JPH02209965A - Resin composition for sealing semiconductor - Google Patents
Resin composition for sealing semiconductorInfo
- Publication number
- JPH02209965A JPH02209965A JP3001189A JP3001189A JPH02209965A JP H02209965 A JPH02209965 A JP H02209965A JP 3001189 A JP3001189 A JP 3001189A JP 3001189 A JP3001189 A JP 3001189A JP H02209965 A JPH02209965 A JP H02209965A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polymer
- formula
- general formula
- bismaleimide
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 19
- 239000011342 resin composition Substances 0.000 title claims description 18
- 238000007789 sealing Methods 0.000 title abstract description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 47
- -1 diamine compound Chemical class 0.000 claims abstract description 45
- 239000003822 epoxy resin Substances 0.000 claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 45
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 35
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 238000005538 encapsulation Methods 0.000 claims description 10
- 229920002379 silicone rubber Polymers 0.000 claims description 9
- 239000004945 silicone rubber Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 2
- 125000004149 thio group Chemical group *S* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 24
- 239000000203 mixture Substances 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 5
- 238000005476 soldering Methods 0.000 abstract description 4
- 229910002026 crystalline silica Inorganic materials 0.000 abstract description 2
- 239000005350 fused silica glass Substances 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 150000004985 diamines Chemical class 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VTHWGYHNEDIPTO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfinylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 VTHWGYHNEDIPTO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RSNDTPFSMDVWCS-UHFFFAOYSA-N 2-(butoxymethyl)prop-2-enamide Chemical group CCCCOCC(=C)C(N)=O RSNDTPFSMDVWCS-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 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 1
- 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
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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 compound CCCC\C(=C\C(O)=O)C(=O)OO QEZDYNRKJXCIFE-WAYWQWQTSA-N 0.000 description 1
- GWYSWOQRJGLJPA-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(F)F GWYSWOQRJGLJPA-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-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
- HIETXQBDOKUUDB-UHFFFAOYSA-N 1-n,4-n-bis[(4-aminophenyl)methyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1CNC(C=C1)=CC=C1NCC1=CC=C(N)C=C1 HIETXQBDOKUUDB-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LLDBOMNUMJVCBX-UHFFFAOYSA-N 2-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CCCCOOC(C)(C)OC(O)=O LLDBOMNUMJVCBX-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
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-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
- 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
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 1
- NQZOFDAHZVLQJO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 NQZOFDAHZVLQJO-UHFFFAOYSA-N 0.000 description 1
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 1
- JERFEOKUSPGKGV-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfanylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(SC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 JERFEOKUSPGKGV-UHFFFAOYSA-N 0.000 description 1
- LUMIUTGJALTAOY-UHFFFAOYSA-N 3-[5-(3-aminophenyl)-[1,3]thiazolo[4,5-d][1,3]thiazol-2-yl]aniline Chemical compound NC1=CC=CC(C=2SC=3SC(=NC=3N=2)C=2C=C(N)C=CC=2)=C1 LUMIUTGJALTAOY-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
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- XECVXFWNYNXCBN-UHFFFAOYSA-N 4-[(4-aminophenyl)-phenylmethyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)C1=CC=CC=C1 XECVXFWNYNXCBN-UHFFFAOYSA-N 0.000 description 1
- KTZLSMUPEJXXBO-UHFFFAOYSA-N 4-[(4-aminophenyl)-phenylphosphoryl]aniline Chemical compound C1=CC(N)=CC=C1P(=O)(C=1C=CC(N)=CC=1)C1=CC=CC=C1 KTZLSMUPEJXXBO-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
- GPXUPINUTNRGMB-UHFFFAOYSA-N 4-[2-[3-[4-(4-aminophenyl)-1,3-thiazol-2-yl]phenyl]-1,3-thiazol-4-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=CSC(C=2C=C(C=CC=2)C=2SC=C(N=2)C=2C=CC(N)=CC=2)=N1 GPXUPINUTNRGMB-UHFFFAOYSA-N 0.000 description 1
- ITKSJWDXNHOFBV-UHFFFAOYSA-N 4-[amino-(4-aminophenyl)methyl]aniline Chemical compound C=1C=C(N)C=CC=1C(N)C1=CC=C(N)C=C1 ITKSJWDXNHOFBV-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- HEHUZGFZNPSQMW-UHFFFAOYSA-N NC1=CC=C(C=C1)C(C1=CC=C(C=C1)N)[PH2]=O Chemical compound NC1=CC=C(C=C1)C(C1=CC=C(C=C1)N)[PH2]=O HEHUZGFZNPSQMW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 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 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-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
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 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
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 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
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 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
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 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 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
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
Landscapes
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高耐熱性および低吸水性に優れた樹脂組成物
、更に耐熱衝撃性に優れた樹脂組成物で高信頼性を要求
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。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a resin composition that is excellent in high heat resistance and low water absorption, and is also a resin composition that is excellent in thermal shock resistance and is required to have high reliability. The present invention relates to a semiconductor encapsulating resin composition suitable for encapsulating electronic components such as semiconductors.
従来、IC,LSI等の半導体封止用樹脂組成物として
は、エポキシ樹脂が原料の低順、大量生産に適するとい
った経済的利点をいかして広く実用化されている。BACKGROUND ART Conventionally, epoxy resins have been widely put into practical use as resin compositions for encapsulating semiconductors such as ICs and LSIs, taking advantage of their economical advantages such as low raw materials and suitability for mass production.
一方、最近の電子部品の高密度実装化の流れにより、半
導体のパッケージは表面実装型のパッケージに変わりつ
つある0表面実装においては、従来の挿入型と違ってパ
ッケージ全体が200°C以上の半田付温度に曝される
ため、封止樹脂として高耐熱性が要求されるようになっ
て来た。従来、このような高耐熱性を得るためには、ビ
スマレイミドが多く使用されて来たが、ビスマレイミド
単独の硬化物は脆いという欠点を有しており、これを改
良するためにジアミンとの共重合体として可境性を付与
する方法が採られた。しかしながら、−船釣にビスマレ
イミド系の硬化物は吸水率が高く、特に半田耐熱性を考
えた場合、この水分が実画時の高温により急激に膨張し
てパッケージにクランクを発生するために不利と考えら
れて来た。On the other hand, with the recent trend toward high-density packaging of electronic components, semiconductor packages are changing to surface-mount packages.Unlike conventional insertion-type packages, the entire package is soldered at temperatures above 200°C. Due to exposure to high temperatures, sealing resins have come to be required to have high heat resistance. Conventionally, bismaleimide has been widely used to obtain such high heat resistance, but the cured product of bismaleimide alone has the disadvantage of being brittle, and to improve this, it has been combined with diamine. A method of imparting delimitability as a copolymer was adopted. However, - Bismaleimide-based cured products have a high water absorption rate for boat fishing, and are disadvantageous, especially when considering soldering heat resistance, because this water expands rapidly due to the high temperature of the actual image and causes a crank in the package. It was thought that.
また、半導体技術のめざましい革新により素子のサイズ
はより太き(、アルミ配線巾は細くなる傾向にある。従
って封止樹脂と素子の熱膨張の差に起因する応力のレベ
ルは更に低い物が要求されており、この点でもビスマレ
イミド系の封止樹脂の高耐熱性と合わせて低応力化の必
要性も生じてきた。In addition, due to the remarkable innovation in semiconductor technology, the size of elements is becoming thicker (and the width of aluminum wiring is becoming thinner. Therefore, the level of stress caused by the difference in thermal expansion between the sealing resin and the element is required to be even lower. In this respect, there has been a need to reduce stress in addition to the high heat resistance of bismaleimide-based sealing resins.
本発明者等は種々検討した結果、特定の構造を有するビ
スマレイミド化合物とジアミンとの硬化物が高いガラス
転移温度(以下Tgという)および低い吸水率を示し、
半田耐熱に優れ更にあわせてシリコーンポリマーの微粒
子が分散した変性エポキシ樹脂を使用する事により優れ
た耐衝撃性をも付与できることを見出し、本発明に達し
た。As a result of various studies, the present inventors have found that a cured product of a bismaleimide compound having a specific structure and a diamine exhibits a high glass transition temperature (hereinafter referred to as Tg) and a low water absorption rate,
The inventors have discovered that it is possible to impart excellent impact resistance by using a modified epoxy resin that has excellent solder heat resistance and in addition has fine particles of silicone polymer dispersed therein, and has thus arrived at the present invention.
即ち、本発明は、
(1)本質的に、
(a)−儀式(1)
よりなる2価の基を表し、Xは直結、炭素数1〜10の
2価の炭化水素基、6フツ素化されたイソプロピリデン
基、カルボニル基、チオ基、スルフィニル基、スルホニ
ル基又はオキシドから成る群より選ばれた基を表す、)
にて表されるビスマレイミド化合物、
(b)−線式(n)
HJ R1NHI (11)(R3は少な
くとも2個の炭素数を有する2価の有機基を表す、)に
て表されるジアミン化合物、(c)無機充填剤、
および、目的によっては、
(d)エポキシ樹脂とビニルポリマーとのグラフト重合
体中にシリコーンポリマーが1.0μ以下の平均粒子径
で均一に゛分散された変性エポキシ樹脂(以下、変成エ
ポキシ樹脂という)
を含有することを特徴とする半導体封止用樹脂組成物。That is, the present invention represents a divalent group consisting essentially of (1) (a)-ritual (1), where X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorine a bismaleimide compound represented by (b) - a group selected from the group consisting of a converted isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or an oxide; A diamine compound represented by HJ R1NHI (11) (R3 represents a divalent organic group having at least 2 carbon atoms), (c) an inorganic filler, and, depending on the purpose, (d) an epoxy A semiconductor encapsulation characterized by containing a modified epoxy resin (hereinafter referred to as modified epoxy resin) in which a silicone polymer is uniformly dispersed in a graft polymer of a resin and a vinyl polymer with an average particle diameter of 1.0 μ or less. Resin composition for stopping.
(2)−線式(1)にて表されるビスマレイミド化合物
と、一般式(II)にて表されるジアミン化合物とを予
めプレポリマー化して用いることを特徴とする半導体封
止用樹脂組成物。(2) A resin composition for semiconductor encapsulation characterized in that a bismaleimide compound represented by the -linear formula (1) and a diamine compound represented by the general formula (II) are prepolymerized and used. thing.
(3)エポキシ樹脂中に分散されたシリコーンポリマー
が、付加反応型のシリコーンポリマーが反応してなるシ
リコーンゴムおよび/またはビニル変性シリコーン重合
体を主体とする軟質ビニル重合体である半導体封止用樹
脂組成物。(3) Semiconductor encapsulation resin which is a silicone rubber obtained by reacting a silicone polymer dispersed in an epoxy resin with an addition reaction type silicone polymer and/or a soft vinyl polymer mainly composed of a vinyl-modified silicone polymer. Composition.
本発明において用いられる(a)の−線式(1)で表さ
れるビスマレイミド化合物は、通常公知の方法により一
般式(III)で表されるシアミン化合物と無水マレイ
ン酸を縮合・脱水反応させて容易に製造できる。The bismaleimide compound represented by the linear formula (1) in (a) used in the present invention is produced by a condensation/dehydration reaction between a cyamine compound represented by the general formula (III) and maleic anhydride by a commonly known method. It can be easily manufactured.
(式中、R1は前記と同様の意味を表す)一般式(II
I)のジアミン化合物は、具体的には1.3−ビス(3
−アミノフェノキシ)ベンゼン、ビス(3−アミノフェ
ノキシ)メタン、1.1−ビス(4−(3〜アミノフエ
ノキシ)フェニル〕エタン、1.2−ビス(4−(3−
アミノフェノキシ)フェニル)エタン、2.2−ビス(
4−(3−アミノフェノキシ)フェニル〕プロパン、2
.2−ビス(4−(3−アミノフェノキシ)フェニルコ
ブタン、2.2−ビス(4−(3−アミノフェノキシ)
フェニル) −1,1,1,3,3,3−へキサフルオ
ロブoハフ、4+4°−ヒス(3−アミノフェノキシ)
ビフェニル、ビス(4−(3−アミノフェノキシ)フェ
ニルコケトン、ビス(4−(3−アミノフェノキシ)フ
ェニル〕スルフィド、ビス(4−(3アミノフエノキシ
)フェニル〕スルホキシド、ビス(4−(3−アミノフ
ェノキシ)フェニル〕スルホン、ビス(4−(3−アミ
ノフェノキシ)フェニルフェーテル等があげられる。(In the formula, R1 represents the same meaning as above) General formula (II
Specifically, the diamine compound I) is 1,3-bis(3
-aminophenoxy)benzene, bis(3-aminophenoxy)methane, 1.1-bis(4-(3-aminophenoxy)phenyl)ethane, 1.2-bis(4-(3-
Aminophenoxy)phenyl)ethane, 2,2-bis(
4-(3-aminophenoxy)phenyl]propane, 2
.. 2-bis(4-(3-aminophenoxy)phenylcobutane, 2.2-bis(4-(3-aminophenoxy)
phenyl) -1,1,1,3,3,3-hexafluorohaf, 4+4°-his(3-aminophenoxy)
Biphenyl, bis(4-(3-aminophenoxy)phenylkoketone, bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy)phenyl)sulfoxide, bis(4-(3-aminophenoxy)phenyl)sulfoxide, bis(4-(3-aminophenoxy)phenyl)sulfoxide, Examples include phenoxy)phenyl]sulfone, bis(4-(3-aminophenoxy)phenyl ether), and the like.
−線式([[)のジアミン化合物と無水マレイン酸を縮
合・脱水反応して得られるビスマレイミド化合物は、具
体的にはN、N’−1,3−ビス(3−アミノフェノキ
シ)ベンゼンビスマレイミド、N、N″】、3−ビス〔
4〜(3−アミノフェノキシ)フェニルコメタンビスマ
レイミド、 N、N’−1,1−ビス(4−(3−アミ
ノフェノキシ)フェニル〕エタンビスマレイミド、N、
N’−1,2−ビス〔4−(3−アミノフェノキシ)フ
ェニル〕エタンビスマレイミド、N、N″−2,2−ビ
ス(4−(3−アミノフェノキシ)フェニル〕プロパン
ビスマレイミド、N、N’−2,2−ビス(4−(3−
アミノフェノキシ)フェニルコブタンビスマレイミド、
N、N’−2,2−ビス(4−(3−アミノフェノ
キシ)フェニル) −1,1,1,3,3,3−へキサ
フルオロプロパンビスマレイミド、N、N’−4,4’
−ビス(3−アミノフェノキシ)ビフェニルビスマレイ
ミド、N、N’−ビス(4−(3−アミノフェノキシ)
フェニルコケトンビスマレイミド、N、 N’−ビス(
4−(3−アミノフェノキシ)フェニルフスルフィドビ
スマレイミド、N、N″−ビス(4−(3−7ミノフエ
ノキシ)フェニル]スルボキシドビスマレイミド、N、
N’−ビス(4−(3−アミノフェノキシ)フェニル
〕スルホンビスマレイミド、N、N’−ビス〔4−(3
−アミノフェノキシ)フェニルフェーテル等があげられ
る。- Specifically, the bismaleimide compound obtained by condensing and dehydrating a diamine compound of the linear formula ([[) and maleic anhydride is N,N'-1,3-bis(3-aminophenoxy)benzene bis maleimide, N, N″], 3-bis[
4-(3-aminophenoxy)phenylcomethane bismaleimide, N, N'-1,1-bis(4-(3-aminophenoxy)phenyl)ethane bismaleimide, N,
N'-1,2-bis[4-(3-aminophenoxy)phenyl]ethane bismaleimide, N, N''-2,2-bis(4-(3-aminophenoxy)phenyl)propane bismaleimide, N, N'-2,2-bis(4-(3-
aminophenoxy) phenylcobutane bismaleimide,
N,N'-2,2-bis(4-(3-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane bismaleimide, N,N'-4,4'
-bis(3-aminophenoxy)biphenylbismaleimide, N,N'-bis(4-(3-aminophenoxy)
Phenylkoketone bismaleimide, N, N'-bis(
4-(3-aminophenoxy)phenyl sulfide bismaleimide, N,N''-bis(4-(3-7minophenoxy)phenyl]sulfoxide bismaleimide, N,
N'-bis(4-(3-aminophenoxy)phenyl)sulfone bismaleimide, N,N'-bis[4-(3
-aminophenoxy) phenyl phether and the like.
なお、本発明においてはN、N’−4,4°−ビス(3
−アミノフェノキシ)ビフェニルビスマレイミド、N、
N’−2,2−ビス(4−(3−アミノフェノキシ)フ
ェニル〕プロパンビスマレイミド、N、N’ビス(4−
(3−アミノフェノキシ)フェニルフスルフィドビスマ
レイミドがこれらの中で好適に使用される。In addition, in the present invention, N, N'-4,4°-bis(3
-aminophenoxy)biphenyl bismaleimide, N,
N'-2,2-bis(4-(3-aminophenoxy)phenyl)propane bismaleimide, N,N'bis(4-
(3-Aminophenoxy) phenyl sulfide bismaleimide is preferably used among these.
また上記ビスマレイミドは単独で使用しても2種以上併
用してもよい、更に、必要に応じて一般式(1)以外の
マレイミド化合物を併用してもよい。Further, the bismaleimides mentioned above may be used alone or in combination of two or more kinds, and if necessary, maleimide compounds other than the general formula (1) may be used in combination.
零願発吸に用いられる一般式(■)で表されるジアミン
化合物は、前記−綴代(Ill)で表されるジアミンは
全て使用可能であり、更にこれ以外の物でも使用可能で
あり、例えば4.4°−ジアミノジシクロヘキシルメタ
ン、1.4−ジアミノシクロヘキサン、2.6−ジアミ
ツビリジン、m−フェニレンジアミン、p−フェニレン
ジアミン、4.4°−ジアミノジフェニルメタン、2,
2°−ビス(3−アミノフェニル)プロパン、ベンジジ
ン、4.4“−ジアミノフェニルオキシド、4.4”−
ジアミノジフェニルスルホン、ビス(4−アミノフェニ
ル)メチルホスフィンオキシド、ビス(4−アミノフェ
ニル)フェニルホスフィンオキシト、ビス(4−アミノ
フェニル)メチルアミン、1.5−ジアミノナフタレン
、m−キシリレンジアミン、1.1−ビス(P−アミノ
フェニル)フラタン、p−キシリレンジアミン、ヘキサ
メチレンジアミン、6.6′−ジアミン−2,2′−ジ
ピリジル、4.4゛−ジアミノベンゾフェノン、4.4
′−ジアミノアゾベンゼン、ビス(4−アミノフェニル
)フェニルメタン、1.1−ビス(4−7ミノフエニル
)シクロヘキサン、1.l−ビス(4−アミノ−3−メ
チルフェニル)シクロヘキサン、 2.5−(m−
アミノフェニル)−1,3,4−オキサジアゾール、2
.5−ビス(p−アミノフェニル) −1,3,4−オ
キサジアゾール、2.5−ビス(m−アミノフェニル)
チアゾロ(4,5−d )チアゾール、5,5゛−ジ(
m−アミノフェニル)−2,2’−ビス(1,3,4−
オキサジアゾル)、4,4°−ジアミノジフェニルエー
テル、4.41−ビス(p−7ミノフエニル) −2,
2°−ジチアゾール、m−ビス(4−p−アミノフェニ
ル−2−チアゾリル)ベンゼン、4,4″−ジアミノベ
ンズアニリド、4.4’−ジアミノフェニルベンゾエー
ト、N、N’−ビス(4−アミノベンジル)−p−フェ
ニレンジアミン、4.4°−メチレンビス(2−クロロ
アニリン)などがあり、これらの少なくとも1種または
211以上のものを混合して用いられる。As for the diamine compound represented by the general formula (■) used for zero-gan suction, all the diamines represented by the above-mentioned -tsuzuriyo (Ill) can be used, and furthermore, compounds other than this can also be used, For example, 4.4°-diaminodicyclohexylmethane, 1.4-diaminodicyclohexane, 2.6-diamitubiridine, m-phenylenediamine, p-phenylenediamine, 4.4°-diaminodiphenylmethane, 2,
2°-bis(3-aminophenyl)propane, benzidine, 4.4"-diaminophenyl oxide, 4.4"-
Diaminodiphenylsulfone, bis(4-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1.1-bis(P-aminophenyl)furatane, p-xylylenediamine, hexamethylenediamine, 6.6'-diamine-2,2'-dipyridyl, 4.4'-diaminobenzophenone, 4.4
'-Diaminoazobenzene, bis(4-aminophenyl)phenylmethane, 1.1-bis(4-7minophenyl)cyclohexane, 1. l-bis(4-amino-3-methylphenyl)cyclohexane, 2.5-(m-
aminophenyl)-1,3,4-oxadiazole, 2
.. 5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis(m-aminophenyl)
Thiazolo(4,5-d)thiazole, 5,5゛-di(
m-aminophenyl)-2,2'-bis(1,3,4-
oxadiazole), 4,4°-diaminodiphenyl ether, 4,41-bis(p-7minophenyl)-2,
2°-Dithiazole, m-bis(4-p-aminophenyl-2-thiazolyl)benzene, 4,4″-diaminobenzanilide, 4,4′-diaminophenylbenzoate, N,N′-bis(4-amino benzyl)-p-phenylenediamine, 4.4°-methylenebis(2-chloroaniline), etc., and at least one of these or a mixture of 211 or more of them is used.
本発明においては、−m式(1)で示されるビスマレイ
ミドと一般式(II)で示されるジアミン化合物は反応
物として用いることが好ましい0反応物として用いない
場合、ビスマレイミドの軟化点が高いために良好な混練
性が得られず、樹脂組成物が不均一となり、成形性の点
で問題となる。In the present invention, the bismaleimide represented by formula (1) and the diamine compound represented by general formula (II) are preferably used as reactants.0 If they are not used as reactants, the softening point of bismaleimide is high. Therefore, good kneading properties cannot be obtained, and the resin composition becomes non-uniform, which causes problems in terms of moldability.
反応物にすることによりビスマレイミドの軟化点を低下
させることができ、良好な混練性を得ることができる。By using it as a reactant, the softening point of bismaleimide can be lowered and good kneading properties can be obtained.
一般弐(1)で示されるビスマレイミドと一般式(I
f)で示されるジアミン化合物の反応物は、以下の示す
方法により得ることができる。Bismaleimide represented by general formula 2 (1) and general formula (I
The diamine compound reactant represented by f) can be obtained by the method shown below.
(1)ビスマレイミドとジアミンを固体状で粉砕混合し
たものを加熱処理してプレポリマーとした後、粉砕して
ベレット又は粉状にする。この場合の加熱条件はプレポ
リマーの段階まで部分硬化させる条件がよ(、−aには
70〜220’Cの温度で5〜240分、望ましくは8
o〜2oo′c)温度テlo〜180分とすることが適
当である。(1) Bismaleimide and diamine are pulverized and mixed in solid form, heat treated to form a prepolymer, and then pulverized to form pellets or powder. In this case, the heating conditions should be such that the prepolymer stage is partially cured.
o to 2oo'c) It is appropriate to set the temperature to 180 minutes.
(2)ビスマレイミドとジアミンを有機溶媒に溶解させ
、次いで貧溶媒中に排出し、析出してきた結晶を濾過乾
燥してベレット又は粉状にするか、または有機溶媒に溶
解後、加熱処理によりプレポリマーの段階まで部分硬化
させた後、貧溶媒中に排出し、析出してきた結晶を濾過
乾燥してベレット又は粉状とする。この場合の条件も(
1)に準する。使用可能な有機溶媒としては両成分と実
質的に反応しない溶媒という点で制限を受けるが、この
ほかに再反応成分に対する良溶媒であることが望ましい
0通常、用いられる反応溶媒は塩化メチレン、ジクロロ
エタン、トリクロロエチルシンなどのハロゲン化炭化水
素、アセトン、メチルエチルケトン、シクロヘキサノン
、ジイソフ“ロピルケトン勉どのケトン類、テトラヒド
ロフラン、ジオキサン、メチルセロソルブなどのエーテ
ル類、ベンゼン、トルエン、クロロベンゼンなどの芳香
族化合物、アセトニトリル、N、N−ジメチルホルムア
ミド、N、N−ジメチルアセトアミド、ジメチルスルホ
キシド、N−メチル−2−ピロリドン、1、3−ジメチ
ル−2−イミダシリンなどの非プロトン極性溶媒等であ
る。(2) Bismaleimide and diamine are dissolved in an organic solvent, then discharged into a poor solvent, and the precipitated crystals are filtered and dried to form pellets or powder, or dissolved in an organic solvent and then heated to preform. After partially curing to the polymer stage, it is discharged into a poor solvent, and the precipitated crystals are filtered and dried to form a pellet or powder. The conditions in this case are also (
Conforms to 1). The organic solvents that can be used are limited by the fact that they do not substantially react with both components, but it is also desirable that they are good solvents for the re-reacted components.Usually, the reaction solvents used are methylene chloride and dichloroethane. , halogenated hydrocarbons such as trichloroethylcine, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diisofuropyl ketone, ethers such as tetrahydrofuran, dioxane, and methylcellosolve, aromatic compounds such as benzene, toluene, and chlorobenzene, acetonitrile, N , N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidacyline, and other aprotic polar solvents.
ビスマレイミド化合物とジアミン化合物の使用割合は、
通常モル比で一般式(1)のビスマレイミド化合物ニー
綴代(If)のジアミン化合物が10=1〜l:3の範
囲である。The usage ratio of bismaleimide compound and diamine compound is
Usually, the molar ratio of the bismaleimide compound of general formula (1) to the diamine compound of knee binding (If) is in the range of 10=1 to 1:3.
また、ビスマレイミドとジアミンの反応物の配合量は、
シリコンポリマーを分散させた変性エポキシ樹脂とあわ
せて使用する場合、変性エポキシ樹脂を含むエポキシ樹
脂と反応物の総量に対して10重■%以上811%以下
が好ましい。10重量%未満では良好な半田耐熱性が得
られず、80重貴重を超えて使用すると弾性率が高くな
り、十分な低応力化ができなくなる。In addition, the amount of the reactant of bismaleimide and diamine is
When used in conjunction with a modified epoxy resin in which a silicone polymer is dispersed, it is preferably 10% by weight or more and 811% or less based on the total amount of the epoxy resin and reactants, including the modified epoxy resin. If it is less than 10% by weight, good soldering heat resistance cannot be obtained, and if it is used in excess of 80% by weight, the elastic modulus becomes high and stress cannot be sufficiently reduced.
本発明に用いられる(c)の無機充填材としては例えば
結晶シリカ、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
ワイト等の粉体、あるいはガラス繊維、炭素繊維等の単
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、溶融性等の破砕状およびまたは
球状シリカ粉末が用いられる。その配合量は、ビスマレ
イミドとジアミンの反応物あるいはビスマレイミドとジ
アミンの反応物および変性エポキシ樹脂を含むエポキシ
樹脂の総量100重量部に対して150〜900重量部
が好ましく、150重量部未満では熱膨張率が大きく、
良好な耐熱衝撃性は得られない。Examples of the inorganic filler (c) used in the present invention include powders such as crystalline silica, fused silica, alumina, talc, calcium silicate, calcium carbonate, mica, clay, and titanium white, or glass fibers and carbon fibers. From the viewpoint of thermal expansion coefficient, thermal conductivity, etc., crushed and/or spherical silica powders that are crystalline or meltable are usually used. The blending amount is preferably 150 to 900 parts by weight based on 100 parts by weight of the total amount of epoxy resin containing the reaction product of bismaleimide and diamine or the reaction product of bismaleimide and diamine and modified epoxy resin. The expansion rate is large,
Good thermal shock resistance cannot be obtained.
また900重量部を超えると樹脂の流動性が低下し、成
形性が悪化する。Moreover, when it exceeds 900 parts by weight, the fluidity of the resin decreases and moldability deteriorates.
本発明の(d)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、電気特性からフェノールノボラ
ック、クレゾールノボラックなどのグリシジル化物等の
ノボラックエポキシ樹脂が好ましいが、その他の1分子
に2ヶ以上の活性水素を有する化合物、例えばビスフェ
ノールA、ビスヒドロキシジフェニルメタン、レゾルシ
ン、ビスヒドロキシジフェニルエーテル、テトラブロム
ビスフェノールA等の多価フェノール類、エチレングリ
コール、ネオペンチルグリコール、クリセリン、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、ポリプロピレングリコール、ビスフェノー
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
シクロベンタジエンジエポキサイド、ブタジェンダイマ
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。As the epoxy resin used in (d) 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 novolac and cresol novolac can be used in view 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 polyhydric phenols such as bisphenol A, bishydroxydiphenylmethane, resorcinol, bishydroxydiphenyl ether, and tetrabromobisphenol A, and ethylene. Glycol, neopentyl glycol, chrycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol, bisphenol A-ethylene oxide adduct, polyhydric alcohols such as trishydroxyethyl isocyanurate, ethylenediamine, polyamino compounds such as aniline, adipic acid,
Glycidyl-type epoxy resins obtained by reacting polyhydric carboxy compounds such as phthalic acid and isophthalic acid with epichlorohydrin or 2-methylepichlorohydrin, aliphatic (alicyclic It is possible to use one or more epoxy resins selected from epoxy resins of the following groups.
本発明の(d)に於ける変成エポキシ樹脂は本出願人に
より開示されている方法により製造することができる。The modified epoxy resin in (d) of the present invention can be produced by the method disclosed by the applicant.
(特開昭62−270617および特開昭62−273
222等)
即ち、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ポリマーをU合する事により製造す
る方法が代表的である。ここでビニルポリマーをつ(る
ために用いるビニルポリマーとしては、スチレン、ビニ
ルトルエン等の如きアルケニル芳香族類、メチルメタア
クリレート、ドデシルメタアクリレート、ブトキシエチ
ルメクアクリレート、グリシジルメタアクリレート、メ
チルアクリレート、ブチルアクリレート、2−エチルへ
キシルアクリレ−1・、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、メタアクリルアミドの如き
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、ビニルパーサテート、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、ブタンジエン
、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、ビニルシリコーン、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、メ
タクリル酸トリフロロエチル、メタクリル酸テトラフロ
ロプロピル等のメタクリル酸、アクリル酸の弗素化合物
等の如き重合性ビニル化合物を用いることもできる。(JP 62-270617 and JP 62-273
222, etc.) That is, a typical method for producing a graft polymer of an epoxy resin and a vinyl polymer is by U-merging the vinyl polymer to produce the vinyl polymer in the presence of the epoxy resin. Examples of vinyl polymers used for forming the vinyl polymer include styrene, alkenyl aromatics such as vinyltoluene, methyl methacrylate, dodecyl methacrylate, butoxyethyl mequaacrylate, glycidyl methacrylate, methyl acrylate, butyl acrylate, etc. , acrylic esters such as 2-ethylhexyl acrylate-1, hydroxyethyl acrylate, and trimethylolpropane triacrylate, acrylic compounds without ester groups such as acrylonitrile, acrylic acid, butoxymethylacrylamide, and methacrylamide, vinyl acetate, Representative examples include non-conjugated vinyl compounds such as vinyl laurate, vinyl persatate, vinyl chloride, vinyldene chloride, ethylene and allyl acetate, and conjugated diene compounds such as butane diene, isoprene and chloroprene. It is also possible to use polymerizable vinyl compounds such as fluorine compounds of methacrylic acid and acrylic acid, such as monomethyl malate, diethyl itaconate, trifluoroethyl methacrylate, and tetrafluoropropyl methacrylate.
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、ターシャリブチ
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、ターシャリブチルパービバレート、ジターシ
ャリブチルパーオキサイド、1.1−ビスターシャリブ
チルパーオキシ3.3.5− )リメチルシクロヘキサ
ン、ジメチルジターシャリブチルバーオキシヘキサン、
ターシャ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、キエメンハイドロパーオキサイド、ターシャリブチ
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、クーシャリブチルパーオキシマレイ
ン酸、琥珀酸パーオキサイド、クーシャリブチルパーオ
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。In order to polymerize the vinyl monomers described above to obtain a vinyl polymer, a radical initiator such as lauroyl peroxide, benzoyl peroxide, tert-butyl perbenzoate, dimethyl dibenzoyl peroxyhexane, tert-butyl pervivalate, diter Chaributyl peroxide, 1.1-bistarcharybutyl peroxy3.3.5-)limethylcyclohexane, dimethyl ditertiarybutyl peroxyhexane,
Tertiary butyl cumyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, quemene hydroperoxide, tertiary butyl peroxyallyl carbonate, dioctyl peroxydicarbonate, kusha butyl peroxymaleic acid, succinic acid peroxide, kushali Typically, radical polymerization is carried out using peroxides such as butylperoxyisopropyl carbonate and hydrogen peroxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile.
又、必要に応じて還元剤を併用していわゆるレドックス
重合させてもよく、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併用してもよ
い。In addition, so-called redox polymerization may be carried out by using a reducing agent in combination as necessary, and a polymerization inhibitor such as hydroquinone,
A chain transfer agent such as dodecyl mercaptan may also be used.
又、グラフト化促進の為にエポキシ樹脂に重合性二重結
合等の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0重合性二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、グリシジルメタアクリレート、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
アクリレートの如き官能基と重合性二重結合とを有する
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。In addition, it is effective to introduce a graftable chemical bond such as a polymerizable double bond into the epoxy resin in order to promote grafting. , methylol acrylamide,
Butoxymethylacrylamide, hydroxyethyl methacrylate, glycidyl methacrylate, maleic anhydride, monoethyl itaconate, monobutyl fumarate, chloromethylstyrene, phosphoxyethyl methacrylate, chlorohydroxypropyl methacrylate, parahydroxystyrene, dimethylaminoethyl A typical method is to react a compound having a functional group and a polymerizable double bond, such as methacrylate, with an epoxy resin in advance.
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
フリーのまま残っていてもかまわない。In the present invention, the epoxy resin or the vinyl polymer may remain free in the graft polymer without being grafted.
(d)の変性エポキシ樹脂は前記したエポキシ樹脂とと
ニルポリマーとのグラフト重合体の存在下に付加反応型
のシリコーンポリマーを常法により付加反応するか、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。The modified epoxy resin (d) can be obtained by addition-reacting an addition-reactive silicone polymer in the presence of the graft polymer of the above-mentioned epoxy resin and nil polymer, or by adding a monomer that forms a soft vinyl polymer. Obtained by polymerization using conventional methods.
即ち、付加反応型シリコーンゴムは、分子内にビニル基
を有するビニル変性シリコーンポリマーと分子内に活性
水素を有するハイドロジエン変性シリコーンポリマーが
シリル化反応による付加反応により生成するゴムであり
、ビニル変性シリコーンポリマーとは、分子の末端ある
いは内部にSi CI Clh結合を少なくとも1
個以上もったポリシロキサンをいい、ハイドロジエン変
性シリコーンポリマーとは、分子の末端あるいは内部に
Si H結合を少なくとも2個以上もったポリシロキ
サンをいう0両者は通常は組み合わせで市販されており
、これらの例としては、例えば東レシリコーン株式会社
のSI!−1821、信越化学株式会社のKE−120
4等があげられる。In other words, addition reaction silicone rubber is a rubber produced by an addition reaction between a vinyl-modified silicone polymer having a vinyl group in the molecule and a hydrogen-modified silicone polymer having active hydrogen in the molecule through a silylation reaction. A polymer has at least one Si CI Clh bond at the end or inside the molecule.
A hydrogen-modified silicone polymer refers to a polysiloxane having at least two or more SiH bonds at the end or inside of the molecule.The two are usually commercially available in combination; For example, Toray Silicone Co., Ltd.'s SI! -1821, KE-120 of Shin-Etsu Chemical Co., Ltd.
4th prize is given.
また、軟質ビニル重合体は軟質ビニル重合体を形成する
七ツマ−を常法により重合することにより得られる。Further, the soft vinyl polymer can be obtained by polymerizing a hexamer forming a soft vinyl polymer by a conventional method.
本発明に使用される軟質系ビニル重合体は、ビニル変性
シリコーンを主体とする重合体でなければならない、ビ
ニル変性シリコーンを主体とする重合体とは、ビニル変
性シリコーンの単独重合体もしくは共重合体またはビニ
ル変性シリコーンと他のビニルモノマーとの共重合体を
いう、ビニル変性シリコーンとしては、例えばメタアク
リロキシプロピルシロキサン、メタアクリロキシプロピ
ルアルコキシシラン、ビニルアルコキシシラン等があげ
られる、また他のビニルモノマーとしては前記のグラフ
ト重合体をつくる際に用いるモノマーは総て用いること
ができる。他のビニルモノマーの使用割合は、得られる
共重合体が軟質、即ち液状ないしゴム状であり、かつそ
の粒子径が1.0μ以下である範囲であり、モノマーの
種類にもよるが通常全七ツマ−の80重量%以下である
。The soft vinyl polymer used in the present invention must be a polymer mainly composed of vinyl-modified silicone. The polymer mainly composed of vinyl-modified silicone means a homopolymer or copolymer of vinyl-modified silicone. The vinyl-modified silicone refers to a copolymer of a vinyl-modified silicone and another vinyl monomer. Examples of the vinyl-modified silicone include methacryloxypropylsiloxane, methacryloxypropyl alkoxysilane, vinyl alkoxysilane, and other vinyl monomers. All the monomers used in preparing the graft polymers mentioned above can be used. The proportion of other vinyl monomers used is such that the obtained copolymer is soft, that is, liquid or rubber-like, and has a particle size of 1.0μ or less, and usually all seven vinyl monomers are used, depending on the type of monomer. It is 80% by weight or less of the total weight.
本発明の目的である低応力化を果たし、耐衝撃性を改良
するためには付加反応型シリコーン及び軟質ビニル重合
体の平均粒子径は1.0μ以下、好ましくは0.5μ以
下、更に好ましくは0.01μ以上2.0μ以下である
。付加反応型シリコーン及び軟質ビニル重合体の平均粒
子径が1.0μを超えると低応力化を果たせず、耐熱衝
撃性も改良されない。In order to achieve the purpose of the present invention of reducing stress and improving impact resistance, the average particle diameter of the addition reaction silicone and soft vinyl polymer is 1.0μ or less, preferably 0.5μ or less, and more preferably 0.5μ or less. It is 0.01μ or more and 2.0μ or less. If the average particle diameter of the addition-reactive silicone and soft vinyl polymer exceeds 1.0 μm, stress reduction cannot be achieved and thermal shock resistance cannot be improved.
付加反応型シリコーン及び軟質ビニル重合体の粒径のコ
ントロールは、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、量、付加反応型シリコーン及
び軟質ビニル重合体を形成するポリマーもしくはモノマ
ー組成の選択によって可能であるが、エポキシ樹脂に導
入する二重結合の量によってコントロールすることがで
きる。The particle size of the addition reaction type silicone and soft vinyl polymer can be controlled by selecting the type and amount of the vinyl polymer that forms the graft polymer with the epoxy resin, and the polymer or monomer composition that forms the addition reaction type silicone and the soft vinyl polymer. However, it can be controlled by the amount of double bonds introduced into the epoxy resin.
エポキシ樹脂とビニルポリマーのグラフト重合体を含ま
ないエポキシ樹脂中にシリコーンポリマーを均一な粒子
と分散させることは、例えばシランカップリング剤、変
性シリコーンオイル等を使用したとしても困難である。It is difficult to disperse a silicone polymer into uniform particles in an epoxy resin that does not contain a graft polymer of an epoxy resin and a vinyl polymer, even if a silane coupling agent, modified silicone oil, etc. are used, for example.
付加反応型シリコーンゴム及び軟質ビニル重合体を形成
するポリマーもしくはモノマーの使用量は、エポキシ樹
脂100重量部に対して1−100重量部である。The amount of the polymer or monomer used to form the addition reaction type silicone rubber and the soft vinyl polymer is 1 to 100 parts by weight per 100 parts by weight of the epoxy resin.
本発明の組成物は(d)の変性エポキシ樹脂を必須成分
とするが、上記付加反応型シリコーンゴム及び/または
軟質ビニル重合体を所望の量に!rI整するために未変
性多官能エポキシを含有してもよい、未変性多官能エポ
キシとしては、前述の(d)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(、異なってい
ても差し支えない。The composition of the present invention contains the modified epoxy resin (d) as an essential component, and the addition reaction type silicone rubber and/or soft vinyl polymer are added in desired amounts! As the unmodified polyfunctional epoxy that may contain an unmodified polyfunctional epoxy to adjust rI, all the epoxy resins used in (d) above can be used, and both may be the same (or different There is no problem.
変性エポキシ樹脂の使用量は、付加反応型シリコーンゴ
ムおよび/または軟質ビニル重合体の所望量と、変性エ
ポキシ樹脂中に含まれる付加反応型シリコーンゴムおよ
び/または軟質ビニル重合体の量により決める事ができ
る。The amount of modified epoxy resin to be used can be determined based on the desired amount of addition reaction type silicone rubber and/or soft vinyl polymer and the amount of addition reaction type silicone rubber and/or soft vinyl polymer contained in the modified epoxy resin. can.
また、付加反応によって得るシリコーンゴムおよび/ま
たは軟質ビニル重合体の量はビスマレイミド、ジアミン
および変性エポキシ樹脂を含むエポキシ樹脂の総量に対
して0.51!1%以上必要であり、特に1〜30重量
%が好ましい、0,5重量%未満では低応力化が達成さ
れない。In addition, the amount of silicone rubber and/or soft vinyl polymer obtained by addition reaction is required to be 0.51% or more based on the total amount of epoxy resin containing bismaleimide, diamine, and modified epoxy resin, particularly 1 to 30%. % by weight is preferred; if it is less than 0.5% by weight, low stress will not be achieved.
本発明の半導体封止用樹脂組成物は前記(a)、(b)
、(c)あるいは(a) 、(b) 、(c) 、(
d)を必須成分として含有するが、実用に際してはノボ
ラック型フェノール樹脂、アラルキル系フェノール樹脂
等のフェノール類、ジアリルフタレート、トリアリルイ
ソシアヌレート、o、 o’−ジアリルビスフェノール
A等のマレイミド樹脂に対して一般的に使用される反応
性希釈剤、イミダゾール類、三級アミン類、第4アンモ
ニウム塩類、有機金属化合物顛、有機ホスフィン類有機
過酸化物、アゾ化合物等の硬化促進剤、脂肪酸アミド、
脂肪酸塩、ワックス等の離型剤、ブロム化合物、アンチ
モン、リン等の難燃剤、カーボンブラック等の着色剤、
シランカップリング剤等適宜配合することも可能である
。The resin composition for semiconductor encapsulation of the present invention includes the above (a) and (b).
, (c) or (a) , (b) , (c) , (
d) as an essential component, but in practical use, it is used for phenols such as novolac type phenolic resins and aralkyl phenolic resins, and maleimide resins such as diallyl phthalate, triallyl isocyanurate, o, o'-diallyl bisphenol A, etc. Commonly used reactive diluents, imidazoles, tertiary amines, quaternary ammonium salts, organometallic compounds, organic phosphines, organic peroxides, curing accelerators such as azo compounds, fatty acid amides,
Fatty acid salts, mold release agents such as wax, bromine compounds, antimony, flame retardants such as phosphorus, colorants such as carbon black,
It is also possible to add a silane coupling agent or the like as appropriate.
本発明の半導体封止用樹脂組成物は、ミキサー等によっ
て十分プレミックスした後、熱ロール、あるいはニーダ
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。The resin composition for semiconductor encapsulation of the present invention can be easily obtained as a molding material by sufficiently premixing with a mixer or the like, kneading with a melt mixer such as a hot roll or kneader, and then cooling and pulverizing. I can do it.
〔実施例〕
本発明を実施例によっ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。[Example] The present invention will be specifically explained with reference to Examples, but the present invention is not limited to the Examples. In the following, parts mean parts by weight unless otherwise specified.
製造例1 (ビスマレイミドとジアミンのプレポリマー
の製造)
N、N’−4,4°−ビス(3−アミノフェノキシ)ビ
フェニルビスマレイミド粉末100重量部、4.4’−
ビス(3−アミノフェノキシ)ビフェニル粉末35重量
部を190’Cの熱ロールで10分間反応させた後冷却
し更に粉砕して、軟化点102’Cのプレポリマー(以
下、a−1という)を得た。Production Example 1 (Production of prepolymer of bismaleimide and diamine) N,N'-4,4°-bis(3-aminophenoxy)biphenylbismaleimide powder 100 parts by weight, 4.4'-
35 parts by weight of bis(3-aminophenoxy)biphenyl powder was reacted with a heated roll at 190'C for 10 minutes, then cooled and further ground to obtain a prepolymer (hereinafter referred to as a-1) with a softening point of 102'C. Obtained.
製造例2(ビスマレイミドとジアミンのプレポリマーの
製造)
N、N″−2,2−ビス(4−(3−アミノフェノキシ
)フェニル〕プロパンビスマレイミド粉末100重量部
、2.2−ビス[4−(3−アミノフェノキシ)フェニ
ル]プロパン粉末35貴重部ヲ160°Cの熱ロールで
10分間反応させた後冷却し更に粉砕して、軟化点95
°Cのプレポリマー(以下、a−2という)を得た。Production Example 2 (Production of prepolymer of bismaleimide and diamine) 100 parts by weight of N,N″-2,2-bis(4-(3-aminophenoxy)phenyl)propane bismaleimide powder, 2.2-bis[4 -(3-Aminophenoxy)phenyl]propane powder 35 The valuable part was reacted with a hot roll at 160°C for 10 minutes, then cooled and further crushed to obtain a softening point of 95.
℃ prepolymer (hereinafter referred to as a-2) was obtained.
製造例3(ビスマレイミドとジアミンのプレポリマーの
製造)
N、 N’−ビス(4−(3−アミノフェノキシ)フェ
ニル〕スルフィドビスマレイミド粉末100重it部、
4,4゛−ジアミノジフェニルメタン粉末18重量部を
150’Cの熱ロールで10分間反応させた後冷却し更
に粉砕して、軟化点78°Cのプレポリマー(以下、a
−3という)を得た。Production Example 3 (Production of prepolymer of bismaleimide and diamine) 100 parts by weight of N,N'-bis(4-(3-aminophenoxy)phenyl)sulfide bismaleimide powder,
18 parts by weight of 4,4'-diaminodiphenylmethane powder was reacted with a heated roll at 150'C for 10 minutes, then cooled and further ground to obtain a prepolymer (hereinafter referred to as a) with a softening point of 78°C.
−3).
比較製造例4(ビスマレイミドとジアミンのプレポリマ
ーの製造)
N、N″−4,4”−ジフェニルメタンビスマレイミド
粉末100重量部、4,4゛−ジアミノジフェニルメタ
ン粉末28重量部を150°Cの熱ロールで20分間反
応させた後冷却し更に粉砕して、軟化点150°Cのプ
レポリマー(以下、a−4という)を得た。Comparative Production Example 4 (Production of prepolymer of bismaleimide and diamine) 100 parts by weight of N,N″-4,4″-diphenylmethane bismaleimide powder and 28 parts by weight of 4,4′-diaminodiphenylmethane powder were heated at 150°C. After reacting with a roll for 20 minutes, the mixture was cooled and further pulverized to obtain a prepolymer (hereinafter referred to as a-4) with a softening point of 150°C.
製造例5(変性エポキシ樹脂の製造)
オルソクレゾールノボラックエポキシ樹脂(エポキシ当
1200) 100部、トルエン10部、メタクリル
酸1.2部を3級アミンの存在下で120〜125゛C
で2時間反応させた後、メタアクリロキシプロピルシリ
コーンオリゴマー(信越化学株式会社製)10部、アブ
ビスイソバレロニトリル0.4部、トルエン50部を8
0℃で4時間反応させる。更に付加反応型シリコーンポ
リマーとして、ビニル変性ポリシロキサン27.5部と
ハイドロジエン変性ポリシロキサン27.5部(いずれ
も信越化学株式会社製KE1204)を加え激しく攪拌
し2時間反応させた。Production Example 5 (Production of modified epoxy resin) 100 parts of orthocresol novolac epoxy resin (1200 parts per epoxy), 10 parts of toluene, and 1.2 parts of methacrylic acid were heated at 120 to 125°C in the presence of a tertiary amine.
After reacting for 2 hours with
React at 0°C for 4 hours. Furthermore, 27.5 parts of vinyl-modified polysiloxane and 27.5 parts of hydrogen-modified polysiloxane (both KE1204 manufactured by Shin-Etsu Chemical Co., Ltd.) were added as addition reaction type silicone polymers, and the mixture was stirred vigorously and allowed to react for 2 hours.
その後、更に130°Cにおいて減圧にて脱溶剤し、粒
径0.2〜0.5μのシリコーンゴムが分散した変性エ
ポキシ樹脂(以下、b−1という)(エポキシ当量33
7)を得た。Thereafter, the solvent was further removed under reduced pressure at 130°C, and the modified epoxy resin (hereinafter referred to as b-1) in which silicone rubber with a particle size of 0.2 to 0.5μ was dispersed (epoxy equivalent: 33
7) was obtained.
製造例6(変性エポキシ樹脂の製造)
オルソクレゾールノボラックエポキシ樹脂(エポキシ当
量200) 100部、トルエン100部、メタクリ
ル酸1.2部を3級アミンの存在下で120〜125°
Cで2時間反応させた後、ブチルアクリレート4部、グ
リシジルヌククリレート0.2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°C
で1時間反応させた。さらにメタクリロキシプロピルシ
ロキサン50部、ネオペンチルグリコールジアクリレー
ト1部、 1.1−ビス(1−ブチルパーオキシ) −
3,3,5−)リシクロヘキサン0.15部を連続滴下
しながら4時間、その後見に4IIS間反応させた後、
減圧にて脱溶剤し、粒径0.2−0.5μの軟質ビニル
重合体が分散した変性エポキシ樹脂(以下、b−2とい
う)(エポキシ当1313)を得た。Production Example 6 (Production of modified epoxy resin) 100 parts of orthocresol novolac epoxy resin (epoxy equivalent: 200), 100 parts of toluene, and 1.2 parts of methacrylic acid were heated at 120 to 125° in the presence of a tertiary amine.
After reacting at C for 2 hours, 4 parts of butyl acrylate, 0.2 part of glycidyl nucleate, and 0.05 part of t-butylperoxy-2-ethylhexanoate were added at 100°C.
The reaction was carried out for 1 hour. Furthermore, 50 parts of methacryloxypropylsiloxane, 1 part of neopentyl glycol diacrylate, 1.1-bis(1-butylperoxy) -
After 4 hours of continuous dropwise addition of 0.15 parts of 3,3,5-)licyclohexane, the reaction was continued for 4 IIS, and then
The solvent was removed under reduced pressure to obtain a modified epoxy resin (hereinafter referred to as b-2) (1313 epoxy resin) in which a soft vinyl polymer having a particle size of 0.2 to 0.5 μm was dispersed.
実施例1−3および比較例1
第1表に示す配合物を90〜120°C熱ロールにて3
分間溶融混合した後、冷却粉砕し打錠した成形用樹脂組
成物を得た。Example 1-3 and Comparative Example 1 The formulations shown in Table 1 were heated in a heated roll at 90 to 120°C.
After melt-mixing for a minute, a resin composition for molding was obtained by cooling, crushing, and tableting.
この組成物を用い、トランスファー成形(185°C1
80kg/c+! 5分間)により物性試験用の試験
片を成形し、150°Cで2時間、200°Cで2時間
、更に250°Cで2時間の後硬化を行った後、各試験
を行った。試験結果を第2表に示す。Using this composition, transfer molding (185°C1
80kg/c+! After molding test pieces for physical property tests (for 5 minutes) and post-curing at 150°C for 2 hours, 200°C for 2 hours, and further 250°C for 2 hours, each test was conducted. The test results are shown in Table 2.
実施例4.5および比較例2.3
第3表に示す配合物を90〜120°C熱ロールにて3
分間溶融混合した後、冷却粉砕し打錠した成形用樹脂組
成物を得た。Example 4.5 and Comparative Example 2.3 The formulations shown in Table 3 were heated in a heated roll at 90-120°C.
After melt-mixing for a minute, a resin composition for molding was obtained by cooling, crushing, and tableting.
この組成物を用い、トランスファー成形(180’C,
70kg/cd 3分間)により試験用の100pi
nフラツトパンケージ(20+*鴎×30IllI×2
.5mm、 10mm×1011Ilsの試験素子搭載
)及び物性測定用の試験片を成形し、200″Cで6時
間後硬化を行った後、各試験を行った。試験結果を第4
表に示す。Using this composition, transfer molding (180'C,
70kg/cd for 3 minutes) for testing at 100pi
n flat pan cage (20+* seagull x 30IllI x 2
.. 5 mm, 10 mm x 1011 Ils test elements) and test pieces for measuring physical properties were molded and post-cured at 200''C for 6 hours, and then each test was conducted.
Shown in the table.
第1表
配合表
第3表記合表
第2表
u3銹吉果
第4表
シラ険1吉果
ず札
〔発明の効果〕
実施例及び比較例にて説明した如く、本説明による半導
体封止用樹脂組成物は、高耐熱性で低吸水率、応力が小
さく、優れた耐熱衝撃性と半田耐熱性を示すことから、
この樹脂組成物を集積度の高い半導体あるいはフラット
パッケージの如き小型・薄型の半導体の封正に用いた場
合、優れた信転性を得ることが出来工業的にきわめて有
益な発明でありまず。Table 1: Combination table: 3: Combination table: Table 2: U3: Lucky fruit; Table: 4: Shiraken: 1: Lucky fruit card [Effects of the invention] As explained in the examples and comparative examples, for semiconductor encapsulation according to the present explanation. The resin composition has high heat resistance, low water absorption, low stress, and exhibits excellent thermal shock resistance and soldering heat resistance.
When this resin composition is used to encapsulate highly integrated semiconductors or small and thin semiconductors such as flat packages, excellent reliability can be obtained, making it an extremely useful invention industrially.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (5)
たは▲数式、化学式、表等があります▼ よりなる2価の基を表し、Xは直結、炭素数1〜10の
2価の炭化水素基、6フッ素化されたイソプロピリデン
基、カルボニル基、チオ基、スルフィニル基、スルホニ
ル基又はオキシドから成る群より選ばれた基を表す。) にて表されるビスマレイミド化合物、 (b)一般式(II) ▲数式、化学式、表等があります▼(II) (R_2は少なくとも2個の炭素数を有する2価の有機
基を表す。)にて表されるジアミン化合物、(c)無機
充填剤、 を含有することを特徴とする半導体封止用樹脂組成物。(1) Essentially (a) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I ) (In the formula, R_1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ represents a divalent group consisting of a direct bond, a divalent hydrocarbon group with 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group or a group selected from the group consisting of oxides.) (b) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (R_2 is at least two A diamine compound represented by (representing a divalent organic group having a carbon number of ); and (c) an inorganic filler.
ビスマレイミド化合物と、一般式(II)にて表されるジ
アミン化合物とを予めプレポリマー化して用いることを
特徴とする請求項(1)項記載の半導体封止用樹脂組成
物。(2) The bismaleimide compound represented by the general formula (I) in claim (1) and the diamine compound represented by the general formula (II) are prepolymerized and used. The resin composition for semiconductor encapsulation according to claim (1).
または▲数式、化学式、表等があります▼ よりなる2価の基を表し、Xは直結、炭素数1〜10の
2価の炭化水素基、6フッ素化されたイソプロピリデン
基、カルボニル基、チオ基、スルフィニル基、スルホニ
ル基又はオキシドから成る群より選ばれた基を表す。) にて表されるビスマレイミド化合物、 (b)一般式(II) ▲数式、化学式、表等があります▼(II) (R_2は少なくとも2個の炭素数を有する2価の有機
基を表す。)にて表されるジアミン化合物、(c)無機
充填剤、 (d)エポキシ樹脂とビニルポリマーとのグラフト重合
体中にシリコーンポリマーが1.0μ以下の平均粒子径
で均一に分散された変性エポキシ樹脂、を含有すること
を特徴とする半導体封止用樹脂組成物。(3) Essentially (a) General formula (I) in claim (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 is ▲ Numerical formulas, chemical formulas, tables, etc. There is▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents a divalent group consisting of represents a group selected from the group consisting of a sulfinyl group, a sulfonyl group, a sulfonyl group, or an oxide. ) A bismaleimide compound represented by (b) General formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (R_2 represents a divalent organic group having at least 2 carbon atoms. ), (c) an inorganic filler, and (d) a modified epoxy in which a silicone polymer is uniformly dispersed in a graft polymer of an epoxy resin and a vinyl polymer with an average particle diameter of 1.0μ or less. A resin composition for semiconductor encapsulation, comprising a resin.
るビスマレイミド化合物と、一般式(II)にて表される
ジアミン化合物とを予めプレポリマー化して用いること
を特徴とする請求項(3)記載の半導体封止用樹脂組成
物。(4) Claim (3) is characterized in that the bismaleimide compound represented by the general formula (I) and the diamine compound represented by the general formula (II) are prepolymerized and used. The resin composition for semiconductor encapsulation according to claim (3).
れたシリコーンポリマーが、付加反応型のシリコーンポ
リマーが反応してなるシリコーンゴムおよび/またはビ
ニル変性シリコーン重合体を主体とする軟質ビニル重合
体である請求項(3)記載の半導体封止用樹脂組成物。(5) In claim (3), the silicone polymer dispersed in the epoxy resin is a silicone rubber formed by reacting an addition reaction type silicone polymer and/or a soft vinyl mainly composed of a vinyl-modified silicone polymer. The resin composition for semiconductor encapsulation according to claim 3, which is a polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3001189A JPH02209965A (en) | 1989-02-10 | 1989-02-10 | Resin composition for sealing semiconductor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3001189A JPH02209965A (en) | 1989-02-10 | 1989-02-10 | Resin composition for sealing semiconductor |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02209965A true JPH02209965A (en) | 1990-08-21 |
Family
ID=12291926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3001189A Pending JPH02209965A (en) | 1989-02-10 | 1989-02-10 | Resin composition for sealing semiconductor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02209965A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010235690A (en) * | 2009-03-30 | 2010-10-21 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminated board and multilayer printed wiring board using the same |
-
1989
- 1989-02-10 JP JP3001189A patent/JPH02209965A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010235690A (en) * | 2009-03-30 | 2010-10-21 | Hitachi Chem Co Ltd | Thermosetting insulating resin composition, and insulating film with support, prepreg, laminated board and multilayer printed wiring board using the same |
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