JPH04266928A - Amino group-containing silicone elastomer fine powder and epoxy resin composition containing the same fine powder - Google Patents
Amino group-containing silicone elastomer fine powder and epoxy resin composition containing the same fine powderInfo
- Publication number
- JPH04266928A JPH04266928A JP4742691A JP4742691A JPH04266928A JP H04266928 A JPH04266928 A JP H04266928A JP 4742691 A JP4742691 A JP 4742691A JP 4742691 A JP4742691 A JP 4742691A JP H04266928 A JPH04266928 A JP H04266928A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- fine powder
- epoxy resin
- emulsion
- silicone elastomer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 50
- 239000000843 powder Substances 0.000 title claims abstract description 44
- 229920002379 silicone rubber Polymers 0.000 title claims description 40
- 125000003277 amino group Chemical group 0.000 title claims description 32
- 239000000839 emulsion Substances 0.000 claims abstract description 59
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 36
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 10
- 101100237844 Mus musculus Mmp19 gene Proteins 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052799 carbon Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 229920001971 elastomer Polymers 0.000 description 18
- 239000000806 elastomer Substances 0.000 description 18
- -1 polysiloxane Polymers 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 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
- 150000003839 salts Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229920002114 octoxynol-9 Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000010680 novolac-type phenolic resin Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- HXODBIRGIPGNQF-UHFFFAOYSA-N 1-oxaspiro[5.5]undecane Chemical compound C1CCCCC21OCCCC2 HXODBIRGIPGNQF-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- BBEAHXXUYVGKPR-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)cyclohexen-1-yl]oxymethyl]oxirane Chemical compound C1OC1COC(CC=1)CCC=1OCC1CO1 BBEAHXXUYVGKPR-UHFFFAOYSA-N 0.000 description 1
- FSYPIGPPWAJCJG-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1OCC1CO1 FSYPIGPPWAJCJG-UHFFFAOYSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical group C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 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
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical compound C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 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
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、エポキシ樹脂の改質用
添加剤等として有用なシリコーンエラストマー微粉末及
び該微粉末を含有する電気、電子部品のパッケージング
に有用なエポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fine silicone elastomer powder useful as an additive for modifying epoxy resins, and an epoxy resin composition containing the fine powder useful for packaging electrical and electronic parts.
【０００２】0002
【従来の技術】電子、電気部品のパッケージングには種
々の熱硬化性樹脂が用いられているが、中でもエポキシ
樹脂は、機械特性、電気特性、耐熱性、接着性、成形加
工性等に優れていることから最も広範囲にしかも多量に
使用されている。電子部品のパッケージはＩＣに代表さ
れるように薄層化、小型化の方向にあるが、従来のエポ
キシ樹脂組成物では冷熱サイクルに供された時にパッケ
ージにクラックが発生し易いという欠点があった。この
欠点を解消する方法として、エポキシ樹脂にシリコーン
の球状粉末を混合する方法（特開昭５９−９６１２２号
公報）、及びエポキシ樹脂にシランカップリング剤で処
理したシリコーン微粉末を混合する方法（特開昭６１−
１０１５１９号公報）が提案されている。[Prior Art] Various thermosetting resins are used for packaging electronic and electrical parts, and epoxy resins have excellent mechanical properties, electrical properties, heat resistance, adhesive properties, moldability, etc. Because of this, it is used most widely and in large quantities. Packages for electronic components, as typified by ICs, are becoming thinner and smaller, but conventional epoxy resin compositions have the disadvantage that they tend to crack when subjected to cooling and heating cycles. . Methods to overcome this drawback include a method of mixing epoxy resin with spherical silicone powder (Japanese Unexamined Patent Publication No. 59-96122), and a method of mixing epoxy resin with fine silicone powder treated with a silane coupling agent (Japanese Patent Application Laid-Open No. 1988-96122). 1986-
101519) has been proposed.
【０００３】0003
【発明が解決しようとする課題】しかし、上記方法はい
ずれもエポキシ樹脂組成物の硬化物の耐衝撃性が不充分
で、かつこれらの組成物を用いて得られる電子部品は耐
湿性が悪いという問題を有し、近年の電子部品のパッケ
ージングに求められている要求を満たすものではなかっ
た。[Problems to be Solved by the Invention] However, in all of the above methods, the impact resistance of the cured product of the epoxy resin composition is insufficient, and the electronic parts obtained using these compositions have poor moisture resistance. This method had problems and did not meet the requirements of packaging for electronic components in recent years.
【０００４】本発明は上記事情に鑑みなされたもので、
エポキシ樹脂組成物に配合した場合、該組成物の硬化物
に優れた耐衝撃性を与え、冷熱サイクルによってパッケ
ージにクラックの発生が起こり難く、かつ耐湿性に優れ
たパッケージを与えるシリコーンエラストマー微粉末及
び該微粉末を含有するエポキシ樹脂組成物を提供するこ
とを目的とする。[0004] The present invention has been made in view of the above circumstances.
A fine silicone elastomer powder and a silicone elastomer powder that, when blended into an epoxy resin composition, give the cured product of the composition excellent impact resistance, make the package less susceptible to cracking during cooling and heating cycles, and provide a package with excellent moisture resistance. The object of the present invention is to provide an epoxy resin composition containing the fine powder.
【０００５】[0005]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を行った結果、１分子中に
１個以上のケイ素原子結合のアミノ基含有有機基及び２
個以上のヒドロキシ基又はアルコキシ基を有するオルガ
ノポリシロキサンと、１分子中に少なくとも２個のアル
コキシ基を有する下記一般式（１）で示される有機ケイ
素化合物又はその部分加水分解縮合物とを主成分とする
組成物を水性エマルジョンとして水中に分散させ、この
分散状態で上記組成物のエマルジョン粒子を硬化用触媒
により硬化させ、アミノ基含有シリコーンエラストマー
の分散液とした後、水を除くことによりアミノ基含有シ
リコーンエラストマー微粉末が得られること、このアミ
ノ基含有シリコーンエラストマー微粉末は表面にアミノ
基を有しているので、エポキシ樹脂に混合した場合、粒
子表面でエポキシ樹脂と強固な結合を形成し、耐衝撃性
、強度の向上をもたらすこと、それ故上記アミノ基含有
シリコーンエラストマー微粉末を配合したエポキシ樹脂
組成物は電子部品のパッケージングに使用した場合、冷
熱サイクルによってパッケージにクラックの発生が起こ
り難く、かつ耐湿性に優れたパッケージを与えることを
見い出し、本発明をなすに至ったものである。[Means and effects for solving the problem] As a result of intensive studies to achieve the above object, the present inventors found that one or more silicon-bonded amino group-containing organic groups and two
The main components are an organopolysiloxane having at least two hydroxy groups or alkoxy groups, and an organosilicon compound represented by the following general formula (1) having at least two alkoxy groups in one molecule, or a partially hydrolyzed condensate thereof. The composition is dispersed in water as an aqueous emulsion, and in this dispersed state, the emulsion particles of the composition are cured with a curing catalyst to form a dispersion of an amino group-containing silicone elastomer, and then the amino groups are removed by removing water. This fine powder of silicone elastomer containing amino groups has an amino group on its surface, so when mixed with epoxy resin, it forms a strong bond with the epoxy resin on the particle surface. This improves impact resistance and strength. Therefore, when an epoxy resin composition containing the above-mentioned amino group-containing silicone elastomer fine powder is used for packaging electronic parts, it is difficult for the package to crack due to cooling and heating cycles. The inventors have discovered that it is possible to provide a package with excellent moisture resistance, and have thus come up with the present invention.
【０００６】従って、本発明は、（Ａ）１分子中に１個
以上のケイ素原子結合のアミノ基含有有機基及び２個以
上のケイ素原子結合のヒドロキシ基又はアルコキシ基を
有するオルガノポリシロキサン、及び
（Ｂ）下記一般式（１）で示される有機ケイ素化合物又
はその部分加水分解縮合物
ＲａＳｉ（ＯＲ１）４−ａ ・
・・・（１）（但し、式中Ｒは同種又は異種の非置換又
は置換一価炭化水素基、Ｒ１は水素原子又は炭素数１〜
６の一価炭化水素基、ａは０，１又は２である。）を主
成分とする組成物の水性エマルジョンの硬化物よりなる
アミノ基含有シリコーンエラストマー微粉末、及び（イ
）エポキシ樹脂、（ロ）硬化剤、（ハ）上記アミノ基含
有シリコーンエラストマー微粉末を主成分とするエポキ
シ樹脂組成物を提供する。Therefore, the present invention provides (A) an organopolysiloxane having one or more silicon-bonded amino group-containing organic groups and two or more silicon-bonded hydroxy or alkoxy groups in one molecule; (B) Organosilicon compound represented by the following general formula (1) or its partially hydrolyzed condensate RaSi(OR1)4-a ・
... (1) (However, in the formula, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, R1 is a hydrogen atom or a carbon number of 1 to
6 monovalent hydrocarbon group, a is 0, 1 or 2. ), and (a) an epoxy resin, (b) a curing agent, and (c) the above-mentioned amino group-containing silicone elastomer fine powder consisting mainly of a cured aqueous emulsion. An epoxy resin composition is provided.
【０００７】以下、本発明について更に詳しく説明する
と、本発明のアミノ基含有シリコーンエラストマー微粉
末は、上述したように（Ａ）成分のオルガノポリシロキ
サンと（Ｂ）成分の有機ケイ素化合物又はその部分加水
分解縮合物を主成分とする組成物の水性エマルジョンを
硬化させてなるものである。[0007] The present invention will be explained in more detail below. As mentioned above, the amino group-containing silicone elastomer fine powder of the present invention is composed of an organopolysiloxane as the component (A) and an organosilicon compound as the component (B) or a partially hydrated component thereof. It is made by curing an aqueous emulsion of a composition whose main component is a decomposition condensate.
【０００８】ここで、（Ａ）成分のオルガノポリシロキ
サンとしては１分子中に１個以上のケイ素原子結合のア
ミノ基含有有機基及び２個以上のケイ素原子結合のヒド
ロキシ基又はアルコキシ基を有するオルガノポリシロキ
サンを使用するものである。このヒドロキシ基又はアル
コキシ基の結合位置は側鎖でも末端でもよいが、両末端
に１つずつ存在することが好ましく、またアミノ基含有
有機基は側鎖に存在することが好ましい。具体的には下
記一般式（２）で示されるオルガノポリシロキサンを好
適に用いることができる。Here, the organopolysiloxane of component (A) is an organopolysiloxane having one or more silicon-bonded amino group-containing organic group and two or more silicon-bonded hydroxy or alkoxy groups in one molecule. It uses polysiloxane. The hydroxy group or alkoxy group may be bonded to either a side chain or a terminal, but it is preferable that one bond exists at each terminal, and it is preferable that the amino group-containing organic group exists at a side chain. Specifically, an organopolysiloxane represented by the following general formula (2) can be suitably used.
【０００９】[0009]
【化１】
（但し、式中Ｒは同種又は異種の非置換又は置換一価炭
化水素基、Ｒ２は水素原子又は低級アルキル基、Ａはア
ミノ基含有有機基、Ｘ，Ｙは１以上の整数である。）上
記式（２）中Ｒは同種又は異種の非置換又は置換一価炭
化水素基であるが、具体的にはメチル基，エチル基，プ
ロピル基，イソプロピル基，ブチル基，ヘキシル基等の
アルキル基、シクロヘキシル基，シクロヘプチル基等の
シクロアルキル基、フェニル基，メチルフェニル基，エ
チルフェニル基等のアリール基、及び３，３，３−トリ
フルオロプロピル基等のハロゲン化炭化水素基などが例
示されるが、Ｒ中の９０モル％以上がメチル基であるこ
とが好ましい。また、Ｒ２は水素原子又はメチル基，エ
チル基，プロピル基，ブチル基等の低級アルキル基であ
る。更に、Ａのアミノ基含有有機基としては、例えば下
記の基を挙げることができる。[Chemical formula 1] (However, in the formula, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, R2 is a hydrogen atom or a lower alkyl group, A is an amino group-containing organic group, and X and Y are integers of 1 or more. ) In the above formula (2), R is the same or different unsubstituted or substituted monovalent hydrocarbon group, specifically methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group. alkyl groups such as cyclohexyl groups, cycloheptyl groups, aryl groups such as phenyl groups, methylphenyl groups, ethylphenyl groups, and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl groups. Examples thereof include, but it is preferable that 90 mol% or more of R is a methyl group. Further, R2 is a hydrogen atom or a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group. Furthermore, examples of the amino group-containing organic group of A include the following groups.
【００１０】0010
【化２】
また、上記式（２）中Ｘは１以上の整数、好ましくは５
〜５００の整数、Ｙは１以上の整数、好ましくは１〜５
０の整数であり、ＸとＹの合計は式（２）で示されるオ
ルガノポリシロキサンの粘度が２５℃において２０〜１
００，０００ｃｓ、特に５０〜５０，０００ｃｓの範囲
となるような値が好ましい。２０ｃｓ未満では得られる
エラストマーの硬度が大きくなりすぎる場合があり、１
００，０００ｃｓを超えると乳化分散が困難になり、し
かも得られるエラストマーの硬度が柔らかくなり、エラ
ストマー粒子同士が融合し易くなるため粉末化が困難と
なる場合がある。[Image Omitted] In the above formula (2), X is an integer of 1 or more, preferably 5
~500 integer, Y is an integer of 1 or more, preferably 1 to 5
is an integer of 0, and the sum of X and Y is such that the viscosity of the organopolysiloxane represented by formula (2) is 20 to 1 at 25°C.
00,000 cs, especially a value in the range of 50 to 50,000 cs. If it is less than 20 cs, the hardness of the obtained elastomer may become too large;
If it exceeds 00,000 cs, emulsification and dispersion becomes difficult, and the hardness of the obtained elastomer becomes soft, and the elastomer particles tend to fuse together, which may make powdering difficult.
【００１１】上記（Ａ）成分のオルガノポリシロキサン
は１分子中に２個以上のケイ素原子結合のヒドロキシ基
又はアルコキシ基を有するものであるが、これらの基の
エラストマー微粉末を得るための適切な含有量は、（Ａ
）成分のオルガノポリシロキサン１００ｇ当たり０．０
０５〜１モル、特に０．０１〜０．６モルの範囲とする
ことが好ましい。ヒドロキシ基又はアルコキシ基の含有
量が（Ａ）成分１００ｇ当たり０．００５モルに満たな
いと架橋点が少なすぎるため生成するエラストマーの硬
度が柔らかくなり、上記した理由により粉末化が困難と
なる場合があり、一方、１モルを超えると生成するエラ
ストマーの硬度が硬くなりすぎてエラストマーの弾性特
性が失われる場合がある。The organopolysiloxane of component (A) has two or more silicon-bonded hydroxy groups or alkoxy groups in one molecule, but an appropriate method is used to obtain a fine elastomer powder of these groups. The content is (A
)0.0 per 100g of organopolysiloxane component
The amount is preferably in the range of 0.05 to 1 mol, particularly 0.01 to 0.6 mol. If the content of hydroxy groups or alkoxy groups is less than 0.005 mol per 100 g of component (A), the hardness of the elastomer produced will be soft due to too few crosslinking points, and it may be difficult to powder it for the reasons mentioned above. On the other hand, if the amount exceeds 1 mol, the hardness of the elastomer produced may become too hard and the elastic properties of the elastomer may be lost.
【００１２】また、アミノ基含有有機基の含有量は（Ａ
）成分のオルガノポリシロキサン１分子中に１個以上で
あればよく、特に制限されないが、エラストマー微粉末
を得るための適切な含有量は、（Ａ）成分のオルガノポ
リシロキサン１００ｇ当たり０．００３〜０．８モル、
特に０．００５〜０．６モルの範囲とすることが好まし
い。アミノ基含有有機基の含有量が（Ａ）成分のオルガ
ノポリシロキサン１００ｇ当たり０．００３モルに満た
ないと、得られるエラストマー微粉末をエポキシ樹脂に
配合した場合エポキシ樹脂との結合が弱いため、十分な
耐衝撃性の向上が望めない場合があり、一方、０．８モ
ルを超えるとエポキシ樹脂との結合が強くなりすぎて組
成物の保存安定性が悪くなり、長期の保管ができなくな
る場合があり、とりわけ得られるシリコーンエラストマ
ー微粉末１００ｇ中０．０１〜０．５モルの範囲となる
ようにすることが好ましい。Further, the content of the amino group-containing organic group is (A
Component (A) may have one or more per molecule of organopolysiloxane, and is not particularly limited, but the appropriate content for obtaining a fine elastomer powder is from 0.003 to 100 g of organopolysiloxane as component (A). 0.8 mol,
In particular, it is preferably in the range of 0.005 to 0.6 mol. If the content of the amino group-containing organic group is less than 0.003 mol per 100 g of the organopolysiloxane (A) component, when the obtained elastomer fine powder is blended with the epoxy resin, the bond with the epoxy resin will be weak, so it will not be sufficient. On the other hand, if the amount exceeds 0.8 mol, the bond with the epoxy resin becomes too strong, resulting in poor storage stability of the composition, and long-term storage may not be possible. In particular, it is preferable that the amount is in the range of 0.01 to 0.5 mol per 100 g of the obtained silicone elastomer fine powder.
【００１３】具体的に（Ａ）成分のオルガノポリシロキ
サンの好適な例を挙げると次のようなものがある。Preferred examples of the organopolysiloxane of component (A) are as follows.
【００１４】[0014]
【化３】
一方、（Ｂ）成分の有機ケイ素化合物は、下記一般式（
１）で示され、１分子中にケイ素原子に結合したヒドロ
キシ基又はアルコキシ基を少なくとも２個有するシラン
又はその部分加水分解縮合物である。[Chemical formula 3] On the other hand, the organosilicon compound of component (B) has the following general formula (
1), which is a silane or a partially hydrolyzed condensate thereof having at least two hydroxy or alkoxy groups bonded to a silicon atom in one molecule.
【００１５】
ＲａＳｉ（ＯＲ１）４−ａ ・
・・・（１）（但し、式中Ｒは同種又は異種の非置換又
は置換一価炭化水素基、Ｒ１は水素原子又は炭素数１〜
６の一価炭化水素基、ａは０，１又は２である。）ここ
で、上記式中のＲとしては上述したものが例示されるが
、好ましくはメチル基である。又、Ｒ１は水素原子又は
メチル基，エチル基，プロピル基，ブチル基等の炭素数
１〜６の１価炭化水素基である。[0015] RaSi(OR1)4-a・
... (1) (However, in the formula, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, R1 is a hydrogen atom or a carbon number of 1 to
6 monovalent hydrocarbon group, a is 0, 1 or 2. ) Here, R in the above formula is exemplified by those mentioned above, but is preferably a methyl group. Further, R1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, ethyl group, propyl group, butyl group.
【００１６】上記式（１）で示されるケイ素化合物とし
ては具体的に次のものが挙げられる。ＣＨ３Ｓｉ（ＯＨ
）３，ＣＨ３Ｓｉ（ＯＣＨ３）３，ＣＨ３Ｓｉ（ＯＨ）
（ＯＣＨ３）２，Ｓｉ（ＯＣ２Ｈ５）４，（ＨＯ）２Ｓ
ｉ（ＯＣ２Ｈ５）２，ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３，Ｃ
Ｈ２＝ＣＨＳｉ（ＯＣＨ３）３，Ｃ６Ｈ５Ｓｉ（ＯＣＨ
３）３，（ＣＨ３）２Ｓｉ（ＯＨ）２，（ＣＨ３）２Ｓ
ｉ（ＯＣＨ３）２，（ＣＨ３）２Ｓｉ（ＯＣ２Ｈ５）２
，ＣＦ３Ｃ２Ｈ４Ｓｉ（ＯＣＨ３）３なお（Ｂ）成分は
、これらの混合物であってもよく、部分加水分解縮合物
であってもよく、このような例としてはエチルポリシリ
ケートやメチルポリシリケート等が例示される。Specific examples of the silicon compound represented by the above formula (1) include the following. CH3Si(OH
)3,CH3Si(OCH3)3,CH3Si(OH)
(OCH3)2, Si(OC2H5)4, (HO)2S
i(OC2H5)2,CH3Si(OC2H5)3,C
H2=CHSi(OCH3)3, C6H5Si(OCH
3) 3, (CH3)2Si(OH)2, (CH3)2S
i(OCH3)2, (CH3)2Si(OC2H5)2
, CF3C2H4Si(OCH3)3 The component (B) may be a mixture of these or a partially hydrolyzed condensate, such as ethyl polysilicate and methyl polysilicate. Ru.
【００１７】この（Ｂ）成分の有機ケイ素化合物の使用
量は、（Ａ）成分のオルガノポリシロキサン１００部（
重量部、以下同様）に対し１〜４０部、特に２〜２０部
の範囲とすることが好ましい。（Ｂ）成分の使用量が１
部に満たないと、得られるエラストマーの硬度が柔らか
いものとなり、粉末として得ることが困難となる場合が
あり、一方、４０部を超えると、得られるエラストマー
の硬度が硬くなり、エラストマーとしての弾性特性が劣
ったものとなる場合がある。The amount of organosilicon compound used as component (B) is 100 parts of organopolysiloxane (component (A)).
It is preferably in the range of 1 to 40 parts, particularly 2 to 20 parts by weight (the same applies hereinafter). (B) The amount of ingredient used is 1
If the amount is less than 40 parts, the hardness of the obtained elastomer will be soft and it may be difficult to obtain it as a powder. On the other hand, if it exceeds 40 parts, the hardness of the obtained elastomer will be hard and the elastic properties as an elastomer will deteriorate. may be inferior.
【００１８】本発明のアミノ基含有シリコーンエラスト
マー微粉末は、上述した（Ａ）成分のオルガノポリシロ
キサン及び（Ｂ）成分の有機ケイ素化合物を主成分とす
る組成物の水性エマルジョンを硬化用触媒により硬化さ
せてなるものである。The amino group-containing silicone elastomer fine powder of the present invention is obtained by curing an aqueous emulsion of a composition containing the above-mentioned organopolysiloxane as the component (A) and an organosilicon compound as the component (B) with a curing catalyst. It is something that can be done.
【００１９】ここで、硬化用触媒は上記（Ａ）成分と（
Ｂ）成分のケイ素原子に結合したヒドロキシ基あるいは
アルコキシ基の間に縮合反応を起こさせてエラストマー
を生成せしめるためのものであり、公知のものを使用す
ることができる。具体的には、ジブチル錫ジラウレート
，ジオクチル錫ジラウレート，ジブチル錫ジアセテート
，ジオクチル錫ジオクトエート，オクチル酸錫，オクチ
ル酸亜鉛，オクチル酸鉄，ラウリル酸錫，ラウリル酸亜
鉛，テトラブチルチタネート等の有機酸の金属塩が例示
され、これらの１種を単独で又は２種以上を併用して用
いることができるが、触媒活性の面より有機錫化合物が
好ましい。この硬化用触媒の使用量は、上記（Ａ）成分
のオルガノポリシロキサン１００部に対し０．０１〜１
０部、特に０．１〜３部の範囲とすることが好ましい。
硬化用触媒の使用量が（Ａ）成分のオルガノポリシロキ
サン１００部に対し０．０１部未満では（Ａ）成分と（
Ｂ）成分を主成分とする組成物の水性エマルジョンを十
分に硬化させることができない場合があり、一方、１０
部を超えて使用しても硬化反応に格別の効果が認められ
ず、かえって得られるエラストマー微粉末中に不純物と
して残留する場合がある。Here, the curing catalyst is composed of the above component (A) and (
It is for producing an elastomer by causing a condensation reaction between the hydroxy groups or alkoxy groups bonded to the silicon atoms of component B), and any known one can be used. Specifically, organic acids such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin dioctoate, tin octylate, zinc octylate, iron octylate, tin laurate, zinc laurate, and tetrabutyl titanate. Metal salts are exemplified, and one type of these can be used alone or two or more types can be used in combination, but organotin compounds are preferable from the viewpoint of catalytic activity. The amount of this curing catalyst used is 0.01 to 1 part per 100 parts of organopolysiloxane as component (A).
The amount is preferably 0 parts, particularly in the range of 0.1 to 3 parts. If the amount of curing catalyst used is less than 0.01 parts per 100 parts of organopolysiloxane (A), component (A) and (
In some cases, the aqueous emulsion of the composition containing component B) as a main component cannot be sufficiently cured;
Even if more than 1 part is used, no particular effect will be observed on the curing reaction, and it may instead remain as impurities in the resulting fine elastomer powder.
【００２０】また、（Ａ）成分のオルガノポリシロキサ
ンと（Ｂ）成分の有機ケイ素化合物を主成分とする組成
物の水性エマルジョンは、これら（Ａ）成分と（Ｂ）成
分を混合し、これを界面活性剤と水とでＯ／Ｗ型エマル
ジョンとすることにより得ることができる。この場合、
硬化用触媒は（Ａ）成分と（Ｂ）成分に直接混合しても
よいが、これらの３成分を混合すると直ちに硬化が始ま
り、硬化速度が速すぎると各成分が完全に混合する前に
硬化し、硬化が不均一になったり、或いはＯ／Ｗ型エマ
ルジョンになる前に硬化して乳化ができなかったりする
おそれがある。これを避けるために硬化用触媒に反応制
御剤を併用するか、或いは次に述べるような２段階に分
けて組成物を形成することが好ましい。[0020] In addition, an aqueous emulsion of a composition whose main components are an organopolysiloxane as a component (A) and an organosilicon compound as a component (B) can be obtained by mixing these components (A) and (B). It can be obtained by forming an O/W type emulsion with a surfactant and water. in this case,
The curing catalyst may be directly mixed with components (A) and (B), but curing will begin immediately when these three components are mixed, and if the curing speed is too fast, curing may occur before each component is completely mixed. However, there is a risk that the curing may be uneven or that the emulsification may not be possible due to curing before it becomes an O/W type emulsion. In order to avoid this, it is preferable to use a reaction control agent together with the curing catalyst, or to form the composition in two stages as described below.
【００２１】即ち、（Ａ）成分と（Ｂ）成分の所定量を
混合してオルガノポリシロキサン混合物を作り、次いで
これに界面活性剤と水を用いてＯ／Ｗ型エマルジョンと
した後、このエマルジョンに硬化用触媒を予め界面活性
剤と水を用いてＯ／Ｗ型エマルジョンとしたものを添加
して、（Ａ）成分、（Ｂ）成分及び硬化用触媒の３成分
からなる組成物を形成させて硬化させることにより、目
的のエラストマーエマルジョンを製造する方法を好適に
採用することができる。That is, an organopolysiloxane mixture is prepared by mixing predetermined amounts of components (A) and (B), and then a surfactant and water are used to form an O/W type emulsion, and this emulsion is A curing catalyst prepared in advance into an O/W type emulsion using a surfactant and water is added to the mixture to form a composition consisting of three components: component (A), component (B), and curing catalyst. By curing the elastomer emulsion, a method for producing the desired elastomer emulsion can be suitably employed.
【００２２】ここで、オルガノポリシロキサン混合物や
硬化用触媒を水中に分散するために使用する界面活性剤
としては、これらを乳化できるものであればよく特に制
限はないが、ポリオキシエチレンアルキルフェニルエー
テル、ポリオキシエチレンアルキルエーテルなどのよう
なノニオン系乳化剤でＨＬＢが１０〜１５のものとする
ことがよく、これらはその２種以上を併用してもよい。Here, the surfactant used to disperse the organopolysiloxane mixture and the curing catalyst in water is not particularly limited as long as it can emulsify them, but polyoxyethylene alkylphenyl ether , polyoxyethylene alkyl ether, etc., with an HLB of 10 to 15, and two or more of these may be used in combination.
【００２３】上記（Ａ）成分と（Ｂ）成分の混合物のＯ
／Ｗ型エマルジョンを形成する際、得られるシリコーン
エラストマー微粉末は平均粒径が１００μｍ以下とする
ことが好ましいため、硬化前のオルガノポリシロキサン
組成物のエマルジョンの平均粒径も１００μｍ以下とす
ることが好ましい。このような微粒子エマルジョンとす
るには、乳化に当たって（Ａ）成分、（Ｂ）成分及び乳
化剤、或いは更に硬化用触媒と必要に応じて反応制御剤
を加えたものを予め混合してまずＷ／Ｏ型エマルジョン
を調整し、次いで分散を続けながら、これに水を徐々に
添加してＷ／Ｏ型をＯ／Ｗ型に転相させる転相乳化法を
採用することが望ましい。この転相時までに要する水量
は（Ａ）成分と（Ｂ）成分の合計量１００部に対し、一
般に１０〜５０部の範囲である。なお、乳化分散に用い
られる装置は特に制限はないが、例えば市販のホモミキ
サー、ホモジナイザーなどを用いることができる。[0023] O of the mixture of the above components (A) and (B)
/ When forming a W-type emulsion, it is preferable that the obtained silicone elastomer fine powder has an average particle size of 100 μm or less, so the average particle size of the emulsion of the organopolysiloxane composition before curing is also preferably 100 μm or less. preferable. To obtain such a fine particle emulsion, during emulsification, components (A), (B) and an emulsifier, or a curing catalyst and, if necessary, a reaction control agent are mixed in advance, and then W/O is first mixed. It is desirable to adopt a phase inversion emulsification method in which a type emulsion is prepared and then, while dispersion is continued, water is gradually added to the emulsion to invert the W/O type to the O/W type. The amount of water required for this phase inversion is generally in the range of 10 to 50 parts per 100 parts of the total amount of components (A) and (B). The device used for emulsification and dispersion is not particularly limited, and for example, a commercially available homomixer, homogenizer, etc. can be used.
【００２４】なお、（Ａ）成分、（Ｂ）成分及び硬化用
触媒を主成分とする組成物の乳化分散物は、硬化触媒の
反応制御剤を含まない場合には室温でも硬化反応が起こ
ってエラストマーを形成するが、反応制御剤を含む場合
には加温してエラストマーを形成させることができる。[0024] It should be noted that the emulsified dispersion of the composition containing component (A), component (B), and a curing catalyst as main components does not undergo a curing reaction even at room temperature if it does not contain a reaction control agent for the curing catalyst. An elastomer is formed, and if a reaction control agent is included, the elastomer can be formed by heating.
【００２５】上記のようにして得られたシリコーンエラ
ストマーのエマルジョンからシリコーンエラストマー微
粒子を分離させる場合、このエマルジョンをフィルター
を用いて濾過したのではかなり細かいメッシュを必要と
し、かつ目詰まりを起こして分離が極めて困難となる。
これを避けるためにはエマルジョンに無機塩類を添加し
エマルジョン粒子を凝集させてから濾過する方法が有効
で、この方法によりフィルターの目詰まりを起こすこと
なくろ別することができる。エマルジョン粒子の凝集状
態は無機塩類の添加条件により調整することができる。
なお、水や有機溶剤を用いて洗浄を繰り返すことにより
無機塩類の添加によるイオン性不純物の除去は極めて容
易であり、また乳化時に使用した界面活性剤の除去も容
易であり、アルコール等の有機溶剤で洗浄することによ
りほぼ完全に除去することができる。When separating silicone elastomer fine particles from the silicone elastomer emulsion obtained as described above, filtering this emulsion using a filter would require a fairly fine mesh, and the separation would be difficult due to clogging. It will be extremely difficult. In order to avoid this, it is effective to add inorganic salts to the emulsion to aggregate the emulsion particles and then filter the emulsion particles.This method allows the emulsion to be filtered without clogging the filter. The state of aggregation of emulsion particles can be adjusted by adjusting the conditions for adding inorganic salts. Note that it is extremely easy to remove ionic impurities by adding inorganic salts by repeating washing with water or organic solvents, and it is also easy to remove surfactants used during emulsification, and organic solvents such as alcohol It can be almost completely removed by washing with
【００２６】このエマルジョン粒子を擬集させるための
無機塩類としては、特に制限はないが具体的には塩化カ
リウム，塩化ナトリウム，塩化カルシウム，硫酸マグネ
シウム，硫酸ナトリウム，硫酸亜鉛，硝酸カルシウム等
が例示され、その添加量はエマルジョン１００部に対し
て１〜３０部、特に３〜２０部の範囲が好ましく、１部
未満では粒子の凝集が十分に起こらない場合があり、ま
た３０部を超えると溶解度を超えるためそれ以上添加し
ても効果が期待できず、後工程での洗浄の効率を悪くす
る原因となる場合がある。さらに、エマルジョン粒子の
凝集をより容易に行うためにアルコール等の有機溶剤を
併用しても良い。[0026] The inorganic salts for aggregating the emulsion particles are not particularly limited, but specific examples include potassium chloride, sodium chloride, calcium chloride, magnesium sulfate, sodium sulfate, zinc sulfate, and calcium nitrate. The amount added is preferably in the range of 1 to 30 parts, particularly 3 to 20 parts, based on 100 parts of the emulsion; if it is less than 1 part, sufficient aggregation of particles may not occur, and if it exceeds 30 parts, the solubility may be reduced. Since the amount exceeds that amount, no effect can be expected even if more than that is added, and this may cause a decrease in the efficiency of cleaning in the subsequent process. Furthermore, an organic solvent such as alcohol may be used in combination to facilitate aggregation of the emulsion particles.
【００２７】このようにして凝集したエマルジョン粒子
をフィルターを用いて分離し、遠心脱水機などにより十
分に脱水した後、洗浄を行い、この脱水と洗浄を繰り返
してから乾燥することにより、目的とするシリコーンエ
ラストマー微粉末を得ることができる。[0027] The emulsion particles thus aggregated are separated using a filter, thoroughly dehydrated using a centrifugal dehydrator, etc., and then washed. After repeating this dehydration and washing, the particles are dried. A fine silicone elastomer powder can be obtained.
【００２８】ここで、乾燥時には凝集を少なくするため
流動乾燥機等のように撹拌または流動させながら乾燥さ
せることが好ましい。この場合、乾燥前に上述した洗浄
工程を十分に行うと、乾燥工程において特別の解砕手段
を用いなくても流動乾燥等により凝集体がくずれ、ほぼ
球状の粒子からなるシリコーンエラストマー微粉末が得
られる。[0028] At the time of drying, it is preferable to dry while stirring or fluidizing, such as in a fluidized fluid dryer, in order to reduce agglomeration. In this case, if the above-mentioned washing step is carried out sufficiently before drying, the aggregates will be broken down by fluidized drying without using any special crushing means in the drying step, and silicone elastomer fine powder consisting of approximately spherical particles will be obtained. It will be done.
【００２９】このようにして得られる本発明のアミノ基
含有シリコーンエラストマー微粉末はほぼ球状であり、
その粒径はエポキシ樹脂組成物に配合する場合は、最大
粒径が２００μｍ以下、平均粒径が１００μｍ以下、更
に好ましくは１０μｍ以下とすることが好ましい。平均
粒径が１００μｍを超えると、粒子が大きすぎることか
らエポキシ樹脂に配合した場合、十分な低応力性、耐熱
衝撃性を与えない場合がある。The amino group-containing silicone elastomer fine powder of the present invention thus obtained is approximately spherical;
When blended into an epoxy resin composition, it is preferable that the maximum particle size is 200 μm or less, the average particle size is 100 μm or less, and more preferably 10 μm or less. If the average particle size exceeds 100 μm, the particles are too large and may not provide sufficient low stress properties and thermal shock resistance when blended into an epoxy resin.
【００３０】ここで、アミノ基含有シリコーンエラスト
マー微粉末を含むエポキシ樹脂組成物について詳述する
と、本発明のエポキシ樹脂組成物に用いられるエポキシ
樹脂としては、分子中にエポキシ基を少なくとも２個有
する化合物が好ましいが、分子構造、分子量等は特に制
限はない。このようなエポキシ樹脂としては、例えば、
２，２’−ビス（４−ヒドロキシフェニル）プロパン又
はこのハロゲン化物のジグリシジルエーテル、ブタジエ
ンジエポキシド、ビニルシクロヘキセンジオキシド、レ
ゾルシンのジグリシジルエーテル、１，４−ビス（２，
３−エポキシプロポキシ）ベンゼン、４，４’−ビス（
２，３−エポキシプロポキシ）ジフェニルエーテル、１
，４−ビス（２，３−エポキシプロポキシ）シクロヘキ
セン、ビス（３，４−エポキシ−６−メチルシクロヘキ
シルメチル）アジぺート、１，２−ジオキシベンゼン或
いはレゾルシノール、多価フェノール又は多価アルコー
ルとエピクロルヒドリンとを縮合させて得られるエポキ
シグリシジルエーテル或いはポリグリシジルエステル、
ノボラック型フェノール樹脂（或いはハロゲン化ノボラ
ック型フェノール樹脂）とエピクロルヒドリンとを縮合
させて得られるエポキシノボラック、過酸化法によりエ
ポキシ化したエポキシ化ポリオレフィン、エポキシ化ポ
リブタジエン、更に、ナフタレン環含有エポキシ樹脂等
が挙げられ、これらの１種を単独で又は２種以上を併用
して使用することができる。[0030] Here, to explain in detail the epoxy resin composition containing the amino group-containing silicone elastomer fine powder, the epoxy resin used in the epoxy resin composition of the present invention is a compound having at least two epoxy groups in the molecule. is preferred, but there are no particular restrictions on the molecular structure, molecular weight, etc. Such epoxy resins include, for example,
diglycidyl ether of 2,2'-bis(4-hydroxyphenyl)propane or its halide, butadiene diepoxide, vinylcyclohexene dioxide, diglycidyl ether of resorcinol, 1,4-bis(2,
3-epoxypropoxy)benzene, 4,4'-bis(
2,3-epoxypropoxy)diphenyl ether, 1
, 4-bis(2,3-epoxypropoxy)cyclohexene, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 1,2-dioxybenzene or resorcinol, polyhydric phenol or polyhydric alcohol. Epoxyglycidyl ether or polyglycidyl ester obtained by condensing with epichlorohydrin,
Examples include epoxy novolac obtained by condensing a novolac type phenolic resin (or halogenated novolac type phenolic resin) and epichlorohydrin, epoxidized polyolefins epoxidized by a peroxidation method, epoxidized polybutadiene, and naphthalene ring-containing epoxy resins. One type of these can be used alone or two or more types can be used in combination.
【００３１】また、上記のエポキシ基を少なくとも２個
有するエポキシ樹脂にモノエポキシ化合物を適宜併用す
ることは差し支えなく、このモノエポキシ化合物として
はスチレンオキシド、シクロヘキセンオキシド、プロピ
レンオキシド、メチルグリシジルエーテル、エチルグリ
シジルエーテル、フェニルグリシジルエーテル、アリル
グリシジルエーテル、オクチレンオキシド、ドデセンオ
キシド等が例示される。[0031] Furthermore, there is no problem in appropriately using a monoepoxy compound in combination with the above-mentioned epoxy resin having at least two epoxy groups, and examples of the monoepoxy compound include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, and ethyl glycidyl. Examples include ether, phenylglycidyl ether, allylglycidyl ether, octylene oxide, and dodecene oxide.
【００３２】次に、本発明の組成物において使用される
硬化剤としては従来から知られている種々のものを使用
することができ、これには、例えば、ジエチレントリア
ミン、トリエチレンテトラミン、ジエチルアミノプロピ
ルアミン、Ｎ−アミノエチルピペラジン、ビス（４−ア
ミノ−３−メチルシクロヘキシル）メタン、メタキシリ
レンアミン、メタンジアミン、３，９−ビス（３−アミ
ノプロピル）２−２，４，８，１０−テトラオキサスピ
ロ（５，５）ウンデカン等のアミン系化合物；エポキシ
樹脂−ジエチレントリアミンアダクト、アミン−エチレ
ンオキサイドアダクト、シアノエチル化ポリアミン等の
変性脂肪族ポリアミン；ビスフェノールＡ、トリ−メチ
ロールアリルオキシフェノ−ル、低重合度のフェノ−ル
ノボラック樹脂、エポキシ化もしくはブチル化フェノ−
ル樹脂あるいは“Ｓｕｐｅｒ Ｂｅｃｋｃｉｔｅ”１
００１（日本ライヒホールド化学工業（株）製）、“Ｈ
ｉｔａｎｏｌ，４０１０（（株）日立製作所製）、Ｓｃ
ａｄｏ ｆｏｒｍＬ．９（オランダＳｃａｄｏ Ｚ
ｗｏｌｌ社製）、Ｍｅｔｈｙｌｏｎ ７５１０８（米
国ゼネラルエレクトリック社製）等の商品名で知られて
いるフェノール樹脂；“Ｂｅｃｋａｍｉｎｅ”Ｐ．１３
８（日本ライヒホールド化学工業（株）製）、“メラン
”（（株）日立製作所製）“Ｕ−Ｖａｎ”１０Ｒ（東洋
高圧工業（株）製）などの商品名で知られている炭素樹
脂；メラミン樹脂、アニリン樹脂等のアミノ樹脂；式Ｈ
Ｓ−（Ｃ２Ｈ４ＯＣＨ２ＯＣ２Ｈ４ＳＳ）ｎ’Ｃ２Ｈ４
ＯＣＨ２ＯＣ２Ｈ４ＳＨ
（ｎ’：１〜１０の整数）で示されるような分子中にメ
ルカプト基を少なくとも２個有するポリスルフィド樹脂
；無水フタル酸、無水ヘキサヒドロフタル酸、テトラヒ
ドロ無水フタル酸、無水ピロメリット酸、メチルナジッ
ク酸、ドデシル無水コハク酸、無水クロレンディック酸
等の有機酸もしくはその無水物等が挙げられる。Next, as the curing agent used in the composition of the present invention, various conventionally known curing agents can be used, such as diethylenetriamine, triethylenetetramine, diethylaminopropylamine, etc. , N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane, metaxylyleneamine, methanediamine, 3,9-bis(3-aminopropyl)2-2,4,8,10-tetra Amine compounds such as oxaspiro(5,5)undecane; modified aliphatic polyamines such as epoxy resin-diethylenetriamine adduct, amine-ethylene oxide adduct, cyanoethylated polyamine; bisphenol A, tri-methylolallyloxyphenol, low polymerization degree phenolic novolak resin, epoxidized or butylated phenolic resin
Le resin or “Super Beckcite”1
001 (manufactured by Nippon Reichhold Chemical Industry Co., Ltd.), “H
itanol, 4010 (manufactured by Hitachi, Ltd.), Sc
ado formL. 9 (Netherlands Scado Z
Phenol resin known by trade names such as "Beckamine" P. 13
8 (manufactured by Nippon Reichhold Chemical Industry Co., Ltd.), "Melan" (manufactured by Hitachi, Ltd.), "U-Van" 10R (manufactured by Toyo Koatsu Kogyo Co., Ltd.), and other carbon resins known by trade names. ; Amino resin such as melamine resin, aniline resin; Formula H
S-(C2H4OCH2OC2H4SS)n'C2H4
Polysulfide resin having at least two mercapto groups in the molecule as shown by OCH2OC2H4SH (n': an integer of 1 to 10); phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, methyl Examples include organic acids such as nadic acid, dodecylsuccinic anhydride, and chlorendic anhydride, or their anhydrides.
【００３３】上述した硬化剤の中でも下記式（３）〜（
７）で示されるフェノール系樹脂は本発明の組成物に良
好な成形作業性（トランスファー成形、インジェクショ
ン成形等）を与え、ＩＣ，ＬＳＩ等の樹脂封止に用いた
場合、優れた耐熱製と高信頼性を与えると共に、毒性が
なく、しかも比較的安価であるので推奨される。Among the above-mentioned curing agents, the following formulas (3) to (
The phenolic resin shown in 7) gives the composition of the present invention good molding workability (transfer molding, injection molding, etc.), and when used for resin encapsulation of ICs, LSIs, etc., it has excellent heat resistance and high performance. It is recommended because it provides reliability, is non-toxic, and is relatively inexpensive.
【００３４】[0034]
【化４】
（上記式中、Ｒは上記と同様の意味を示し、ｎは１〜１
０の整数である。）これらの硬化剤は、その１種を単独
で又は硬化性能等に応じて２種類以上を併用して使用す
ることができ、その使用量は種類によって相違し、必ず
しも制限されるものではないが、一般には上記エポキシ
樹脂１００部に対して１〜１００部、特に５〜５０部の
範囲とすることが好ましい。１部未満の配合量ではエポ
キシ樹脂を良好に硬化させることが困難となる場合があ
り、一方１００部を超えると経済的に不利となるだけで
なく、エポキシ樹脂が希釈されて硬化に長時間を要する
ようになり、その上硬化物の物性が低下するという問題
が生じる場合がある。[Image Omitted] (In the above formula, R has the same meaning as above, and n is 1 to 1
It is an integer of 0. ) These curing agents can be used alone or in combination of two or more depending on the curing performance, etc., and the amount used varies depending on the type and is not necessarily limited. Generally, it is preferably in the range of 1 to 100 parts, particularly 5 to 50 parts, based on 100 parts of the epoxy resin. If the amount is less than 1 part, it may be difficult to cure the epoxy resin well, while if it exceeds 100 parts, not only will it be economically disadvantageous, but the epoxy resin will be diluted and it will take a long time to cure. In addition, there may be a problem that the physical properties of the cured product deteriorate.
【００３５】また、上述した本発明のアミノ基含有シリ
コーンエラストマー微粉末の配合量はエポキシ樹脂１０
０部に対し０．１〜５０部、特に１〜１０部の範囲とす
ることが好ましい。０．１部未満の配合量では十分な耐
衝撃性を与えない場合があり、一方５０部を超えて配合
すると機械的強度が低下する場合がある。Furthermore, the blending amount of the above-mentioned amino group-containing silicone elastomer fine powder of the present invention is 10% of the epoxy resin.
It is preferably in the range of 0.1 to 50 parts, particularly 1 to 10 parts. A blending amount of less than 0.1 part may not provide sufficient impact resistance, while a blending amount of more than 50 parts may reduce mechanical strength.
【００３６】本発明のエポキシ樹脂組成物には上述した
成分以外に無機質充填剤、硬化触媒、低応力化剤を配合
することができる。この場合、無機質充填剤は硬化物の
膨張係数を小さくし、半導体素子の封止に用いた場合に
は素子に加わる応力を低下させるためのものである。こ
のような無機質充填剤としては、破砕状、球状の形状を
持った溶融シリカ、結晶性シリカが主に用いられ、この
ほかにアルミナ、チッ化ケイ素、チッ化アルミニウム等
も使用可能である。なお、無機質充填剤の平均粒径とし
ては５〜２０μｍのものが好ましいが、硬化物の低膨張
化と成形性を両立させるためには球状と破砕品のブレン
ド、或いは球状品のみを用いた方がよい。In addition to the above-mentioned components, the epoxy resin composition of the present invention may contain an inorganic filler, a curing catalyst, and a stress reducing agent. In this case, the inorganic filler is used to reduce the coefficient of expansion of the cured product and, when used for sealing a semiconductor device, to reduce the stress applied to the device. As such an inorganic filler, fused silica or crystalline silica having a crushed or spherical shape is mainly used, and in addition to these, alumina, silicon nitride, aluminum nitride, etc. can also be used. Note that the average particle size of the inorganic filler is preferably 5 to 20 μm, but in order to achieve both low expansion and moldability of the cured product, it is recommended to use a blend of spherical and crushed products, or use only spherical products. Good.
【００３７】無機質充填剤の充填量はエポキシ樹脂と硬
化剤との合計量１００部に対し２００〜１６００部が好
ましく、２００部未満では膨張係数が大きくなり半導体
素子に加わる応力が増大し、素子特性の劣化を招く場合
がある。また、１６００部を超えると成形時の粘度が高
くなり成形性が悪くなる場合がある。The amount of the inorganic filler to be filled is preferably 200 to 1,600 parts per 100 parts of the total amount of the epoxy resin and curing agent. If it is less than 200 parts, the expansion coefficient becomes large and the stress applied to the semiconductor device increases, resulting in poor device characteristics. may lead to deterioration. Moreover, if it exceeds 1,600 parts, the viscosity during molding may increase and moldability may deteriorate.
【００３８】なお、この種の無機質充填剤は予めシラン
カップリング剤で表面処理して使用した方がよく、この
シランカップリング剤としては例えば次のようなものを
挙げることができる。[0038] It is better to use this type of inorganic filler after surface treatment with a silane coupling agent in advance, and examples of the silane coupling agent include the following.
【００３９】[0039]
【化５】
また、硬化触媒としては、イミダゾールもしくはその誘
導体、ホスフィン誘導体、シクロアミジン誘導体が代表
例として挙げられる。硬化触媒の配合量としてはエポキ
シ樹脂１００部に対し０．００１〜５部、好ましくは０
．１〜２部である。０．００１部以下では短時間で硬化
させることができない場合があり、５部を超えると硬化
速度が速すぎて良好な成形品が得られない場合がある。embedded image Typical examples of curing catalysts include imidazole or its derivatives, phosphine derivatives, and cycloamidine derivatives. The amount of curing catalyst blended is 0.001 to 5 parts, preferably 0.001 to 5 parts per 100 parts of epoxy resin.
．． 1 to 2 parts. If it is less than 0.001 part, it may not be possible to cure it in a short time, and if it exceeds 5 parts, the curing rate may be too fast and a good molded product may not be obtained.
【００４０】本発明のエポキシ樹脂組成物の硬化物に可
とう性を付与するための低応力化剤としては、シリコー
ン変性樹脂、メタクリル酸メチル−スチレン−ブタジエ
ン共重合体、スチレン−エチレン−ブテン−スチレン共
重合体等の熱可塑性樹脂を添加することができる。また
二液タイプのシリコーンゴムやシリコーンゲルで無機質
充填剤表面を処理したものを用いてもよい。中でも次式
で示されるシリコーン変性樹脂やシリコーン変性エポキ
シ樹脂あるいはスチレン−ブタジエン−メタクリル酸メ
チル共重合体がエポキシ樹脂の低応力化に効果がある。As the stress reducing agent for imparting flexibility to the cured product of the epoxy resin composition of the present invention, silicone modified resin, methyl methacrylate-styrene-butadiene copolymer, styrene-ethylene-butene- Thermoplastic resins such as styrene copolymers can be added. Alternatively, an inorganic filler surface treated with a two-component type silicone rubber or silicone gel may be used. Among them, silicone-modified resins, silicone-modified epoxy resins, and styrene-butadiene-methyl methacrylate copolymers represented by the following formulas are effective in reducing the stress of epoxy resins.
【００４１】[0041]
【化６】
（但し、式中Ｒ３は水素原子又はグリシジル基、ｔは０
以上の整数である。）なお、本発明の組成物には必要に
応じ、カルナバワックス、高級脂肪酸、合成ワックス類
等の離型剤、更にシランカップリング剤、酸化アンチモ
ン、リン化合物などを配合してもよい。[Formula 6] (However, in the formula, R3 is a hydrogen atom or a glycidyl group, and t is 0
is an integer greater than or equal to ) The composition of the present invention may contain release agents such as carnauba wax, higher fatty acids, and synthetic waxes, as well as silane coupling agents, antimony oxide, phosphorus compounds, and the like, as required.
【００４２】本発明の組成物は、上記した各成分を加熱
ロールによる溶融混練、ニーダーによる溶融混練、連続
押し出し機による溶融混練等で製造することができる。
なお、成分の配合順序に特に制限はない。The composition of the present invention can be produced by melt-kneading the above-mentioned components using heated rolls, a kneader, a continuous extruder, or the like. Note that there is no particular restriction on the order of blending the components.
【００４３】かくして得られる本発明のエポキシ樹脂組
成物はＤＩＰ型、フラットパック型、ＰＬＣＣ型、ＳＯ
型等の半導体パッケージに有効で、この場合、従来より
採用されている成形法、例えばトランスファー成形、イ
ンジェクション成形、注型法等を採用して行うことがで
きる。なお、本発明のエポキシ樹脂組成物の成形温度は
１５０〜１８０℃、ポストキュアーは１５０〜１８５℃
で２〜１６時間行うことが好ましい。The epoxy resin composition of the present invention thus obtained can be used in DIP type, flat pack type, PLCC type, SO
It is effective for semiconductor packages such as molds, and in this case, conventionally employed molding methods such as transfer molding, injection molding, and casting methods can be employed. The molding temperature of the epoxy resin composition of the present invention is 150 to 180°C, and the post-curing temperature is 150 to 185°C.
It is preferable to carry out the treatment for 2 to 16 hours.
【００４４】[0044]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に説明するが、本発明は下記実施例に制限されるもの
ではない。[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００４５】［実施例１］下記式[Example 1] The following formula
【００４６】[0046]
【化７】
で示される分子鎖末端に水酸基を有し、側鎖にアミノ基
を有するオルガノポリシロキサン１００部とメチルトリ
メトキシシラン２部との混合物３０部に界面活性剤とし
てＨＬＢが１３．５のポリオキシエチレンオクチルフェ
ニルエーテル１部を添加してホモミキサーで均一になる
まで混合分散した。ホモミキサーで分散しながらこれに
水６９部を加えて乳化分散し、更にこれを３００ｋｇ／
ｃｍ２の圧力でガウリンホモジナイザーを２回通して均
質化したところ、均一なオルガノポリシロキサンエマル
ジョンを得た。embedded image HLB of 13.5 as a surfactant was added to 30 parts of a mixture of 100 parts of an organopolysiloxane having a hydroxyl group at the end of the molecular chain and an amino group in the side chain and 2 parts of methyltrimethoxysilane. 1 part of polyoxyethylene octylphenyl ether was added and mixed and dispersed using a homomixer until uniform. While dispersing with a homomixer, add 69 parts of water to emulsify and disperse, and then add 300 kg/
A homogeneous organopolysiloxane emulsion was obtained by passing it twice through a Gaulin homogenizer at a pressure of cm 2 to obtain a homogeneous emulsion.
【００４７】また、ジオクチル錫ジラウレート３０部に
上記ポリオキシエチレンオクチルフェニルエーテル３部
を添加し、水６７部を用いて上述したと同様にホモミキ
サーとガウリンホモジナイザーで乳化分散したものを調
製し、この硬化性触媒エマルジョン５部を上記オルガノ
ポリシロキサンエマルジョンに添加し、２５℃で２０時
間撹拌しながら反応させたところ、体積平均粒径が２．
５μｍのシリコーンエラストマーエマルジョンが得られ
た。[0047] Also, 3 parts of the above polyoxyethylene octylphenyl ether was added to 30 parts of dioctyltin dilaurate, and emulsified and dispersed using a homomixer and a Gaulin homogenizer using 67 parts of water in the same manner as described above. When 5 parts of the curable catalyst emulsion was added to the above organopolysiloxane emulsion and reacted with stirring at 25°C for 20 hours, the volume average particle size was 2.
A 5 μm silicone elastomer emulsion was obtained.
【００４８】次いで、このエマルジョン１００部に硫酸
ナトリウム１０部を添加し、８５℃に加熱してエマルジ
ョン粒子を凝集、破壊した。このものを４００メッシュ
のフィルターを取り付けた遠心脱水機を用いて脱水して
ケーキ状とし、更にイオン交換水３００部を加えて撹拌
洗浄した後、同様に遠心脱水を行い、これを２回繰り返
して含水率約３０％のケーキ状物を得た。このケーキ状
物を熱風循環式の流動乾燥機（入口温度１００℃、出口
温度６０℃）を用いて乾燥し、含水率０．１％、トルエ
ン抽出分が２．２％のシリコーンエラストマー微粉末Ａ
を得た。Next, 10 parts of sodium sulfate was added to 100 parts of this emulsion and heated to 85° C. to coagulate and destroy the emulsion particles. This material was dehydrated using a centrifugal dehydrator equipped with a 400 mesh filter to form a cake, and after adding 300 parts of ion-exchanged water and washing with stirring, centrifugal dehydration was performed in the same manner, and this was repeated twice. A cake-like product with a moisture content of about 30% was obtained. This cake-like product was dried using a hot air circulation type fluidized dryer (inlet temperature 100°C, outlet temperature 60°C), and silicone elastomer fine powder A with a water content of 0.1% and a toluene extractable content of 2.2% was dried.
I got it.
【００４９】［実施例２］下記式[Example 2] The following formula
【００５０】[0050]
【化８】
で示される分子鎖両末端にメトキシ基を有し、側鎖にア
ミノ基を有するオルガノポリシロキサン１００部とメチ
ルトリメトキシシラン２部との混合物３０部を用いた以
外は実施例１と同様の方法で体積平均粒径が２．１μｍ
のシリコーンエラストマーエマルジョンを得た。次いで
、このエマルジョン１００部に硫酸ナトリウム１０部と
イソプロパノール２０部を加えて８５℃に加熱し、エマ
ルジョン粒子を凝集、破壊した。このものを実施例１と
同様に脱水、洗浄、乾燥を行って含水率０．２％、トル
エン抽出分が２．５％のシリコーンエラストマー微粉末
Ｂを得た。Example 1 except that 30 parts of a mixture of 100 parts of an organopolysiloxane having a methoxy group at both ends of the molecular chain and an amino group in the side chain and 2 parts of methyltrimethoxysilane was used. The volume average particle size was 2.1 μm using the same method as
A silicone elastomer emulsion was obtained. Next, 10 parts of sodium sulfate and 20 parts of isopropanol were added to 100 parts of this emulsion and heated to 85°C to coagulate and destroy the emulsion particles. This product was dehydrated, washed and dried in the same manner as in Example 1 to obtain silicone elastomer fine powder B having a water content of 0.2% and a toluene extractable content of 2.5%.
【００５１】［実施例３］下記式[Example 3] The following formula
【００５２】[0052]
【化９】
で示される分子鎖両末端にアルコキシ基を有し、側鎖に
アミノ基を有するオルガノポリシロキサン１００部とビ
ニルトリメトキシシラン３部との混合物３０部を用いた
以外は実施例１と同様の方法で体積平均粒子径が２．８
μｍのシリコーンエラストマーエマルジョンを得た。次
いでこのエマルジョン１００部に硫酸ナトリウム１０部
とイソプロパノール２０部とを加えて８５℃に加熱し、
エマルジョン粒子を凝集、破壊した。このものを実施例
１と同様に脱水、洗浄、乾燥を行って含水率０．２％、
トルエン抽出分が２．０％のシリコーンエラストマー微
粉末Ｃを得た。Example 1 except that 30 parts of a mixture of 100 parts of an organopolysiloxane having an alkoxy group at both ends of the molecular chain and an amino group in the side chain and 3 parts of vinyltrimethoxysilane was used. The volume average particle diameter is 2.8 using the same method as
A μm silicone elastomer emulsion was obtained. Next, 10 parts of sodium sulfate and 20 parts of isopropanol were added to 100 parts of this emulsion and heated to 85°C.
The emulsion particles were flocculated and destroyed. This material was dehydrated, washed, and dried in the same manner as in Example 1 to obtain a water content of 0.2%.
A silicone elastomer fine powder C having a toluene extractable content of 2.0% was obtained.
【００５３】［比較例１］分子鎖両末端がジメチルビニ
ルシロキシ基で封鎖された２５℃での粘度が４００ｃｓ
のジメチルポリシロキサン（≡ＳｉＣＨ＝ＣＨ２含有量
０．０１８５モル／１００ｇ）１００部に、分子鎖両末
端がトリメチルシロキシ基で封鎖された２５℃での粘度
が１７０ｃｓのメチルハイドロジェンポリシロキサン（
≡ＳｉＨ含有量０．７４５モル／１００ｇ）３部を配合
して混合し、≡ＳｉＨ基と≡ＳｉＣＨ＝ＣＨ２とのモル
比が１．２である組成物を調製した。次いで、この組成
物３０部に界面活性剤としてＨＬＢが１３．５のポリオ
キシエチレンオクチルフェニルエーテル１部を添加して
ホモミキサーで均一になるまで混合分散した。ホモミキ
サーで分散しながらこれに水６９部を加えて乳化分散し
、更にこれを３００ｋｇ／ｃｍ２の圧力で、ガウリンホ
モジナイザーを２回通して均質化してエマルジョンを得
た。次に、このエマルジョン１００部に塩化白金酸オレ
フィン錯塩を白金量として０．００１部を添加して２５
℃で２０時間撹拌しながら反応させたところ、体積平均
粒径が３．４μｍのシリコーンエラストマーエマルジョ
ンが得られた。[Comparative Example 1] Both ends of the molecular chain were blocked with dimethylvinylsiloxy groups, and the viscosity at 25°C was 400 cs.
To 100 parts of dimethylpolysiloxane (≡SiCH=CH2 content 0.0185 mol/100g) was added methylhydrogenpolysiloxane (≡SiCH=CH2 content 0.0185 mol/100g) with a viscosity of 170 cs at 25°C, in which both ends of the molecular chain were blocked with trimethylsiloxy groups.
3 parts of ≡SiH content: 0.745 mol/100 g) were blended and mixed to prepare a composition in which the molar ratio of ≡SiH groups to ≡SiCH=CH2 was 1.2. Next, 1 part of polyoxyethylene octylphenyl ether having an HLB of 13.5 was added as a surfactant to 30 parts of this composition, and the mixture was mixed and dispersed using a homomixer until the mixture became uniform. While dispersing with a homomixer, 69 parts of water was added to emulsify and disperse the mixture, which was then homogenized twice through a Gaulin homogenizer at a pressure of 300 kg/cm2 to obtain an emulsion. Next, 0.001 part of chloroplatinic acid olefin complex salt was added to 100 parts of this emulsion to give a total of 25 parts of platinum.
When the mixture was reacted for 20 hours with stirring at .degree. C., a silicone elastomer emulsion having a volume average particle size of 3.4 .mu.m was obtained.
【００５４】次いで、このエマルジョン１００部に硫酸
ナトリウム５部を添加して８５℃に加熱し、エマルジョ
ン粒子を凝集、破壊した。このものを実施例１と同様に
脱水、洗浄、乾燥を行って含水率０．１％、トルエン抽
出分が０．４％のシリコーンエラストマー微粉末Ｄを得
た。Next, 5 parts of sodium sulfate was added to 100 parts of this emulsion and heated to 85°C to coagulate and break the emulsion particles. This product was dehydrated, washed and dried in the same manner as in Example 1 to obtain silicone elastomer fine powder D having a water content of 0.1% and a toluene extractable content of 0.4%.
【００５５】［比較例２］下記式[Comparative Example 2] The following formula
【００５６】[0056]
【化１０】
で示される分子鎖両末端に水酸基を有するジメチルポリ
シロキサン１００部とメチルトリメトキシシラン２部と
の組成物３０部を用いた以外は実施例１と同様の方法で
体積平均粒子径が２．２μｍのシリコーンエラストマー
エマルジョンを得た。次いでこのエマルジョン１００部
に硫酸ナトリウム１０部を加え、８５℃に加熱してエマ
ルジョン粒子を凝集、破壊した。このものを実施例１と
同様に脱水、洗浄、乾燥を行って含水率０．２％、トル
エン抽出分が１．５％のシリコーンエラストマー微粉末
Ｅを得た。The volume average particle diameter was determined in the same manner as in Example 1 except that 30 parts of a composition of 100 parts of dimethylpolysiloxane having hydroxyl groups at both ends of the molecular chain and 2 parts of methyltrimethoxysilane were used. A silicone elastomer emulsion having a diameter of 2.2 μm was obtained. Next, 10 parts of sodium sulfate was added to 100 parts of this emulsion and heated to 85°C to coagulate and destroy the emulsion particles. This product was dehydrated, washed and dried in the same manner as in Example 1 to obtain silicone elastomer fine powder E having a water content of 0.2% and a toluene extractable content of 1.5%.
【００５７】［比較例３］比較例２に用いた分子鎖両末
端に水酸基を有するジメチルポリシロキサン１００部と
Ｈ２Ｎ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３１０部との混合
物３０部を用いた以外は実施例１と同様の方法で体積平
均粒子径が２．０μｍのシリコーンエラストマーエマル
ジョンを得た。次いでこのエマルジョン１００部に硫酸
ナトリウム１０部とイソプロパノール２０部を加え８５
℃に加熱してエマルジョン粒子を凝集破壊した。このも
のを実施例１と同様に脱水、洗浄、乾燥を行ったところ
、粒子の一部が凝集し、表面が粘着感のあるシリコーン
エラストマー微粉末Ｆが得られた。[Comparative Example 3] Example except that 30 parts of the mixture of 100 parts of dimethylpolysiloxane having hydroxyl groups at both ends of the molecular chain used in Comparative Example 2 and 310 parts of H2N(CH2)3Si(OCH3) was used. A silicone elastomer emulsion having a volume average particle diameter of 2.0 μm was obtained in the same manner as in Example 1. Next, 10 parts of sodium sulfate and 20 parts of isopropanol were added to 100 parts of this emulsion to make 85% of the emulsion.
The emulsion particles were cohesively broken by heating to .degree. When this material was dehydrated, washed, and dried in the same manner as in Example 1, a portion of the particles agglomerated to obtain silicone elastomer fine powder F with a sticky surface.
【００５８】これらの微粉末Ａ〜Ｆの一般特性を表１及
び表２に示すThe general properties of these fine powders A to F are shown in Tables 1 and 2.
【００５９】[0059]
【表１】[Table 1]
【００６０】[0060]
【表２】[Table 2]
【００６１】［実施例４〜９、比較例４〜６］次に、上
述のように得られたシリコーンエラストマー微粉末Ａ〜
Ｆを用い、エポキシ樹脂組成物を調製し、これらのエポ
キシ樹脂組成物について諸特性を測定した。[Examples 4 to 9, Comparative Examples 4 to 6] Next, the silicone elastomer fine powders A to 6 obtained as described above were
Epoxy resin compositions were prepared using F, and various properties of these epoxy resin compositions were measured.
【００６２】表３に示す成分に加え、ブロム化エポキシ
樹脂１０部、三酸化アンチモン１０部、溶融シリカ５０
０部、γ−グリシドキシプロピルトリメトキシシラン１
．５部、ワックスＥ１．５部、カーボンブラック１．０
部及びトリフェニルホスフィン０．８部を加えて得られ
た配合物を熱二本ロールで均一に溶融混練し、１０種の
エポキシ樹脂組成物を調製した。In addition to the components shown in Table 3, 10 parts of brominated epoxy resin, 10 parts of antimony trioxide, 50 parts of fused silica
0 parts, γ-glycidoxypropyltrimethoxysilane 1 part
．． 5 parts, wax E 1.5 parts, carbon black 1.0
and 0.8 parts of triphenylphosphine were uniformly melt-kneaded using two heated rolls to prepare 10 types of epoxy resin compositions.
【００６３】これらのエポキシ樹脂組成物について下記
の（イ）〜（ホ）の諸特性を測定した。結果を表３に併
記する。
（イ）スパイラルフロー
ＥＭＭＩ規格に準じた金型を使用して、１７５℃、７０
Ｋｇ／ｃｍ２の条件で測定した。
（ロ）機械的強度（曲げ強度、曲げ弾性率）ＪＩＳＫ６
９１１に準じて１７５℃、７０Ｋｇ／ｃｍ２、成形時間
２分の条件で１０×１００×４ｍｍの坑折棒を成形し、
１８０℃で４時間ポストキュアーしたもので測定した。
（ハ）ガラス転移温度、膨張係数
１７５℃、７０Ｋｇ／ｃｍ２、成形時間２分の条件で４
×４×１５ｍｍの試験片を成形し、１８０℃で４時間ポ
ストキュアーしたものを用い、ディラトメターにより毎
分５℃で昇温させることにより測定した。
（ニ）吸湿後の半田クラック性及び耐湿性１７５℃、７
０Ｋｇ／ｃｍ２、成形時間２分の条件でアルミニウム配
線腐食測定用の耐湿性試験用半導体装置を厚さ２ｍｍの
フラットパッケージに封止し、１８０℃で４時間ポスト
キュアーした。このパッケージを８５℃／８５％ＲＨの
雰囲気中７２時間放置して吸湿処理を行った後、これを
２６０℃の半田浴に１０秒浸漬した。この時に発生する
パッケージのクラック発生数を確認した後、良品のみを
１２０℃の飽和水蒸気雰囲気中に２００時間放置し、不
良発生率を調べた。
（ホ）耐クラック性
９．０×４．５×０．５ｍｍの大きさのシリコンチップ
を１４ＰＩＮ−ＩＣフレーム（４２アロイ）に接着し、
これにエポキシ樹脂組成物を成形条件１７５℃×２分で
成形し、１８０℃で４時間ポストキュアーした後、−１
９６℃×１分〜２６０℃×３０秒の熱サイクルを繰り返
して加え、１００サイクル後の樹脂クラック発生率を測
定した（試験数＝５０）。The following properties (a) to (e) were measured for these epoxy resin compositions. The results are also listed in Table 3. (a) Using a mold that complies with spiral flow EMMI standards, 175℃, 70℃
It was measured under the condition of Kg/cm2. (b) Mechanical strength (bending strength, bending modulus) JISK6
According to 911, a 10 x 100 x 4 mm drill rod was formed under the conditions of 175°C, 70 kg/cm2, and 2 minutes of forming time,
Measurements were made after post-curing at 180°C for 4 hours. (c) Glass transition temperature, expansion coefficient 175℃, 70Kg/cm2, molding time 2 minutes 4
A test piece of 4 x 15 mm was molded, post-cured at 180°C for 4 hours, and measured using a dilatometer at a rate of 5°C per minute. (d) Solder crack resistance and moisture resistance after moisture absorption 175°C, 7
A semiconductor device for moisture resistance testing for aluminum wiring corrosion measurement was sealed in a flat package with a thickness of 2 mm under conditions of 0 kg/cm 2 and a molding time of 2 minutes, and post-cured at 180° C. for 4 hours. This package was left in an atmosphere of 85° C./85% RH for 72 hours to perform moisture absorption treatment, and then immersed in a 260° C. solder bath for 10 seconds. After confirming the number of cracks that occurred in the package at this time, only the non-defective products were left in a saturated steam atmosphere at 120° C. for 200 hours, and the rate of failure occurrence was investigated. (e) Crack resistance A silicon chip with a size of 9.0 x 4.5 x 0.5 mm is glued to a 14PIN-IC frame (42 alloy).
An epoxy resin composition was molded onto this under molding conditions of 175°C x 2 minutes, and after post-curing at 180°C for 4 hours, -1
A heat cycle of 96° C. x 1 minute to 260° C. x 30 seconds was repeatedly applied, and the resin crack occurrence rate after 100 cycles was measured (number of tests = 50).
【００６４】[0064]
【表３】
基含有オルガノポリシロキサンとの付加反応生成物表３
の結果より、本発明のアミノ基含有シリコーンエラスト
マー微粉末を配合したエポキシ樹脂は、吸湿性が少なく
、かつ耐熱衝撃性が優れていることが認められる。
これに対しアミノ基を含有しないシリコーンエラストマ
ー微粉末Ｄ及びＥを配合したもの、アミノ基をオルガノ
ポリシロキサンではなくシラン化合物の方に有するもの
で得られたシリコーンエラストマー微粉末は吸湿性があ
り、熱衝撃性に劣ることが認められる。[Table 3] Addition reaction products with group-containing organopolysiloxane Table 3
From the results, it is recognized that the epoxy resin blended with the amino group-containing silicone elastomer fine powder of the present invention has low hygroscopicity and excellent thermal shock resistance. On the other hand, silicone elastomer fine powders obtained by blending silicone elastomer fine powders D and E that do not contain amino groups or having amino groups in the silane compound rather than the organopolysiloxane are hygroscopic and heat-absorbing. It is recognized that impact resistance is inferior.
【００６５】[0065]
【発明の効果】以上説明したように、本発明のアミノ基
含有シリコーンエラストマー微粉末は、表面にアミノ基
を有するのでエポキシ樹脂と強固な結合を形成し、エポ
キシ樹脂の耐衝撃性や強度を向上させることができるも
のであり、かかるアミノ基含有シリコーンエラストマー
微粉末を配合した本発明のエポキシ樹脂組成物は、成形
特性に優れ、かつ高ガラス転移温度を保持しながら、耐
湿性、耐クラック性、耐半田特性に優れた硬化物を与え
るもので、半導体パッケージ用として好適に使用される
ものである。Effects of the Invention As explained above, the amino group-containing silicone elastomer fine powder of the present invention has amino groups on the surface, so it forms a strong bond with the epoxy resin, improving the impact resistance and strength of the epoxy resin. The epoxy resin composition of the present invention blended with such amino group-containing silicone elastomer fine powder has excellent molding properties and maintains a high glass transition temperature while exhibiting moisture resistance, crack resistance, It provides a cured product with excellent solder resistance and is suitable for use in semiconductor packages.
Claims (2)
子結合のアミノ基含有有機基及び２個以上のケイ素原子
結合のヒドロキシ基又はアルコキシ基を有するオルガノ
ポリシロキサン、及び （Ｂ）下記一般式（１）で示される有機ケイ素化合物又
はその部分加水分解縮合物 ＲａＳｉ（ＯＲ１）４−ａ ・
・・・（１）（但し、式中Ｒは同種又は異種の非置換又
は置換一価炭化水素基、Ｒ１は水素原子又は炭素数１〜
６の一価炭化水素基、ａは０，１又は２である。）を主
成分とする組成物の水性エマルジョンの硬化物よりなる
アミノ基含有シリコーンエラストマー微粉末。Claim 1: (A) an organopolysiloxane having one or more silicon-bonded amino group-containing organic groups and two or more silicon-bonded hydroxy or alkoxy groups in one molecule, and (B) the following: Organosilicon compound represented by general formula (1) or its partially hydrolyzed condensate RaSi(OR1)4-a ・
... (1) (However, in the formula, R is the same or different unsubstituted or substituted monovalent hydrocarbon group, R1 is a hydrogen atom or a carbon number of 1 to
6 monovalent hydrocarbon group, a is 0, 1 or 2. ) A fine powder of an amino group-containing silicone elastomer, which is a cured product of an aqueous emulsion of a composition containing as a main component.
（ハ）請求項１記載のアミノ基含有シリコーンエラスト
マー微粉末を主成分とするエポキシ樹脂組成物。Claim 2: (a) epoxy resin, (b) curing agent,
(c) An epoxy resin composition containing the amino group-containing silicone elastomer fine powder according to claim 1 as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047426A JP2508550B2 (en) | 1991-02-21 | 1991-02-21 | Method for producing fine powder of silicone elastomer containing amino group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047426A JP2508550B2 (en) | 1991-02-21 | 1991-02-21 | Method for producing fine powder of silicone elastomer containing amino group |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23026694A Division JP2671819B2 (en) | 1994-08-31 | 1994-08-31 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04266928A true JPH04266928A (en) | 1992-09-22 |
| JP2508550B2 JP2508550B2 (en) | 1996-06-19 |
Family
ID=12774833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3047426A Expired - Fee Related JP2508550B2 (en) | 1991-02-21 | 1991-02-21 | Method for producing fine powder of silicone elastomer containing amino group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2508550B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002356617A (en) * | 2001-05-30 | 2002-12-13 | Asahi Denka Kogyo Kk | Curable composition |
| JP2007119568A (en) * | 2005-10-27 | 2007-05-17 | Shin Etsu Chem Co Ltd | Manufacturing method of high molecular weight organopolysiloxane, composition comprising high molecular weight organopolysiloxane, and optical semiconductor apparatus sealed with cured product thereof |
| WO2008142997A1 (en) | 2007-05-16 | 2008-11-27 | Dow Corning Toray Co., Ltd. | Curable epoxy resin composition and cured body thereof |
| WO2008142998A1 (en) * | 2007-05-16 | 2008-11-27 | Dow Corning Toray Co., Ltd. | Cross-linked silicone particles and method of manufacturing thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61168619A (en) * | 1985-01-21 | 1986-07-30 | Nippon Zeon Co Ltd | Production of epoxy resin composition for semiconductor sealing |
| JPS62127348A (en) * | 1985-11-27 | 1987-06-09 | Shin Etsu Chem Co Ltd | Room-temperature curing silicone rubber composition |
| JPH02240142A (en) * | 1989-01-19 | 1990-09-25 | Rhone Poulenc Chim | Manufacture of non-tacky particle based on organopolysiloxane composition crosslinked by polycondensation reaction |
-
1991
- 1991-02-21 JP JP3047426A patent/JP2508550B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61168619A (en) * | 1985-01-21 | 1986-07-30 | Nippon Zeon Co Ltd | Production of epoxy resin composition for semiconductor sealing |
| JPS62127348A (en) * | 1985-11-27 | 1987-06-09 | Shin Etsu Chem Co Ltd | Room-temperature curing silicone rubber composition |
| JPH02240142A (en) * | 1989-01-19 | 1990-09-25 | Rhone Poulenc Chim | Manufacture of non-tacky particle based on organopolysiloxane composition crosslinked by polycondensation reaction |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002356617A (en) * | 2001-05-30 | 2002-12-13 | Asahi Denka Kogyo Kk | Curable composition |
| JP2007119568A (en) * | 2005-10-27 | 2007-05-17 | Shin Etsu Chem Co Ltd | Manufacturing method of high molecular weight organopolysiloxane, composition comprising high molecular weight organopolysiloxane, and optical semiconductor apparatus sealed with cured product thereof |
| WO2008142997A1 (en) | 2007-05-16 | 2008-11-27 | Dow Corning Toray Co., Ltd. | Curable epoxy resin composition and cured body thereof |
| WO2008142998A1 (en) * | 2007-05-16 | 2008-11-27 | Dow Corning Toray Co., Ltd. | Cross-linked silicone particles and method of manufacturing thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2508550B2 (en) | 1996-06-19 |
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