JPH0588864B2 - - Google Patents
Info
- Publication number
- JPH0588864B2 JPH0588864B2 JP11614186A JP11614186A JPH0588864B2 JP H0588864 B2 JPH0588864 B2 JP H0588864B2 JP 11614186 A JP11614186 A JP 11614186A JP 11614186 A JP11614186 A JP 11614186A JP H0588864 B2 JPH0588864 B2 JP H0588864B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- epoxy resin
- acrylate
- resin
- vinyl polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 claims description 59
- 229920000647 polyepoxide Polymers 0.000 claims description 59
- 229920002554 vinyl polymer Polymers 0.000 claims description 37
- 239000011342 resin composition Substances 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 12
- 238000005538 encapsulation Methods 0.000 claims description 10
- 229920000578 graft copolymer Polymers 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- -1 polypropylene Polymers 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 14
- 239000000178 monomer Substances 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 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 10
- 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 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 239000004843 novolac epoxy resin Substances 0.000 description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000005350 fused silica glass Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000004203 carnauba wax Substances 0.000 description 5
- 235000013869 carnauba wax Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 5
- 239000010680 novolac-type phenolic resin Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- RSNDTPFSMDVWCS-UHFFFAOYSA-N 2-(butoxymethyl)prop-2-enamide Chemical group CCCCOCC(=C)C(N)=O RSNDTPFSMDVWCS-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- MRIKSZXJKCQQFT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) prop-2-enoate Chemical compound OCC(C)(C)COC(=O)C=C MRIKSZXJKCQQFT-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 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 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- ZAFBPXUQKNWAEZ-UHFFFAOYSA-N (3-chloro-3-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(O)Cl ZAFBPXUQKNWAEZ-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- QEZDYNRKJXCIFE-WAYWQWQTSA-N (z)-3-carbonoperoxoylhept-2-enoic acid Chemical group CCCC\C(=C\C(O)=O)C(=O)OO QEZDYNRKJXCIFE-WAYWQWQTSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical group C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- UJXFNIQSAHCTTA-UHFFFAOYSA-N 1-butylperoxyhexane Chemical group CCCCCCOOCCCC UJXFNIQSAHCTTA-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical group CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical group CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical group OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- RTTAGBVNSDJDTE-UHFFFAOYSA-N 4-ethoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCOC(=O)CC(=C)C(O)=O RTTAGBVNSDJDTE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N para-hydroxystyrene Natural products OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
〔産業上の利用分野〕
本発明は、低弾性率、低熱膨張率で、なおかつ
耐熱性を損なうことなく、耐熱衝撃性に優れた高
信頼性を要求される半導体等電子部品の封止用に
適した半導体封止用樹脂組成物に関するものであ
る。
〔従来の技術〕
近年、半導体を封止する方法としてエポキシ樹
脂に代表される熱硬化性樹脂を使用したいわゆる
プラスチツク封止が原料の低廉、大量生産に適す
るといつた経済的利点をいかして広く実用化され
ている。特に多官能エポキシ樹脂、ノボラツク型
フエノール樹脂、無機質充填材を主成分とした樹
脂組成物が耐熱性、成形性、電気特性に優れてい
るため封止樹脂の主流となつている。
〔発明が解決しようとする問題点〕
一方、半導体チツプの高集積化が進み、それに
伴いチツプサイズが大型化してきた。またパツケ
ージの形状は基板への高密度実装化に伴い、チツ
プの大型化とは逆にフラツトパツケージに見られ
る如く小型化・薄型化の傾向にある。このため従
来の封止樹脂では見られなかつた不良現象が派生
するようになつた。すなわち、封止樹脂とチツプ
の熱膨張率の差に起因する樹脂の応力がチツプの
大型化、樹脂層の薄肉化のため、熱衝撃によりパ
ツシベーシヨン膜のクラツク、あるいは封止樹脂
のクラツクといつた破壊現象を引き起こし、半導
体の耐湿性を低下させ、ひいては信頼性を低下さ
せる原因となつている。従つて、封止樹脂として
はこの応力の小さい封止樹脂の開発が望まれてい
る。
応力を小さくする方法としては、樹脂の熱膨張
率を小さくしてチツプのそれとの差を小さくする
事が考えられるが、樹脂の熱膨張率とチツプのそ
れとの差は大きく、これを縮めるためには熱膨張
率の小さい無機質充填材を樹脂中に多量に使用し
なければならないが、現在すでにかなり多量の無
機質充填材が使用されていて、更にこれを増量す
る事は成形性の悪化の原因となる。一方、樹脂の
弾性率を下げて応力を小さくするという目的で可
塑材を添加したり、可撓性を有したエポキシ樹脂
あるいはフエノール樹脂を用いたりする事試みら
れたが、この方法により得られた硬化物は耐熱性
の点で問題があつた。
また特開昭58−108220に代表される如くゴム粒
子を封止樹脂中に分散させる事により耐熱性を保
持しつつ、耐クラツク性を付与する方法等も発明
されているが、これらの方法では金型汚染、ある
いは半田浴の如き封止樹脂のガラス転移温度を超
える高温における耐衝撃性に劣る等いくつかの問
題点があつた。金型汚染が激しいと金型の清掃を
煩雑に行わなければならず、生産性が低下する
為、極めて不都合である。また高温の熱衝撃性に
劣る場合は、ハンダデイツプ後の信頼性が低下す
るが、これはIC等の封止材料においては致命的
な欠陥となる。
本発明は、高集積回路等の高い信頼性を要求さ
れる半導体の封止用樹脂に対して要求されている
応力が小さく耐熱衝撃性等に優れ、また成形時に
おける金型汚染のない半導体封止用樹脂組成物を
提供することを目的とする。
〔問題点を解決するための手段〕
本発明者等は、種々検討した結果、アクリル酸
エステル類を主成分とする軟質ビニル重合体の微
粒子を樹脂組成物中に均一に分散させる事が有効
であることを見出し、更にビニル重合体組成及び
粒子径等について検討を加えた結果本発明に達し
た。即ち本発明は、
a エポキシ樹脂とビニルポリマーとのグラフト
重合体中に炭素数4以上のアルキル基を持つア
ルキルアクリレートを主体とする軟質ビニール
重合体が0.5μ以下の粒子径で均一に分散された
変性エポキシ樹脂、
b 硬化剤、
c 無機充填剤、および必要に応じ
d エポキシ樹脂、
を主成分とすることを特徴とする半導体封止用樹
脂組成物である。
本発明のa)に使用されるエポキシ樹脂は多価
エポキシ樹脂であれば一般的に使用されるエポキ
シ樹脂が使用可能であり、耐熱性、電気特性から
フエノールノボラツク、クレゾールノボラツクな
どのグリシジル化物等のノボラツクエポキシ樹脂
が好ましいが、その他の1分子に2ケ以上の活性
水素を有する化合物、例えばビスフエノールA、
ビスヒドロキシジフエニルメタン、レゾルシン、
ビスヒドロキシジフエニルエーテル、テトラブロ
ムビスフエノールA等の多価フエノール類、エチ
レングリコール、ネオペンチルグリコース、グリ
セリン、トリメチロールプロパン、ペンタエリス
リトール、ジエチレングリコール、ポリプロピレ
ングルコース、ビスフエノールA−エチレンオキ
サイド付加物、トリスヒドロキシエチルイソシア
ヌレート等の多価アルコール、エチレンジアミ
ン、アニリン等のポリアミノ化合物、アジピン
酸、フタル酸、イソフタル酸等の多価カルボキシ
化合物等とエピクロルヒドリン又は2−メチルエ
ピクロルヒドリンを反応させて得られるグリシジ
ル型のエポキシ樹脂、ジシクロペンタジエンジエ
ポキサイド、ブタジエンダイマージエポキサイド
等の如き脂肪族(脂環族を含む)のエポキシ樹脂
などから選ばれた1種以上のエポキシ樹脂を使用
することが出来る。
本発明のa)に於けるエポキシ樹脂とビニルポ
リマーとのグラフト重合体は、エポキシ樹脂の存
在下に前記ビニルポリマーを生成させるべくビニ
ルモノマーを重合する事により製造する方法が代
表的である。ここでグラフト重合体なる語は通常
ブロツク重合体と呼ぶものを含む。ここでビニル
ポリマーをつくるために用いるビニルモノマーと
しては、スチレン、ビニルトルエン等の如きアル
ケニル芳香族類、メチルメタクリレート、ドデシ
ルメタクリレート、ブトキシエチルメタクリレー
ト、グリシジルメタクリレート、メチルアクリレ
ート、ブチルアクリレート、2−エチルヘキシル
アクリレート、ヒドロキシエチルアクリレート、
トリメチロールプロパントリアクリレート等の如
きアクリルエステル類、アクリルニトリル、アク
リル酸、ブトキシメチルアクリルアミド、メタク
リルアミド等の如きエステル基を持たないアクリ
ル化合物、ビニルアセテート、ビニルラウレー
ト、ビニルバーサテート、ビニルクロライド、ビ
ニルデンクロライド、エチレン、アクリルアセテ
ート等の如き非共役性ビニル化合物、ブタジエ
ン、イソプレン、クロロプレンの如き共役ジエン
化合物が代表的で、その他、ジブチルフマレー
ト、モノメチルマレート、ジエチルイタコネート
等の如き重合性ビニル化合物を用いることもでき
る。前記したビニルモノマーを重合してビニルポ
リマーとするには、通常ラジカル開始剤、例えば
ラウロイルパーオキサイド、ベンゾイルパーオキ
サイド、ターシヤリブチルパーベンゾエート、ジ
メチルジベンゾイルパーオキシヘキサン、ターシ
ヤリブチルパーピバレート、ジターシヤリブチル
パーオキサイド、1,1−ビスターシヤリブチル
パーオキシ3,3,5−トリメチルシクロヘキサ
ン、ジメチルジターシヤリブチルパーオキシヘキ
サン、ターシヤリブチルクミルパーオキサイド、
メチルエチルケトンパーオキサイド、シクロヘキ
サノンパーオキサイド、キユメンハイドロパーオ
キサイド、ターシヤリブチルパーオキシアリルカ
ーボネート、ジオクチルパーオキシジカーボネー
ト、ターシヤリブチルパーオキシマレイン酸、琥
珀酸パーオキサイド、ターシヤリブチルパーオキ
シイソプロピルカーボネート、過酸化水素の如き
パーオキサイド、アゾビスイソブチロニトリル、
アゾビスジメチルバレロニトリルの如きアゾ化合
物を用いてラジカル重合するのが代表的である。
又、必要に応じて還元剤を併用していわゆるレ
ドツクス重合をさせてもよく、ハイドロキノンの
如き重合禁止剤、ドデシルメルカプタンの如き連
鎖移動剤を使用してもよい。
又、グラフト化促進の為に、エポキシ樹脂に重
合性2重結合やグラフト可能な化学結合を導入し
ておく方法が有効である。重合性2重結合の導入
方法には、例えばアクリル酸、アクリルアミド、
メチロールアクリルアミド、ブトキシメチルアク
リルアミド、ヒドロキシエチルメタアクリレー
ト、グリシジルメタクリレート、無水マレイン
酸、モノエチルイタコネート、モノブチルフマレ
ート、クロルメチルスチレン、ホスホキシエチル
メタアクリレート、クロルヒドロキシプロピルメ
タアクリレート、パラヒドロキシスチレン、ジメ
チルアミノエチルメタクリレートの如き官能基と
重合性2重結合とを有する化合物を、エポキシ樹
脂とあらかじめ反応させておく方法が代表的であ
る。
なお、本発明に於いて前記グラフト重合体中に
は前記エポキシ樹脂や前記ビニルポリマーがグラ
フトしないでフリーのまま残つていてもかまわな
い。
a)の変性エポキシ樹脂は前記したエポキシ樹
脂とビニルポリマーとのグラフト重合体の存在下
に軟質系ビニル重合体を形成するモノマーを常法
により重合することにより得られる。本発明に使
用される軟質系ビニル重合体は炭素数4以上、好
ましくは20以下のアルキル基を有するアクリレー
トを主体とする重合体でなければならない。炭素
数4未満のアルキルアクリレートを主体とする重
合体では、得られる軟質ビニル系重合体の粒子径
は0.5μmを越えて、本発明の目的である低応力を
果たせず、耐熱衝撃性も改良されない。炭素数4
以上のアルキル基を持つアルキルアクリレートを
主体とする軟質ビニル系重合体とは例えばブチル
アクリレート、2−エチルヘキシルアクリレー
ト、オクチルアクリレート、デシルアクリレー
ト、ラウリルアクリレート、トリデシルアクリレ
ート、ミリスチルアクリレート、セチルアクリレ
ート等の1種以上を主体とする重合体であり、こ
れらのアクリレートと共重合可能な単量体を共重
合させることも可能であるが、その使用割合は得
られる共重合体が軟質、すなわち液上ないしゴム
上でありかつその粒子径が0.5μ以下である範囲で
あり、そのモノマー種類によるが、通常全モノマ
ー中80重量%以下である。これらの単量体として
は特に限定はしないが、例えばメチルアクリレー
ト、エチルアクリレート、プロピルアクリレート
等のアクリレート、炭素数1〜24のアルキル基を
有するアルキルメタクリレート、シクロヘキシル
アクリレート、ベンジルアクリレート、フエノキ
シエチルアクリレート、フエノキシジエチレング
リコールアクリレート、テトラヒドロフルフリル
アルコールアクリレート、イソボロニルアクリレ
ート、ジシクロペンタジエニルアクリレート、ヒ
ドロキシエチルアクリレート、ヒドロキシエチル
メタクリレート、ヒドロキシプロピルアクリレー
ト、グリシジルメタクリレート、1,6−ヘキサ
ングリコールジアクリレート、ネオペンチルグリ
コールジアクリレート、ポリプロピレングリコー
ルジアクリレート、トリメチロールプロパントリ
アクリレート等の各種のアクリル酸、メタクリル
酸、エステル酸、アクリルニトリル、アクリル
酸、ブトキシメチルアクリルアミド、メタアクリ
ルアミド等の如きエステル基を持たないアクリル
化合物、ビニルアセテート、ビニルラウレート、
ビニルバーサテート、ビニルクロライド、ビニル
デンクロライド、エチレン、アリルアセテート等
の如き非共役性ビニル化合物、ブタジエン、イソ
プレン、クロロプレンの如き共役ジエン化合物が
代表的で、その他、ジブチルフマレート、モノエ
チルマレエート、ジエチルイタコネート等の如き
重合性ビニル化合物を用いることが出来る。
前述した様に変性エポキシ樹脂はエポキシ樹脂
とビニルポリマーのグラフト重合体の存在下で軟
質系ビニル重合体を形成するモノマーを常法によ
り重合することにより、軟質系ビニル重合体がほ
ぼ球状に分散した組成物として得られるが、その
粒径はビニルポリマーの種類、軟質ビニル重合体
の種類により差異があるが、粒径が0.5μを越えた
場合には本発明の目的を達することが出来ず、本
発明の目的である低応力を果たし、耐衝撃性を改
良する為には0.5μ以下、好ましくは0.2μ以下0.01μ
以上の粒径でなければならない。軟質系ビニル重
合体の粒径コントロールについては、エポキシ樹
脂とグラフト重合体を形成するビニルポリマーの
種類、軟質ビニル重合体を形成するモノマー組成
の選択によるが、エポキシ樹脂に導入する二重結
合の量によつてもコントロールする事ができる。
本発明の組成物は所望によりd)としてエポキ
シ樹脂を含有していてもよい。d)のエポキシ樹
脂としては前述のa)において使用するエポキシ
樹脂が総て使用でき、両者は同じでもよく、異な
つていても差し支えない。
又、軟質系ビニル重合体はa)及びd)に使用
されるエポキシ樹脂の合計に対して5重量%以上
必要であり特に10〜20重量%が好ましい。5重量
%未満では低応力化が達成されない。又、20重量
%を超えると強度の低下が著しい実用に供し難
い。
上記の軟質系ビニル重合体を所望の量に調節す
るにはa)の変性エポキシ樹脂を製造する差異に
使用するビニルモノマーの量を調節してもよい
が、d)のエポキシ樹脂の量を変化させることに
より行うのがより簡単で、このような点からも
d)のエポキシ樹脂を併用するのが好ましい。
本発明に用いられるb)の硬化剤としては、フ
エノール、アルキルフエノール等のフエノール類
とホルムアルデヒドあるいはパラホルムアルデヒ
ドを反応させて得られるノボラツク型フエノール
樹脂が一般的であるが、その他に変性ノボラツク
型フエノール樹脂、アラルキル系のフエノール樹
脂及び一般的に用いられるアミン系硬化剤や酸無
水物等を単独または混合して使用する事ができ
る。その配合量については特に制限はないが、エ
ポキシ樹脂のエポキシ基と硬化剤の官能基の化学
論量が好ましい。
本発明に用いられるc)の無機質充填材として
は例えば結晶性シリカ、溶融シリカ、アルミナ、
タルク、ケイ酸カルシウム、炭酸カルシウム、マ
イカ、クレー、チタンホワイト等の粉耐、あるい
はガラス繊維、炭素繊維の単独または混合物が挙
げられるが、熱膨張率、熱伝導率等の点から通常
は結晶性、溶融性等のシリカ粉末が用いられる。
その配合量は上記エポキシ樹脂100重量部に対し
て200〜800重量部が好ましく、200重量部未満で
は熱膨張率が大きく、良好な耐衝撃性は得られな
い。また800重量部を超えると樹脂の流動性が低
下し成形性が悪く実用に供し難い。
本発明の半導体封止用樹脂組成物はa)エポキ
シ樹脂とビニルポリマーとのグラフト重合体中に
炭素数4以上のアルキル基を持つアルキルアクリ
レートを主体とする軟質ビニル重合体が0.5μ以下
の粒子径で均一に分散された変性エポキシ樹脂、
b)硬化材、c)無機質充填剤、および必要に応
じてd)エポキシ樹脂、を主成分とするが実用に
際してはイミダゾール類、三級アミン類、フエノ
ール類、有機金属化合物類、有機ホスフイン類等
の硬化促進剤、脂肪酸アミド、脂肪酸塩、ワツク
ス等の離型剤、プロム化合物、アンチモン、リン
等の難燃剤、カーボンブラツク等の着色剤、シラ
ンカツプリング剤等を適宜配合することも可能で
ある。
本発明の半導体封止用樹脂組成物は、ミキサー
等によつて十分プレミツクスした後、熱ロール、
あるいはニーダーの如き溶融混合機で混練し、次
いで冷却粉砕を行うことにより、成形材料として
容易に得ることが出来る。
このようにして得られた本発明の半導体封止用
樹脂組成物は弾性率が低く、熱膨張率が小さく、
優れた耐熱衝撃性を示すことから、この樹脂組成
物を集積度の高い半導体、あるいはフラツトパツ
ケージの如き小型・薄型の半導体の封止に用いた
場合、優れた信頼性を得ることが出来る。また、
成型時における金型汚染がなく、長時間の連続生
産に適している。
〔実施例〕
本発明を実施例によつて具体的に説明するが、
本発明は実施例に限定されるものではない。以下
において部は特記せぬ限り重量部を意味する。
実施例 1
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸1部を3級アミンの存在下で120〜125℃で2
時間反応させた後、ブチルアクリレート3.6部、
グリシジルメタクリレート0.1部、t−ブチルパ
ーオキシ2−エチルヘキサノエート0.05部を100
℃で1時間反応させる。さらにブチルアクリレー
ト30部、ネオペンチルグリコールジアクリレート
0.6部、1,1−ビス(t−ブチルパーオキシ)
3,3,5−トリシクロヘキサン0.15部を連続滴
下しながら4時間、その後更に4時間反応させた
後、減圧にて脱溶剤し、変性エポキシ樹脂(A)(エ
ポキシ当量285)を得た。
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)56部、変性エポキシ樹脂(A)44部、
ノボラツク型フエノール樹脂(フエノール当量
106)41部、トリフエニルホスフイン0.85部、あ
らかじめシランカツプリング剤で処理した溶融シ
リカ400部、カーボンブラツク2部、カルナバワ
ツクス2.5部をミキサーで混合し、更に80〜90℃
の熱ロールにて3分間溶融混合後、冷却粉砕し、
成形用樹脂組成物を得た。
この組成物を用い、トランスフア成形(175℃、
30Kg/cm2、3分間)により物性試験用の試験片及
び熱衝撃試験用の16pin DIP(4×8m/mの素
子搭載)を得た。これらの試験片は成形後175℃
で4時間の後硬化を行つた後、各種試験を行つ
た。
実施例 2
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸0.6部を三級アミン存在下で120〜125℃で2
時間反応させた後、2−エチルヘキシルアクリレ
ート3.6部、グリシジルメタクリレート0.1部、t
−ブチルパーオキシ2−エチルヘキサノエート
0.05部を100℃で1時間反応させる。更に2−エ
チルヘキシルアクリレート30部、グリシジルメタ
クリレート0.4部、ネオペンチルグリコールアク
リレート0.4部、1,1−ビス(t−ブチルパー
オキシ)3,3,5−トリシクロヘキサン0.15部
を連続滴下しながら4時間、その後更に4時間反
応させた後、減圧にて脱溶剤し変性エポキシ樹脂
(B))(エポキシ当量297)を得た。
上記変性エポキシ樹脂を用い、以下実施例1と
同様にして各種試験を行つた。
実施例 3
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸1部を三級アミン存在下で120〜125℃で2時
間反応させた後、2−エチルヘキシルアクリレー
ト3.6部、グリシジルメタクリレート0.1部、t−
ブチルパーオキシ2−エチルヘキサノエート0.05
部を100℃で1時間反応させる。更に2−エチル
ヘキシルアクリレート30部、グリシジルメタクリ
レート0.4部、ネオペンチルグリコールアクリレ
ート0.4部、1,1−ビス(t−ブチルパーオキ
シ)3,3,5−トリシクロヘキサン0.15部を連
続滴下しながら4時間、その後更に4時間反応さ
せた後、減圧にて脱溶剤し変性エポキシ樹脂(C))
(エポキシ当量296)を得た。
上記変性エポキシ樹脂を用い、以下実施例1と
同様にして各種試験を行つた。
実施例 4
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸0.9部を三級アミン存在下で120〜125℃で2
時間反応させて後、ラウリルアクリレート3.6部、
グリシジルメタクリレート0.1部、t−ブチルパ
ーオキシ2−エチルヘキサノエート0.05部を100
℃で1時間反応させる。更にラウリルアクリレー
ト30部、グリシジルメタクリレート0.4部、ネオ
ペンチルグリコールジアクリレート0.6部、1,
1−ビス(t−ブチルパーオキシ)3,3,5−
トリシクロヘキサン0.15部を連続滴下しながら4
時間、その後更に4時間反応させた後、減圧にて
脱溶剤し変性エポキシ樹脂(D)(エポキシ当量305)
を得た。
上記変性エポキシ樹脂を用い、以下実施例1と
同様にして各種試験を行つた。
実施例 5
実施例3の成形用樹脂組成物の製造にあたつ
て、オルソクレゾールノボラツクエポキシ樹脂の
量を13部に、変性エポキシ樹脂(B)の量を87部に変
更した以外は実施例3と同様にして行つた。
実施例 6
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸0.4部を3級アミンの存在下で120〜125℃で
2時間反応させた後、2−エチルヘキシルアクリ
レート1.3部、t−ブチルパーオキシ2−エチル
キサノエート0.02部を100℃で1時間反応させる。
更に、2−エチルヘキシルアクリレート11部、ネ
オペンチルグリコールジアクリレート0.2部、1,
1−ビス(t−ブチルパーオキシ)3,3,5−
トリシクロヘキサン0.06部を連続滴下しながら4
時間、その後更に4時間反応させた後、減圧にて
脱溶剤し、変性エポキシ樹脂(G)(エポキシ当
量245)を得た。
上記変性エポキシ樹脂100部、ノボラツク型フ
エノール樹脂(フエノール当量106)43部、トリ
フエニルホスフイン0.85部、予めシランカツプリ
ング剤で処理した溶融シリカ400部、カーボンブ
ラツク2部、カルナバワツクス2.5部を実施例1
と同様にして成形用樹脂組成物を得、更に試験片
を作成した。各試験を行つた。
比較例 1
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、ノボラツク型フエノール
樹脂(フエノール当量106)49部、トルフエニル
ホスフイン0.85部、あらかじめシランカツリング
剤で処理した溶融シリカ412部、カーボンブラツ
ク2部、カルナバワツクス2.5部をミキサーで混
合し、更に80〜90℃の熱ロールにて3分間溶融混
合後、冷却粉砕した成形用樹脂組成物を得た。
この組成物を用い、トランスフア成形(175℃、
30Kg/cm2、3分間)により物性試験用の試験片お
よび熱衝撃試験用の16pin DIP(4×8m/mの
素子搭載)を得た。これらの試験片は成形後、
175℃、4時間の後硬化を行つた後、各試験片を
行つた。
比較例 2
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸0.9部を三級アミン存在下で120〜125℃、2
時間反応させて後、エチルアクリレート3.6部、
グリシジルメタクリレート0.1部、t−ブチルパ
ーオキシ2−エチルヘキサノエート0.05部を100
℃で1時間反応させる。更にエチルアクリレート
30部、グリシジルメタクリレート0.4部、ネオペ
ンチルグリコールジアクリレート0.6部、1,1
−ビス(t−ブチルパーオキシ)3,3,5−ト
リシクロヘキサン0.15部を連続滴下しながら4時
間、その後更に4時間反応させた後、減圧にて脱
溶剤し変性エポキシ樹脂(E)(エポキシ当量298)
を得た。
上記変性エポキシ樹脂を用い、以下実施例1と
同様にして各種試験を行つた。
比較例 3
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)100部、トルエン10部、メタクリ
ル酸0.5部を三級アミン存在下で120〜125℃、2
時間反応させて後、ブチルアクリレート3.6部、
グリシジルメタクリレート0.1部、t−ブチルパ
ーオキシ2−エチルヘキサノエート0.05部を100
℃で1時間反応させる。更にブチルアクリレート
30部、グリシジルメタクリレート0.4部、ネオペ
ンチルグリコールジアクリレート0.6部、1,1
−ビス(t−ブチルパーオキシ)3,3,5−ト
リシクロヘキサン0.15部を連続滴下しながら4時
間、その後更に4時間反応させた後、減圧にて脱
溶剤し変性エポキシ樹脂(F)(エポキシ当量306)
を得た。
上記変性エポキシ樹脂を用い、以下実施例1と
同様にして各種試験を行つた。
比較例 4
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)90部、ビスフエノールAジグリ
シジルエーテル(エポキシ当量190)10部、ノボ
ラツク型フエノール樹脂(フエノール当量106)
49部、トリフエニルホスフイン0.85部、あらかじ
めカツプリング剤で処理した溶融シリカ412部、
カーボンブラツク2部、カルナバワツクス2.5部
を実施例1と同様にして成形用樹脂組成物を得、
更に試験片を作成、各試験を行つた。
比較例 5
オルソクレゾールノボラツクエポキシ樹脂(エ
ポキシ当量217)90部、スチレンブタジエンゴム
10部、ノボラツク型フエノール樹脂(フエノール
当量106)44部、トリフエニルホスフイン0.85部、
予めカツプリング剤で処理した溶融シリカ400部、
カーボンブラツク2部、カルナバワツクス2.5部
を実施例1と同様にして成形用樹脂組成物を得、
更に試験片を作成、各試験を行つた。
以上の実施例及び比較例の内容を第1表、試験
結果を第2表に示す。
[Industrial Application Field] The present invention is suitable for encapsulating electronic components such as semiconductors that require high reliability with low elastic modulus and low thermal expansion coefficient and excellent thermal shock resistance without impairing heat resistance. The present invention relates to a resin composition suitable for semiconductor encapsulation. [Prior art] In recent years, so-called plastic encapsulation, which uses thermosetting resins such as epoxy resins, has become widely used as a method for encapsulating semiconductors, taking advantage of its economic advantages such as low raw materials and suitability for mass production. It has been put into practical use. In particular, resin compositions containing polyfunctional epoxy resins, novolac type phenolic resins, and inorganic fillers as main components have become mainstream as sealing resins because of their excellent heat resistance, moldability, and electrical properties. [Problems to be Solved by the Invention] On the other hand, the integration of semiconductor chips has progressed, and the chip size has accordingly increased. In addition, the shape of packages is becoming smaller and thinner, as seen in flat packages, in contrast to the increase in chip size due to higher density mounting on boards. This has led to the occurrence of defective phenomena that were not seen with conventional sealing resins. In other words, as the chip becomes larger and the resin layer becomes thinner, stress in the resin due to the difference in coefficient of thermal expansion between the sealing resin and the chip can lead to cracks in the packaging film or the sealing resin due to thermal shock. This causes destruction phenomena, lowers the moisture resistance of semiconductors, and ultimately lowers reliability. Therefore, it is desired to develop a sealing resin that has less stress. One possible way to reduce stress is to reduce the coefficient of thermal expansion of the resin to reduce the difference between it and that of the chip, but the difference between the coefficient of thermal expansion of the resin and that of the chip is large, and in order to reduce this, requires the use of a large amount of inorganic filler with a low coefficient of thermal expansion in the resin, but currently a considerable amount of inorganic filler is already being used, and further increasing this amount may cause deterioration of moldability. Become. On the other hand, attempts have been made to add plasticizers or to use flexible epoxy resins or phenolic resins in order to lower the elastic modulus of the resin and reduce stress; The cured product had a problem in terms of heat resistance. Furthermore, as exemplified by JP-A-58-108220, methods have been invented in which rubber particles are dispersed in a sealing resin to provide crack resistance while maintaining heat resistance. There were several problems, such as mold contamination and poor impact resistance at high temperatures exceeding the glass transition temperature of the sealing resin, such as in a solder bath. If the mold is heavily contaminated, the mold must be cleaned in a complicated manner, which reduces productivity, which is extremely inconvenient. In addition, if the thermal shock resistance at high temperatures is poor, the reliability after soldering will decrease, but this is a fatal defect in encapsulating materials such as ICs. The present invention is a semiconductor encapsulation resin that has low stress, excellent thermal shock resistance, etc., and does not cause mold contamination during molding, which is required for encapsulation resin for semiconductors that require high reliability such as highly integrated circuits. The purpose of the present invention is to provide a resin composition for stopping use. [Means for solving the problem] As a result of various studies, the present inventors have found that it is effective to uniformly disperse fine particles of a soft vinyl polymer containing acrylic acid esters as a main component in a resin composition. As a result of this discovery, and further studies on the vinyl polymer composition, particle size, etc., the present invention was achieved. That is, the present invention provides: (a) A soft vinyl polymer mainly composed of alkyl acrylate having an alkyl group having 4 or more carbon atoms is uniformly dispersed in a graft polymer of an epoxy resin and a vinyl polymer with a particle size of 0.5 μ or less. A resin composition for semiconductor encapsulation characterized by containing as main components a modified epoxy resin, (b) a curing agent, (c) an inorganic filler, and, if necessary, (d) an epoxy resin. As the epoxy resin used in a) of the present invention, commonly used epoxy resins can be used as long as they are polyhydric epoxy resins, and glycidylated compounds such as phenol novolak and cresol novolak can be used because of their heat resistance and electrical properties. Preferred are novolak epoxy resins such as, but other compounds having two or more active hydrogens in one molecule, such as bisphenol A,
Bishydroxydiphenylmethane, resorcinol,
Bishydroxydiphenyl ether, polyhydric phenols such as tetrabromobisphenol A, ethylene glycol, neopentyl glycose, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glucose, bisphenol A-ethylene oxide adduct, trishydroxy Glycidyl-type epoxy resin obtained by reacting epichlorohydrin or 2-methylepichlorohydrin with polyhydric alcohols such as ethyl isocyanurate, polyamino compounds such as ethylenediamine, aniline, polycarboxylic compounds such as adipic acid, phthalic acid, isophthalic acid, etc. One or more epoxy resins selected from aliphatic (including alicyclic) epoxy resins such as , dicyclopentadiene diepoxide, butadiene dimer diepoxide, etc. can be used. The graft polymer of an epoxy resin and a vinyl polymer in step (a) of the present invention is typically produced by polymerizing a vinyl monomer to form the vinyl polymer in the presence of an epoxy resin. The term graft polymer herein includes what is commonly called a block polymer. Vinyl monomers used to make the vinyl polymer include alkenyl aromatics such as styrene and vinyltoluene, methyl methacrylate, dodecyl methacrylate, butoxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate,
Acrylic esters such as trimethylolpropane triacrylate, acrylic compounds without ester groups such as acrylonitrile, acrylic acid, butoxymethylacrylamide, methacrylamide, etc., vinyl acetate, vinyl laurate, vinyl versatate, vinyl chloride, vinyl Representative examples include non-conjugated vinyl compounds such as denchloride, ethylene, and acrylic acetate, and conjugated diene compounds such as butadiene, isoprene, and chloroprene.In addition, polymerizable vinyl compounds such as dibutyl fumarate, monomethyl maleate, diethyl itaconate, etc. Compounds can also be used. In order to polymerize the vinyl monomers described above to obtain a vinyl polymer, a radical initiator such as lauroyl peroxide, benzoyl peroxide, tertiary butyl perbenzoate, dimethyl dibenzoyl peroxyhexane, tertiary butyl perpivalate, dimethyl dibenzoyl peroxide, etc. is usually used. tertiary butyl peroxide, 1,1-bisterciabutyl peroxy 3,3,5-trimethylcyclohexane, dimethyl ditertiary butyl peroxyhexane, tertiary butyl cumyl peroxide,
Methyl ethyl ketone peroxide, cyclohexanone peroxide, kyumene hydroperoxide, tertiary butyl peroxyallyl carbonate, dioctyl peroxydicarbonate, tertiary butyl peroxymaleic acid, succinic acid peroxide, tertiary butyl peroxyisopropyl carbonate, peroxide Peroxides such as hydrogen oxide, azobisisobutyronitrile,
Typically, radical polymerization is carried out using an azo compound such as azobisdimethylvaleronitrile. Further, if necessary, a reducing agent may be used in combination to carry out so-called redox polymerization, and a polymerization inhibitor such as hydroquinone or a chain transfer agent such as dodecyl mercaptan may be used. Furthermore, in order to promote grafting, it is effective to introduce a polymerizable double bond or a chemical bond that can be grafted into the epoxy resin. Examples of methods for introducing polymerizable double bonds include acrylic acid, acrylamide,
Methylol acrylamide, butoxymethyl acrylamide, hydroxyethyl methacrylate, glycidyl methacrylate, maleic anhydride, monoethyl itaconate, monobutyl fumarate, chloromethylstyrene, phosphoxyethyl methacrylate, chlorohydroxypropyl methacrylate, parahydroxystyrene, dimethyl A typical method is to react a compound having a functional group and a polymerizable double bond, such as aminoethyl methacrylate, with an epoxy resin in advance. In the present invention, the epoxy resin or the vinyl polymer may remain free in the graft polymer without being grafted. The modified epoxy resin a) can be obtained by polymerizing a monomer that forms a flexible vinyl polymer in the presence of the above-mentioned graft polymer of an epoxy resin and a vinyl polymer by a conventional method. The flexible vinyl polymer used in the present invention must be a polymer mainly composed of acrylate having an alkyl group having 4 or more carbon atoms, preferably 20 or less carbon atoms. In the case of a polymer mainly composed of alkyl acrylate having less than 4 carbon atoms, the particle size of the obtained soft vinyl polymer exceeds 0.5 μm, and the low stress that is the objective of the present invention cannot be achieved, and the thermal shock resistance cannot be improved. . Carbon number 4
Examples of soft vinyl polymers mainly composed of alkyl acrylates having the above alkyl groups include butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, and cetyl acrylate. It is a polymer mainly composed of the above, and it is also possible to copolymerize monomers that can be copolymerized with these acrylates, but the proportion used depends on whether the resulting copolymer is soft, that is, on liquid or rubber. and its particle size is 0.5μ or less, and although it depends on the type of monomer, it is usually 80% by weight or less of the total monomers. These monomers are not particularly limited, but include, for example, acrylates such as methyl acrylate, ethyl acrylate, and propyl acrylate, alkyl methacrylates having an alkyl group having 1 to 24 carbon atoms, cyclohexyl acrylate, benzyl acrylate, and phenoxyethyl acrylate. , phenoxydiethylene glycol acrylate, tetrahydrofurfuryl alcohol acrylate, isobornyl acrylate, dicyclopentadienyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate, 1,6-hexane glycol diacrylate, neo Various acrylic acids such as pentyl glycol diacrylate, polypropylene glycol diacrylate, and trimethylolpropane triacrylate, methacrylic acid, ester acids, acrylonitrile, acrylic acid, butoxymethylacrylamide, methacrylamide, and other acrylic compounds without ester groups. , vinyl acetate, vinyl laurate,
Representative examples include non-conjugated vinyl compounds such as vinyl versatate, vinyl chloride, vinyldene chloride, ethylene and allyl acetate, and conjugated diene compounds such as butadiene, isoprene and chloroprene.Other examples include dibutyl fumarate, monoethyl maleate, Polymerizable vinyl compounds such as diethyl itaconate and the like can be used. As mentioned above, the modified epoxy resin is produced by polymerizing monomers that form a soft vinyl polymer in the presence of a graft polymer of an epoxy resin and a vinyl polymer by a conventional method, so that the soft vinyl polymer is dispersed in an approximately spherical shape. Although it is obtained as a composition, the particle size varies depending on the type of vinyl polymer and the type of soft vinyl polymer, but if the particle size exceeds 0.5μ, the purpose of the present invention cannot be achieved. In order to achieve the purpose of the present invention of low stress and improve impact resistance, 0.5μ or less, preferably 0.2μ or less 0.01μ
The particle size must be greater than or equal to Particle size control of the soft vinyl polymer depends on the type of vinyl polymer that forms the graft polymer with the epoxy resin and the monomer composition that forms the soft vinyl polymer, but it also depends on the amount of double bonds introduced into the epoxy resin. It can also be controlled by The composition of the invention may optionally contain an epoxy resin as d). As the epoxy resin in d), all the epoxy resins used in a) above can be used, and the two may be the same or different. Further, the amount of the soft vinyl polymer is required to be 5% by weight or more, and preferably 10 to 20% by weight, based on the total amount of the epoxy resins used in a) and d). If it is less than 5% by weight, low stress cannot be achieved. Moreover, if it exceeds 20% by weight, the strength will drop significantly and it will be difficult to put it into practical use. In order to adjust the above-mentioned soft vinyl polymer to the desired amount, the amount of the vinyl monomer used in producing the modified epoxy resin in a) may be adjusted, but the amount of the epoxy resin in d) may be adjusted. It is easier to carry out the process by making the epoxy resin d), and from this point of view, it is preferable to use the epoxy resin d) in combination. The curing agent b) used in the present invention is generally a novolac type phenolic resin obtained by reacting phenols such as phenol and alkylphenol with formaldehyde or paraformaldehyde, but modified novolac type phenolic resins are also available. , aralkyl-based phenolic resins, commonly used amine-based curing agents, acid anhydrides, and the like can be used alone or in combination. Although there is no particular restriction on the amount to be added, a stoichiometric amount of the epoxy group of the epoxy resin and the functional group of the curing agent is preferred. Examples of the inorganic filler c) used in the present invention include crystalline silica, fused silica, alumina,
Examples include powder-resistant materials such as talc, calcium silicate, calcium carbonate, mica, clay, and titanium white, as well as glass fibers and carbon fibers alone or in combination, but crystalline materials are usually used in terms of thermal expansion coefficient, thermal conductivity, etc. , meltable silica powder, etc. are used.
The blending amount is preferably 200 to 800 parts by weight per 100 parts by weight of the epoxy resin, and if it is less than 200 parts by weight, the coefficient of thermal expansion will be large and good impact resistance will not be obtained. Moreover, if it exceeds 800 parts by weight, the fluidity of the resin decreases and moldability deteriorates, making it difficult to put it into practical use. The resin composition for semiconductor encapsulation of the present invention includes a) particles of 0.5μ or less of a soft vinyl polymer mainly composed of an alkyl acrylate having an alkyl group having 4 or more carbon atoms in a graft polymer of an epoxy resin and a vinyl polymer; Modified epoxy resin uniformly distributed in diameter,
The main components are b) a curing agent, c) an inorganic filler, and optionally d) an epoxy resin, but in practical use imidazoles, tertiary amines, phenols, organometallic compounds, organic phosphines, etc. It is also possible to appropriately blend curing accelerators, fatty acid amides, fatty acid salts, mold release agents such as wax, flame retardants such as prom compounds, antimony, phosphorus, coloring agents such as carbon black, silane coupling agents, etc. . The resin composition for semiconductor encapsulation of the present invention is sufficiently premixed using a mixer or the like, and then heated and rolled.
Alternatively, it can be easily obtained as a molding material by kneading with a melt mixer such as a kneader, followed by cooling and pulverization. The resin composition for semiconductor encapsulation of the present invention thus obtained has a low elastic modulus, a low coefficient of thermal expansion,
Since this resin composition exhibits excellent thermal shock resistance, excellent reliability can be obtained when this resin composition is used for encapsulating highly integrated semiconductors or small and thin semiconductors such as flat packages. Also,
There is no mold contamination during molding, making it suitable for long-term continuous production. [Example] The present invention will be specifically explained using examples.
The invention is not limited to the examples. In the following, parts mean parts by weight unless otherwise specified. Example 1 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 1 part of methacrylic acid were mixed at 120-125°C in the presence of a tertiary amine.
After reacting for an hour, 3.6 parts of butyl acrylate,
0.1 part of glycidyl methacrylate, 0.05 part of t-butylperoxy 2-ethylhexanoate to 100%
Incubate at ℃ for 1 hour. Additionally, 30 parts of butyl acrylate, neopentyl glycol diacrylate
0.6 parts, 1,1-bis(t-butylperoxy)
After reacting for 4 hours while continuously adding 0.15 part of 3,3,5-tricyclohexane dropwise and then for another 4 hours, the solvent was removed under reduced pressure to obtain a modified epoxy resin (A) (epoxy equivalent: 285). Orthocresol novolac epoxy resin (epoxy equivalent: 217) 56 parts, modified epoxy resin (A) 44 parts,
Novolac type phenolic resin (phenol equivalent
106) Mix 41 parts of triphenylphosphine, 0.85 parts of triphenylphosphine, 400 parts of fused silica previously treated with a silane coupling agent, 2 parts of carbon black, and 2.5 parts of carnauba wax, and then heat to 80 to 90°C.
After melting and mixing for 3 minutes with a hot roll, cool and grind.
A molding resin composition was obtained. Using this composition, transfer molding (175℃,
30Kg/cm 2 for 3 minutes) to obtain a test piece for physical property testing and a 16-pin DIP (equipped with a 4×8 m/m element) for thermal shock testing. These specimens were molded at 175°C.
After post-curing for 4 hours, various tests were conducted. Example 2 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 0.6 parts of methacrylic acid were mixed at 120 to 125°C in the presence of a tertiary amine.
After reacting for an hour, 3.6 parts of 2-ethylhexyl acrylate, 0.1 part of glycidyl methacrylate, t
-Butylperoxy 2-ethylhexanoate
0.05 part was reacted at 100°C for 1 hour. Further, 30 parts of 2-ethylhexyl acrylate, 0.4 parts of glycidyl methacrylate, 0.4 parts of neopentyl glycol acrylate, and 0.15 parts of 1,1-bis(t-butylperoxy)3,3,5-tricyclohexane were continuously added dropwise for 4 hours. After that, after reacting for another 4 hours, the solvent was removed under reduced pressure and the modified epoxy resin
(B)) (epoxy equivalent weight 297) was obtained. Various tests were conducted in the same manner as in Example 1 using the above modified epoxy resin. Example 3 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 1 part of methacrylic acid were reacted at 120 to 125°C for 2 hours in the presence of a tertiary amine, and then 3.6 parts of 2-ethylhexyl acrylate was added. , glycidyl methacrylate 0.1 part, t-
Butyl peroxy 2-ethylhexanoate 0.05
react at 100°C for 1 hour. Further, 30 parts of 2-ethylhexyl acrylate, 0.4 parts of glycidyl methacrylate, 0.4 parts of neopentyl glycol acrylate, and 0.15 parts of 1,1-bis(t-butylperoxy)3,3,5-tricyclohexane were continuously added dropwise for 4 hours. After that, after reacting for another 4 hours, the solvent was removed under reduced pressure and the modified epoxy resin (C)
(Epoxy equivalent: 296) was obtained. Various tests were conducted in the same manner as in Example 1 using the above modified epoxy resin. Example 4 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 0.9 parts of methacrylic acid were mixed at 120 to 125°C in the presence of a tertiary amine.
After reacting for an hour, 3.6 parts of lauryl acrylate;
100 parts of glycidyl methacrylate, 0.05 parts of t-butyl peroxy 2-ethylhexanoate
Incubate at ℃ for 1 hour. Furthermore, 30 parts of lauryl acrylate, 0.4 parts of glycidyl methacrylate, 0.6 parts of neopentyl glycol diacrylate, 1,
1-bis(t-butylperoxy)3,3,5-
4 while continuously dropping 0.15 part of tricyclohexane.
After reacting for another 4 hours, the solvent was removed under reduced pressure and the modified epoxy resin (D) (epoxy equivalent: 305)
I got it. Various tests were conducted in the same manner as in Example 1 using the above modified epoxy resin. Example 5 In producing the molding resin composition of Example 3, the same as Example 3 except that the amount of orthocresol novolak epoxy resin was changed to 13 parts and the amount of modified epoxy resin (B) was changed to 87 parts. I did it in the same way as 3. Example 6 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 0.4 part of methacrylic acid were reacted at 120 to 125°C for 2 hours in the presence of a tertiary amine, and then 1.3 parts of 2-ethylhexyl acrylate was reacted. 1 part and 0.02 part of t-butylperoxy 2-ethylxanoate were reacted at 100°C for 1 hour.
Furthermore, 11 parts of 2-ethylhexyl acrylate, 0.2 parts of neopentyl glycol diacrylate, 1,
1-bis(t-butylperoxy)3,3,5-
4 while continuously dropping 0.06 part of tricyclohexane.
After reacting for an additional 4 hours, the solvent was removed under reduced pressure to obtain a modified epoxy resin (G) (epoxy equivalent: 245). 100 parts of the above modified epoxy resin, 43 parts of novolak type phenolic resin (phenol equivalent: 106), 0.85 parts of triphenylphosphine, 400 parts of fused silica previously treated with a silane coupling agent, 2 parts of carbon black, and 2.5 parts of carnauba wax. Example 1
A molding resin composition was obtained in the same manner as above, and a test piece was also prepared. Each test was conducted. Comparative Example 1 100 parts of orthocresol novolak epoxy resin (epoxy equivalent: 217), 49 parts of novolak type phenolic resin (phenol equivalent: 106), 0.85 parts of tolphenylphosphine, 412 parts of fused silica previously treated with a silane cutting agent, carbon 2 parts of black and 2.5 parts of carnauba wax were mixed in a mixer, and then melted and mixed for 3 minutes with a heated roll at 80 to 90°C, cooled and ground to obtain a molding resin composition. Using this composition, transfer molding (175℃,
30 Kg/cm 2 for 3 minutes) to obtain a test piece for physical property testing and a 16-pin DIP (equipped with a 4×8 m/m element) for thermal shock testing. After forming these test pieces,
After post-curing at 175°C for 4 hours, each test piece was tested. Comparative Example 2 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 0.9 parts of methacrylic acid were heated at 120 to 125°C in the presence of a tertiary amine at 2
After reacting for an hour, 3.6 parts of ethyl acrylate;
0.1 part of glycidyl methacrylate, 0.05 part of t-butylperoxy 2-ethylhexanoate to 100%
Incubate at ℃ for 1 hour. Furthermore, ethyl acrylate
30 parts, glycidyl methacrylate 0.4 parts, neopentyl glycol diacrylate 0.6 parts, 1,1
-Bis(t-butylperoxy)3,3,5-tricyclohexane (0.15 parts) was continuously added dropwise for 4 hours, and then the reaction was continued for another 4 hours.The solvent was removed under reduced pressure and the modified epoxy resin (E) (epoxy equivalent weight 298)
I got it. Various tests were conducted in the same manner as in Example 1 using the above modified epoxy resin. Comparative Example 3 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), 10 parts of toluene, and 0.5 part of methacrylic acid were heated at 120 to 125°C in the presence of a tertiary amine at 2
After reacting for an hour, 3.6 parts of butyl acrylate,
0.1 part of glycidyl methacrylate, 0.05 part of t-butylperoxy 2-ethylhexanoate to 100%
Incubate at ℃ for 1 hour. Furthermore, butyl acrylate
30 parts, glycidyl methacrylate 0.4 parts, neopentyl glycol diacrylate 0.6 parts, 1,1
-Bis(t-butylperoxy)3,3,5-tricyclohexane (0.15 parts) was continuously added dropwise for 4 hours, and then the reaction was continued for another 4 hours.The solvent was removed under reduced pressure and the modified epoxy resin (F) (epoxy equivalent weight 306)
I got it. Various tests were conducted in the same manner as in Example 1 using the above modified epoxy resin. Comparative Example 4 90 parts of orthocresol novolak epoxy resin (epoxy equivalent: 217), 10 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190), novolak type phenolic resin (phenol equivalent: 106)
49 parts, 0.85 parts of triphenylphosphine, 412 parts of fused silica previously treated with a coupling agent,
A molding resin composition was obtained using 2 parts of carbon black and 2.5 parts of carnauba wax in the same manner as in Example 1.
Furthermore, test pieces were prepared and various tests were conducted. Comparative Example 5 90 parts of orthocresol novolac epoxy resin (epoxy equivalent: 217), styrene-butadiene rubber
10 parts, novolac type phenolic resin (phenol equivalent 106) 44 parts, triphenylphosphine 0.85 parts,
400 parts of fused silica, previously treated with a coupling agent;
A molding resin composition was obtained using 2 parts of carbon black and 2.5 parts of carnauba wax in the same manner as in Example 1.
Furthermore, test pieces were prepared and various tests were conducted. The contents of the above examples and comparative examples are shown in Table 1, and the test results are shown in Table 2.
【表】【table】
【表】【table】
実施例及び比較例にて説明した来た如く、本発
明による半導体封止用樹脂組成物は弾性率が低
く、熱膨張率が小さく、優れた耐衝撃性を示すこ
とから、この樹脂組成物を集積度の高い半導体あ
るいはフラツトパツケージの如き小型・薄型の半
導体の封止に用いた場合、優れた信頼性を得るこ
とが出来、また、金型汚染がなく長時間連続生産
に適することから工業的に有益な発明であるとい
える。
As explained in the Examples and Comparative Examples, the resin composition for semiconductor encapsulation according to the present invention has a low elastic modulus, a small coefficient of thermal expansion, and exhibits excellent impact resistance. When used for encapsulating small and thin semiconductors such as highly integrated semiconductors or flat packages, it can achieve excellent reliability, and is suitable for long-term continuous production without mold contamination, making it an industrial choice. It can be said that this invention is useful in terms of
Claims (1)
フト重合体中に炭素数4以上のアルキル基を持
つアルキルアクリレートを主体とする軟質ビニ
ール重合体が0.5μ以下の粒子径で均一に分散さ
れた変性エポキシ樹脂、 b 硬化剤、 c 無機充填剤、 を主成分とすることを特徴とする半導体封止用樹
脂組成物。 2 a エポキシ樹脂とビニルポリマーとのグラ
フト重合体中に炭素数4以上のアルキル基を持
つアルキルアクリレートを主体とする軟質ビニ
ル重合体が0.5μ以下の粒子径で均一に分散され
た変性エポキシ樹脂、 b 硬化剤、 c 無機充填剤、 d エポキシ樹脂、 を主成分とすることを特徴とする半導体封止用樹
脂組成物。[Claims] 1a A soft vinyl polymer mainly composed of an alkyl acrylate having an alkyl group having 4 or more carbon atoms is uniformly dispersed in a graft polymer of an epoxy resin and a vinyl polymer with a particle size of 0.5μ or less 1. A resin composition for semiconductor encapsulation, characterized in that the main components thereof are: (b) a curing agent; and (c) an inorganic filler. 2a A modified epoxy resin in which a soft vinyl polymer mainly composed of an alkyl acrylate having an alkyl group having 4 or more carbon atoms is uniformly dispersed in a graft polymer of an epoxy resin and a vinyl polymer with a particle size of 0.5 μ or less, 1. A resin composition for encapsulating a semiconductor, comprising: (b) a curing agent, (c) an inorganic filler, and (d) an epoxy resin.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2603086 | 1986-02-10 | ||
JP61-26030 | 1986-02-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62275149A JPS62275149A (en) | 1987-11-30 |
JPH0588864B2 true JPH0588864B2 (en) | 1993-12-24 |
Family
ID=12182305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11614186A Granted JPS62275149A (en) | 1986-02-10 | 1986-05-22 | Resin composition for use in sealing semiconductor |
Country Status (1)
Country | Link |
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JP (1) | JPS62275149A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5691416A (en) * | 1992-11-05 | 1997-11-25 | Nippon Shokubai Co., Ltd. | (Meth)acrylate polymer particles dispersed in epoxy resin |
-
1986
- 1986-05-22 JP JP11614186A patent/JPS62275149A/en active Granted
Also Published As
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JPS62275149A (en) | 1987-11-30 |
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