JP2008163116A - Resin composition for sealing semiconductor, and semiconductor device - Google Patents
Resin composition for sealing semiconductor, and semiconductor device Download PDFInfo
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- JP2008163116A JP2008163116A JP2006352347A JP2006352347A JP2008163116A JP 2008163116 A JP2008163116 A JP 2008163116A JP 2006352347 A JP2006352347 A JP 2006352347A JP 2006352347 A JP2006352347 A JP 2006352347A JP 2008163116 A JP2008163116 A JP 2008163116A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 54
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 238000007789 sealing Methods 0.000 title claims abstract description 24
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 229920001400 block copolymer Polymers 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical group 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- -1 siloxane unit Chemical group 0.000 claims description 90
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000001923 cyclic compounds Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000005538 encapsulation Methods 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 239000003341 Bronsted base Substances 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims 1
- 230000035939 shock Effects 0.000 abstract description 13
- 239000003566 sealing material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- 150000002430 hydrocarbons Chemical group 0.000 description 22
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 18
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910000679 solder Inorganic materials 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 150000001721 carbon Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000006039 1-hexenyl group Chemical group 0.000 description 3
- 125000005999 2-bromoethyl group Chemical group 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 125000000068 chlorophenyl group Chemical group 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000004212 difluorophenyl group Chemical group 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-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
- 239000004593 Epoxy Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QHMVQKOXILNZQR-UHFFFAOYSA-N 1-methoxyprop-1-ene Chemical group COC=CC QHMVQKOXILNZQR-UHFFFAOYSA-N 0.000 description 1
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910002026 crystalline silica Inorganic materials 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 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 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明はポリエステル−ポリシロキサンブロック共重合体が配合されてなる半導体封止用樹脂組成物に関し、さらに詳しくはエポキシ樹脂との相溶性や親和性に優れたポリエステルセグメントとポリシロキサンセグメントからなるブロック共重合体をエポキシ樹脂に対して分散・固定化し、低応力性、耐熱性、耐熱衝撃性、耐湿性、成形性などの特性を向上させた半導体封止用樹脂組成物ならびに半導体装置に関する。 The present invention relates to a resin composition for encapsulating a semiconductor in which a polyester-polysiloxane block copolymer is blended. More specifically, the present invention relates to a block copolymer comprising a polyester segment and a polysiloxane segment having excellent compatibility and affinity with an epoxy resin. The present invention relates to a resin composition for semiconductor encapsulation and a semiconductor device in which a polymer is dispersed and fixed in an epoxy resin to improve characteristics such as low stress, heat resistance, thermal shock resistance, moisture resistance, and moldability.
近年、ダイオード、トランジスタ、集積回路などの電子部品を熱硬化性樹脂を用いて封止することが広く行われている。これは、ガラス、金属、セラミックスを用いたハーメチックシール方式に比較して原料コストが安い上に大量生産に適するといった経済的利点を有するからである。この種の封止樹脂としては、熱硬化性樹脂のなかでもエポキシ樹脂が一般的に用いられており、特にノボラック型フェノール樹脂を硬化剤として配合したエポキシ樹脂組成物が、他の硬化剤を使用したものに比べて、成形性、耐湿性に優れ、かつ安価であるために封止用樹脂材料の主流となっている。 In recent years, electronic parts such as diodes, transistors, and integrated circuits have been widely sealed using a thermosetting resin. This is because the raw material cost is lower than that of the hermetic seal method using glass, metal, and ceramics, and it has economic advantages such as being suitable for mass production. As this kind of sealing resin, epoxy resin is generally used among thermosetting resins, especially epoxy resin composition containing novolak type phenol resin as a curing agent uses other curing agents. Compared to the above, it is excellent in moldability and moisture resistance, and is inexpensive, so it has become the mainstream of resin materials for sealing.
特に最近では、半導体チップの高集積化が進み、それに伴いチップサイズが大型化してきており、またパッケージの形状は基板への高密度実装化、表面実装化に伴い、チップの大型化とは逆にフラットパッケージに見られる如く薄型化傾向にある。このため従来の樹脂封止では見られなかった不良現象が発生するようになった。すなわち、封止樹脂とチップの熱膨張率の差に起因する樹脂の応力がチップの大型化、封止樹脂層の薄肉化のため、熱衝撃によりパッシベーション膜のクラック、アルミ配線スライドあるいは封止樹脂のクラックといった破壊現象を引き起こし、また、表面実装化に伴いパッケージそのものが半田浴温度にさらされるため、パッケージ内の水分が急激に膨張し、パッケージにクラックといっ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要因となっている。したがって、この応力が小さく、半田浴耐熱性に優れた封止用樹脂材料の開発が望まれている。また、エポキシ樹脂組成物は、表面実装のためにアンダーフィルとしても用いられ、この場合には、硬化物が上記の応力緩和効果を有すると共に、エポキシ樹脂組成物が基板とチップとの間に均一に封入できるように、低粘度で良好な流動性を有することが必要になっている。 In particular, recently, the integration density of semiconductor chips has increased, and the chip size has increased accordingly, and the shape of the package is opposite to the increase in size of the chip due to higher density mounting on the substrate and surface mounting. However, as seen in the flat package, it tends to be thinner. For this reason, the defect phenomenon which was not seen with the conventional resin sealing came to generate | occur | produce. That is, the stress of the resin due to the difference in thermal expansion coefficient between the sealing resin and the chip causes the chip to be larger and the sealing resin layer to be thinner. In addition, since the package itself is exposed to the solder bath temperature due to surface mounting, the moisture in the package rapidly expands, causing a breakdown phenomenon such as a crack in the package, thereby improving the moisture resistance of the semiconductor. This is a factor that lowers the reliability. Therefore, it is desired to develop a sealing resin material that has a low stress and is excellent in solder bath heat resistance. The epoxy resin composition is also used as an underfill for surface mounting. In this case, the cured product has the stress relaxation effect described above, and the epoxy resin composition is uniform between the substrate and the chip. It is necessary to have a low viscosity and good fluidity so that it can be encapsulated.
かか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ップのそれとの差を小さくすることが考えられるが、樹脂とチップの熱膨張率の差は大きく、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配合しなければならず、成形性を損なうおそれがある。一方、上記問題に対処して、樹脂に可塑剤を添加したり、あるいは可とう性を有する樹脂を用いることにより、樹脂の弾性率を下げて応力を小さくすることが試みられたが、この方法により得られた硬化物は耐熱性が低いという難点があった。 As a method of reducing such stress, it is conceivable to reduce the thermal expansion coefficient of the resin to reduce the difference from that of the chip. However, the difference between the thermal expansion coefficient of the resin and the chip is large, and in order to reduce this, A large amount of an inorganic filler having a low coefficient of thermal expansion must be blended in the resin, which may impair the moldability. On the other hand, in order to cope with the above problem, an attempt was made to reduce the stress by reducing the elastic modulus of the resin by adding a plasticizer to the resin or using a resin having flexibility. The cured product obtained by the above method had a drawback of low heat resistance.
また、特許文献１には封止樹脂中に有機系ゴムを粒子状に分散させることにより耐熱性を保持しつつ耐クラック性を付与する方法が提案されているが、この方法により得られる硬化物は、半田浴の如き封止樹脂のガラス転移温度を越える高温における耐衝撃性に劣るなどの難点があった。さらに、特許文献２には直鎖状シロキサン部分を１０重量％以上含む微粒子状のシリコーン硬化物を、また特許文献３には熱硬化性シリコーン組成物を熱風中に噴霧してエラストマー状に硬化させた球状硬化物を封止樹脂に配合し、熱膨張係数および内部応力を改善する方法が提案されている。しかしながら、これらの硬化物は凝集性が強いために分散性が悪く、また強度が低いために配合時に破壊を受けやすいことから、耐熱性、耐熱衝撃性、低応力性などのシリコーン本来の樹脂改質機能が発現しにくいという欠点を有しており、上記問題の改善には不十分であった。 Further, Patent Document 1 proposes a method of imparting crack resistance while maintaining heat resistance by dispersing organic rubber in a sealing resin in the form of particles, and a cured product obtained by this method. However, there are problems such as inferior impact resistance at a high temperature exceeding the glass transition temperature of a sealing resin such as a solder bath. Furthermore, Patent Document 2 sprays a particulate silicone cured product containing a linear siloxane moiety of 10% by weight or more, and Patent Document 3 sprays a thermosetting silicone composition into hot air to cure it into an elastomer. There has been proposed a method for improving the thermal expansion coefficient and internal stress by blending a spherical cured product with a sealing resin. However, these hardened products have poor cohesiveness due to their strong cohesiveness, and because of their low strength, they are susceptible to breakage during compounding, so that the silicone's original resin modifications such as heat resistance, thermal shock resistance, and low stress properties have been improved. It has a defect that the quality function is difficult to be expressed, and is insufficient for improving the above problem.
さらに、特許文献４にはエポキシ樹脂にポリカプロラクトン−ポリシロキサンブロック共重合体を含有する熱硬化性組成物が提案されているが、この発明で好適とされるポリカプロラクトン−ポリシロキサンブロック共重合体の製造方法は特許文献５に開示されているものの、この製造方法は工業的に難易度が高いためにコストも高いものとなり、さらには得られるブロック共重合体の構造にも制約があり、結果としてエポキシ樹脂に混合した場合の成形加工性、耐熱性、耐熱衝撃性などの性能面の向上も不十分であった。
本発明の目的は、半導体封止材用途に好適に用いて、格段に向上した低応力性、耐熱性、耐熱衝撃性、耐湿性、成形性などの特性を有すると共に、アンダーフィルに用いて優れた流動性を有する半導体封止用樹脂組成物、ならびに当該組成物によって封止された半導体装置を提供することにある。 The object of the present invention is suitably used for semiconductor encapsulant applications, and has characteristics such as markedly improved low stress, heat resistance, thermal shock resistance, moisture resistance and moldability, and is excellent for use in underfill. Another object of the present invention is to provide a semiconductor sealing resin composition having fluidity and a semiconductor device sealed with the composition.
本発明者らは上記目的を達成するため鋭意検討を重ねた結果、特定のポリエステルセグメントと特定のポリシロキサンセグメントからなるブロック共重合体を配合した半導体封止用樹脂組成物が上記目的を達成することを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have achieved the above object by using a resin composition for encapsulating a semiconductor comprising a block copolymer comprising a specific polyester segment and a specific polysiloxane segment. As a result, the present invention has been completed.
すなわち、本発明は、（ａ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂 １００重量部、
（ｂ）１分子中に２個以上のフェノール性水酸基を有する化合物 （ａ）のエポキシ樹脂と（ｂ）のフェノール性水酸基含有化合物の当量比（（ｂ）の水酸基数／（ａ）のエポキシ基数）が０．５〜１．５の範囲になる量、
および（ｃ）一般式（１）
Ｂは一般式（３）
(B) Compound having two or more phenolic hydroxyl groups in one molecule Equivalent ratio of (a) epoxy resin and (b) phenolic hydroxyl group-containing compound (number of hydroxyl groups in (b) / number of epoxy groups in (a) ) In the range of 0.5 to 1.5,
And (c) General formula (1)
B is the general formula (3)
本発明の半導体封止用組成物は、低応力性、耐熱性、耐熱衝撃性、耐湿性、成形性に優れ、アンダーフィルに用いるに適した流動性を有する。本発明の組成物により封止した半導体装置は、これらの特性を具備することにより、例えば、ボンディングワイヤの変形、ボンディングワイヤのオープン、樹脂クラック、ペレットクラックなどの不都合の発生が防止され、２５０℃以上の半田浴浸漬後においても耐湿性や機械的強度などの特性が低下することもなく、信頼性の高いものとなる。 The composition for semiconductor encapsulation of the present invention is excellent in low stress property, heat resistance, thermal shock resistance, moisture resistance and moldability, and has fluidity suitable for use in underfill. The semiconductor device encapsulated with the composition of the present invention has these characteristics, thereby preventing the occurrence of inconveniences such as deformation of the bonding wire, opening of the bonding wire, resin crack, pellet crack, and the like. Even after immersion in the solder bath as described above, characteristics such as moisture resistance and mechanical strength do not deteriorate, and the reliability is high.
以下、本発明について具体的に説明する。本発明の（ａ）１分子中に２個以上のエポキシ基を有するエポキシ樹脂としては、半導体封止用エポキシ樹脂成形材料で一般に使用されているものであれば制限はなく、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール類とアルデヒド類のノボラック樹脂をエポキシ化したもの、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、アルキル置換ビフェノールなどのジグリシジルエーテル、ジアミノジフェニルメタン、イソシアヌル酸などのポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂、オレフィン結合を過酢酸などの過酸で酸化して得られる線状脂肪族エポキシ樹脂、及び脂環族エポキシ樹脂等を挙げることができ単独又は２種類以上併用してもよい。 Hereinafter, the present invention will be specifically described. The epoxy resin having two or more epoxy groups in one molecule of the present invention is not limited as long as it is generally used in epoxy resin molding materials for semiconductor encapsulation, and is a phenol novolac type epoxy resin. Epoxidized phenol and aldehyde novolak resins including orthocresol novolac type epoxy resins, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted biphenols, diaminodiphenylmethane, isocyanuric acid, etc. A glycidylamine type epoxy resin obtained by reaction of polyamine and epichlorohydrin, a linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peracid such as peracetic acid, and an alicyclic epoxy resin can be mentioned alone or 2 It may be used in combination more than kind.
本発明において用いられる（ｂ）成分の１分子中に２個以上のフェノール性水酸基を有する化合物は、（ａ）成分のエポキシ樹脂と反応させて硬化させる成分であり、フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦなどのフェノール類又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド類とを酸性触媒下で縮合又は共縮合させて得られる樹脂、ポリパラビニルフェノール樹脂、フェノール類とジメトキシパラキシレンから合成されるキシリレン基を有するフェノール・アラルキル樹脂、脂環骨格を構造中に持つフェノール化合物などがあり、単独又は２種類以上併用してもよい。また、（ａ）のエポキシ樹脂と（ｂ）のフェノール性水酸基を有する化合物の当量比（（ｂ）の水酸基数／（ａ）のエポキシ基数）は、特に限定はされないが、それぞれの未反応分を少なく抑えるために０．５〜１．５の範囲に設定することが好ましく、より好ましくは０．７〜１．３の範囲である。 The compound having two or more phenolic hydroxyl groups in one molecule of the component (b) used in the present invention is a component that is cured by reacting with the epoxy resin of the component (a), and is phenol, cresol, xylenol, resorcinol Condensation of phenols such as catechol, bisphenol A, bisphenol F or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene with aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst Or a resin obtained by co-condensation, a polyparavinylphenol resin, a phenol / aralkyl resin having a xylylene group synthesized from phenols and dimethoxyparaxylene, and a phenol compound having an alicyclic skeleton in the structure. May be used alone or in combination of two or more. Further, the equivalent ratio of the epoxy resin (a) to the compound (b) having a phenolic hydroxyl group (number of hydroxyl groups in (b) / number of epoxy groups in (a)) is not particularly limited. Is preferably set in the range of 0.5 to 1.5, more preferably in the range of 0.7 to 1.3.
次に、本発明の（ｃ）成分を構成するポリエステル−ポリシロキサンブロック共重合体は、前記一般式（１）
一般式（１）のＡは前記一般式（２）
式（２）のＸは、酸素又はＮＲＸ基であり、ＲＸは一つの炭素原子が酸素原子で置換されても良い一価の置換又は非置換の炭素数１〜２０の炭化水素基、水素基、もしくは−ＳｉＲ’２−Ｒ２−ＮＲ１ ２基である。ＲＸの一つの炭素原子が酸素原子で置換されても良い一価の置換又は非置換の炭素数１〜２０の炭化水素基としては、例えば具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基などのアルキル基；ビニル基、アリル基、１−ブテニル基、１−ヘキセニル基などのアルケニル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基などのシクロアルキル基；フェニル基、トリル基、キシリル基、ビフェニル基、ナフチル基、ビニルフェニル基などのアリール基；ベンジル基、フェニルエチル基、フェニルプロピル基、メチルベンジル基などのアラルキル基；これらの炭化水素基中の水素原子の一部又は全部がハロゲン原子、シアノ基などによって置換されたクロロメチル基、２−ブロモエチル基、３，３，３−トリフルオロプロピル基、３−クロロプロピル基、クロロフェニル基、ジブロモフェニル基、テトラクロロフェニル基、ジフルオロフェニル基、β−シアノエチル基、γ−シアノプロピル基、β−シアノプロピル基などの置換炭化水素基、メトキシメチレン基、メトキシエチレン基、メトキシプロピレン基などを挙げることができる。 X in Formula (2) is oxygen or an NR X group, and R X is a monovalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms in which one carbon atom may be substituted with an oxygen atom, it is a hydrogen radical, or -SiR '2 -R 2 -NR 1 2 groups. Examples of the monovalent substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms in which one carbon atom of R X may be substituted with an oxygen atom include, for example, a methyl group, an ethyl group, a propyl group, Alkyl groups such as isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; vinyl group, Alkenyl groups such as allyl group, 1-butenyl group, 1-hexenyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group; phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, vinylphenyl group Aryl groups such as aralkyl such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group A group: a chloromethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, a 3-chloro group in which some or all of the hydrogen atoms in these hydrocarbon groups are substituted by a halogen atom, a cyano group, or the like Substituted hydrocarbon groups such as propyl group, chlorophenyl group, dibromophenyl group, tetrachlorophenyl group, difluorophenyl group, β-cyanoethyl group, γ-cyanopropyl group, β-cyanopropyl group, methoxymethylene group, methoxyethylene group, methoxy A propylene group etc. can be mentioned.
式（２）のＸ基のＮＲΧとしてあげたＲΧの一つである−ＳｉＲ’２−Ｒ２−ＮＲ１ ２基において、Ｒ’は炭化水素基であって、前記のＲ１で例示した炭化水素基をあげることができ、Ｒ１は、式（２）のＲ１と同様な炭化水素基又は水素である。 'In 2 -R 2 -NR 1 2 groups, R' -SiR is one of R chi that give as the NR chi X group of formula (2) is a hydrocarbon group, exemplified above for R 1 And R 1 is the same hydrocarbon group or hydrogen as R 1 in formula (2).
前記式（２）のｎは３〜１０の整数であり、６以下が好ましく、特に好ましくは４又は５である。さらにｍは１〜１０００の整数であり、２００以下が好ましく、特に好ましくは１〜２００である。 N in the formula (2) is an integer of 3 to 10, preferably 6 or less, particularly preferably 4 or 5. Furthermore, m is an integer of 1-1000, 200 or less is preferable, Most preferably, it is 1-200.
一方、一般式（１）のＢは前記一般式（３）
さらに、前記一般式（３）のシロキサン単位において、ｐは０〜３０００の整数、ｑは０〜５０の整数、ｒは０以上の整数、ｔは１以上の整数であり、これらの合計（ｐ＋ｑ＋ｒ＋ｔ）は３〜２００００の範囲が好ましく、より好ましくは５〜１０００の範囲である。この代表的な例としては、ｐは１以上の高重合度、ｑおよびｒは０、ｔは２であるシロキサン単位、又はｐは１以上の高重合度、ｑは１、ｒは０、ｔは１であるシロキサン単位などが挙げられる。 Furthermore, in the siloxane unit of the general formula (3), p is an integer of 0 to 3000, q is an integer of 0 to 50, r is an integer of 0 or more, t is an integer of 1 or more, and the sum of these (p + q + r + t ) Is preferably in the range of 3 to 20000, and more preferably in the range of 5 to 1000. As a typical example, p is a high degree of polymerization of 1 or more, q and r are 0, t is a siloxane unit of 2, or p is a high degree of polymerization of 1 or more, q is 1, r is 0, t Is a siloxane unit of 1.
一般式（１）で表されるポリエステル−ポリシロキサンブロック共重合体は、一般式（４）
一般式（４）で表される環状エステル化合物において、反応性の点でｂは６以下が好ましく、特に好ましくは４又は５である。この環状エステル化合物と一般式（５）で表されるシロキサン化合物の重合反応は２０〜２５０℃の温度で行なうことが可能であり、少なくとも５０℃以上の反応温度が好ましい。特に好ましい反応条件としては、シロキサン化合物の分解を抑制するため、初期段階では５０〜１００℃で反応させ、反応の進行に合わせて１００〜２００℃へ昇温して反応を行なうことがより好ましい。この重合反応の速度は触媒を使用することによって早めることが可能であり、触媒としてはカプロラクトン共重合体の合成に対して有効なあらゆる有機スズ化合物、例えばジブチルスズジラウレートなどのジブチルスズ脂肪族モノカルボン酸塩などを使用することができる。この使用量は環状エステル化合物とシロキサン化合物の合計量に対して２０〜２０００ｐｐｍであり、より好ましくは１００〜１０００ｐｐｍの範囲である。この触媒を使用した場合の反応時間は０．５〜４８時間であり、より好ましくは２〜１０時間である。そして、この反応後に余剰となる未反応の環状エステル化合物やシロキサン化合物は減圧下で加熱留去することが可能であり、その場合、減圧度１００ｍｂａｒ以下、１００℃以上の減圧加熱条件で行なうことができる。 In the cyclic ester compound represented by the general formula (4), b is preferably 6 or less, particularly preferably 4 or 5, in terms of reactivity. The polymerization reaction of the cyclic ester compound and the siloxane compound represented by the general formula (5) can be performed at a temperature of 20 to 250 ° C., and a reaction temperature of at least 50 ° C. or higher is preferable. As a particularly preferable reaction condition, in order to suppress decomposition of the siloxane compound, it is more preferable that the reaction is performed at 50 to 100 ° C. in the initial stage and the temperature is raised to 100 to 200 ° C. according to the progress of the reaction. The rate of this polymerization reaction can be accelerated by using a catalyst, which can be any organotin compound effective for the synthesis of a caprolactone copolymer, for example a dibutyltin aliphatic monocarboxylate such as dibutyltin dilaurate. Etc. can be used. The amount used is 20 to 2000 ppm, more preferably 100 to 1000 ppm, based on the total amount of the cyclic ester compound and the siloxane compound. When this catalyst is used, the reaction time is 0.5 to 48 hours, more preferably 2 to 10 hours. And the unreacted cyclic ester compound and siloxane compound which become surplus after this reaction can be distilled off by heating under reduced pressure. In this case, the reaction can be carried out under reduced pressure heating conditions of 100 mbar or less and 100 ° C. or more. it can.
さらに、この重合反応は溶剤希釈下で行なうことができるが、適切な反応器内において溶剤を使用することなく実施することがより好ましい。また、この重合反応は必要により減圧下、加圧下又は常圧下で実施され、連続的プロセス又は非連続的プロセスで行なうことができる。溶剤としては、例えばヘプタンやデカンなどの脂肪族炭化水素、トルエンやキシレンなどの芳香族炭化水素などの不活性溶剤を使用することができ、この溶剤の使用量は反応混合物を十分に均一化できる量である。また、常圧で１００℃以上の沸点又は沸点範囲を持った溶剤あるいは溶剤混合物がより好ましく用いられる。 Further, this polymerization reaction can be carried out under solvent dilution, but it is more preferred to carry out without using a solvent in a suitable reactor. Moreover, this polymerization reaction is carried out under reduced pressure, pressurized pressure or normal pressure as necessary, and can be carried out in a continuous process or a discontinuous process. As the solvent, for example, an inert solvent such as an aliphatic hydrocarbon such as heptane or decane or an aromatic hydrocarbon such as toluene or xylene can be used, and the amount of the solvent used can sufficiently homogenize the reaction mixture. Amount. A solvent or solvent mixture having a boiling point or boiling range of 100 ° C. or higher at normal pressure is more preferably used.
一方、一般式（５）で表されるシロキサン化合物は、一般式（６）
本発明において、この一般式（７）で表される環状化合物又はその開環重合物としてより好ましいものは、一般式（８）
さらに、一般式（７）で表される環状化合物として好ましい他の例として、一般式（９）
一般式（５）で表されるシロキサン化合物を製造するための、一般式（６）のシロキサンと一般式（７）〜（９）のいずれかの環状化合物との反応は、無触媒下において０〜２００℃の温度範囲で行われ、少なくとも２０℃以上での実施が好ましい。また、この反応は触媒の使用によって反応条件を大幅に改善することが可能であり、反応温度の低下や反応時間の短縮を行なうことができる。この触媒としては、無機又は有機のルイス酸又はルイス塩基、有機ブレンステッド酸又は塩基、有機金属化合物又はハロゲン化塩などが挙げられる。好ましい酸としてはギ酸や酢酸などのカルボン酸類やリン酸が挙げられる。 The reaction of the siloxane of general formula (6) with any of the cyclic compounds of general formulas (7) to (9) to produce the siloxane compound represented by general formula (5) is 0 in the absence of a catalyst. It is carried out in a temperature range of ˜200 ° C. and is preferably carried out at least at 20 ° C. or higher. Further, this reaction can greatly improve the reaction conditions by using a catalyst, and the reaction temperature can be lowered and the reaction time can be shortened. Examples of the catalyst include inorganic or organic Lewis acids or Lewis bases, organic Bronsted acids or bases, organometallic compounds, or halogenated salts. Preferred acids include carboxylic acids such as formic acid and acetic acid, and phosphoric acid.
一般式（５）で表されるシロキサン化合物を製造するための触媒として、好ましい酸としてはギ酸や酢酸などのカルボン酸類やリン酸が挙げられる。好ましい塩基としてはアルキルアンモニウムヒドロキシド、アルキルアンモニウムシラノレート、アンモニウムアルコキシド、アルキルアンモニウムフルオリド、アミン塩あるいは金属アルコキシド又は有機金属化合物が挙げられ、特に好ましい金属アルコキシドはリチウム又はナトリウムアルコキシドである。また、好ましい有機金属化合物としては有機スズ化合物、有機亜鉛化合物、アルコキシチタン化合物、有機リチウム化合物あるいはグリニャール試薬が挙げられ、さらに好ましいハロゲン化塩としてはテトラアルキルアンモニウムフルオリドが挙げられる。また、一般式（１０）
一般式（５）で表されるシロキサン化合物の製造において使用された触媒は、シラノール基への官能基導入反応の後に、Ｓｉ−Ｏ−Ｓｉグループの開裂が引き起こされる前に、いわゆる反触媒又は触媒毒の添加によって不活性化される。この不活性化反応は使用される触媒に依存し、必ずしも必要とされず、場合によっては実施する必要がない。触媒毒の例は、例えば酸が使用された場合には塩基を、また、例えば塩基が使用された場合には酸を使用することによって、ろ過や抽出により容易に分離可能な中和物の生成を伴って容易に中和することができる。 The catalyst used in the production of the siloxane compound represented by the general formula (5) is a so-called anti-catalyst or catalyst after the functional group introduction reaction to the silanol group and before the cleavage of the Si—O—Si group is caused. Inactivated by the addition of poison. This deactivation reaction depends on the catalyst used and is not necessarily required and in some cases need not be carried out. Examples of catalyst poisons include the generation of neutralized products that can be easily separated by filtration or extraction, for example by using a base when an acid is used, or by using an acid when a base is used, for example. Can be easily neutralized.
一般式（５）のシロキサン化合物の製造において、一般式（７）の環状化合物の使用量は一般式（６）のシロキサンにおけるシラノール基の量を示すｓの数に依存する。シラノール基すべてを封止する場合には少なくともシラノール量と当量の環状化合物を使用する必要がある。また、反応後に蒸留による余剰環状化合物の留去、又は余剰環状化合物の加水分解および必要により蒸留留去が可能であれば、シラノールに対して過剰の環状化合物を使用することができる。 In the production of the siloxane compound of the general formula (5), the amount of the cyclic compound of the general formula (7) used depends on the number of s indicating the amount of silanol groups in the siloxane of the general formula (6). When sealing all the silanol groups, it is necessary to use a cyclic compound equivalent to at least the amount of silanol. In addition, if the excess cyclic compound can be distilled off by distillation after the reaction, or if the excess cyclic compound can be hydrolyzed and distilled off if necessary, an excess of the cyclic compound relative to silanol can be used.
一般式（５）のシロキサン化合物の製造は、適切な反応器内において、溶剤の使用下又は使用せずに行なうこともできる。また、この製造は必要であれば、減圧下、加圧下あるいは常圧下で実施される。溶剤としては、例えばヘプタンやデカンなどの脂肪族炭化水素、トルエンやキシレンなどの芳香族炭化水素などの不活性溶剤を使用することができ、同様に、ＴＨＦ、ジエチルエーテル、ＭＴＢＥ（メチル−ｔｅｒｔ−ブチルエーテル）などのエーテルを用いることができる。この溶剤の使用量は反応混合物を十分に均一化できる量である。また、常圧で１２０℃以上の沸点又は沸点範囲を持った溶剤あるいは溶剤混合物がより好ましく用いられる。 The production of the siloxane compound of the general formula (5) can also be carried out in a suitable reactor with or without the use of a solvent. Further, this production is carried out under reduced pressure, increased pressure or normal pressure if necessary. As the solvent, inert solvents such as aliphatic hydrocarbons such as heptane and decane, and aromatic hydrocarbons such as toluene and xylene can be used. Similarly, THF, diethyl ether, MTBE (methyl-tert- Ether such as butyl ether) can be used. The amount of the solvent used is an amount that can sufficiently homogenize the reaction mixture. Further, a solvent or a solvent mixture having a boiling point or boiling range of 120 ° C. or higher at normal pressure is more preferably used.
本発明の半導体封止用樹脂組成物の各原材料の配合割合は、（ａ）エポキシ樹脂１００重量部に対し、（ｂ）フェノール水酸基を有する化合物を（ａ）のエポキシ樹脂と（ｂ）のフェノール水酸基を有する化合物の当量比（（ｂ）の水酸基数／（ａ）のエポキシ基数）が０．５〜１．５の範囲になる量、（ｃ）一般式（１）で表されるポリエステル−ポリシロキサンブロック共重合体０．１〜５０重量部、好ましくは０．５〜２０重量部である。（ｃ）成分の配合量が０．１重量部未満では良好な低応力性、耐熱衝撃性、耐湿性、成形性などが得られず、一方、５０重量部を超えると半導体封止用樹脂としての耐熱性が得られない。 The blending ratio of each raw material of the resin composition for semiconductor encapsulation of the present invention is as follows: (a) 100 parts by weight of the epoxy resin, (b) a compound having a phenol hydroxyl group, (a) the epoxy resin, and (b) the phenol. An amount in which the equivalent ratio of the hydroxyl group-containing compound (number of hydroxyl groups in (b) / number of epoxy groups in (a)) is in the range of 0.5 to 1.5, (c) polyester represented by the general formula (1) The amount of the polysiloxane block copolymer is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight. When the compounding amount of the component (c) is less than 0.1 parts by weight, good low stress property, thermal shock resistance, moisture resistance, moldability and the like cannot be obtained. The heat resistance of is not obtained.
なお、本発明の半導体封止用樹脂組成物には、エポキシ樹脂とフェノール性水酸基を有する化合物の硬化反応を促進する硬化促進剤を配合することができる。この硬化促進剤としては、例えば、１，８−ジアザビシクロ（５，４，０）ウンデセン−７、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノールなどの三級アミン類、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−ヘプタデシルイミダゾールなどのイミダゾール類、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィンなどの有機ホスフィン類、テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、２−エチル−４−メチルイミダゾールテトラフェニルボレート、Ｎ−メチルモルホリンテトラフェニルボレートなどのテトラフェニルボロン塩等が挙げられる。 In addition, the hardening accelerator which accelerates | stimulates hardening reaction of an epoxy resin and the compound which has a phenolic hydroxyl group can be mix | blended with the resin composition for semiconductor sealing of this invention. Examples of the curing accelerator include three compounds such as 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. Primary amines, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. Organic phosphines, tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate Tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate and the like.
また、本発明の半導体封止用樹脂組成物には、無機質充填材として、溶融シリカ、結晶シリカ、合成シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化珪素、窒化ホウ素、ベリリア、ジルコニア、などの粉体、又はこれらを球形化したビーズ、チタン酸カリウム、炭化珪素、窒化珪素、アルミナなどの単結晶繊維、ガラス繊維などを１種類以上配合することができる。無機質充填材の配合量としては、吸湿性、線膨張係数の低減及び強度向上の観点から、組成物全体に対して４０重量％以上が好ましい。上記の無機充填材の中で、線膨張係数低減の観点からは溶融シリカが、高熱伝導性の観点からはアルミナが好ましく、充填材形状は成形時の流動性及び金型摩耗性の点から球形が好ましい。 The resin composition for semiconductor encapsulation of the present invention includes, as an inorganic filler, fused silica, crystalline silica, synthetic silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, boron nitride, beryllia, zirconia, etc. One or more kinds of these powders, beads obtained by spheroidizing these, single crystal fibers such as potassium titanate, silicon carbide, silicon nitride, and alumina, glass fibers, and the like can be blended. As a compounding quantity of an inorganic filler, 40 weight% or more is preferable with respect to the whole composition from a viewpoint of a hygroscopic property, reduction of a linear expansion coefficient, and intensity | strength improvement. Among the above inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is spherical from the viewpoint of fluidity and mold wear during molding. Is preferred.
さらに、本発明の半導体封止用樹脂組成物には、高級脂肪酸、高級脂肪酸金属塩、エステル系ワックス、ポリエチレン系ワックスなどの離型剤、カーボンブラックなどの着色剤、エポキシシラン、アミノシラン、アルキルシラン、ビニルシラン、有機チタネート、アルミニウムアルコレートなどのカップリング剤、Ｂｒ化ビスフェノールＡ又はそのエポキシ化物などのハロゲン化物や三酸化アンチモン、五酸化アンチモン、水酸化アルミニウムなどの難燃剤、その他、老化防止剤、安定剤、可塑剤、軟化剤、架橋剤、帯電防止剤などを使用することができる。 Further, the resin composition for encapsulating a semiconductor of the present invention includes a release agent such as a higher fatty acid, a higher fatty acid metal salt, an ester wax, a polyethylene wax, a colorant such as carbon black, an epoxy silane, an amino silane, and an alkyl silane. , Coupling agents such as vinyl silane, organic titanate, aluminum alcoholate, halides such as Br bisphenol A or epoxidized products thereof, flame retardants such as antimony trioxide, antimony pentoxide, aluminum hydroxide, and other anti-aging agents, Stabilizers, plasticizers, softeners, crosslinking agents, antistatic agents and the like can be used.
本発明の半導体封止用樹脂組成物の配合方法は特に制限されるものではないが、例えば、（ａ）エポキシ樹脂、（ｂ）フェノール水酸基を有する化合物、（ｃ）ポリエステル−ポリシロキサンブロック共重合体および必要に応じて配合する他の成分をミキサーなどによって均一になるように混合した後、ロール、ニーダー、押し出し機などを用いて溶融混練する方法が挙げられる。 The compounding method of the resin composition for encapsulating a semiconductor of the present invention is not particularly limited. For example, (a) an epoxy resin, (b) a compound having a phenol hydroxyl group, (c) a polyester-polysiloxane block copolymer Examples include a method of mixing and mixing other components to be blended as necessary with a mixer or the like, and then melt-kneading using a roll, a kneader, an extruder or the like.
また、本発明の半導体装置は半導体素子を前記の半導体封止用樹脂組成物の硬化物で封止したものである。前記の半導体封止用組成物を用いて半導体素子を封止し、本発明の半導体装置を製造する方法としては、低圧トランスファ成形法が最も一般的であるが、インジェクション成形、圧縮成形、注型などの方法によっても可能である。 Moreover, the semiconductor device of this invention seals a semiconductor element with the hardened | cured material of the said resin composition for semiconductor sealing. As a method for producing a semiconductor device of the present invention by encapsulating a semiconductor element using the above composition for encapsulating a semiconductor, the low-pressure transfer molding method is the most common, but injection molding, compression molding, casting It is also possible by such a method.
以上説明したように、本発明の半導体封止用樹脂組成物は低応力性、耐熱性、耐熱衝撃性、耐湿性および成形性に特に優れており、これを用いた本発明の半導体装置はこれらの特性を具備したものとして、例えば、ボンディングワイヤの変形、ボンディングワイヤのオープン、樹脂クラック、ペレットクラックなどの不都合の発生が防止され、また、２５０℃以上の半田浴浸漬後においても耐湿性や機械的強度などの特性が低下することもなく、信頼性の高い半導体装置を得ることができる。 As described above, the resin composition for encapsulating a semiconductor of the present invention is particularly excellent in low stress, heat resistance, thermal shock resistance, moisture resistance and moldability, and the semiconductor device of the present invention using the same For example, inconveniences such as deformation of bonding wires, opening of bonding wires, resin cracks and pellet cracks can be prevented, and moisture resistance and mechanical properties can be maintained even after immersion in a solder bath at 250 ° C. or higher. A highly reliable semiconductor device can be obtained without degrading characteristics such as mechanical strength.
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記実施例に
限定されるものではない。なお、実施例中の部および％は、特に断らない限り重量部および重量％である。
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, unless otherwise indicated, the part and% in an Example are a weight part and weight%.
［調製例１］ 両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ１）の調製
撹拌機、温度計およびジムロートコンデンサーを装着した３Ｌの四つ口フラスコに数平均分子量８９０ｇ／ｍｏｌのα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサン２，０００ｇ（２．２５ｍｏｌ）および２，２−ジメチル−［１，４］ジオキサ−２−シラ−シクロヘキサン５９６ｇ（４．５１ｍｏｌ）を入れ、窒素雰囲気下、６０℃へ昇温し、１０％リチウムメチラート／メタノール溶液７．８ｇ（３００ｐｐｍ）を添加し、６０℃で７時間、加熱撹拌を行なった。次いで、１Ｈ−ＮＭＲおよび２９Ｓｉ−ＮＭＲによってα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサンのヒドロキシル基がヒドロキシエチルメチルエーテル基へと置換されたことを確認したのち、弱酸性のイオン交換樹脂を加えて中和を行い、次いで、ろ過および減圧ストリッピングを行い、目的とする両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ１）２，５００ｇを得た。こうして得られた両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ１）の粘度は１５ｍｍ２／ｓ（２５℃）であった。
[Preparation Example 1] Preparation of both end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A1) α, ω having a number average molecular weight of 890 g / mol in a 3 L four-necked flask equipped with a stirrer, thermometer and Dimroth condenser -2,000 g (2.25 mol) of dihydroxy-poly (dimethyl) siloxane and 596 g (4.51 mol) of 2,2-dimethyl- [1,4] dioxa-2-sila-cyclohexane were added, and the mixture was heated at 60 ° C under a nitrogen atmosphere. Then, 7.8 g (300 ppm) of a 10% lithium methylate / methanol solution was added, and the mixture was heated and stirred at 60 ° C. for 7 hours. Next, after confirming that the hydroxyl group of α, ω-dihydroxy-poly (dimethyl) siloxane was replaced with a hydroxyethyl methyl ether group by 1 H-NMR and 29 Si-NMR, a weakly acidic ion exchange resin was obtained. In addition, neutralization was performed, followed by filtration and stripping under reduced pressure to obtain 2,500 g of the desired polydimethylsiloxane (A1) capped with hydroxyethyl methyl ether groups at both ends. The viscosity of the both end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A1) thus obtained was 15 mm 2 / s (25 ° C.).
［調製例２］ 両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ２）の調製
撹拌機、温度計およびジムロートコンデンサーを装着した３Ｌの四つ口フラスコに数平均分子量１１，０００ｇ／ｍｏｌのα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサン２，２００ｇ（０．２０ｍｏｌ）および２，２−ジメチル−［１，４］ジオキサ−２−シラ−シクロヘキサン５４．２ｇ（０．４１ｍｏｌ）を入れ、窒素雰囲気下、１００℃へ昇温し、１０％リチウムメチラート／メタノール溶液６．８ｇ（３００ｐｐｍ）を添加し、１００℃で７時間、加熱撹拌を行なった。次いで、１Ｈ−ＮＭＲおよび２９Ｓｉ−ＮＭＲによってα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサンのヒドロキシル基がヒドロキシエチルメチルエーテル基へと置換されたことを確認したのち、弱酸性のイオン交換樹脂を加えて中和を行い、次いで、ろ過および減圧ストリッピングを行い、目的とする両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ２）２，２２０ｇを得た。こうして得られた両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ２）の粘度は５００ｍｍ２／ｓ（２５℃）であった。
[Preparation Example 2] Preparation of both end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A2) A 3L four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser is an α having a number average molecular weight of 11,000 g / mol. , Ω-dihydroxy-poly (dimethyl) siloxane 2,200 g (0.20 mol) and 2,2-dimethyl- [1,4] dioxa-2-sila-cyclohexane 54.2 g (0.41 mol) were placed in a nitrogen atmosphere. Then, the temperature was raised to 100 ° C., 6.8 g (300 ppm) of a 10% lithium methylate / methanol solution was added, and the mixture was heated and stirred at 100 ° C. for 7 hours. Next, after confirming that the hydroxyl group of α, ω-dihydroxy-poly (dimethyl) siloxane was replaced with a hydroxyethyl methyl ether group by 1 H-NMR and 29 Si-NMR, a weakly acidic ion exchange resin was obtained. In addition, neutralization was performed, followed by filtration and stripping under reduced pressure to obtain 2,220 g of the desired polydimethylsiloxane (A2) capped with hydroxyethyl methyl ether groups at both ends. The viscosity of the both end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A2) thus obtained was 500 mm 2 / s (25 ° C.).
［調製例３］ 両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ３）の調製
撹拌機、温度計およびジムロートコンデンサーを装着した３Ｌの四つ口フラスコに数平均分子量２，６００ｇ／ｍｏｌのα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサン２，６００ｇ（１．００ｍｏｌ）および２，２−ジメチル−［１，４］ジオキサ−２−シラ−シクロヘキサン２６６ｇ（２．０１ｍｏｌ）を入れ、窒素雰囲気下、８０℃へ昇温し、１０％リチウムメチラート／メタノール溶液８．６ｇ（３００ｐｐｍ）を添加し、８０℃で４時間、加熱撹拌を行なった。次いで、１Ｈ−ＮＭＲおよび２９Ｓｉ−ＮＭＲによってα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサンのヒドロキシル基がヒドロキシエチルメチルエーテル基へと置換されたことを確認したのち、弱酸性のイオン交換樹脂を加えて中和を行い、次いで、ろ過および減圧ストリッピングを行い、目的とする両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ３）２，８００ｇを得た。こうして得られた両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ３）の粘度は７０ｍｍ２／ｓ（２５℃）であった。
[Preparation Example 3] Preparation of both end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A3) α having a number average molecular weight of 2,600 g / mol in a 3 L four-necked flask equipped with a stirrer, thermometer and Dimroth condenser , Ω-dihydroxy-poly (dimethyl) siloxane 2,600 g (1.00 mol) and 2,2-dimethyl- [1,4] dioxa-2-sila-cyclohexane 266 g (2.01 mol) were placed under a nitrogen atmosphere. The temperature was raised to 80 ° C., 8.6 g (300 ppm) of 10% lithium methylate / methanol solution was added, and the mixture was heated and stirred at 80 ° C. for 4 hours. Next, after confirming that the hydroxyl group of α, ω-dihydroxy-poly (dimethyl) siloxane was replaced with a hydroxyethyl methyl ether group by 1 H-NMR and 29 Si-NMR, a weakly acidic ion exchange resin was obtained. In addition, neutralization was performed, followed by filtration and stripping under reduced pressure to obtain 2,800 g of the desired polydimethylsiloxane (A3) having both ends hydroxyethyl methyl ether group-capped. The viscosity of the both end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A3) thus obtained was 70 mm 2 / s (25 ° C.).
［調製例４］ 片末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ４）の調製
撹拌機、温度計およびジムロートコンデンサーを装着した５Ｌの四つ口フラスコに数平均分子量１，１００ｇ／ｍｏｌのα−ヒドロキシ−ω−トリメチルシロキシ−ポリ（ジメチル）シロキサン３，３００ｇ（３．００ｍｏｌ）および２，２−ジメチル−［１，４］ジオキサ−２−シラ−シクロヘキサン３９８ｇ（３．０１ｍｏｌ）を入れ、窒素雰囲気下、８０℃へ昇温し、１０％リチウムメチラート／メタノール溶液１１．１ｇ（３００ｐｐｍ）を添加し、８０℃で３時間、加熱撹拌を行なった。次いで、１Ｈ−ＮＭＲおよび２９Ｓｉ−ＮＭＲによってα−ヒドロキシ−ω−トリメチルシロキシ−ポリ（ジメチル）シロキサンのヒドロキシル基がヒドロキシエチルメチルエーテル基へと置換されたことを確認したのち、弱酸性のイオン交換樹脂を加えて中和を行い、次いで、ろ過および減圧ストリッピングを行い、目的とする片末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ４）３，６２０ｇを得た。こうして得られた片末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ４）の粘度は１４ｍｍ２／ｓ（２５℃）であった。
[Preparation Example 4] Preparation of single-end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A4) A 5 L four-necked flask equipped with a stirrer, thermometer and Dimroth condenser was used for α having a number average molecular weight of 1,100 g / mol. 3-hydroxy-ω-trimethylsiloxy-poly (dimethyl) siloxane 3,300 g (3.00 mol) and 2,2-dimethyl- [1,4] dioxa-2-sila-cyclohexane 398 g (3.01 mol) were added, and nitrogen was added. Under an atmosphere, the temperature was raised to 80 ° C., 11.1 g (300 ppm) of a 10% lithium methylate / methanol solution was added, and the mixture was heated and stirred at 80 ° C. for 3 hours. Next, after confirming that the hydroxyl group of α-hydroxy-ω-trimethylsiloxy-poly (dimethyl) siloxane was replaced with a hydroxyethyl methyl ether group by 1 H-NMR and 29 Si-NMR, a weakly acidic ion The exchange resin was added for neutralization, followed by filtration and stripping under reduced pressure to obtain 3,620 g of the desired one-terminal hydroxyethyl methyl ether group-capped polydimethylsiloxane (A4). The viscosity of the thus obtained one-end hydroxyethyl methyl ether group-capped polydimethylsiloxane (A4) was 14 mm 2 / s (25 ° C.).
［調製例５］ 両末端３−アミノプロピル基封止ポリジメチルシロキサン（Ａ５）の調製
撹拌機、温度計およびジムロートコンデンサーを装着した５Ｌの四つ口フラスコに数平均分子量３，０００ｇ／ｍｏｌのα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサン３，０００ｇ（１．００ｍｏｌ）を入れ、窒素雰囲気下、室温で撹拌しながら、Ｎ−［（３−アミノプロピル）−ジメチルシリル］−２，２−ジメチル−１−アザ−２−シラシクロペンタン２３３ｇ（１．０１ｍｏｌ）を３０分かけて滴下し、さらに室温で２時間撹拌を行なった。次いで、１Ｈ−ＮＭＲおよび２９Ｓｉ−ＮＭＲによってα，ω−ジヒドロキシ−ポリ（ジメチル）シロキサンのヒドロキシル基が（３−アミノプロピル）ジメチルシロキシ基へと置換されたことを確認したのち、減圧ストリッピングを行い、目的とする両末端３−アミノプロピル基封止ポリジメチルシロキサン（Ａ５）３，２１０ｇを得た。こうして得られた両末端３−アミノプロピル基封止ポリジメチルシロキサン（Ａ５）の粘度は５５ｍｍ２／ｓ（２５℃）であった。
[Preparation Example 5] Preparation of both ends of 3-aminopropyl group-capped polydimethylsiloxane (A5) α having a number average molecular weight of 3,000 g / mol in a 5 L four-necked flask equipped with a stirrer, thermometer and Dimroth condenser , Ω-dihydroxy-poly (dimethyl) siloxane (3,000 g, 1.00 mol) was added while stirring at room temperature under a nitrogen atmosphere while N-[(3-aminopropyl) -dimethylsilyl] -2,2-dimethyl was added. -1-aza-2-silacyclopentane (233 g, 1.01 mol) was added dropwise over 30 minutes, and the mixture was further stirred at room temperature for 2 hours. Next, after confirming that the hydroxyl group of α, ω-dihydroxy-poly (dimethyl) siloxane was replaced with (3-aminopropyl) dimethylsiloxy group by 1 H-NMR and 29 Si-NMR, stripping under reduced pressure was performed. To obtain 3,210 g of the desired polydimethylsiloxane (A5) having both ends of 3-aminopropyl groups. The viscosity of the polydimethylsiloxane having both ends 3-aminopropyl group sealed (A5) thus obtained was 55 mm 2 / s (25 ° C.).
［調製例６］ ポリエステル−ポリシロキサンブロック共重合体（Ｂ１）の調製
撹拌機、温度計およびジムロートコンデンサーを装着した３Ｌの四つ口フラスコに調製例１で得た両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ１）１，０００ｇ、ε−カプロラクトン１，０００ｇおよびジブチルスズジラウレート１ｇ（５００ｐｐｍ）を入れ、窒素雰囲気下、７０℃へ昇温し、この温度で１時間加熱撹拌を行なった。次いで、１４０℃へ昇温して６時間加熱撹拌を行ない、ε−カプロラクトンが消失していることをガスクロマトグラフで確認したのち、１０ｍｂａｒ以下で減圧ストリッピングを行い、目的とするポリエステル−ポリシロキサンブロック共重合体（Ｂ１）１，９２０ｇを得た。こうして得られたポリエステル−ポリシロキサンブロック共重合体（Ｂ１）を１Ｈ−ＮＭＲで分析した結果、シリコーン含有量は５２％であり、ＧＰＣで測定した数平均分子量（Ｍｎ）は２，１００ｇ／ｍｏｌであった。
[Preparation Example 6] Preparation of Polyester-Polysiloxane Block Copolymer (B1) Sealed on both ends with hydroxyethyl methyl ether obtained in Preparation Example 1 in a 3 L four-necked flask equipped with a stirrer, thermometer and Dimroth condenser 1,000 g of polydimethylsiloxane (A1), 1,000 g of ε-caprolactone and 1 g (500 ppm) of dibutyltin dilaurate were added, the temperature was raised to 70 ° C. in a nitrogen atmosphere, and the mixture was heated and stirred at this temperature for 1 hour. Next, the temperature was raised to 140 ° C., and the mixture was heated and stirred for 6 hours. After confirming that ε-caprolactone had disappeared by gas chromatography, vacuum stripping was performed at 10 mbar or less, and the desired polyester-polysiloxane block was obtained. 1,920 g of copolymer (B1) was obtained. The polyester-polysiloxane block copolymer (B1) thus obtained was analyzed by 1H-NMR. As a result, the silicone content was 52%, and the number average molecular weight (Mn) measured by GPC was 2,100 g / mol. there were.
［調製例７〜１０］ ポリエステル−ポリシロキサンブロック共重合体（Ｂ２）〜（Ｂ５）の調製
調製例６において、両末端ヒドロキシエチルメチルエーテル基封止ポリジメチルシロキサン（Ａ１）の代わりに調製例２〜５で得たポリジメチルシロキサン（Ａ２）〜（Ａ５）をそれぞれ用いた以外は調製例６と同様にして、ポリエステル−ポリシロキサンブロック共重合体（Ｂ２）〜（Ｂ５）を調製した。得られたブロック共重合体（Ｂ２）〜（Ｂ５）のシリコーン含有量および数平均分子量（Ｍｎ）を表１にそれぞれ示す。
[Preparation Examples 7 to 10] Preparation of Polyester-Polysiloxane Block Copolymers (B2) to (B5) In Preparation Example 6, Preparation Example 2 was used instead of polydimethylsiloxane (A1) having both terminal hydroxyethyl methyl ether groups blocked. Polyester-polysiloxane block copolymers (B2) to (B5) were prepared in the same manner as in Preparation Example 6 except that the polydimethylsiloxanes (A2) to (A5) obtained in ~ 5 were used. Table 1 shows the silicone content and number average molecular weight (Mn) of the obtained block copolymers (B2) to (B5).
［実施例１〜７、比較例１〜４］
以下の組成物配合処方に基づき、表２に示すポリエステル−ポリシロキサンブロック共重合体又はゴム状改質剤を用いて、次の手順に従って半導体封止用樹脂組成物を得た。
［組成物配合処方 （部）］
・（ａ）クレゾールノボラック型エポキシ樹脂；１００重量部（エポキシ当量２００）
・（ｂ）フェノール化合物（ノボラック型）； ５３重量部（水酸基等量１０３）
・（ｃ）ポリエステル−ポリシロキサンブロック共重合体又はゴム状改質剤； 表２に示す部数
・溶融シリカ粉（平均粒径 ５μｍ）；３４０重量部
・トリフェニルホスフィン；１．８重量部
・赤リン；３重量部
・カーボンブラック；０．６重量部
・カルナウバワックス；１．８重量部
・３−グリシドキシプロピルトリメトキシシラン；２．４重量部
[Examples 1-7, Comparative Examples 1-4]
Based on the following composition formulation, a resin composition for semiconductor encapsulation was obtained according to the following procedure using the polyester-polysiloxane block copolymer or rubber-like modifier shown in Table 2.
[Composition formulation (parts)]
(A) Cresol novolac type epoxy resin; 100 parts by weight (epoxy equivalent 200)
(B) Phenol compound (novolak type); 53 parts by weight (hydroxyl equivalent 103)
-(C) Polyester-polysiloxane block copolymer or rubbery modifier; Number of parts shown in Table 2-Fused silica powder (average particle size 5 m); 340 parts by weight-Triphenylphosphine; 1.8 parts by weight-Red Phosphor; 3 parts by weight, carbon black; 0.6 parts by weight, carnauba wax; 1.8 parts by weight, 3-glycidoxypropyltrimethoxysilane; 2.4 parts by weight
上記配合処方の各原料を、ヘンシェルミキサーを用いて３０００ｒｐｍの回転速度で５分間均一になるように撹拌混合した。次いで、この混合物を１００℃に設定した熱ロールで３分間溶融混練し、冷却した後、粉砕して半導体封止用樹脂組成物を得た。この半導体封止用樹脂組成物を用いて物性評価用の試験片を作成し、この試験片について熱膨張率、曲げ弾性率、スパイラルフローを測定するとともに、耐湿性、耐熱衝撃性、半田浴耐熱性、歪特性を調べたところ、表２に示すような結果が得られた。表２から明らかなように、実施例１〜７の本発明の半導体封止用樹脂組成物であり、本発明の目的とする硬化物が得られた。なお、測定ないし試験方法は以下の通りである。 Each raw material of the above blended formulation was stirred and mixed using a Henschel mixer at a rotational speed of 3000 rpm so as to be uniform for 5 minutes. Next, this mixture was melt-kneaded for 3 minutes with a hot roll set at 100 ° C., cooled, and then pulverized to obtain a resin composition for semiconductor encapsulation. Using this resin composition for encapsulating semiconductors, a test piece for evaluating physical properties is prepared, and the thermal expansion coefficient, bending elastic modulus and spiral flow of the test piece are measured, and moisture resistance, thermal shock resistance, solder bath heat resistance are measured. As a result, the results shown in Table 2 were obtained. As is clear from Table 2, it was the resin composition for semiconductor encapsulation of the present invention of Examples 1 to 7, and the cured product targeted by the present invention was obtained. The measurement or test method is as follows.
・熱膨張率：ＡＳＴＭ−Ｄ６９６に基く測定法にしたがい、半導体封止用樹脂組成物を１７０℃、３分間の条件でトランスファー成形した後、１８０℃の雰囲気中に８時間放置して硬化を進め、得られた硬化試験体について測定した。
・曲げ弾性率：ＪＩＳ Ｋ６９１１に準拠して測定した。
・スパイラルフロー：ＥＭＭＩ−１−６６に準拠して測定した。
・耐湿性試験：半導体封止用樹脂組成物を用いて２本のアルミニウム配線を有する電気部品を１７０℃、３分間の条件でトランスファー成形し、次いで１８０℃で８時間硬化させた。得られた電気部品１００個について、１２０℃の高圧水蒸気中で耐湿性試験を行い、アルミニウム腐食による５０％の断線（不良発生）が起こる時間により、耐湿性を評価した。
-Thermal expansion coefficient: According to the measurement method based on ASTM-D696, the resin composition for semiconductor encapsulation is transfer molded at 170 ° C. for 3 minutes and then left in an atmosphere at 180 ° C. for 8 hours to proceed with curing. The obtained cured specimen was measured.
Flexural modulus: measured in accordance with JIS K6911.
Spiral flow: Measured according to EMMI-1-66.
Moisture resistance test: An electrical component having two aluminum wirings was transfer molded at 170 ° C. for 3 minutes using a resin composition for semiconductor encapsulation, and then cured at 180 ° C. for 8 hours. The 100 electrical components obtained were subjected to a moisture resistance test in high-pressure steam at 120 ° C., and the moisture resistance was evaluated based on the time during which 50% disconnection (defect generation) occurred due to aluminum corrosion.
・耐熱衝撃性サイクル試験：耐湿性試験の場合と同様にして３０×２５×５ｍｍの試験用成形品を作成した。次いで、これらの試験用成形品の底面に２５×２５×３ｍｍの銅板を埋め込み−４０℃と２００℃の恒湿槽へ交互に３０分ずつ入れ、これを１サイクルとして１５サイクル繰り返し、樹脂クラックが生じた成形品の割合、すなわちクラックの発生した成形品数／全成形品数を求めて耐熱衝撃性を評価した。
・半田浴耐熱性試験：２本のアルミニウム配線を有する電気部品を、樹脂組成物を用いて通常の４２アロイフレームに接着し、１７０℃で３分間の条件でトランスファー成形して５×１０×１．５ｍｍのフラットパッケージ型成形品を得た。この成形品はその後１８０℃で８時間硬化させた。次いでこの成形品を温度４０℃、相対湿度９０％の雰囲気中に１００時間放置して吸湿処理を施した後、２５０℃の半田浴に１０秒間浸漬した。この後、１２７℃、２．５５気圧の飽和水蒸気中でプレッシャークッカーテストを行い、アルミニウム腐食により断線したものを不良品として数え、不良品数／全成形品数で半田浴耐熱性を評価した。
・歪試験：ＤＩＰ１６ピンリードフレームのアイランド部に市販のストレイジゲージを接着し、１８０℃で８時間硬化させた後の歪を測定した。
・接着性：試験片材料としてアルミニウムを使用し、１８０℃、８時間の効果条件で得られた試験体をＪＩＳ Ｋ６８５０に準拠して測定した。
Thermal shock resistance cycle test: A test molded product of 30 × 25 × 5 mm was prepared in the same manner as in the moisture resistance test. Next, a copper plate of 25 × 25 × 3 mm is embedded in the bottom surface of these test molded articles, and alternately placed in a constant humidity bath at −40 ° C. and 200 ° C. for 30 minutes. The thermal shock resistance was evaluated by determining the ratio of the formed products, that is, the number of molded products with cracks / the total number of molded products.
Solder bath heat resistance test: An electrical component having two aluminum wirings is bonded to a normal 42 alloy frame using a resin composition, and transfer molded at 170 ° C. for 3 minutes to form 5 × 10 × 1. A flat package mold product of 0.5 mm was obtained. This molded article was then cured at 180 ° C. for 8 hours. Next, the molded article was left in an atmosphere of 40 ° C. and 90% relative humidity for 100 hours for moisture absorption treatment, and then immersed in a solder bath at 250 ° C. for 10 seconds. Thereafter, a pressure cooker test was performed in saturated steam at 127 ° C. and 2.55 atm, and the ones broken by aluminum corrosion were counted as defective products, and the solder bath heat resistance was evaluated by the number of defective products / the total number of molded products.
Strain test: A commercially available storage gauge was bonded to the island part of the DIP 16-pin lead frame, and the strain after curing at 180 ° C. for 8 hours was measured.
Adhesiveness: Aluminum was used as a test piece material, and a test specimen obtained under an effect condition of 180 ° C. and 8 hours was measured according to JIS K6850.
［比較例１〜４］
表３に示すポリエステル−ポリシロキサンブロック共重合体、ブタジエン−アクリロニトリルゴム（ＪＳＲ（株）製Ｎ２２０Ｓ）又はシリコーンゴムパウダー（信越化学工業（株）製ＫＭＰ−５９７：平均粒径５μｍ、粒径分布１〜１０μｍ、真比重０．９７）を用いて、実施例１と同様の評価を行った。結果を表３に示す。表３から明らかなように、比較例１は、（ｃ）成分として用いたポリエステル−ポリシロキサンブロック共重合体の配合量が本発明の範囲に満たない例であり、熱膨張率、曲げ弾性率、耐湿性、耐熱衝撃性、半田浴耐熱性、歪、接着性が劣る。比較例２は、（ｃ）成分のポリエステル−ポリシロキサンブロック共重合体の配合量が本発明の範囲を超えた例であり、耐湿性、半田浴耐熱性が劣る。比較例３、４は、（ｃ）成分として、市販のブタジエン−アクリロニトリルゴム又はシリコーンゴムパウダーを用いた本発明の範囲外の例であり、熱膨張率、耐湿性、耐熱衝撃性、半田浴耐熱性、歪、接着性が劣る。比較例５は、（ｃ）成分を全く使用しない例であり、比較のための物性を挙げた。
[Comparative Examples 1-4]
Polyester-polysiloxane block copolymer shown in Table 3, butadiene-acrylonitrile rubber (N220S manufactured by JSR Corp.) or silicone rubber powder (KMP-597 manufactured by Shin-Etsu Chemical Co., Ltd.): average particle size 5 μm, particle size distribution 1 10 μm, true specific gravity 0.97), and the same evaluation as in Example 1 was performed. The results are shown in Table 3. As apparent from Table 3, Comparative Example 1 is an example in which the blending amount of the polyester-polysiloxane block copolymer used as the component (c) is less than the range of the present invention, and the thermal expansion coefficient and flexural modulus are Inferior in moisture resistance, thermal shock resistance, solder bath heat resistance, strain and adhesion. Comparative Example 2 is an example in which the blending amount of the polyester-polysiloxane block copolymer of component (c) exceeds the range of the present invention, and the moisture resistance and solder bath heat resistance are inferior. Comparative Examples 3 and 4 are examples outside the scope of the present invention using commercially available butadiene-acrylonitrile rubber or silicone rubber powder as the component (c), and have a coefficient of thermal expansion, moisture resistance, thermal shock resistance, and solder bath heat resistance. Inferior properties, distortion and adhesion. Comparative Example 5 is an example in which component (c) is not used at all, and physical properties for comparison are listed.
本発明の組成物は、ダイオード、トランジスタ、集積回路などの電子部品の封止に用いることができ、特に、高集積化、薄型化、大型化された半導体チップの封止、アンダーフィルに好適に用いることができる。この半導体チップの封止としては、従来の挿入タイプのＤＩＰ（Ｄｕａｌ Ｉｎｌｉｎｅ Ｐａｃｋａｇｅ）、表面実装タイプのＳＯＰ（Ｓｍａｌｌ Ｏｕｔｌｉｎｅ Ｐａｃｋａｇｅ）、ＱＦＰ（Ｑｕａｄ Ｆｌａｔ Ｐａｃｋａｇｅ）、ならびに高密度化に対応できる表面実装タイプのＢＧＡ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ Ｓｉｚｅ Ｐａｃｋａｇｅ）などのあらゆるパッケージ形状に適用が可能であり、さらにＢＧＡやＣＳＰの基板への実装に際してアンダーフィルとして好適に使用することができる。本発明の組成物によって封止された本発明の半導体は、電子機器の小型化、軽量化、高性能化の実現に有効な高密度実装、表面実装に好適に用いることができる。 The composition of the present invention can be used for sealing electronic parts such as diodes, transistors, and integrated circuits, and is particularly suitable for sealing high-density, thin, and large-sized semiconductor chips and underfill. Can be used. As sealing of this semiconductor chip, conventional insertion type DIP (Dual Inline Package), surface mount type SOP (Small Outline Package), QFP (Quad Flat Package), and surface mount type that can cope with high density The present invention can be applied to all package shapes such as BGA (Ball Grid Array) and CSP (Chip Size Package), and can be suitably used as an underfill when mounting BGA or CSP on a substrate. The semiconductor of the present invention encapsulated with the composition of the present invention can be suitably used for high-density mounting and surface mounting effective for realizing miniaturization, weight reduction, and high performance of electronic devices.
Claims (9)
（ｂ）１分子中に２個以上のフェノール性水酸基を有する化合物 （ａ）のエポキシ樹脂と（ｂ）のフェノール性水酸基含有化合物の当量比（（ｂ）の水酸基数／（ａ）のエポキシ基数）が０．５〜１．５の範囲になる量、および（ｃ）一般式（１）
Ｂは一般式（３）
(B) Compound having two or more phenolic hydroxyl groups in one molecule Equivalent ratio of (a) epoxy resin and (b) phenolic hydroxyl group-containing compound (number of hydroxyl groups in (b) / number of epoxy groups in (a) ) In the range of 0.5 to 1.5, and (c) the general formula (1)
B is the general formula (3)
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| JP2011079893A (en) * | 2009-10-05 | 2011-04-21 | Hitachi Chem Co Ltd | Urethane resin composition, cured product and optical semiconductor device using the cured product |
| JP2012509970A (en) * | 2008-11-28 | 2012-04-26 | ワッカー ケミー アクチエンゲゼルシャフト | Epoxy resin containing siloxane mixture, process for producing the same and use thereof |
| JP2013509465A (en) * | 2009-10-30 | 2013-03-14 | ワッカー ケミー アクチエンゲゼルシャフト | Method for producing (hydroxymethyl) polysiloxane |
| WO2019004458A1 (en) * | 2017-06-29 | 2019-01-03 | 日立化成株式会社 | Resin composition for encapsulation, rearranged wafer, semiconductor package, and method for manufacturing semiconductor package |
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| US20220106479A1 (en) * | 2016-06-08 | 2022-04-07 | Hexion Inc. | Composition comprising a polymer based on epoxide compounds |
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2006
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