JP4788053B2 - Epoxy resin composition for semiconductor encapsulation and resin-encapsulated semiconductor device - Google Patents
Epoxy resin composition for semiconductor encapsulation and resin-encapsulated semiconductor device Download PDFInfo
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- JP4788053B2 JP4788053B2 JP2001091152A JP2001091152A JP4788053B2 JP 4788053 B2 JP4788053 B2 JP 4788053B2 JP 2001091152 A JP2001091152 A JP 2001091152A JP 2001091152 A JP2001091152 A JP 2001091152A JP 4788053 B2 JP4788053 B2 JP 4788053B2
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- Prior art keywords
- epoxy resin
- resin composition
- semiconductor
- wax
- semiconductor device
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- 229920000647 polyepoxide Polymers 0.000 title claims description 63
- 239000003822 epoxy resin Substances 0.000 title claims description 62
- 239000004065 semiconductor Substances 0.000 title claims description 36
- 239000000203 mixture Substances 0.000 title claims description 25
- 238000005538 encapsulation Methods 0.000 title claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 claims description 23
- 239000004204 candelilla wax Substances 0.000 claims description 17
- 235000013868 candelilla wax Nutrition 0.000 claims description 17
- 229940073532 candelilla wax Drugs 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 10
- 239000001993 wax Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 description 16
- 239000004203 carnauba wax Substances 0.000 description 15
- 235000013869 carnauba wax Nutrition 0.000 description 15
- 229920003986 novolac Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- -1 polyethylene Polymers 0.000 description 9
- 239000006082 mold release agent Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 5
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000004668 long chain fatty acids Chemical class 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 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 3
- 238000004898 kneading Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- HRSLYNJTMYIRHM-UHFFFAOYSA-N 2-[[4-[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]-2,6-dimethylphenoxy]methyl]oxirane Chemical group CC1=CC(C=2C=C(C)C(OCC3OC3)=C(C)C=2)=CC(C)=C1OCC1CO1 HRSLYNJTMYIRHM-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 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
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent 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
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 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
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical group C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- AAAFDWGBVIAZQZ-UHFFFAOYSA-N 2-[2,2-bis(2-hydroxyphenyl)ethyl]phenol Chemical compound OC1=CC=CC=C1CC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O AAAFDWGBVIAZQZ-UHFFFAOYSA-N 0.000 description 1
- RKGBFWIXGAFCRF-UHFFFAOYSA-N 2-[[2,6-dibutyl-4-[3,5-dibutyl-4-(oxiran-2-ylmethoxy)phenyl]phenoxy]methyl]oxirane Chemical group CCCCC1=CC(C=2C=C(CCCC)C(OCC3OC3)=C(CCCC)C=2)=CC(CCCC)=C1OCC1CO1 RKGBFWIXGAFCRF-UHFFFAOYSA-N 0.000 description 1
- KLWDDBHWNBBEBZ-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-1-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C1=CC=C2)=CC=CC1=C2OCC1CO1 KLWDDBHWNBBEBZ-UHFFFAOYSA-N 0.000 description 1
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- MHEPBAWJFVJKKU-UHFFFAOYSA-N 2-tert-butyl-4-[2-(5-tert-butyl-4-hydroxy-2-methylphenyl)ethenyl]-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1C=CC1=CC(C(C)(C)C)=C(O)C=C1C MHEPBAWJFVJKKU-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- KPXPRDVAGAEHLT-UHFFFAOYSA-N 4-[2-(2-tert-butyl-4-hydroxy-5-methylphenyl)ethenyl]-2,6-dimethylphenol Chemical compound CC1=CC(=CC(=C1O)C)C=CC2=C(C=C(C(=C2)C)O)C(C)(C)C KPXPRDVAGAEHLT-UHFFFAOYSA-N 0.000 description 1
- WTWMJYNGYCJIGR-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)ethenyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C=CC=2C=C(C)C(O)=C(C)C=2)=C1 WTWMJYNGYCJIGR-UHFFFAOYSA-N 0.000 description 1
- KVZMKJCPDJQRIK-UHFFFAOYSA-N 4-[2-[4-[2-(4-hydroxy-3-methylphenyl)propan-2-yl]phenyl]propan-2-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=CC(=CC=2)C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 KVZMKJCPDJQRIK-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OWEOAOVIPDYHKL-UHFFFAOYSA-N 6-tert-butyl-2-[2-(4-hydroxy-3,5-dimethylphenyl)ethenyl]-3-methylphenol Chemical compound CC1=C(O)C(C)=CC(C=CC=2C(=C(C=CC=2C)C(C)(C)C)O)=C1 OWEOAOVIPDYHKL-UHFFFAOYSA-N 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 241000233788 Arecaceae Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 241001553290 Euphorbia antisyphilitica Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- TXOFSCODFRHERQ-UHFFFAOYSA-N N,N-Dimethylphenethylamine Chemical compound CN(C)CCC1=CC=CC=C1 TXOFSCODFRHERQ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 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
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IKGXNCHYONXJSM-UHFFFAOYSA-N methanolate;zirconium(4+) Chemical compound [Zr+4].[O-]C.[O-]C.[O-]C.[O-]C IKGXNCHYONXJSM-UHFFFAOYSA-N 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-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
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、半導体装置中の部材に対して密着性が高く、かつ、成形時の離型性に優れる、半導体封止用として好適なエポキシ樹脂組成物、および該封止用組成物で封止してなる半導体装置に関するものである。
【０００２】
【従来の技術】
エポキシ樹脂は耐熱性、耐湿性、電気特性および接着性などに優れており、さらに配合処方により種々の特性が付加できるため、塗料、接着剤、電気絶縁材料など工業材料として利用されている。
【０００３】
例えば、半導体装置などの電子回路部品の封止方法として、従来より金属やセラミックスによるハーメチックシールとフェノール樹脂、シリコーン樹脂、エポキシ樹脂などによる樹脂封止が提案されている。その中でも、生産性、物性のバランスの点からエポキシ樹脂による樹脂封止が最も盛んに行われている。そして、エポキシ樹脂による封止方法は、エポキシ樹脂に硬化剤、充填剤などを添加した組成物を用い、半導体素子を金型にセットしてトランスファー成形法などにより封止する方法が一般的に行われている。
【０００４】
トランスファー成形において、成形により封止された半導体を金型から取り出せるようにするにはあらかじめエポキシ樹脂組成物中に内部離型剤を添加することが常法である。
【０００５】
最近はプリント基板への半導体装置パッケージの実装において高密度化、自動化が進められており、従来のリードピンを基板の穴に挿入する挿入実装方式に替わり、基板表面に半導体装置パッケージを半田付けする表面実装方式が主流になってきた。それに伴い、半導体装置パッケージも従来のＤＩＰ（デュアル・インライン・パッケージ）から、高密度実装・表面実装に適した薄型のＦＰＰ（フラット・プラスチック・パッケージ）に移行してきた。その中でも最近では、微細加工技術の進歩により、厚さ２ｍｍ以下のＴＳＯＰ、ＴＱＦＰ、ＬＱＦＰが主流となっている。そのため湿度や温度など外部からの影響をいっそう受けやすくなり、半田耐熱性、高温信頼性、耐熱信頼性などの信頼性が今後ますます重要となってくる。
【０００６】
表面実装においては、通常半田リフローによる実装が行われる。この方法では、基板の上に半導体装置を乗せ、これらを２００℃以上の高温にさらし、基板にあらかじめつけられた半田を溶融させて半導体装置を基板表面に接着させる。このような実装方法では半導体装置パッケージ全体が高温にさらされるために封止樹脂組成物の耐湿性が悪いと吸湿した水分が半田リフロー時に爆発的に膨張し、クラックが生じるという現象や、半導体の各種部材と封止材界面の間に剥離が発生する。従って半導体用封止樹脂組成物において耐湿性は非常に重要となる。
【０００７】
更に、近年では環境保護の点から鉛を含んでいない鉛フリー半田の使用が進んでいる。鉛フリー半田は融点が高く、そのためリフロー温度も上がることになりこれまで以上の半田耐熱性、半導体装置中の部材との高密着性が求められている。
【０００８】
一方、封止用成形材料では成形時良好な離型性が求められる。しかし、上述の通り封止用樹脂組成物は各部材との良好な密着性を示す必要もあり、よってこれらは相反する要求特性である。これまで、エポキシ樹脂組成物の金型との離型性を得るためにモンタン酸エステルワックスやポリエチレンワックスなどを用いていた。しかし、これらは離型性が良好ではあるが部材との密着性が低下し半導体装置の信頼性を低下させていた。また、部材との密着性を向上させるためにカルナウバワックスなどを離型剤として用いていたが、金型離型性が余り良好ではなかった。したがって、これまでは上記の離型性と密着性を両立できる離型剤が無く、これらを両立できる離型剤が求められていた。
【０００９】
【発明が解決しようとする課題】
本発明の目的は、半導体装置中の部材との密着性が高く、かつ離型性に優れた半導体封止用樹脂組成物およびそれを用いて封止した半導体装置を提供することにある。
【００１０】
【課題を解決するための手段】
本発明者らは、離型剤としてキャンデリラワックスとカルナウバワックスとを用いることにより、上記の課題を達成することができ、目的に合致したエポキシ樹脂組成物と半導体装置が得られることを見いだし、本発明に到達した。
【００１１】
すなわち本発明は、主として次の構成を有する。すなわち、「 エポキシ樹脂（Ａ）、硬化剤（Ｂ）、充填剤（Ｃ）および、離型剤（Ｄ）を含有する樹脂組成物であって、離型剤（Ｄ）としてキャンデリラワックス（ｄ１）とカルナウバワックス（ｄ２）とを含むことを特徴とする半導体封止用エポキシ樹脂組成物。」である。
【００１２】
【発明の実施の形態】
以下、本発明の構成を詳述する。
【００１３】
本発明の半導体封止用エポキシ樹脂組成物はエポキシ樹脂（Ａ）、硬化剤（Ｂ）、充填材（Ｃ）および離型剤（Ｄ）を含有する。
【００１４】
本発明においてエポキシ樹脂（Ａ）は１分子中に２個以上のエポキシ基を有する化合物であれば特に限定されず、具体例としてはクレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、４，４’−ビス（２，３−エポキシプロポキシ）ビフェニル、４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラメチルビフェニル、４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラエチルビフェニル、４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラブチルビフェニルなどのビフェニル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、１，５−ジ（２，３−エポキシプロポキシ）ナフタレン、１，６−ジ（２，３−エポキシプロポキシ）ナフタレン、ナフトールアラルキル型エポキシ樹脂などのナフタレン型エポキシ樹脂、３−ｔ−ブチル−２，４’−ジヒドロキシ−３’，５’，６−トリメチルスチルベンのジグリシジルエーテル、３−ｔ−ブチル−４，４’−ジヒドロキシ−３’，５，５’−トリメチルスチルベンのジグリシジルエーテル、４，４’−ジヒドロキシ−３，３’，５，５’−テトラメチルスチルベンのジグリシジルエーテル、４，４’−ジヒドロキシ−３，３’−ジ−ｔ−ブチル−６，６’−ジメチルスチルベンのジグリシジルエーテルなどのスチルベン型エポキシ樹脂、ジシクロペンタジエン骨格含有エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、１，４−ビス（３−メチル−４−ヒドロキシクミル）ベンゼンのジグリシジルエーテル、４，４’−ジヒドロキシジフェニルエーテルのジグリシジルエーテル、２，２−ジメチル−５，５’−ジ−ｔｅｒｔ−ブチル−４，４’−ジヒドロキシジフェニルスフィドなどのビスフェノール型エポキシ樹脂、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、テトラメチルビスフェノールＦ型エポキシ樹脂、鎖状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂およびハロゲン化エポキシ樹脂などがあげられる。特に耐熱性の点からクレゾールノボラック型エポキシ樹脂、式（Ｉ）で表されるビフェニル型エポキシ樹脂などが好ましく、エポキシ当量５００以下、特に３００以下のエポキシ樹脂が好ましい。なかでも４，４’−ビス（２，３−エポキシプロポキシ）−３，３’，５，５’−テトラメチルビフェニルがより好ましい。これらエポキシ樹脂は２種以上を併用することもできる。
【００１５】
【化２】
本発明においてエポキシ樹脂（Ａ）の配合量は、全樹脂組成物に対して通常２．５〜５．０重量％である。
【００１７】
本発明にはエポキシ樹脂（Ａ）を硬化させるために硬化剤（Ｂ）を用いる。その種類はエポキシ樹脂（Ａ）と反応して硬化させるものであれば特に限定されず、それらの具体例としては、例えばフェノールノボラック、クレゾールノボラックなどのノボラック樹脂、ビスフェノールＡなどのビスフェノール化合物、無水マレイン酸、無水フタル酸、無水ピロメリット酸などの酸無水物およびメタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンなどの芳香族アミンなどがあげられる。なかでも、半導体装置封止用としては、耐熱性、耐湿性および保存性に優れる点から、フェノール性水酸基を有する硬化剤が好ましい。フェノール性水酸基を有する硬化剤の具体例としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトールノボラック樹脂などのノボラック樹脂、トリス（ヒドロキシフェニル）メタン、１，１，２−トリス（ヒドロキシフェニル）エタン、１，１，３−トリス（ヒドロキシフェニル）プロパン、テルペンとフェノールの縮合化合物、ジシクロペンタジエン骨格含有フェノール樹脂、フェノールアラルキル樹脂、ビフェニルノボラック樹脂、ナフトールアラルキル樹脂などがあげられる。なかでも、フェノールアラルキル樹脂、フェノールノボラック樹脂、ビフェニルノボラック樹脂が好ましい。また、これらは２種類以上併用しても良い。
【００１８】
本発明において、硬化剤の配合量は、全樹脂組成物に対して通常２．５〜５．０重量％である。さらには、エポキシ樹脂（Ａ）と硬化剤の配合比は、機械的性質および耐湿性の点から（Ａ）に対する硬化剤の化学当量比が０．５〜２．０、特に０．６〜１．５の範囲にあることが好ましい。
【００１９】
また、本発明においてエポキシ樹脂（Ａ）と硬化剤の硬化反応を促進するため硬化促進剤を用いても良い。硬化促進剤は硬化反応を促進するものであれば特に限定されず、たとえば２−メチルイミダゾール、２，４−ジメチルイミダゾール、２−エチル−４−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化合物、トリエチルアミン、ベンジルジメチルアミン、ジメチルベンジルメチルアミン、２−（ジメチルアミノメチル）フェノール、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）ウンデセン−７などの３級アミン化合物およびそれらの塩、ジルコニウムテトラメトキシド、ジルコニウムテトラプロポキシド、テトラキス（アセチルアセトナト）ジルコニウム、トリ（アセチルアセトナト）アルミニウムなどの有機金属化合物およびトリフェニルホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリ（ｐ−メチルフェニル）ホスフィン、トリ（ノニルフェニル）ホスフィンなどの有機ホスフィン化合物およびそれらの塩などがあげられる。
【００２０】
これらの硬化促進剤は、用途によっては二種以上を併用してもよく、その添加量はエポキシ樹脂（Ａ）１００重量部に対して０．１〜１０重量部の範囲が望ましい。
【００２１】
本発明における充填剤（Ｃ）は特に限定されないが、溶融シリカを用いることが好ましく、形状は球状である事が好ましく、平均粒径は１０〜３０μｍが好ましい。一般に充填剤（Ｃ）の割合が大きくなるにつれて流動性などの成形性は悪化するが、球状の充填剤を使用することにより流動性の悪化をより抑えることができる。用途によっては２種類以上の充填剤を併用することができ、併用する充填剤としては、無機質充填剤が好ましく、具体的には溶融シリカ、結晶性シリカ、炭酸カルシウム、炭酸マグネシウム、アルミナ、マグネシア、クレー、タルク、ケイ酸カルシウム、酸化チタン、アスベスト、ガラス繊維などがあげられる。
【００２２】
本発明において離型剤（Ｄ）としてキャンデリラワックス（ｄ１）を含有している必要がある。キャンデリラワックスとはキャンデリラ草から得られる植物系天然ろうのことである。キャンデリラワックスは高級炭化水素（炭素数２８〜３３）が主成分であり、この他に遊離脂肪酸（炭素数２０〜３５）や遊離アルコール（炭素数２６〜３４）、高級脂肪酸と高級アルコールのエステルなどを含むものである。キャンデリラワックスとしてはセラリカ野田製”精製キャンデリラワックスＮｏ．１”等が市販されている。
【００２３】
また、本発明において離型剤（Ｄ）として上述のキャンデリラワックス（ｄ１）とカルナウバワックス（ｄ２）を併用すると密着性に関して相乗効果が発現し、キャンデリラワックス（ｄ１）を単体で用いた場合と比べ、離型性を良好な状態で維持しながらさらに良好な密着性が得られる。カルナウバワックスとはヤシ科のパーム樹から採取される植物系天然ろうである。カルナウバワックスは高級脂肪酸と高級アルコールのエステルが主成分であり、この他に遊離アルコール、炭化水素などを含むものである。カルナウバワックスとしてはセラリカ野田製”精製カルナウバワックスＮｏ．１”等が市販されている。
【００２４】
離型剤（Ｄ）の配合量は全エポキシ樹脂組成物中に０．０１〜１．０重量％、特に０．１〜０．５重量％含まれていることが好ましい。また、ポリスチレンなどの熱可塑性樹脂、長鎖脂肪酸、長鎖脂肪酸の金属塩、長鎖脂肪酸のエステル、長鎖脂肪酸のアミド、パラフィンワックスなどの離型剤を本発明の効果を損なわない範囲で２種類以上併用しても良い。その含有量としては０．０１〜０．３重量％が好ましい。キャンデリラワックス（ｄ１）とカルナウバワックス（ｄ２）とを併用する種類と比率としては、たとえば、ポリエチレンワックスやモンタン酸エステルワックスとを重量比で０．１対１〜１対０．１の割合で添加するのが好ましい。
【００２５】
本発明のエポキシ樹脂組成物には、各種カップリング剤、カーボンブラック、酸化鉄などの着色剤、シリコーンゴム、スチレン系ブロック共重合体、オレフィン系重合体、変性ニトリルゴム、変性ポリブタジエンゴムなどのエラストマー、および有機過酸化物など架橋剤を任意に添加することができる。
【００２６】
本発明のエポキシ樹脂組成物の製造方法としては、たとえば溶融混練による方法が好ましく、各種原料をミキサーなどで混合した後、通常は６０〜１４０℃で、たとえばバンバリーミキサー、ニーダー、ロール、単軸もしくは二軸の押出機およびコニーダーなどの公知の混練方法を用いて溶融混練することにより製造できる。このエポキシ樹脂組成物は通常粉末またはタブレット状態から、成形によって半導体封止に供される。半導体素子を封止する方法としては、低圧トランスファー成形法が一般的であるがインジェクション成形法や圧縮成形法も可能である。成形条件としては、たとえばエポキシ樹脂組成物を成形温度１５０℃〜２００℃、成形圧力５〜１５ＭＰａ、成形時間３０〜３００秒で成形し、エポキシ樹脂組成物の硬化物とすることによって半導体装置が製造される。また、必要に応じて上記成形物を１００〜２００℃で２〜１５時間、追加加熱処理も行われる。
【００２７】
【実施例】
以下、実施例により本発明を具体的に説明するが、これらに限定されるものではない。
【００２８】
[実施例１〜３、参考例１〜８、比較例１〜４]
本発明で使用した原料を表１に示す。なお、粘度はＩＣＩ粘度（１５０℃）を示す。
【００２９】
＜エポキシ樹脂＞
ａ１：ビフェニル型エポキシ樹脂（ジャパンエポキシレジン（株）”ＹＸ４０００Ｈ”、エポキシ当量１９３、粘度０．２ポイズ）
ａ２：エポキシ樹脂（新日鉄化学（株）”ＹＳＬＶ−８０ＸＹ”、エポキシ当量１９２、粘度０．０８ポイズ）
＜充填剤＞
平均粒径25μmの球状溶融シリカ
＜硬化剤＞
ｂ１：フェノールアラルキル樹脂（明和化成（株）”ＭＥＨ７８００ＳＳ”水酸基当量１７５、粘度０．７ポイズ）
ｂ２：フェノーノボラック樹脂（明和化成（株）”Ｈ−１”水酸基当量１０６、粘度２．０ポイズ）
＜硬化促進剤＞
トリフェニルホスフィン（ケイ・アイ化成（株）”ＰＰ−３６０”）
＜カップリング剤＞
γ−グリシドキシプロピルトリメトキシシラン（信越化学（株）”ＫＢＭ４０３”）
＜着色剤＞
カーボンブラック（三菱化学（株）”♯７５０Ｂ”）
＜離型剤＞
ｄ１：キャンデリラワックス（セラリカ野田（株）”精製キャンデリラワックスＮｏ．１”）
ｄ２：カルナウバワックス（セラリカ野田（株）”精製カルナウバワックスＮｏ．１”）
ｄ３：モンタン酸エステルワックス（クラリアントジャパン（株）”ＬＩＣＯＷＡＸ−Ｅ”）
ｄ４：酸化ポリエステルワックス（クラリアントジャパン（株）”ＬＩＣＯＷＡＸ−ＰＥＤ５２２”）
【００３０】
【表１】
各成分を、表２、３に示した組成比（重量比）で、計量し、ミキサーによりドライブレンドした。これを、ロール表面温度９０℃のミキシングロールを用いて５分間加熱混練後、冷却、粉砕して半導体封止用のエポキシ樹脂組成物を得た。
【００３２】
この樹脂組成物を用いて、低圧トランスファー成形法により１７５℃、キュアータイム２分間の条件で、模擬素子を搭載した、チップサイズ１０×１０ｍｍの１７６ｐｉｎＬＱＦＰ（外形：２４×２４×１．４ｍｍ、フレーム材料：銅）を成形し、１７５℃、４時間の条件でポストキュアーして下記の物性測定法により各樹脂組成物の物性を評価した。
【００３３】
密着性：１７６ｐｉｎＬＱＦＰを２０個成形し、８５℃／６０％ＲＨで１６８時間加湿後、最高温度２６０℃のＩＲリフロー炉で２分間加熱処理した。なお、リフロー炉の温度プロファイルは、１５０℃〜２００℃の領域を6０秒から１００秒、２００℃から２６０℃の昇温速度を１．５〜２．５℃／秒、２６０℃から２００℃の降温速度を１．５〜２．５℃／秒である。加熱処理後、超音波探傷機によりリードフレームの銀メッキ部分を観察し、剥離が生じている部分の面積を計算し剥離率とした。
【００３４】
離型性：金型をメラミン樹脂により十分に洗浄した後、直径１ｃｍ、長さ２ｃｍの円柱の成形を１０回繰り返し、その都度成形直後に金型から突き出すために必要な力をプッシュプルゲージを用いて測定した。なお、成形条件としては、成形温度１７５℃、成形圧力７ＭＰａ、成形時間６０秒で成形で行った。また、金型の材質は超鋼で梨地のないもので行った。
【００３５】
表２、３に評価結果を示す。表２の実施例１〜３、参考例１〜８に見られるようにキャンデリラワックス（離型剤（ｄ１））を含有する本発明のエポキシ樹脂組成物は密着性、離型性、に優れている。また、実施例１〜３に見られるようにキャンデリラワックス（離型剤（ｄ１））とカルナウバワックス（離型剤（ｄ２））を併用することによってさらに密着性に優れたエポキシ樹脂組成物が得られる。
【００３６】
【表２】
【表３】
一方、これに対してカルナウバワックス（離型剤（ｄ２））のみを使用した比較例１では密着性は良好であるが十分な離型性が得られていない。また、その他の離型剤（ｄ３）、（ｄ４）を用いた比較例２〜４は、離型性は良好であるが、十分な密着性は得られていない。
【００３９】
このように離型剤としてキャンデリラワックスとカルナウバワックスとを併用することによって充分な性能が発揮されることが分かる。
【００４０】
【発明の効果】
離型剤としてキャンデリラワックスとカルナウバワックスとを含有することによりリフロー実装時の半導体装置宙の部材との密着性が良好であり、成形時に良好な金型離型性を併せ持つ樹脂封止型半導体装置及び半導体封止用エポキシ樹脂組成物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention provides an epoxy resin composition suitable for semiconductor encapsulation, which has high adhesion to members in a semiconductor device and is excellent in releasability during molding, and sealing with the sealing composition The present invention relates to a semiconductor device.
[0002]
[Prior art]
Epoxy resins are excellent in heat resistance, moisture resistance, electrical characteristics, adhesiveness, and the like, and can be added with various characteristics depending on the formulation, and thus are used as industrial materials such as paints, adhesives, and electrical insulating materials.
[0003]
For example, as a sealing method for electronic circuit components such as semiconductor devices, conventionally, hermetic sealing with metal or ceramics and resin sealing with phenol resin, silicone resin, epoxy resin or the like have been proposed. Among them, resin sealing with an epoxy resin is most actively performed from the viewpoint of the balance between productivity and physical properties. As a sealing method using an epoxy resin, a method of using a composition obtained by adding a curing agent, a filler, or the like to an epoxy resin, setting a semiconductor element in a mold, and sealing by a transfer molding method or the like is generally performed. It has been broken.
[0004]
In transfer molding, an internal mold release agent is usually added to the epoxy resin composition in advance so that the semiconductor sealed by molding can be removed from the mold.
[0005]
Recently, the mounting of semiconductor device packages on printed circuit boards has become increasingly dense and automated. Instead of the conventional mounting method in which lead pins are inserted into holes in the substrate, the surface on which the semiconductor device package is soldered to the substrate surface Implementation methods have become mainstream. Accordingly, the semiconductor device package has also shifted from the conventional DIP (dual in-line package) to a thin FPP (flat plastic package) suitable for high-density mounting and surface mounting. Among them, recently, TSOP, TQFP, and LQFP having a thickness of 2 mm or less have become mainstream due to advances in microfabrication technology. Therefore, it becomes more susceptible to external influences such as humidity and temperature, and reliability such as solder heat resistance, high temperature reliability and heat resistance reliability will become increasingly important in the future.
[0006]
In surface mounting, mounting is usually performed by solder reflow. In this method, semiconductor devices are placed on a substrate, these are exposed to a high temperature of 200 ° C. or higher, solder previously applied to the substrate is melted, and the semiconductor device is bonded to the substrate surface. In such a mounting method, since the entire semiconductor device package is exposed to high temperature, if the moisture resistance of the encapsulating resin composition is poor, moisture absorbed will explode during solder reflow, causing cracks, Peeling occurs between the various members and the sealing material interface. Therefore, moisture resistance is very important in a semiconductor sealing resin composition.
[0007]
Furthermore, in recent years, the use of lead-free solder containing no lead has been promoted from the viewpoint of environmental protection. Lead-free solder has a high melting point, so that the reflow temperature also rises, so that higher solder heat resistance and higher adhesion to members in semiconductor devices are required.
[0008]
On the other hand, the molding material for sealing is required to have good releasability during molding. However, as described above, the sealing resin composition also needs to exhibit good adhesion to each member, and thus these are conflicting required characteristics. Until now, in order to obtain mold releasability from the mold of the epoxy resin composition, montanic ester wax or polyethylene wax has been used. However, these have good releasability, but the adhesion to the member is lowered, and the reliability of the semiconductor device is lowered. In addition, carnauba wax or the like was used as a release agent in order to improve the adhesion to the member, but the mold releasability was not so good. Therefore, there has been no mold release agent that can achieve both of the above-mentioned mold release properties and adhesiveness, and a mold release agent that can achieve both of these has been demanded.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition for encapsulating a semiconductor that has high adhesion to members in a semiconductor device and is excellent in releasability, and a semiconductor device encapsulated using the same.
[0010]
[Means for Solving the Problems]
The present inventors have found that by using candelilla wax and carnauba wax as mold release agents, the above-described problems can be achieved, and an epoxy resin composition and a semiconductor device that meet the purpose can be obtained. The present invention has been reached.
[0011]
That is, the present invention mainly has the following configuration. That is, “a resin composition containing an epoxy resin (A), a curing agent (B) , a filler (C), and a release agent (D), and a candelilla wax (d1) as the release agent (D) And carnauba wax (d2) . ”An epoxy resin composition for encapsulating semiconductors”.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of the present invention will be described in detail.
[0013]
The epoxy resin composition for semiconductor encapsulation of the present invention contains an epoxy resin (A), a curing agent (B), a filler (C) and a release agent (D).
[0014]
In the present invention, the epoxy resin (A) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, and 4,4 ′. -Bis (2,3-epoxypropoxy) biphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (2, Biphenyl such as 3-epoxypropoxy) -3,3 ′, 5,5′-tetraethylbiphenyl, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetrabutylbiphenyl Type epoxy resin, phenol aralkyl type epoxy resin, biphenyl novolac type epoxy resin, 1,5-di (2,3-epoxypropoxy) naphthalene, 1,6-di ( 2,3-epoxypropoxy) naphthalene, naphthalene-type epoxy resins such as naphthol aralkyl-type epoxy resin, diglycidyl ether of 3-t-butyl-2,4′-dihydroxy-3 ′, 5 ′, 6-trimethylstilbene, 3 Diglycidyl ether of t-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, diglycidyl of 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethylstilbene Ether, stilbene type epoxy resin such as diglycidyl ether of 4,4′-dihydroxy-3,3′-di-t-butyl-6,6′-dimethylstilbene, dicyclopentadiene skeleton-containing epoxy resin, triphenylmethane type Epoxy resin, 1,4-bis (3-methyl-4-hydroxycumyl) benzene diglycidyl ether Diglycidyl ether of 4,4′-dihydroxydiphenyl ether, bisphenol type epoxy resin such as 2,2-dimethyl-5,5′-di-tert-butyl-4,4′-dihydroxydiphenyl sulfide, bisphenol A type epoxy resin Bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, chain aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, halogenated epoxy resin and the like. In particular, from the viewpoint of heat resistance, a cresol novolac type epoxy resin, a biphenyl type epoxy resin represented by the formula (I), and the like are preferable, and an epoxy equivalent of 500 or less, particularly 300 or less is preferable. Of these, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is more preferable. Two or more of these epoxy resins can be used in combination.
[0015]
[Chemical 2]
In this invention, the compounding quantity of an epoxy resin (A) is 2.5 to 5.0 weight% normally with respect to all the resin compositions.
[0017]
In the present invention, the curing agent (B) is used to cure the epoxy resin (A). The type is not particularly limited as long as it can be cured by reacting with the epoxy resin (A). Specific examples thereof include novolak resins such as phenol novolak and cresol novolak, bisphenol compounds such as bisphenol A, and anhydrous maleic acid. Examples thereof include acid anhydrides such as acid, phthalic anhydride and pyromellitic anhydride, and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Among these, a curing agent having a phenolic hydroxyl group is preferable for sealing a semiconductor device because it is excellent in heat resistance, moisture resistance and storage stability. Specific examples of the curing agent having a phenolic hydroxyl group include novolak resins such as phenol novolak resin, cresol novolak resin, naphthol novolak resin, tris (hydroxyphenyl) methane, 1,1,2-tris (hydroxyphenyl) ethane, 1 1,3-tris (hydroxyphenyl) propane, terpene and phenol condensation compounds, dicyclopentadiene skeleton-containing phenol resins, phenol aralkyl resins, biphenyl novolac resins, naphthol aralkyl resins, and the like. Of these, phenol aralkyl resins, phenol novolac resins, and biphenyl novolac resins are preferable. Two or more of these may be used in combination.
[0018]
In this invention, the compounding quantity of a hardening | curing agent is 2.5 to 5.0 weight% normally with respect to all the resin compositions. Furthermore, the compounding ratio of the epoxy resin (A) and the curing agent is such that the chemical equivalent ratio of the curing agent to (A) is 0.5 to 2.0, particularly 0.6 to 1 in terms of mechanical properties and moisture resistance. Preferably it is in the range of .5.
[0019]
In the present invention, a curing accelerator may be used to accelerate the curing reaction between the epoxy resin (A) and the curing agent. The curing accelerator is not particularly limited as long as it accelerates the curing reaction. For example, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4 -Imidazole compounds such as methylimidazole and 2-heptadecylimidazole, triethylamine, benzyldimethylamine, dimethylbenzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, 1, Tertiary amine compounds such as 8-diazabicyclo (5,4,0) undecene-7 and their salts, zirconium tetramethoxide, zirconium tetrapropoxide, tetrakis (acetylacetonato) zirconium, tri (acetylacetonato) a Organometallic compound and triphenylphosphine, such Miniumu, trimethylphosphine, triethylphosphine, tributylphosphine, tri (p- methylphenyl) phosphine, an organic phosphine compounds and their salts, such as tri (nonylphenyl) phosphine and the like.
[0020]
These curing accelerators may be used in combination of two or more depending on the application, and the addition amount is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin (A).
[0021]
The filler (C) in the present invention is not particularly limited, but it is preferable to use fused silica, the shape is preferably spherical, and the average particle size is preferably 10 to 30 μm. Generally, moldability such as fluidity deteriorates as the proportion of the filler (C) increases, but the deterioration of fluidity can be further suppressed by using a spherical filler. Depending on the application, two or more kinds of fillers can be used in combination, and the filler used in combination is preferably an inorganic filler, specifically, fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, Examples include clay, talc, calcium silicate, titanium oxide, asbestos, and glass fiber.
[0022]
In this invention, it is necessary to contain the candelilla wax (d1) as a mold release agent (D). Candelilla wax is a plant-based natural wax obtained from candelilla grass. Candelilla wax is mainly composed of higher hydrocarbons (28 to 33 carbon atoms). In addition, free fatty acids (20 to 35 carbon atoms), free alcohols (26 to 34 carbon atoms), esters of higher fatty acids and higher alcohols. Etc. As the candelilla wax, “Purified Candelilla Wax No. 1” manufactured by Celerica Noda is commercially available.
[0023]
In the present invention, when the above-mentioned candelilla wax (d1) and carnauba wax (d2) are used in combination as the release agent (D), a synergistic effect is exhibited with respect to adhesion, and the candelilla wax (d1) is used alone. Compared to the case, better adhesion can be obtained while maintaining the releasability in a good state. Carnauba wax is a plant-based natural wax collected from the palm tree of the palm family. Carnauba wax is mainly composed of esters of higher fatty acids and higher alcohols, and also contains free alcohols, hydrocarbons and the like. As the carnauba wax, “Purified Carnauba Wax No. 1” manufactured by Celalica Noda is commercially available.
[0024]
It is preferable that the compounding quantity of a mold release agent (D) is 0.01-1.0 weight%, especially 0.1-0.5 weight% is contained in all the epoxy resin compositions. In addition, a release agent such as a thermoplastic resin such as polystyrene, a long-chain fatty acid, a metal salt of a long-chain fatty acid, an ester of a long-chain fatty acid, an amide of a long-chain fatty acid, or paraffin wax is used within a range that does not impair the effects of the present invention. You may use together more than a kind. The content is preferably 0.01 to 0.3% by weight. As a kind and ratio which use candelilla wax (d1) and carnauba wax (d2) together, for example, the ratio of 0.1 to 1 to 0.1 by weight ratio of polyethylene wax or montanic acid ester wax Is preferably added.
[0025]
The epoxy resin composition of the present invention includes various coupling agents, colorants such as carbon black and iron oxide, elastomers such as silicone rubber, styrene block copolymer, olefin polymer, modified nitrile rubber, and modified polybutadiene rubber. , And a crosslinking agent such as an organic peroxide can be optionally added.
[0026]
As a method for producing the epoxy resin composition of the present invention, for example, a method by melt kneading is preferable. After mixing various raw materials with a mixer or the like, usually at 60 to 140 ° C., for example, a Banbury mixer, kneader, roll, uniaxial or It can be manufactured by melt kneading using a known kneading method such as a twin screw extruder and a kneader. This epoxy resin composition is usually used for semiconductor encapsulation by molding from a powder or tablet state. As a method for sealing a semiconductor element, a low-pressure transfer molding method is generally used, but an injection molding method or a compression molding method is also possible. As a molding condition, for example, an epoxy resin composition is molded at a molding temperature of 150 ° C. to 200 ° C., a molding pressure of 5 to 15 MPa, a molding time of 30 to 300 seconds, and a cured product of the epoxy resin composition is manufactured. Is done. Moreover, the said molded object is further heat-processed for 2 to 15 hours at 100-200 degreeC as needed.
[0027]
【Example】
Hereinafter, the present invention will be specifically described by way of examples, but is not limited thereto.
[0028]
[ Examples 1-3, Reference Examples 1-8 , Comparative Examples 1-4]
Table 1 shows the raw materials used in the present invention. In addition, a viscosity shows ICI viscosity (150 degreeC).
[0029]
<Epoxy resin>
a1: Biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd. “YX4000H”, epoxy equivalent 193, viscosity 0.2 poise)
a2: Epoxy resin (Nippon Steel Chemical Co., Ltd. “YSLV-80XY”, epoxy equivalent 192, viscosity 0.08 poise)
<Filler>
Spherical fused silica with an average particle size of 25 μm <curing agent>
b1: Phenol aralkyl resin (Maywa Kasei Co., Ltd. “MEH7800SS” hydroxyl group equivalent 175, viscosity 0.7 poise)
b2: Phenonovolak resin (Maywa Kasei Co., Ltd. "H-1" hydroxyl group equivalent 106, viscosity 2.0 poise)
<Curing accelerator>
Triphenylphosphine (Kay Eye Chemicals Co., Ltd. “PP-360”)
<Coupling agent>
γ-Glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. “KBM403”)
<Colorant>
Carbon black (Mitsubishi Chemical Corporation “# 750B”)
<Release agent>
d1: Candelilla wax (Serarica Noda Co., Ltd. “refined candelilla wax No. 1”)
d2: Carnauba wax (Serarica Noda Co., Ltd. “refined carnauba wax No. 1”)
d3: Montanate ester wax (Clariant Japan Co., Ltd. “LICOWAX-E”)
d4: Oxidized polyester wax (Clariant Japan KK "LICOWAX-PED522")
[0030]
[Table 1]
Each component was weighed at a composition ratio (weight ratio) shown in Tables 2 and 3 and dry blended with a mixer. This was heated and kneaded for 5 minutes using a mixing roll having a roll surface temperature of 90 ° C., then cooled and pulverized to obtain an epoxy resin composition for semiconductor encapsulation.
[0032]
Using this resin composition, a 176-pin LQFP chip having a chip size of 10 × 10 mm (outside: 24 × 24 × 1.4 mm, frame material) mounted with a simulated element under the conditions of 175 ° C. and cure time of 2 minutes by low-pressure transfer molding method : Copper) was molded, post-cured at 175 ° C. for 4 hours, and the physical properties of each resin composition were evaluated by the following physical property measurement methods.
[0033]
Adhesiveness: 20 pieces of 176 pin LQFP were molded, humidified at 85 ° C./60% RH for 168 hours, and then heat-treated in an IR reflow furnace having a maximum temperature of 260 ° C. for 2 minutes. The temperature profile of the reflow furnace is as follows: the region of 150 ° C. to 200 ° C. is 60 seconds to 100 seconds, the temperature rising rate of 200 ° C. to 260 ° C. is 1.5 to 2.5 ° C./second, and 260 ° C. to 200 ° C. The temperature lowering rate is 1.5 to 2.5 ° C./second. After the heat treatment, the silver-plated portion of the lead frame was observed with an ultrasonic flaw detector, and the area of the portion where peeling occurred was calculated as the peeling rate.
[0034]
Releasability: After the mold is sufficiently washed with melamine resin, molding of a cylinder with a diameter of 1 cm and a length of 2 cm is repeated 10 times, each time using a push-pull gauge to push the force necessary to protrude from the mold immediately after molding. And measured. The molding conditions were molding at a molding temperature of 175 ° C., a molding pressure of 7 MPa, and a molding time of 60 seconds. The material of the mold was made of super steel with no texture.
[0035]
Tables 2 and 3 show the evaluation results. As seen in Examples 1 to 3 and Reference Examples 1 to 8 in Table 2, the epoxy resin composition of the present invention containing a candelilla wax (release agent (d1)) is excellent in adhesion and release properties. ing. In addition, as seen in Examples 1 to 3 , an epoxy resin composition having excellent adhesion by using candelilla wax (release agent (d1)) and carnauba wax (release agent (d2)) in combination. Is obtained.
[0036]
[Table 2]
[Table 3]
On the other hand, in Comparative Example 1 using only carnauba wax (release agent (d2)), the adhesion is good, but sufficient release properties are not obtained. In Comparative Examples 2 to 4 using other mold release agents (d3) and (d4), the mold release property is good, but sufficient adhesion is not obtained.
[0039]
Thus, it can be seen that sufficient performance is exhibited by using candelilla wax and carnauba wax in combination as a release agent.
[0040]
【The invention's effect】
Resin-sealed mold that contains candelilla wax and carnauba wax as mold release agents, and has good adhesion to semiconductor device components during reflow mounting, and also has good mold releasability during molding An epoxy resin composition for semiconductor devices and semiconductor encapsulation is obtained.
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