JP5261880B2 - Epoxy resin curing accelerator, epoxy resin composition, and semiconductor device - Google Patents
Epoxy resin curing accelerator, epoxy resin composition, and semiconductor device Download PDFInfo
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- JP5261880B2 JP5261880B2 JP2006050992A JP2006050992A JP5261880B2 JP 5261880 B2 JP5261880 B2 JP 5261880B2 JP 2006050992 A JP2006050992 A JP 2006050992A JP 2006050992 A JP2006050992 A JP 2006050992A JP 5261880 B2 JP5261880 B2 JP 5261880B2
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- epoxy resin
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 119
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 118
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims description 60
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 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 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 238000007259 addition reaction Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- KGYYLUNYOCBBME-UHFFFAOYSA-M 4-fluoro-2-phenyl-4-(4-propylcyclohexyl)cyclohexa-1,5-diene-1-carboxylate Chemical compound C1CC(CCC)CCC1C1(F)C=CC(C([O-])=O)=C(C=2C=CC=CC=2)C1 KGYYLUNYOCBBME-UHFFFAOYSA-M 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 229910000679 solder Inorganic materials 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 125000000962 organic group Chemical group 0.000 abstract description 10
- 125000001424 substituent group Chemical group 0.000 description 39
- -1 phosphonium phenolate compound Chemical class 0.000 description 32
- 125000001931 aliphatic group Chemical group 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000011342 resin composition Substances 0.000 description 13
- 125000000623 heterocyclic group Chemical group 0.000 description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 12
- 229920001187 thermosetting polymer Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 150000004053 quinones Chemical group 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 7
- 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 7
- 125000005843 halogen group Chemical group 0.000 description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 5
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 5
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000004203 carnauba wax Substances 0.000 description 5
- 235000013869 carnauba wax Nutrition 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 4
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 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 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000002541 furyl group Chemical group 0.000 description 4
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 4
- LVLZXBIWQHFREA-UHFFFAOYSA-N phenol;phosphane Chemical class [PH4+].[O-]C1=CC=CC=C1 LVLZXBIWQHFREA-UHFFFAOYSA-N 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([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
- 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
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 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
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 2
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 2
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 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
- 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
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 230000002349 favourable effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- ZJKWJHONFFKJHG-UHFFFAOYSA-N 2-Methoxy-1,4-benzoquinone Chemical compound COC1=CC(=O)C=CC1=O ZJKWJHONFFKJHG-UHFFFAOYSA-N 0.000 description 1
- WOGWYSWDBYCVDY-UHFFFAOYSA-N 2-chlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=CC(=O)C=CC1=O WOGWYSWDBYCVDY-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
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- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 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
- 125000003277 amino group Chemical group 0.000 description 1
- LSOTZYUVGZKSHR-UHFFFAOYSA-N anthracene-1,4-dione Chemical compound C1=CC=C2C=C3C(=O)C=CC(=O)C3=CC2=C1 LSOTZYUVGZKSHR-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
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Abstract
Description
本発明は、エポキシ樹脂用硬化促進剤、エポキシ樹脂組成物及び半導体装置に関するものである。 The present invention relates to an epoxy resin curing accelerator, an epoxy resin composition, and a semiconductor device.
近年、半導体素子の封止に用いられるエポキシ樹脂組成物には、生産効率の向上を目的とした速硬化性の向上と、半導体を封止した際の、耐熱性や信頼性の向上のため、無機質の充填材を高充填しても損なわれることのない高流動性が求められるようになってきている。 In recent years, epoxy resin compositions used for sealing semiconductor elements have improved fast curability for the purpose of improving production efficiency and for improving heat resistance and reliability when sealing semiconductors. High fluidity that is not impaired even when highly filled with an inorganic filler has been demanded.
このようなエポキシ樹脂組成物には、硬化時における樹脂の硬化反応を促進する目的で、速硬化性に優れる第三級ホスフィンとキノン類との付加反応物が硬化促進剤として添加される(例えば、特許文献1参照。)。 In such an epoxy resin composition, for the purpose of accelerating the curing reaction of the resin at the time of curing, an addition reaction product of a tertiary phosphine and a quinone excellent in rapid curing is added as a curing accelerator (for example , See Patent Document 1).
前記硬化促進剤においては、吸湿時に硬化性の低下が起こり、安定した成形性を得ることが難しいことが知られており、エポキシ樹脂組成物として利用する際の、湿度管理や可使時間管理など、取り扱いが非常に煩雑であることが問題であった。 In the curing accelerator, it is known that the curability is lowered at the time of moisture absorption, and it is difficult to obtain a stable moldability. When used as an epoxy resin composition, humidity management and pot life management, etc. The problem was that the handling was very complicated.
これらを改善するべく、同様の構造でより硬化性に優れる、３置換ホスホニウムフェノラートを硬化促進剤として用いる技術も開示されている（例えば特許文献２参照。）。しかし、このホスホニウムフェノラート硬化促進剤は、前述第三級ホスフィンとキノン類の付加反応物に比べ、合成が非常に難しく、コストが高くなるために、汎用性の高いものではなかった。
本発明は、エポキシ樹脂に有用で、可使時間に優れる硬化促進剤、硬化性、流動性、及びハンドリングが良好なエポキシ樹脂組成物ならびに耐半田クラック性や耐湿信頼性に優れる半導体装置を提供することにある。 The present invention provides a curing accelerator that is useful for epoxy resins and has excellent pot life, an epoxy resin composition that has good curability, fluidity, and handling, and a semiconductor device that is excellent in solder crack resistance and moisture resistance reliability. There is.
本発明者は、前述したような問題点を解決すべく、鋭意検討を重ねた結果、第三級ホスフィン化合物とキノン類との付加反応物に代表される特定のホスホニウムフェノラート化合物から誘導される燐化合物を、硬化促進剤として用いることで、硬化性、流動性及びハンドリングが良好なエポキシ樹脂組成物が得られ、またそれを用いて製作した半導体装置は、耐半田クラック性や耐湿信頼性に優れることを見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventor is derived from a specific phosphonium phenolate compound represented by an addition reaction product of a tertiary phosphine compound and quinones. By using a phosphorus compound as a curing accelerator, an epoxy resin composition having good curability, fluidity, and handling can be obtained, and a semiconductor device manufactured using the epoxy resin composition has improved solder crack resistance and moisture resistance reliability. As a result, the present invention was found.
即ち、下記（１）〜（６）の本発明により達成される。 That is, the present invention is achieved by the following (1) to (6).
（１） 下記式（１）で表される構造を有するエポキシ樹脂用硬化促進剤。 (1) A curing accelerator for epoxy resin having a structure represented by the following formula (1).
（２） 前記硬化促進剤は、Ｘとして、下記一般式（２）で表されるものである上記（１）に記載のエポキシ樹脂用硬化促進剤。 (2) The said hardening accelerator is a hardening accelerator for epoxy resins as described in said (1) which is represented by following General formula (2) as X.
（３） １分子内にエポキシ基を２個以上有する化合物と、１分子内にフェノール性水酸基を２個以上有する化合物と、上記（１）又は（２）に記載のエポキシ樹脂用潜伏性触媒とを含むエポキシ樹脂組成物。
（４） さらに無機充填材を含む上記（３）に記載のエポキシ樹脂組成物。
（５） 前記無機充填材の含有量が、全エポキシ樹脂組成物中６０〜９５重量％である上記（４）に記載のエポキシ樹脂組成物。
（６） 上記（５）に記載のエポキシ樹脂組成物の硬化物により電子部品を封止してなる半導体装置。
(3) A compound having two or more epoxy groups in one molecule, a compound having two or more phenolic hydroxyl groups in one molecule, and the latent catalyst for epoxy resins according to (1) or (2) above An epoxy resin composition comprising:
(4) The epoxy resin composition according to (3), further including an inorganic filler.
(5) The epoxy resin composition according to (4), wherein the content of the inorganic filler is 60 to 95% by weight in the total epoxy resin composition.
(6) A semiconductor device formed by sealing an electronic component with a cured product of the epoxy resin composition according to (5).
本発明のエポキシ樹脂用硬化促進剤は、エポキシ樹脂の硬化促進に極めて有用であり、これをエポキシ樹脂組成物に混合した場合、優れた流動性と硬化性の両立し、ハンドリングが良好なエポキシ樹脂組成物を得ることができる。 The curing accelerator for epoxy resins of the present invention is extremely useful for accelerating the curing of epoxy resins, and when mixed with an epoxy resin composition, the epoxy resin has excellent fluidity and curability and good handling. A composition can be obtained.
また、本発明の半導体装置は、高温に曝された場合であっても、耐半田クラック性や耐湿性信頼性に優れる。 Further, the semiconductor device of the present invention is excellent in solder crack resistance and moisture resistance reliability even when exposed to high temperatures.
以下、本発明のエポキシ樹脂用硬化促進剤、エポキシ樹脂組成物及び半導体装置の好適実施形態について説明する。 Hereinafter, preferred embodiments of the curing accelerator for epoxy resin, the epoxy resin composition, and the semiconductor device of the present invention will be described.
［本発明のエポキシ樹脂用硬化促進剤］
本発明のエポキシ樹脂用硬化促進剤は、前記一般式（１）で表される構造を有する化合物である。
[Curing accelerator for epoxy resin of the present invention]
The curing accelerator for epoxy resins of the present invention is a compound having a structure represented by the general formula (1).
ここで、前記一般式（１）で表される構造において、リン原子に結合する置換基Ｒ1、Ｒ2及びＲ3は、それぞれ、置換もしくは無置換の芳香族基、置換もしくは無置換の複素環基、及び置換もしくは無置換の脂肪族基のいずれかを示し、互いに同一であっても異なっていてもよい。 Here, in the structure represented by the general formula (1), the substituents R 1 , R 2, and R 3 bonded to the phosphorus atom are substituted or unsubstituted aromatic groups, substituted or unsubstituted complex groups, respectively. A cyclic group and a substituted or unsubstituted aliphatic group are shown and may be the same or different.
これらの置換基Ｒ1、Ｒ2及びＲ3としては、例えば、フェニル基及びナフチル基などの芳香族基、ピリジニル基及びフリル基などの複素環基、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ペンチル基、ヘキシル基、オクチル基及びドデシル基などの炭素数１〜１２の鎖状脂肪族基、シクロペンチル基、シクロヘキシル基及びシクロオクチル基などの環状脂肪族基などの脂肪族機が挙げられる。また、これらの基は、置換基を有していても良く、そのような置換基としては、メトキシ基及びエトキシ基などのアルコキシ基、炭素数１〜５の脂肪族基、フルオロ基、クロロ基及びブロモ基などのハロゲン基などを挙げることができ、複数の置換基を有していても良い。これら置換基を有する基としては、例えば、イソプロピル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、３−メトキシヘキシル基及び２−クロロエチル基などの置換基を有する脂肪族基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、４−エチルフェニル基、２，４−ジクロロフェニル基及び２，４−ジメトキシフェニル基などの置換基を有する芳香族基、Ｎ−メチル−２−ピリジニル基などの置換基を有する複素環基などが挙げられる。また、これらのうちでも、フェニル基、置換基を有するフェニル基、炭素数２〜６の無置換の脂肪族基、及び炭素数３〜６の置換基を有する脂肪族基が、良好な硬化性を発揮する為に好ましく、例えば、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、４−エチルフェニル基及び２，４−ジクロロフェニル基などの置換基を有するフェニル基、メチル基、エチル基、ｎ−プロピル基及びｎ−ブチル基などの無置換の脂肪族基、イソプロピル基及びｔｅｒｔ−ブチル基などの置換基を有する脂肪族基が挙げられる。 Examples of these substituents R 1 , R 2 and R 3 include aromatic groups such as a phenyl group and a naphthyl group, heterocyclic groups such as a pyridinyl group and a furyl group, a methyl group, an ethyl group, an n-propyl group, Aliphatic machines such as C1-C12 chain aliphatic groups such as n-butyl group, pentyl group, hexyl group, octyl group and dodecyl group, and cyclic aliphatic groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group Is mentioned. In addition, these groups may have a substituent, such as an alkoxy group such as a methoxy group and an ethoxy group, an aliphatic group having 1 to 5 carbon atoms, a fluoro group, and a chloro group. And a halogen group such as a bromo group, and may have a plurality of substituents. Examples of the group having a substituent include an isopropyl group, a tert-butyl group, a sec-butyl group, an aliphatic group having a substituent such as a 3-methoxyhexyl group and a 2-chloroethyl group, a 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-ethylphenyl group, 2,4-dichlorophenyl group and 2,4-dimethoxyphenyl group And an aromatic group having a substituent such as a heterocyclic group having a substituent such as an N-methyl-2-pyridinyl group. Among these, a phenyl group, a phenyl group having a substituent, an unsubstituted aliphatic group having 2 to 6 carbon atoms, and an aliphatic group having a substituent having 3 to 6 carbon atoms have good curability. For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4- Phenyl group having a substituent such as ethylphenyl group and 2,4-dichlorophenyl group, unsubstituted aliphatic group such as methyl group, ethyl group, n-propyl group and n-butyl group, isopropyl group and tert-butyl group And an aliphatic group having a substituent such as.
また、前記一般式（１）で表される構造において、リン原子に結合する芳香環上の置換基Ｒ4、Ｒ5及びＲ6は、それぞれ、水素原子、ハロゲン原子、置換もしくは無置換の芳香族基、置換もしくは無置換の複素環基、及び置換もしくは無置換の脂肪族基のいずれかを示し、互いに同一であっても異なっていてもよい。 In the structure represented by the general formula (1), the substituents R 4 , R 5 and R 6 on the aromatic ring bonded to the phosphorus atom are each a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group. An aromatic group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aliphatic group, which may be the same or different from each other.
これらの置換基Ｒ4、Ｒ5及びＲ6として、水素原子の他、前記ハロゲン原子としては、例えば、フルオロ基、クロロ基及びブロモ基などが挙げられ、前記脂肪族基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基及びｔｅｒｔ−ブチル基、などの鎖状脂肪族基、シクロヘキシル基などの環状脂肪族基が挙げられ、前記芳香族基としては、例えば、フェニル基及びナフチル基などが挙げられ、前記複素環基としては、例えば、ピリジニル基及びフリル基などが挙げられる。これらの基は、置換基を有していても良く、そのような置換基としては、アルキル基、アルコキシ基、アリール基、アリールオキシ基、アミノ基及びハロゲン等が挙げられる。例えば、置換基を有する芳香族基として、４−メチルフェニル基、２−メトキシフェニル基及びペンタフルオロフェニル基などの置換基を有するフェニル基などが挙げられる。これらのうちでも、水素原子、及び炭素数１〜８の、直鎖状、分岐状、もしくは環状の脂肪族基が、良好な硬化性を発揮する為に好ましい。 As these substituents R 4 , R 5 and R 6 , in addition to a hydrogen atom, examples of the halogen atom include a fluoro group, a chloro group, and a bromo group. Examples of the aliphatic group include a methyl group. A chain aliphatic group such as a group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group, and a cyclic aliphatic group such as a cyclohexyl group, Examples of the group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a pyridinyl group and a furyl group. These groups may have a substituent, and examples of such a substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, and a halogen. For example, the aromatic group having a substituent includes a phenyl group having a substituent such as a 4-methylphenyl group, a 2-methoxyphenyl group, and a pentafluorophenyl group. Among these, a hydrogen atom and a linear, branched, or cyclic aliphatic group having 1 to 8 carbon atoms are preferable in order to exhibit good curability.
また、前記一般式（１）で表される構造において、リン原子に結合する芳香環上の、リン原子が結合した炭素に対しメタ位に、酸素原子を介して結合する有機基Ｘは、フェノール性水酸基と反応しうる有機基の反応残基である。フェノール性水酸基と反応しうる有機基の反応残基とは、フェノール性水酸基と反応しうる有機基を有する化合物が、前記リン原子に結合する芳香環上のメタ位に位置するフェノール性水酸基と脱水縮合又は付加結合することで生じる基のことであり、その構造は反応の形態により種々異なる。 In the structure represented by the general formula (1), the organic group X bonded via an oxygen atom to the meta position with respect to the carbon bonded to the phosphorus atom on the aromatic ring bonded to the phosphorus atom is phenol. It is a reaction residue of an organic group that can react with a functional hydroxyl group. The reaction residue of an organic group capable of reacting with a phenolic hydroxyl group means that a compound having an organic group capable of reacting with a phenolic hydroxyl group is dehydrated with a phenolic hydroxyl group located at the meta position on the aromatic ring bonded to the phosphorus atom. It is a group generated by condensation or addition bonding, and its structure varies depending on the form of reaction.
前記フェノール性水酸基と反応しうる有機基を有する化合物としては、カルボキシル基、水酸基、シアノ基、イソシアノ基、酸無水物基及びエポキシ基などの反応性基を有する化合物が挙げられる。これら反応性基のうちでも、カルボキシル基、酸無水物基、及びエポキシ基は、フェノール性水酸基との反応性に優れ、これらの反応性基を有する化合物は反応が容易に行なえるため好ましい。 Examples of the compound having an organic group capable of reacting with the phenolic hydroxyl group include compounds having a reactive group such as a carboxyl group, a hydroxyl group, a cyano group, an isocyano group, an acid anhydride group, and an epoxy group. Among these reactive groups, a carboxyl group, an acid anhydride group, and an epoxy group are preferable because they are excellent in reactivity with phenolic hydroxyl groups, and compounds having these reactive groups can be easily reacted.
本発明の硬化促進剤は、前記一般式（１）におけるＸとして、前記式（２）で表される基を有することが、好ましい。前記一般式（２）で表される構造において、置換基Ｒ7は、置換もしくは無置換の芳香族基、置換もしくは無置換の複素環基、及び置換もしくは無置換の脂肪族基のいずれかを示す。
このような置換基Ｒ7としては、例えば、フェニル基及びナフチル基などの芳香族基、ピリジニル基及びフリル基などの複素環基、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ペンチル基、ヘキシル基、オクチル基及びドデシル基などの炭素数１〜１２の鎖状脂肪族基、シクロペンチル基、シクロヘキシル基及びシクロオクチル基などの環状脂肪族基が挙げられる。また、これらの基は、置換基を有していても良く、そのような置換基としては、メトキシ基及びエトキシ基などのアルコキシ基、炭素数１〜５の脂肪族基、フルオロ基、クロロ基及びブロモ基などのハロゲン基などを挙げることができ、複数の置換基を有していても良い。これら置換基を有する基としては、例えば、イソプロピル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、３−メトキシヘキシル基及び２−クロロエチル基などの置換基を有する鎖状脂肪族基などの脂肪族基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、４−エチルフェニル基、２，４−ジクロロフェニル基及び２，４−ジメトキシフェニル基などの置換基を有する芳香族基、Ｎ−メチル−２−ピリジニル基などの置換基を有する複素環基などが挙げられる。また、これらのうちでも、フェニル基、置換基を有するフェニル基、炭素数２〜６の無置換の脂肪族基、及び炭素数３〜６の置換基を有する脂肪族基が、良好な硬化性を発揮する為に好ましく、例えば、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、４−エチルフェニル基及び２，４−ジクロロフェニル基などの置換基を有するフェニル基、メチル基、エチル基、ｎ−プロピル基及びｎ−ブチル基などの無置換の脂肪族基、イソプロピル基及びｔｅｒｔ−ブチル基などの置換基を有する脂肪族基が挙げられる。このような置換基Ｒ7を有する基は、硬化促進剤の合成の際に、フェノール性水酸基との反応性に優れ、効率よく本発明の硬化促進剤を得ることができるのに加え、エポキシ樹脂組成物における吸湿時の硬化性の低下が、他の構造に比べ少なく、エポキシ樹脂組成物の可使時間がより長くなるため好ましい。
上記のような反応残基は、カルボキシル化合物又は酸無水物を、上記のフェノール性水酸基に反応させて得ることができる。このようなカルボキシル化合物としては、蟻酸、酢酸およびプロピル酸などの脂肪族カルボン酸、安息香酸などの芳香族カルボン酸などが挙げられ、酸無水物としては、無水酢酸および無水安息香酸などが挙げられる。
It is preferable that the hardening accelerator of this invention has group represented by the said Formula (2) as X in the said General formula (1). In the structure represented by the general formula (2), the substituent R 7 is any one of a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aliphatic group. Show.
Examples of such substituent R 7 include aromatic groups such as phenyl group and naphthyl group, heterocyclic groups such as pyridinyl group and furyl group, methyl group, ethyl group, n-propyl group, n-butyl group, Examples thereof include chain aliphatic groups having 1 to 12 carbon atoms such as a pentyl group, hexyl group, octyl group and dodecyl group, and cyclic aliphatic groups such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. In addition, these groups may have a substituent, such as an alkoxy group such as a methoxy group and an ethoxy group, an aliphatic group having 1 to 5 carbon atoms, a fluoro group, and a chloro group. And a halogen group such as a bromo group, and may have a plurality of substituents. Examples of the group having these substituents include aliphatic groups such as chain aliphatic groups having substituents such as isopropyl group, tert-butyl group, sec-butyl group, 3-methoxyhexyl group and 2-chloroethyl group. 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-ethylphenyl group, 2,4-dichlorophenyl group, and An aromatic group having a substituent such as 2,4-dimethoxyphenyl group, a heterocyclic group having a substituent such as N-methyl-2-pyridinyl group, and the like can be given. Among these, a phenyl group, a phenyl group having a substituent, an unsubstituted aliphatic group having 2 to 6 carbon atoms, and an aliphatic group having a substituent having 3 to 6 carbon atoms have good curability. For example, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4- Phenyl group having a substituent such as ethylphenyl group and 2,4-dichlorophenyl group, unsubstituted aliphatic group such as methyl group, ethyl group, n-propyl group and n-butyl group, isopropyl group and tert-butyl group And an aliphatic group having a substituent such as. Such a group having a substituent R 7 is excellent in reactivity with a phenolic hydroxyl group in the synthesis of a curing accelerator, and in addition to being able to efficiently obtain the curing accelerator of the present invention, an epoxy resin The lowering of curability at the time of moisture absorption in the composition is less than that of other structures, and it is preferable because the pot life of the epoxy resin composition becomes longer.
The reaction residue as described above can be obtained by reacting a carboxyl compound or acid anhydride with the phenolic hydroxyl group. Examples of such carboxyl compounds include aliphatic carboxylic acids such as formic acid, acetic acid and propyl acid, and aromatic carboxylic acids such as benzoic acid, and examples of acid anhydrides include acetic anhydride and benzoic anhydride. .
ここで、本発明のエポキシ樹脂用硬化促進剤の製造方法を説明するが、これらに限定されない。 Here, although the manufacturing method of the hardening accelerator for epoxy resins of this invention is demonstrated, it is not limited to these.
本発明のエポキシ樹脂用硬化促進剤の合成方法としては、例えば、まず、第三級ホスフィン化合物と、キノン類とを付加反応させて、ホスフィンとキノンとの付加物であるホスホニウムフェノラート化合物を合成し、次いで、これを、フェノール性水酸基と反応し得る有機基を有する化合物と加熱して反応させて、本発明の硬化促進剤を合成することができる。
更に具体例の一つとして、前記一般式（１）におけるＸとして、前記式（２）で表される基を有する硬化促進剤の合成方法について説明すると、例えば、第三級ホスフィン化合物と１，４−ベンゾキノンなどのキノン類とを、それぞれアセトンなどの有機溶剤に溶解し、その溶液を混合することで、付加反応物であるホスホニウムフェノラート化合物を合成し、生成物を分離精製後に、フェノール性水酸基と反応し得る化合物として、無水酢酸などの酸無水物とともに、ピリジン、アセトン、ジメチルホルムアミド及びトルエンなどの有機溶剤に溶解し、加熱反応することにより得ることができる。その合成工程は、下記反応式（３）のように表される。かかる合成法により、容易かつ高収率で合成することが可能である。
As a method for synthesizing the curing accelerator for epoxy resin of the present invention, for example, first, a tertiary phosphine compound and a quinone are subjected to an addition reaction to synthesize a phosphonium phenolate compound which is an adduct of phosphine and quinone. Then, this is heated and reacted with a compound having an organic group capable of reacting with a phenolic hydroxyl group, so that the curing accelerator of the present invention can be synthesized.
As a specific example, a method for synthesizing a curing accelerator having a group represented by the formula (2) as X in the general formula (1) will be described. For example, a tertiary phosphine compound and 1, A phosphonium phenolate compound, which is an addition reaction product, is synthesized by dissolving quinones such as 4-benzoquinone in an organic solvent such as acetone and mixing the solutions. A compound capable of reacting with a hydroxyl group can be obtained by dissolving in an organic solvent such as pyridine, acetone, dimethylformamide and toluene together with an acid anhydride such as acetic anhydride and heating. The synthesis process is represented by the following reaction formula (3). By such a synthesis method, it is possible to synthesize easily and with high yield.
また、この他の例としては、前記一般式（１）におけるＸとして、前記一般式（２）で表される基以外の基を有する硬化促進剤の合成方法において、フェノール性水酸基と反応し得る有機基を有する化合物として、エポキシ基やその他の反応性基を有する化合物を用いる際も、同様にして実施できる。例えば、上記同様にして、ホスホニウムフェノラート化合物を合成し、これを、グリシジルフェニルエーテルなどのエポキシ化合物ともに、有機溶剤中で反応させることで、エポキシ基を有する化合物の反応残基を有する硬化促進剤が容易に合成できる。 In addition, as another example, in the synthesis method of a curing accelerator having a group other than the group represented by the general formula (2) as X in the general formula (1), it can react with a phenolic hydroxyl group. When using a compound having an epoxy group or other reactive group as the compound having an organic group, the same can be carried out. For example, in the same manner as described above, a phosphonium phenolate compound is synthesized, and this is reacted with an epoxy compound such as glycidyl phenyl ether in an organic solvent to thereby have a curing accelerator having a reaction residue of a compound having an epoxy group. Can be easily synthesized.
ここで、前記第三級ホスフィン化合物としては、前記一般式（１）で表される構造を得ることができるホスフィン化合物を選択すれば良く、フェニル基及びナフチル基などの無置換の芳香族基、ピリジニル基及びフリル基などの無置換の複素環基、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ペンチル基、ヘキシル基、オクチル基及びドデシル基などの炭素数１〜１２の無置換の鎖状脂肪族基、シクロペンチル基、シクロヘキシル基及びシクロオクチル基などの無置換の環状脂肪族基、及び、これら無置換の基が、メトキシ基及びエトキシ基などのアルコキシ基、炭素数１〜５の脂肪族基、フルオロ基、クロロ基及びブロモ基などのハロゲン基を置換基として有する基より選ばれる、同一又はお互いに異なる３つの基を有する第３級ホスフィン化合物が用いることができる。これらの置換基としては、前記一般式（１）におけるＲ1、Ｒ2及びＲ3と同様のものを挙げることができる。
そのような具体例としては、トリブチルホスフィン、トリイソブチルホスフィン、トリペンチルホスフィン、トリフェニルホスフィン、トリフリルホスフィン、トリ−（４−メトキシフェニル）ホスフィン、トリ−（２−エトキシフェニル）ホスフィン、トリ−（２−エチルフェニル）ホスフィン、トリ−（２，６−ジメトキシフェニル）ホスフィン及びモノプロピルジフェニルホスフィンなどが挙げられるが、これらに限定されない。
Here, as the tertiary phosphine compound, a phosphine compound capable of obtaining the structure represented by the general formula (1) may be selected, an unsubstituted aromatic group such as a phenyl group and a naphthyl group, Non-substituted heterocyclic group such as pyridinyl group and furyl group, methyl group, ethyl group, n-propyl group, n-butyl group, pentyl group, hexyl group, octyl group and dodecyl group Substituted chain aliphatic groups, unsubstituted cycloaliphatic groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group, and these unsubstituted groups are alkoxy groups such as methoxy group and ethoxy group, 1 to 1 carbon atoms A third group having three groups which are the same or different from each other, selected from groups having 5 halogen groups such as aliphatic groups, fluoro groups, chloro groups and bromo groups as substituents; It can be a phosphine compound used. Examples of these substituents include the same groups as R 1 , R 2 and R 3 in the general formula (1).
Specific examples thereof include tributylphosphine, triisobutylphosphine, tripentylphosphine, triphenylphosphine, trifurylphosphine, tri- (4-methoxyphenyl) phosphine, tri- (2-ethoxyphenyl) phosphine, tri- ( Examples include, but are not limited to, 2-ethylphenyl) phosphine, tri- (2,6-dimethoxyphenyl) phosphine, and monopropyldiphenylphosphine.
前記キノン類としては、前記一般式（１）で表される構造を得ることができるキノン類を選択すれば良く、そのような具体例としては、１，４−ベンゾキノン、又は１，４−ベンゾキノンの、２，３，５位に、置換基を有する置換キノン化合物を用いることが好ましい。前記置換キノン化合物における、置換基としては、例えば、水素原子、ハロゲン原子、置換もしくは無置換の芳香族基、置換もしくは無置換の複素環基、及び置換もしくは無置換の脂肪族基などが挙げられ、２，３，５位の置換基が同一であってもお互いに異なっていても良い。これらの置換基としては、前記一般式（１）におけるＲ4、Ｒ5及びＲ6と同様のものを挙げることができる。このような置換キノン化合物としては、２−クロロ−１，４−ベンゾキノン、２−フェニル−１，４−ベンゾキノン、２−メトキシ−１，４−ベンゾキノンなどが挙げられるが、これらに限定されない。
さらに、上記キノン類の具体例に加え、１，４−ナフトキノン、又は１，４−ナフトキノンが、１，４位以外に置換基を有する置換ナフトキノン類、１，４−アントラキノン、同様に１，４、−アントラキノンが１，４位以外に置換基を有する置換アントラキノン類などの、多核芳香環を有するキノン類を挙げることができる。しかし、これらの多核芳香環を有するキノン類は、入手が困難であり、前述したベンゾキノン類に比べ、量産性の面で劣る。
As the quinones, quinones capable of obtaining the structure represented by the general formula (1) may be selected. Examples of such quinones include 1,4-benzoquinone and 1,4-benzoquinone. It is preferable to use a substituted quinone compound having a substituent at positions 2, 3, and 5. Examples of the substituent in the substituted quinone compound include a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aliphatic group. The substituents at the 2, 3, and 5 positions may be the same or different from each other. Examples of these substituents include the same groups as R 4 , R 5 and R 6 in the general formula (1). Examples of such substituted quinone compounds include, but are not limited to, 2-chloro-1,4-benzoquinone, 2-phenyl-1,4-benzoquinone, 2-methoxy-1,4-benzoquinone, and the like.
Furthermore, in addition to the specific examples of the quinones, 1,4-naphthoquinone or 1,4-naphthoquinone has a substituted naphthoquinone having a substituent other than the 1,4-position, 1,4-anthraquinone, and 1,4 ,-Anthraquinone can include quinones having a polynuclear aromatic ring, such as substituted anthraquinones having a substituent other than the 1 and 4 positions. However, these quinones having a polynuclear aromatic ring are difficult to obtain and are inferior in mass productivity as compared to the benzoquinones described above.
前記フェノール性水酸基と反応しうる有機基を有する化合物としては、前記同様にして、カルボキシル基、水酸基、シアノ基、イソシアノ基、酸無水物基及びエポキシ基などの反応性基を有する化合物が挙げられる。これらのなかでも、前記一般式（２）で表される基を有する化合物が、好ましく、そのような化合物として、蟻酸、酢酸およびプロピル酸などの脂肪族カルボン酸、安息香酸などの芳香族カルボン酸などカルボキシル化合物が挙げられ、また、無水酢酸および無水安息香酸など酸無水物が挙げられる。また、前記エポキシ基を有する化合物としては、グリシジルフェニルエーテル、グリシジルプロピルエーテルなどが挙げられる。 Examples of the compound having an organic group capable of reacting with the phenolic hydroxyl group include compounds having a reactive group such as a carboxyl group, a hydroxyl group, a cyano group, an isocyano group, an acid anhydride group, and an epoxy group in the same manner as described above. . Among these, compounds having a group represented by the general formula (2) are preferable, and examples of such compounds include aliphatic carboxylic acids such as formic acid, acetic acid and propyl acid, and aromatic carboxylic acids such as benzoic acid. Carboxyl compounds, and acid anhydrides such as acetic anhydride and benzoic anhydride. Examples of the compound having an epoxy group include glycidyl phenyl ether and glycidyl propyl ether.
［本発明のエポキシ樹脂組成物］
本発明のエポキシ樹脂組成物は、１分子内にエポキシ基を２個以上有する化合物（Ａ）と、１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）と、本発明の硬化促進剤（Ｃ）と、必要に応じ無機充填材（Ｄ）とを含むものである。かかるエポキシ樹脂組成物は、硬化性、及び流動性に優れたものである。
[Epoxy resin composition of the present invention]
The epoxy resin composition of the present invention comprises a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and the curing accelerator of the present invention. (C) and an inorganic filler (D) as needed are included. Such an epoxy resin composition is excellent in curability and fluidity.
以下、本発明のエポキシ樹脂組成物に用いる各成分について、順次説明する。 Hereinafter, each component used for the epoxy resin composition of this invention is demonstrated one by one.
［１分子内にエポキシ基を２個以上有する化合物（Ａ）］
本発明に用いる１分子内にエポキシ基を２個以上有する化合物（Ａ）としては、１分子内にエポキシ基を２個以上有するモノマー、オリゴマー及びポリマーの全般を挙げることができ、その分子量、分子構造は特に限定するものではないが、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニレン及び／又はビフェニレン骨格を有するナフトールアラルキル型エポキシ樹脂等が挙げられ、これらは単独でも混合して用いても差し支えない。これらの内では、樹脂硬化物特性の信頼性向上と、成形時の流動性の確保の観点から、溶融粘度の低さと硬化物の熱時強度などの物理特性に優れるフェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂を用いることが好ましい。
[Compound (A) having two or more epoxy groups in one molecule]
Examples of the compound (A) having two or more epoxy groups in one molecule for use in the present invention include monomers, oligomers and polymers generally having two or more epoxy groups in one molecule. The structure is not particularly limited. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, hydroquinone type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin , Triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, phenol arral having phenylene and / or biphenylene skeleton Le epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resin, naphthol aralkyl type epoxy resin having a phenylene and / or biphenylene skeleton and the like, which no problem be used singly or in admixture. Among these, from the viewpoint of improving the reliability of the cured resin properties and ensuring fluidity during molding, a phenylene and / or biphenylene skeleton that is excellent in physical properties such as low melt viscosity and heat strength of the cured product. It is preferable to use the phenol aralkyl type epoxy resin which has.
［１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）］
本発明に用いる１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）としては、１分子内にフェノール性水酸基を２個以上有するモノマー、オリゴマー及びポリマーの全般を挙げることができ、その分子量、分子構造を特に限定するものではないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、トリフェノールメタン型フェノール樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、フェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル樹脂、フェニレン及び／又はビフェニレン骨格を有するナフトールアラルキル樹脂、ビスフェノール化合物等が挙げられ、これらは単独でも混合して用いても差し支えない。これらの内では、樹脂硬化物特性の信頼性向上と、成形時の流動性の確保の観点から、溶融粘度の低さと硬化物の熱時強度などの物理特性に優れるフェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル樹脂を用いることが好ましい。
[Compound (B) having two or more phenolic hydroxyl groups in one molecule]
Examples of the compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention include monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule, and the molecular weight thereof. Although the molecular structure is not particularly limited, for example, phenol novolac resin, cresol novolac resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol having phenylene and / or biphenylene skeleton Examples thereof include aralkyl resins, naphthol aralkyl resins having a phenylene and / or biphenylene skeleton, and bisphenol compounds. These may be used alone or in combination. Among these, from the viewpoint of improving the reliability of the cured resin properties and ensuring fluidity during molding, a phenylene and / or biphenylene skeleton that is excellent in physical properties such as low melt viscosity and heat strength of the cured product. The phenol aralkyl resin having is preferably used.
［硬化促進剤（Ｃ）］
本発明のエポキシ樹脂組成物に用いる硬化促進剤（Ｃ）としては、上記で得られるエポキシ樹脂用硬化促進剤が挙げられ、これらのうちの１種又は２種以上を組み合わせて用いることができる。また、本発明のエポキシ樹脂用硬化促進剤の特性を損なわない程度で、一般に封止材料に使用するものを併用することができる。例えば、１，８−ジアザビシクロ（５，４，０）ウンデセン−７等のジアザビシクロアルケン及びその誘導体、トリブチルアミン及びベンジルジメチルアミン等のアミン系化合物、２−メチルイミダゾール等のイミダゾール化合物、トリフェニルホスフィン及びメチルジフェニルホスフィン等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、テトラフェニルホスホニウム・テトラ安息香酸ボレート、テトラフェニルホスホニウム・テトラナフトイックアシッドボレート、テトラフェニルホスホニウム・テトラナフトイルオキシボレート及びテトラフェニルホスホニウム・テトラナフチルオキシボレート等のテトラ置換ホスホニウム・テトラ置換ボレート等が挙げられ、これらは単独でも混合して併用しても差し支えない。
[Curing accelerator (C)]
As a hardening accelerator (C) used for the epoxy resin composition of this invention, the hardening accelerator for epoxy resins obtained above is mentioned, Among these, it can use combining 1 type (s) or 2 or more types. Moreover, what is generally used for a sealing material can be used together in such an extent that the characteristics of the curing accelerator for epoxy resins of the present invention are not impaired. For example, diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof, amine compounds such as tributylamine and benzyldimethylamine, imidazole compounds such as 2-methylimidazole, triphenyl Organic phosphines such as phosphine and methyldiphenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, tetraphenylphosphonium / tetranaphthoic acid borate, tetraphenylphosphonium / tetranaphthoyloxyborate and tetraphenyl Examples include tetra-substituted phosphonium and tetra-substituted borates such as phosphonium and tetranaphthyloxyborate. These may be used alone or in combination. Enoi.
［無機充填材（Ｄ）］
本発明のエポキシ樹脂組成物において、任意に用いる無機充填材（Ｄ）としては、得られる半導体装置の耐半田性向上や、難燃性の付与を目的として、エポキシ樹脂組成物中に配合（混合）されるものであり、一般に半導体封止用エポキシ樹脂組成物に使用されているものを用いることができる。
例えば、溶融球状シリカ、溶融破砕シリカ、結晶シリカ、タルク、アルミナ、水酸化アルミニウム、チタンホワイト、窒化珪素等が挙げられ、最も好適に使用されるものとしては、球状溶融シリカである。これらの無機充填剤は、単独でも混合して用いても差し支えない。またこれらがカップリング剤により表面処理されていてもかまわない。無機充填材の形状としては、流動性改善のために、できるだけ真球状であり、かつ粒度分布がブロードであることが好ましい。
無機充填材の含有量としては、特に限定されないが、全エポキシ樹脂組成物中６０〜９５重量％が好ましい。前記好ましい範囲において、硬化物における耐半田性及び成形時の流動性が特に好ましい。
[Inorganic filler (D)]
In the epoxy resin composition of the present invention, the inorganic filler (D) optionally used is blended (mixed) in the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor device and imparting flame resistance. In general, those used in epoxy resin compositions for semiconductor encapsulation can be used.
For example, fused spherical silica, fused crushed silica, crystalline silica, talc, alumina, aluminum hydroxide, titanium white, silicon nitride and the like can be mentioned. Spherical fused silica is most preferably used. These inorganic fillers may be used alone or in combination. These may be surface-treated with a coupling agent. The shape of the inorganic filler is preferably as spherical as possible and the particle size distribution is broad in order to improve fluidity.
Although it does not specifically limit as content of an inorganic filler, 60 to 95 weight% is preferable in all the epoxy resin compositions. In the above preferred range, the solder resistance and the fluidity during molding in the cured product are particularly preferred.
本発明のエポキシ樹脂組成物において、硬化促進剤（Ｃ）の含有量（配合量）は、特に限定されないが、前記１分子内にエポキシ基を２個以上有する化合物（Ａ）及び前記１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）の樹脂成分に対して、０．０１〜１０重量％程度であるのが好ましく、０．１〜５重量％程度であるのが、より好ましい。これにより、エポキシ樹脂組成物の硬化性、流動性、保存性及び硬化物特性がバランスよく発現する。 In the epoxy resin composition of the present invention, the content (blending amount) of the curing accelerator (C) is not particularly limited, but the compound (A) having two or more epoxy groups in one molecule and the one molecule It is preferably about 0.01 to 10% by weight, more preferably about 0.1 to 5% by weight, based on the resin component of the compound (B) having 2 or more phenolic hydroxyl groups. Thereby, the sclerosis | hardenability, fluidity | liquidity, preservability, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.
また、前記１分子内にエポキシ基を２個以上有する化合物（Ａ）と、前記１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）との配合比は、エポキシ基の総数と、硬化剤に加えその他の添加成分に由来するものも含むフェノール性水酸基の総数の比（エポキシ基／フェノール性水酸基）において、０．８〜１．３であることが好ましい。前記好ましい範囲において、エポキシ樹脂組成物の硬化性や、硬化物のガラス転移温度及び耐湿信頼性などがより好ましいものとなる。 The compounding ratio of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule is determined by the total number of epoxy groups and curing In the ratio of the total number of phenolic hydroxyl groups including those derived from other additive components in addition to the agent (epoxy group / phenolic hydroxyl group), it is preferably 0.8 to 1.3. In the preferable range, the curability of the epoxy resin composition, the glass transition temperature of the cured product, the moisture resistance reliability, and the like are more preferable.
また、本発明のエポキシ樹脂組成物には、上記成分以外に、必要に応じて、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン及びビニルシラン等のシランカップリング剤や、チタネートカップリング剤、アルミニウムカップリング剤、アルミニウム／ジルコニウムカップリング剤等のカップリング剤、フェニルシラン及びナフチルシランなどの高流動化成分、カーボンブラック及びベンガラ等の着色剤、カルナバワックス等の天然ワックス、酸化もしくは非酸化のポリエチレンワックス、エステルワックス及びポリアルキレンオキサイド等の合成ワックス、ステアリン酸やステアリン酸亜鉛等の高級脂肪酸及びその金属塩類並びにパラフィン等の離型剤、シリコーンオイル及びシリコーンゴム等の低応力化成分、臭素化エポキシ樹脂や三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛、硼酸亜鉛、モリブデン酸亜鉛及びフォスファゼン等の難燃剤、マグネシウム、アルミニウム、チタン及びビスマス系（酸化ビスマス水和物）等の無機イオン交換体等、種々の添加剤を適宜配合しても差し支えない。 In addition to the above components, the epoxy resin composition of the present invention, if necessary, silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane and vinyl silane, titanate coupling agent, Aluminum coupling agents, coupling agents such as aluminum / zirconium coupling agents, highly fluidizing components such as phenylsilane and naphthylsilane, colorants such as carbon black and bengara, natural waxes such as carnauba wax, oxidized or non-oxidized Low stress such as synthetic waxes such as polyethylene wax, ester wax and polyalkylene oxide, higher fatty acids such as stearic acid and zinc stearate and metal salts thereof, mold release agents such as paraffin, silicone oil and silicone rubber Ingredients, flame retardants such as brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc oxide, zinc borate, zinc molybdate and phosphazene, magnesium, aluminum, titanium and bismuth (bismuth oxide hydrate) Various additives such as inorganic ion exchangers such as the above may be appropriately blended.
本発明のエポキシ樹脂組成物は、前記１分子内にエポキシ基を２個以上有する化合物（Ａ）、前記１分子内にフェノール性水酸基を２個以上有する化合物（Ｂ）、前記硬化促進剤（Ｃ）、任意に用いる無機充填材（Ｄ）及びその他の添加剤等を、混合機を用いて、充分に均一に混合した後、更に混練機で溶融混練し、冷却後粉砕して得られる。なお、混合機としては、特に限定しないが、例えばボールミル、ヘンシェルミキサー、及びＶブレンダーやダブルコーンブレンダー、コンクリートミキサーやリボンブレンダー等のブレンダー類などが挙げられる。また、混練機も特に限定しないが、熱ロール、加熱ニーダー及び一軸もしくは二軸のスクリュー型混練機等が好適に挙げられる。 The epoxy resin composition of the present invention comprises a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and the curing accelerator (C ), Optionally used inorganic filler (D), other additives, and the like are sufficiently uniformly mixed using a mixer, then melt-kneaded with a kneader, cooled and pulverized. In addition, although it does not specifically limit as a mixer, For example, blenders, such as a ball mill, a Henschel mixer, a V blender, a double cone blender, a concrete mixer, a ribbon blender, etc. are mentioned. The kneader is not particularly limited, and preferred examples include a hot roll, a heating kneader, and a uniaxial or biaxial screw type kneader.
本発明のエポキシ樹脂組成物を用いて、半導体素子等の各種の電子部品を封止し、半導体装置を製造するには、トランスファーモールド、コンプレッションモールド及びインジェクションモールド等の従来からの成形方法で硬化成形すればよい。 The epoxy resin composition of the present invention is used to encapsulate various electronic components such as semiconductor elements, and to manufacture semiconductor devices by conventional molding methods such as transfer molding, compression molding, and injection molding. do it.
本発明の半導体装置の形態としては、特に限定されないが、例えば、ＳＩＰ（Single Inline Package）、ＨＳＩＰ（SIP with Heatsink）、ＺＩＰ（Zig-zag Inline Package）、ＤＩＰ（Dual Inline Package）、ＳＤＩＰ（Shrink Dual Inline Package）、ＳＯＰ（Small Outline Package）、ＳＳＯＰ（Shrink Small Outline Package）、ＴＳＯＰ（Thin Small Outline Package）、ＳＯＪ（Small Outline J-leaded Package）、ＱＦＰ（Quad Flat Package）、ＱＦＰ(ＦＰ）（QFP Fine Pitch）、ＴＱＦＰ（Thin Quad Flat Package）、ＱＦＪ（ＰＬＣＣ）（Quad Flat J-leaded Package）、ＢＧＡ（Ball Grid Array）等が挙げられる。 The form of the semiconductor device of the present invention is not particularly limited. For example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (Shrink) Dual Inline Package), SOP (Small Outline Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline J-leaded Package), QFP (Quad Flat Package), QFP (FP) ( QFP Fine Pitch), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-leaded Package), BGA (Ball Grid Array), and the like.
このようにして得られた本発明の半導体装置は、耐半田クラック性及び耐湿信頼性に優れる。 The semiconductor device of the present invention thus obtained is excellent in solder crack resistance and moisture resistance reliability.
また、本実施形態では、本発明のエポキシ樹脂組成物を、半導体装置の封止材料として用いる場合について説明したが、本発明のエポキシ樹脂組成物の用途としては、これに限定されるものではない。 In the present embodiment, the case where the epoxy resin composition of the present invention is used as a sealing material for a semiconductor device has been described. However, the use of the epoxy resin composition of the present invention is not limited thereto. .
以上、本発明のエポキシ樹脂用硬化促進剤、エポキシ樹脂組成物及び半導体装置の好適実施形態について説明したが、本発明は、これに限定されるものではない。 The preferred embodiments of the curing accelerator for epoxy resin, the epoxy resin composition, and the semiconductor device of the present invention have been described above, but the present invention is not limited to this.
次に、本発明の具体的実施例について説明するが、本発明はこれらに限定されない。 Next, specific examples of the present invention will be described, but the present invention is not limited thereto.
まず、比較例の硬化促進剤である、トリフェニルホスフィン−ベンゾキノン付加物（以下ＴＰＰ−ＢＱ）、トリ（４−メトキシフェニル）ホスフィン−ナフトキノン付加物（以下ＴＰＡＰ−ＮＱ）、および本発明の硬化促進剤であるＣ１〜Ｃ３を用意した。 First, triphenylphosphine-benzoquinone adduct (hereinafter TPP-BQ), tri (4-methoxyphenyl) phosphine-naphthoquinone adduct (hereinafter TPAP-NQ), which are curing accelerators of comparative examples, and the curing acceleration of the present invention. C1-C3 which are agents were prepared.
（ＴＰＰ−ＢＱの合成）
冷却管及び撹拌装置付きのセパラブルフラスコ（容量：２００ｍＬ）に、ベンゾキノン６．４９ｇ（０．０６０ｍｏｌ）、トリフェニルホスフィン１７．３ｇ（０．０６６ｍｏｌ）及びアセトン４０ｍＬ仕込み、攪拌下室温で反応した。析出した結晶をアセトンで洗浄後、濾過・乾燥し、暗緑色の結晶を得た。
(Synthesis of TPP-BQ)
A separable flask (volume: 200 mL) equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 mL of acetone, and reacted at room temperature with stirring. The precipitated crystals were washed with acetone, filtered and dried to obtain dark green crystals.
この化合物を、1Ｈ−ＮＭＲ、マススペクトル、元素分析で分析した結果、下記式（４）で表される目的のTＴＰＰ−ＢＱであることが確認された。得られたＴＰＰ−ＢＱの収率は、９４％であった。 As a result of analyzing this compound by 1 H-NMR, mass spectrum and elemental analysis, it was confirmed that it was the target TTPP-BQ represented by the following formula (4). The yield of TPP-BQ obtained was 94%.
（ＴＰＡＰ−ＮＱの合成）
冷却管及び撹拌装置付きのセパラブルフラスコ（容量：２００ｍＬ）に、１，４−ナフトキノン６．４９ｇ（０．０６０ｍｏｌ）、トリ（４−メトキシフェニル）ホスフィン２３．３ｇ（０．０６６ｍｏｌ）及びアセトン１００ｍＬ仕込み、攪拌下室温で反応した。析出した結晶をアセトンで洗浄後、濾過・乾燥し、暗緑色の結晶を得た。これを回収、再結晶し、３１．７ｇの黄褐色結晶を得た。
(Synthesis of TPAP-NQ)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 6.49 g (0.060 mol) of 1,4-naphthoquinone, 23.3 g (0.066 mol) of tri (4-methoxyphenyl) phosphine and 100 mL of acetone The reaction was carried out at room temperature with stirring. The precipitated crystals were washed with acetone, filtered and dried to obtain dark green crystals. This was recovered and recrystallized to obtain 31.7 g of tan crystals.
この化合物を、1Ｈ−ＮＭＲ、マススペクトル、元素分析で分析した結果、下記式（５）で表される目的のＴＰＡＰ−ＮＱであることが確認された。得られたＴＰＡＰ−ＮＱの収率は、９４％であった。 As a result of analyzing this compound by 1 H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target TPAP-NQ represented by the following formula (5). The yield of the obtained TPAP-NQ was 94%.
（化合物Ｃ１の合成）
冷却管及び撹拌装置付きのセパラブルフラスコ（容量：５００ｍＬ）に、上記で得たＴＰＰ−ＢＱ １４．８ｇ（０．０４０ｍｏｌ）、無水酢酸４．０８ｇ（０．０４０ｍｏｌ）、及びピリジン１００ｍLを仕込み、１４０℃に加熱し、攪拌しながら２時間還流反応させた。反応溶液を冷却後、ヨウ化ナトリウム１０ｇを溶解した水５００ｍLに滴下すると、肌色の沈殿が発生した。これを回収、再結晶し、１５．３ｇの淡褐色結晶を得た。
(Synthesis of Compound C1)
A separable flask (capacity: 500 mL) equipped with a condenser and a stirrer was charged with 14.8 g (0.040 mol) of TPP-BQ obtained above, 4.08 g (0.040 mol) of acetic anhydride, and 100 mL of pyridine. The mixture was heated to 140 ° C. and refluxed for 2 hours with stirring. When the reaction solution was cooled and dropped into 500 mL of water in which 10 g of sodium iodide was dissolved, a skin-colored precipitate was generated. This was recovered and recrystallized to obtain 15.3 g of light brown crystals.
この化合物をＣ１とした。化合物Ｃ１を、1Ｈ−ＮＭＲ、マススペクトル、元素分析で分析した結果、下記式（６）で表される目的のホスホニウムフェノラートであることが確認された。得られた化合物Ｃ１の収率は、９３％であった。 This compound was designated C1. As a result of analyzing the compound C1 by 1 H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target phosphonium phenolate represented by the following formula (6). The yield of the obtained compound C1 was 93%.
（化合物Ｃ２の合成）
冷却管及び撹拌装置付きのセパラブルフラスコ（容量：５００ｍＬ）に、上記で得たＴＰＰ−ＢＱ １４．８ｇ（０．０４０ｍｏｌ）、グリシジルフェニルエーテル６．０ｇ（０．０４０ｍｏｌ）、及びピリジン１００ｍLを仕込み、１４０℃に加熱し、攪拌しながら２時間還流反応させた。反応溶液を冷却後、ヨウ化ナトリウム１０ｇを溶解した水５００ｍLに滴下すると、褐色の沈殿が発生した。これを回収、再結晶し、１７．５ｇの褐色粉末を得た。
(Synthesis of Compound C2)
A separable flask (capacity: 500 mL) equipped with a condenser and a stirrer was charged with 14.8 g (0.040 mol) of TPP-BQ obtained above, 6.0 g (0.040 mol) of glycidyl phenyl ether, and 100 mL of pyridine. The mixture was heated to 140 ° C. and refluxed for 2 hours with stirring. After cooling the reaction solution, it was added dropwise to 500 mL of water in which 10 g of sodium iodide was dissolved, and a brown precipitate was generated. This was recovered and recrystallized to obtain 17.5 g of a brown powder.
この化合物をＣ２とした。化合物Ｃ２を、1Ｈ−ＮＭＲ、マススペクトル、元素分析で分析した結果、下記式（７）で表される目的のホスホニウムフェノラートであることが確認された。得られた化合物Ｃ２の収率は、８４％であった。 This compound was designated C2. Compound C2 was analyzed by 1 H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target phosphonium phenolate represented by the following formula (7). The yield of the obtained compound C2 was 84%.
［エポキシ樹脂組成物の調製及び半導体装置の製造］
以下のようにして、前記化合物Ｃ１、Ｃ２及びトリフェニルホスフィン、ＴＰＰ−ＢＱ、ＴＰＡＰ−ＮＱを、それぞれ含むエポキシ樹脂組成物を調製し、半導体装置を製造した。
[Preparation of epoxy resin composition and manufacture of semiconductor device]
As described below, an epoxy resin composition containing each of the compounds C1 and C2 and triphenylphosphine, TPP-BQ, and TPAP-NQ was prepared to manufacture a semiconductor device.
（実施例１）
まず、化合物（Ａ）としてビフェニル型エポキシ樹脂（ジャパンエポキシレジン（株）製ＹＸ−４０００ＨＫ）、化合物（Ｂ）としてフェノールアラルキル樹脂（三井化学（株）製ＸＬＣ−ＬＬ）、硬化促進剤（Ｃ）として化合物Ｃ１、無機充填材（Ｄ）として溶融球状シリカ（平均粒径１５μｍ）、その他の添加剤として、カーボンブラック、臭素化ビスフェノールＡ型エポキシ樹脂及びカルナバワックスを、それぞれ用意した。
Example 1
First, a biphenyl type epoxy resin (YX-4000HK, manufactured by Japan Epoxy Resin Co., Ltd.) as the compound (A), a phenol aralkyl resin (XLC-LL, manufactured by Mitsui Chemicals) as the compound (B), and a curing accelerator (C) As compound C1, fused spherical silica (average particle size 15 μm) as inorganic filler (D), and carbon black, brominated bisphenol A epoxy resin and carnauba wax as other additives were prepared.
次に、前記ビフェニル型エポキシ樹脂：５２重量部、前記フェノールアラルキル樹脂：４８重量部、化合物Ｃ１：２．０６重量部、溶融球状シリカ：７３０重量部、カーボンブラック：２重量部、臭素化ビスフェノールＡ型エポキシ樹脂：２重量部、カルナバワックス：２重量部を、まず室温で混合し、次いで、熱ロールを用いて９５℃で８分間混練した後、冷却粉砕して、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得た。 Next, the biphenyl type epoxy resin: 52 parts by weight, the phenol aralkyl resin: 48 parts by weight, compound C1: 2.06 parts by weight, fused spherical silica: 730 parts by weight, carbon black: 2 parts by weight, brominated bisphenol A Type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 95 ° C. for 8 minutes using a hot roll, then cooled and pulverized to obtain an epoxy resin composition (thermosetting Resin composition).
次に、このエポキシ樹脂組成物をモールド樹脂として用い、１００ピンＴＱＦＰのパッケージ（半導体装置）を８個、及び、１６ピンＤＩＰのパッケージ（半導体装置）を１５個、それぞれ製造した。 Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.
１００ピンＴＱＦＰは、金型温度１７５℃、注入圧力７．４ＭＰａ、硬化時間２分でトランスファーモールド成形し、１７５℃、８時間で後硬化させることにより製造した。 The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.
なお、この１００ピンＴＱＦＰのパッケージサイズは、１４×１４ｍｍ、厚み１．４ｍｍ、シリコンチップ（半導体素子）サイズは、８．０×８．０ｍｍ、リードフレームは、４２アロイ製とした。 The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.
また、１６ピンＤＩＰは、金型温度１７５℃、注入圧力６．８ＭＰａ、硬化時間２分でトランスファーモールド成形し、１７５℃、８時間で後硬化させることにより製造した。 The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.
なお、この１６ピンＤＩＰのパッケージサイズは、６．４×１９．８ｍｍ、厚み３．５ｍｍ、シリコンチップ（半導体素子）サイズは、３．５×３．５ｍｍ、リードフレームは、４２アロイ製とした。 The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .
（実施例２）
まず、化合物（Ａ）としてビフェニルアラルキル型エポキシ樹脂（日本化薬（株）製ＮＣ−３０００）、化合物（Ｂ）としてビフェニルアラルキル型フェノール樹脂（明和化成（株）製ＭＥＨ−７８５１ＳＳ）、潜伏性触媒（Ｃ）として化合物Ｃ１、無機充填材（Ｄ）として溶融球状シリカ（平均粒径１５μｍ）、その他の添加剤としてカーボンブラック、臭素化ビスフェノールＡ型エポキシ樹脂及びカルナバワックスを、それぞれ用意した。
(Example 2)
First, a biphenyl aralkyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as the compound (A), a biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.) as the compound (B), and a latent catalyst. Compound (C1) was prepared as (C), fused spherical silica (average particle size: 15 μm) as inorganic filler (D), and carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives.
次に、前記ビフェニルアラルキル型エポキシ樹脂：５７重量部、前記ビフェニルアラルキル型フェノール樹脂：４３重量部、化合物Ｃ１：２．０６重量部、溶融球状シリカ：６５０重量部、カーボンブラック：２重量部、臭素化ビスフェノールＡ型エポキシ樹脂：２重量部、カルナバワックス：２重量部を、まず室温で混合し、次いで熱ロールを用いて１０５℃で８分間混練した後、冷却粉砕して、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得た。 Next, said biphenyl aralkyl type epoxy resin: 57 parts by weight, said biphenyl aralkyl type phenol resin: 43 parts by weight, compound C1: 2.06 parts by weight, fused spherical silica: 650 parts by weight, carbon black: 2 parts by weight, bromine Bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 105 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition ( A thermosetting resin composition) was obtained.
次に、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。 Next, using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.
（実施例３）
化合物Ｃ１に代わり、化合物Ｃ２：２．６０重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 2.60 parts by weight of compound C2 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.
（実施例４）
化合物Ｃ１に代わり、化合物Ｃ２：２．６０重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
Example 4
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.60 parts by weight of compound C2 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.
（比較例１）
化合物Ｃ１に代わり、トリフェニルホスフィン：１．００重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 1)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.00 part by weight of triphenylphosphine was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 1.
（比較例２）
化合物Ｃ１に代わり、トリフェニルホスフィン：１．００重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 2)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.00 part by weight of triphenylphosphine was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 2.
（比較例３）
化合物Ｃ１に代わり、ＴＰＰ−ＢＱ：１．８５重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 1.85 parts by weight of TPP-BQ was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 1.
（比較例４）
化合物Ｃ１に代わり、ＴＰＰ−ＢＱ：１．８５重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 1.85 parts by weight of TPP-BQ was used instead of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 2.
（比較例５）
化合物Ｃ１に代わり、ＴＰＡＰ−ＮＱ：２．５５重量部を用いた以外は、前記実施例１と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例１と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 2.55 parts by weight of TPAP-NQ was used instead of Compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 1.
（比較例６）
化合物Ｃ１に代わり、ＴＰＡＰ−ＮＱ：２．５５重量部を用いた以外は、前記実施例２と同様にして、エポキシ樹脂組成物（熱硬化性樹脂組成物）を得、このエポキシ樹脂組成物を用いて、前記実施例２と同様にしてパッケージ（半導体装置）を製造した。
(Comparative Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.55 parts by weight of TPAP-NQ was used in place of compound C1, and this epoxy resin composition was obtained. Then, a package (semiconductor device) was manufactured in the same manner as in Example 2.
［特性評価］
各実施例及び各比較例で得られたエポキシ樹脂組成物の特性評価（１）〜（３）、及び、各実施例及び各比較例で得られた半導体装置の特性評価（４）及び（５）を、それぞれ、以下のようにして行った。
[Characteristic evaluation]
Characteristic evaluation (1) to (3) of the epoxy resin composition obtained in each example and each comparative example, and characteristic evaluation (4) and (5) of the semiconductor device obtained in each example and each comparative example ) Was performed as follows.
（１）：スパイラルフロー
ＥＭＭＩ−Ｉ−６６に準じたスパイラルフロー測定用の金型を用い、金型温度１７５℃、注入圧力６．８ＭＰａ、硬化時間２分で測定した。
(1): Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a curing time of 2 minutes.
このスパイラルフローは、流動性のパラメータであり、数値が大きい程、流動性が良好であることを示す。 This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.
（２）：硬化トルク
キュラストメーター（オリエンテック（株）製、ＪＳＲキュラストメーターＩＶ ＰＳ型）を用い、１７５℃、４５秒後のトルクを測定した。
この硬化トルクは、数値が大きい程、硬化性が良好であることを示す。
(2): Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.
（３）：吸湿後硬化トルク 吸湿後トルク率
得られたエポキシ樹脂組成物を、温度３０℃、相対湿度６０％ＲＨで1日保存した後、前記（２）と同様にして硬化トルクを測定した。また、調製直後の硬化トルクに対する百分率（％）をトルク率として求めた。
この吸湿後トルクは、変化が少ないほど、コンパウンドの耐湿性が良好であることを示す。また、吸湿後トルク率が１００％に近いほど、同様にコンパウンドの耐湿性が良好であることを示す。
(3): Curing torque after moisture absorption Torque ratio after moisture absorption After the obtained epoxy resin composition was stored at a temperature of 30 ° C. and a relative humidity of 60% RH for 1 day, the curing torque was measured in the same manner as in (2) above. . Moreover, the percentage (%) with respect to the hardening torque immediately after preparation was calculated | required as a torque rate.
The smaller the change in the torque after moisture absorption, the better the moisture resistance of the compound. Moreover, it shows that the moisture resistance of a compound is so favorable that the torque rate after moisture absorption is near 100%.
（４）：耐半田クラック性
１００ピンＴＱＦＰを８５℃、相対湿度８５％の環境下で１６８時間放置し、その後、２６０℃の半田槽に１０秒間浸漬した。
(4): Solder crack resistance 100 pin TQFP was left in an environment of 85 ° C. and relative humidity 85% for 168 hours, and then immersed in a solder bath at 260 ° C. for 10 seconds.
その後、顕微鏡下に、外部クラックの発生の有無を観察し、クラック発生率＝（クラックが発生したパッケージ数）／（全パッケージ数）×１００として、百分率（％）で表示した。 Then, the presence or absence of the occurrence of external cracks was observed under a microscope, and displayed as a percentage (%) as crack generation rate = (number of packages in which cracks occurred) / (total number of packages) × 100.
また、シリコンチップとエポキシ樹脂組成物の硬化物との剥離面積の割合を、超音波探傷装置を用いて測定し、剥離率＝（剥離面積）／（シリコンチップの面積）×１００として、８個のパッケージの平均値を求め、百分率（％）で表示した。 Further, the ratio of the peeled area between the silicon chip and the cured epoxy resin composition was measured using an ultrasonic flaw detector, and the peel rate = (peeled area) / (silicon chip area) × 100. The average value of the package was obtained and expressed as a percentage (%).
これらのクラック発生率及び剥離率は、それぞれ、数値が小さい程、耐半田クラック性が良好であることを示す。 These crack generation rate and peel rate indicate that the smaller the numerical value, the better the solder crack resistance.
（５）：耐湿信頼性
１６ピンＤＩＰに、１２５℃、相対湿度１００％の水蒸気中で、２０Ｖの電圧を印加し、断線不良を調べた。１５個のパッケージのうち８個以上に不良が出るまでの時間を不良時間とした。
(5): Moisture resistance reliability A voltage of 20 V was applied to a 16-pin DIP in water vapor at 125 ° C. and a relative humidity of 100%, and the disconnection failure was examined. The time until a defect appears in 8 or more of the 15 packages was defined as a defect time.
なお、測定時間は、最長で５００時間とし、その時点で不良パッケージ数が８個未満であったものは、不良時間を５００時間超（＞５００）と示す。
この不良時間は、数値が大きい程、耐湿信頼性に優れることを示す。
各特性評価（１）〜（５）の結果を、表１に示す。
Note that the measurement time is 500 hours at the longest, and when the number of defective packages is less than 8 at that time, the defective time is indicated as over 500 hours (> 500).
This failure time indicates that the larger the numerical value, the better the moisture resistance reliability.
Table 1 shows the results of the characteristic evaluations (1) to (5).
表１に示すように、実施例１〜４で得られたエポキシ樹脂組成物（本発明のエポキシ樹脂組成物）は、いずれも、硬化性及び流動性が良好であり、さらに、この硬化物で封止された各実施例のパッケージ（本発明の半導体装置）は、いずれも、耐半田クラック性、耐湿信頼性が良好なものであった。また、吸湿処理による硬化トルクの変化が少なく、吸湿後トルク率が高い。 As shown in Table 1, each of the epoxy resin compositions (epoxy resin compositions of the present invention) obtained in Examples 1 to 4 has good curability and fluidity. All the sealed packages of the examples (semiconductor devices of the present invention) had good solder crack resistance and moisture resistance reliability. Moreover, there is little change in the curing torque due to moisture absorption treatment, and the torque rate after moisture absorption is high.
これに対し、比較例１及び比較例２で得られたエポキシ樹脂組成物は、吸湿処理によるトルク変化は少ないものの、いずれも、流動性に劣り、これらの比較例で得られたパッケージは、いずれも、耐半田クラック性に劣るとともに、耐湿信頼性が極めて低いものであった。また、比較例３〜６で得られたエポキシ樹脂組成物は、いずれも、吸湿処理によるトルク変化が大きく、トルク率が低い。これらの比較例で得られたパッケージは、いずれも、耐半田クラック性に劣るものであった。 On the other hand, the epoxy resin compositions obtained in Comparative Example 1 and Comparative Example 2 have less torque change due to moisture absorption treatment, but both have poor fluidity, and the packages obtained in these Comparative Examples are However, the solder crack resistance was inferior and the moisture resistance reliability was extremely low. Moreover, as for the epoxy resin composition obtained by Comparative Examples 3-6, all have a large torque change by a moisture absorption process, and a torque rate is low. All of the packages obtained in these comparative examples were inferior in solder crack resistance.
かかる潜伏性触媒によれば硬化性、流動性が良好なエポキシ樹脂組成物を得ることができ、かつ、その樹脂組成物の耐湿性に優れることから、エポキシ樹脂と同様にホスフィンやホスホニウム塩などを硬化促進剤とする熱硬化性樹脂組成物にも好適である。また、これらの樹脂組成物は、電気・電子材料分野に好適に使用することができる。 According to such a latent catalyst, an epoxy resin composition having good curability and fluidity can be obtained, and since the resin composition has excellent moisture resistance, phosphine, phosphonium salt, etc. can be used in the same manner as the epoxy resin. It is also suitable for a thermosetting resin composition used as a curing accelerator. Moreover, these resin compositions can be suitably used in the electric / electronic material field.
Claims (5)
［式中、Ｒ1、Ｒ2及びＲ3は、それぞれ、無置換のフェニル基を示し、互いに同一であっ
ても異なっていてもよい。式中Ｒ4、Ｒ5及びＲ6は、それぞれ、水素原子を示す。式中Ｘ
は、無水酢酸、グリシジルフェニルエーテルがリン原子に結合する芳香環上のメタ位に位置するフェノール水酸基と脱水縮合又は付加反応して生じる基である。］ The hardening accelerator for epoxy resins which has a structure represented by following formula (1).
[Wherein R 1 , R 2 and R 3 each represents an unsubstituted phenyl group, and may be the same or different from each other. In the formula, R 4 , R 5 and R 6 each represent a hydrogen atom. Where X
Is a group produced by dehydration condensation or addition reaction with a phenol hydroxyl group located at the meta position on the aromatic ring where acetic anhydride and glycidyl phenyl ether are bonded to the phosphorus atom. ]
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| JP3603483B2 (en) * | 1996-07-11 | 2004-12-22 | 日立化成工業株式会社 | Semiconductor element sealing material and semiconductor device using the same |
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