanings as above)] and an addition reaction product of a compound having at least one glycidyl group in the molecule An epoxy resin composition comprising 0.01 to 5.0 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63097691A JPH0725866B2 (en) | 1988-04-19 | 1988-04-19 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63097691A JPH0725866B2 (en) | 1988-04-19 | 1988-04-19 | Epoxy resin composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63171446A Division JPH0737510B2 (en) | 1988-07-09 | 1988-07-09 | Dispersion stabilizer for silicone resin particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01268717A true JPH01268717A (en) | 1989-10-26 |
| JPH0725866B2 JPH0725866B2 (en) | 1995-03-22 |
Family
ID=14198977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63097691A Expired - Fee Related JPH0725866B2 (en) | 1988-04-19 | 1988-04-19 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725866B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0251521A (en) * | 1988-08-12 | 1990-02-21 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH03277653A (en) * | 1990-03-27 | 1991-12-09 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH0797433A (en) * | 1993-08-24 | 1995-04-11 | Siemens Ag | Siloxane-containing casting resin system, its production and coating for opto-electric structural element |
| JP2004277697A (en) * | 2002-10-07 | 2004-10-07 | General Electric Co <Ge> | Epoxy resin composition, solid element encapsulated with this composition, and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01108254A (en) * | 1987-10-19 | 1989-04-25 | Shin Etsu Chem Co Ltd | Curable epoxy resin composition |
-
1988
- 1988-04-19 JP JP63097691A patent/JPH0725866B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01108254A (en) * | 1987-10-19 | 1989-04-25 | Shin Etsu Chem Co Ltd | Curable epoxy resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0251521A (en) * | 1988-08-12 | 1990-02-21 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH03277653A (en) * | 1990-03-27 | 1991-12-09 | Matsushita Electric Works Ltd | Epoxy resin composition |
| JPH0797433A (en) * | 1993-08-24 | 1995-04-11 | Siemens Ag | Siloxane-containing casting resin system, its production and coating for opto-electric structural element |
| JP2004277697A (en) * | 2002-10-07 | 2004-10-07 | General Electric Co <Ge> | Epoxy resin composition, solid element encapsulated with this composition, and method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725866B2 (en) | 1995-03-22 |
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