JP4483655B2 - Epoxy resin composition for semiconductor encapsulation and semiconductor device - Google Patents
Epoxy resin composition for semiconductor encapsulation and semiconductor device Download PDFInfo
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- JP4483655B2 JP4483655B2 JP2005099389A JP2005099389A JP4483655B2 JP 4483655 B2 JP4483655 B2 JP 4483655B2 JP 2005099389 A JP2005099389 A JP 2005099389A JP 2005099389 A JP2005099389 A JP 2005099389A JP 4483655 B2 JP4483655 B2 JP 4483655B2
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- epoxy resin
- resin composition
- colorant
- semiconductor
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- 229920000647 polyepoxide Polymers 0.000 title claims description 63
- 239000003822 epoxy resin Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 41
- 239000004065 semiconductor Substances 0.000 title claims description 36
- 238000005538 encapsulation Methods 0.000 title claims description 11
- 239000003086 colorant Substances 0.000 claims description 33
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 230000007547 defect Effects 0.000 description 11
- -1 etc.) Chemical group 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000010330 laser marking Methods 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000001721 transfer moulding Methods 0.000 description 7
- 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 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 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
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 3
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 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
- 239000005350 fused silica glass Substances 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 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
- 230000001133 acceleration Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 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 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 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
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical group S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-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
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、半導体封止用エポキシ樹脂組成物、及びこれを用いた半導体装置に関するものである。 The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device using the same.
ＩＣ、ＬＳＩ等の半導体素子の封止方法として、エポキシ樹脂組成物のトランスファー成形が低コスト、大量生産に適しており、採用されて久しく、信頼性の点でもエポキシ樹脂や硬化剤であるフェノール樹脂の改良により特性の向上が図られてきた。しかし、近年の電子機器の小型化、軽量化、高性能化の市場動向において、半導体の高集積化も年々進み、また半導体装置の表面実装化が促進されるなかで、半導体封止用エポキシ樹脂組成物への要求は益々厳しいものとなってきている。このため、従来からのエポキシ樹脂組成物では解決出来ない問題点も出てきている。 As a sealing method for semiconductor elements such as IC and LSI, transfer molding of epoxy resin composition is suitable for mass production at low cost and has been adopted for a long time, and phenol resin that is epoxy resin and curing agent also from the viewpoint of reliability Improvements have been made to improve the characteristics. However, due to the recent trend toward smaller, lighter, and higher performance electronic devices, semiconductors have been increasingly integrated and the surface mounting of semiconductor devices has been promoted. The demand for compositions has become increasingly severe. For this reason, the problem which cannot be solved with the conventional epoxy resin composition has also come out.
従来、主にエポキシ樹脂組成物で封止された半導体装置は、その組成に着色剤としてカーボンブラックを含んでいる。これは半導体素子を遮蔽するためと半導体装置に品名やロット番号等をマーキングする際、背景が黒だとより鮮明な印字が得られるからである。また最近では取り扱いが容易な、ＹＡＧレーザーマーキングを採用する電子部品メーカーが増加しているためである。ＹＡＧレーザーマーキング性を向上させる手法に関しては、「カーボン含有量が９９．５重量％以上、水素含有量が０．３重量％以下であるカーボンブラック」が同目的に効果的であることが開示されており（例えば、特許文献１参照。）、また、その他の種々の研究もなされている。
しかし、最近の半導体装置のファインピッチ化に伴い、導電性着色剤であるカーボンブラックを着色剤とした半導体封止材を用いた場合、カーボンブラックの凝集物等が粗大粒子としてインナーリード間、ワイヤー間に存在すると、配線のショート不良およびリーク不良といった電気特性不良を生じてしまうという点で問題となってきている。またカーボンブラックの凝集物等の粗大粒子が狭くなったワイヤー間に挟まることでワイヤーが応力を受け、これも電気特性不良の原因となるという点でも問題となってきている。これら電気的不良を回避するために、凝集物の最大粒径が１００μｍ以下であるカーボンブラックを用いた半導体封止用エポキシ樹脂組成物が提案されている（例えば、特許文献２参照。）が、この方法でも十分に良好な半導体封止用エポキシ樹脂組成物は得られるには至っていない。
Conventionally, a semiconductor device sealed mainly with an epoxy resin composition contains carbon black as a colorant in its composition. This is because a clearer print can be obtained if the background is black in order to shield the semiconductor element and mark the product name, lot number, etc. on the semiconductor device. This is also because the number of electronic component manufacturers that adopt YAG laser marking, which is easy to handle, has increased recently. Regarding the method for improving the YAG laser marking property, it is disclosed that “carbon black having a carbon content of 99.5% by weight or more and a hydrogen content of 0.3% by weight or less” is effective for the same purpose. (See, for example, Patent Document 1), and various other studies have been conducted.
However, with the recent trend toward finer pitches in semiconductor devices, when a semiconductor encapsulant using carbon black, which is a conductive colorant, is used as the colorant, aggregates of carbon black and the like are formed as coarse particles between the inner leads and wires. If they are present between them, there is a problem in that defective electrical characteristics such as a short circuit failure and a leakage failure occur. In addition, the wire is subjected to stress by being sandwiched between wires in which coarse particles such as carbon black aggregates are narrowed, and this also causes a problem in electrical characteristics. In order to avoid these electrical defects, an epoxy resin composition for semiconductor encapsulation using carbon black having a maximum aggregate particle size of 100 μm or less has been proposed (see, for example, Patent Document 2). Even with this method, a sufficiently good epoxy resin composition for semiconductor encapsulation has not been obtained.
本発明は、配線のショート、リーク不良等の電気不良を生ずることがなく、かつ優れたレーザーマーキング性を有する半導体封止用エポキシ樹脂組成物、及びこれを用いた半導体装置を提供することにある。 An object of the present invention is to provide an epoxy resin composition for encapsulating a semiconductor that does not cause electrical failures such as a short circuit of wiring and a leakage failure, and has excellent laser marking properties, and a semiconductor device using the same. .
本発明は、
［１］ （Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂、（Ｃ）無機充填材、（Ｄ）硬化促進剤、（Ｅ）着色剤を含むエポキシ樹脂組成物において、前記着色剤（Ｅ）が体積抵抗率１０３Ω・ｃｍ以上の黒色系酸化チタンを含み、着色剤（Ｅ）の配合量が全エポキシ樹脂組成物中に対して１．０重量％以上、２．５重量％以下であることを特徴とする半導体封止用エポキシ樹脂組成物、
［２］ 前記着色剤（Ｅ）が、Ｔｉ４Ｏ７、Ｔｉ５Ｏ９、Ｔｉ６Ｏ１１のうちから選ばれるいずれか１種以上を含む請求項１に記載の半導体封止用エポキシ樹脂組成物、
［３］ 第［１］又は［２］項に記載の半導体封止用エポキシ樹脂組成物を用いて半導体素子を封止してなることを特徴とする半導体装置、
である。
The present invention
[1] In an epoxy resin composition containing (A) an epoxy resin, (B) a phenol resin, (C) an inorganic filler, (D) a curing accelerator, and (E) a colorant, the colorant (E) is in a volume. look including a resistivity 10 3 Ω · cm or more blackish titanium oxide, the amount of the colorant (E) is 1.0 wt% or more based on the total the epoxy resin composition medium, is 2.5 wt% or less An epoxy resin composition for semiconductor encapsulation, characterized in that
[2] The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the colorant (E) contains one or more selected from Ti 4 O 7 , Ti 5 O 9 , and Ti 6 O 11. object,
[3] A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor sealing according to [1] or [2],
It is.
本発明に従うと、配線のショート、リーク不良等の電気不良を生ずることがなく、かつ優れたレーザーマーキング性を有する半導体封止用エポキシ樹脂組成物、及び半導体装置が得られるものである。 According to the present invention, it is possible to obtain an epoxy resin composition for semiconductor encapsulation and a semiconductor device which do not cause electrical defects such as wiring short-circuits and leakage defects, and have excellent laser marking properties.
本発明は、エポキシ樹脂、フェノール樹脂、硬化促進剤、無機充填材、着色剤として体積抵抗率が１０３Ω・ｃｍ以上である黒色系酸化チタンを必須成分として含むことにより、配線のショート、リーク不良等の電気不良を生ずることがなく、かつ優れたレーザーマーキング性を有する半導体封止用エポキシ樹脂組成物が得られるものである。
以下、本発明について詳細に説明する。
The present invention includes an epoxy resin, a phenolic resin, a curing accelerator, an inorganic filler, and a black titanium oxide having a volume resistivity of 10 3 Ω · cm or more as an essential component as a colorant, so that wiring short-circuiting and leakage It is possible to obtain an epoxy resin composition for semiconductor encapsulation that does not cause electrical defects such as defects and has excellent laser marking properties.
Hereinafter, the present invention will be described in detail.
本発明に用いるエポキシ樹脂（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、ポリマー全般を言い、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、ビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂、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、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、フェノールアラルキル型エポキシ樹脂（フェニレン骨格、ビフェニレン骨格等を有する）、硫黄原子含有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。 The epoxy resin (A) used in the present invention refers to monomers, oligomers and polymers in general having two or more epoxy groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited. For example, biphenyl type Epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene Examples include modified phenol type epoxy resins, phenol aralkyl type epoxy resins (having a phenylene skeleton, biphenylene skeleton, etc.), sulfur atom-containing type epoxy resins, and the like, and these may be used alone or in combination.
本発明に用いるフェノール樹脂（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、ポリマー全般を言い、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、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂、フェノールアラルキル樹脂（フェニレン骨格、ビフェニレン骨格等を有する）、硫黄原子含有型フェノール樹脂等が挙げられ、これらは単独でも混合して用いても差し支えない。 The phenol resin (B) used in the present invention is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak Resin, cresol novolac resin, dicyclopentadiene modified phenolic resin, terpene modified phenolic resin, triphenolmethane type resin, phenol aralkyl resin (having phenylene skeleton, biphenylene skeleton, etc.), sulfur atom containing type phenol resin, etc. May be used alone or in combination.
本発明に用いるエポキシ樹脂（Ａ）とフェノール樹脂（Ｂ）の配合量としては、全エポキシ樹脂のエポキシ基数と全フェノール樹脂のフェノール性水酸基数の比が０．８以上、１．３以下であることが好ましい。この範囲であると、エポキシ樹脂組成物の硬化性の低下、或いは硬化物のガラス転移温度の低下、耐湿信頼性の低下等を抑えることができる。 As a blending amount of the epoxy resin (A) and the phenol resin (B) used in the present invention, the ratio of the number of epoxy groups of all epoxy resins to the number of phenolic hydroxyl groups of all phenol resins is 0.8 or more and 1.3 or less. It is preferable. Within this range, a decrease in curability of the epoxy resin composition, a decrease in glass transition temperature of the cured product, a decrease in moisture resistance reliability, and the like can be suppressed.
本発明に用いる無機充填材（Ｃ）としては、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、溶融シリカ、結晶シリカ、タルク、アルミナ、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、球状の溶融シリカである。これらの無機充填材は、単独でも混合して用いても差し支えない。無機充填材（Ｃ）の含有量は、特に限定されないが、全エポキシ樹脂組成物中８０重量％以上、９４重量％以下が好ましい。この範囲であると、耐半田性の低下、流動性の低下等を抑えることができる。 As an inorganic filler (C) used for this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used. Examples thereof include fused silica, crystalline silica, talc, alumina, silicon nitride and the like, and the most preferably used is spherical fused silica. These inorganic fillers may be used alone or in combination. Although content of an inorganic filler (C) is not specifically limited, 80 weight% or more and 94 weight% or less are preferable in all the epoxy resin compositions. Within this range, a decrease in solder resistance, a decrease in fluidity, and the like can be suppressed.
本発明で用いられる硬化促進剤（Ｄ）としては、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、ホスフィン化合物とキノン化合物との付加物、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、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、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、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１種又は２種類以上を併用してもよい。 As a hardening accelerator (D) used by this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used. For example, adducts of phosphine compounds and quinone compounds, diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof, amine compounds such as tributylamine, benzyldimethylamine, -Imidazole compounds such as methylimidazole, organic phosphines such as triphenylphosphine and methyldiphenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, tetraphenylphosphonium / tetranaphthoic acid borate, tetraphenyl And tetrasubstituted phosphonium / tetrasubstituted borates such as phosphonium / tetranaphthoyloxyborate and tetraphenylphosphonium / tetranaphthyloxyborate. Al may be used in combination with one or two or more types.
本発明に用いる着色剤（Ｅ）として体積抵抗率１０３Ω・ｃｍ以上の黒色系酸化チタンを用いることで、配線のショート、リーク不良等の電気不良の発生を生じることなく、かつ優れた着色性、レーザーマーキング性を有する樹脂組成物を得ることができる。一般に酸化チタンはＴｉｎＯ（２ｎ−１）（ここでｎは正の整数。）として存在するが、ｎの値が大きくなり、酸素欠損が少なくなるほど抵抗値が高くなることが知られており、体積抵抗率が１０３Ω・ｃｍ以上となるためには、ｎ＝４以上であることが好ましい。またｎ＝４以上であると、樹脂中での分散性が向上する点でも好ましい。しかし逆に酸素欠損が少な過ぎると、着色性、レーザーマーキング性が低下するので、ｎ＝６以下であることが好ましい。
体積抵抗率の測定方法は、下部に真鍮製電極を取り付けたテトラフルオロエチレン製容器（内径３８ｍｍ）に着色剤を入れ、真鍮製電極で蓋をした後、荷重を掛けていき、５０ｋｇｆ時の抵抗値をＡＤＶＡＮＴＥＳＴ製デジタルマルチメーターＴＲ６８７７で測定した。同時にその荷重時の着色剤の厚みも測定し、以下の式から体積抵抗率を算出した。
体積抵抗率（Ω・ｃｍ）＝
抵抗値（Ω）×着色剤の断面積（ｃｍ２）÷着色剤の厚み（ｃｍ）
By using black titanium oxide having a volume resistivity of 10 3 Ω · cm or more as the colorant (E) used in the present invention, it is possible to produce excellent coloration without causing electrical defects such as wiring short-circuits and leakage defects. And a resin composition having laser marking properties can be obtained. (Here n is a positive integer.) In general the titanium oxide Ti n O (2n-1) is present as the value of n becomes large, it is known that the resistance value as the oxygen deficiency is reduced is higher In order for the volume resistivity to be 10 3 Ω · cm or more, it is preferable that n = 4 or more. Further, n = 4 or more is preferable from the viewpoint of improving dispersibility in the resin. However, if there are too few oxygen vacancies, the colorability and laser marking properties are degraded, so n = 6 or less is preferable.
The volume resistivity is measured by placing a colorant in a tetrafluoroethylene container (inner diameter: 38 mm) with a brass electrode attached to the bottom, covering with a brass electrode, applying a load, and resistance at 50 kgf The value was measured with a digital multimeter TR6877 manufactured by ADVANTEST. At the same time, the thickness of the colorant at that load was also measured, and the volume resistivity was calculated from the following equation.
Volume resistivity (Ω · cm) =
Resistance value (Ω) × colorant cross-sectional area (cm 2 ) ÷ colorant thickness (cm)
本発明に用いる着色剤（Ｅ）の配合量は、特に限定されないが、全エポキシ樹脂組成物中０．０５重量％以上、５重量％以下が望ましく、より好ましくは０．１重量％以上、３重量％以下、特に好ましくは０．５重量％以上、２．５重量％以下である。上記範囲内であると、良好な着色性及びレーザーマーキング性が得られ、また着色剤の凝集による配線のショート、リーク不良等の電気不良等を抑えることができる。 The blending amount of the colorant (E) used in the present invention is not particularly limited, but is preferably 0.05% by weight or more and 5% by weight or less, more preferably 0.1% by weight or more and 3% by weight in the total epoxy resin composition. % By weight or less, particularly preferably 0.5% by weight or more and 2.5% by weight or less. Within the above range, good colorability and laser marking properties can be obtained, and electrical defects such as wiring shorts and leakage defects due to aggregation of colorants can be suppressed.
本発明のエポキシ樹脂組成物には必要に応じてシランカップリング剤を用いることができる。使用できるシランカップリング剤としては、従来公知のものを用いることができるが、例えば、エポキシシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等が挙げられ、これらを例示すると、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−フェニルγ−アミノプロピルトリエトキシシラン、Ｎ−フェニルγ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、Ｎ−６−（アミノヘキシル）3−アミノプロピルトリメトキシシラン、Ｎ−（３−（トリメトキシシリルプロピル）−１，３−ベンゼンジメタナン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−（３，４エポキシシクロヘキシル）エチルトリメトキシシラン、メチルトリメトキシシランン、γ−ウレイドプロピルトリエトキシシラン、ビニルトリエトキシシランなどが挙げられ、これらは１種類単独でも２種以上併用しても構わない。これらのうち２級アミノシラン、メルカプトシランが好ましい。シランカップリング剤の配合量は、特に限定されないが、全エポキシ樹脂組成物中０．０１重量％以上、１重量％以下が望ましく、より好ましくは０.０５重量％以上、０．８重量％以下である。上記範囲内であると、良好な粘度特性及び流動特性が得られ、また硬化性の低下を抑えることができる。また、これらシランカップリング剤は、予め水或いは必要に応じて酸又はアルカリを添加して、加水分解処理して用いてもよく、また予め無機充填材に処理されていてもよい。 If necessary, a silane coupling agent can be used in the epoxy resin composition of the present invention. As the silane coupling agent that can be used, conventionally known silane coupling agents can be used, and examples thereof include epoxy silane, amino silane, alkyl silane, ureido silane, vinyl silane, and the like. For example, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane N-phenyl γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -aminopropyltrimethoxysilane, N- (3- (tri Methoxysilylpropyl) -1,3-benze Dimethanane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, methyltrimethoxysilane , Γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc., and these may be used alone or in combination of two or more, among which secondary aminosilane and mercaptosilane are preferred, silane coupling. Although the compounding quantity of an agent is not specifically limited, 0.01 to 1 weight% is desirable in all the epoxy resin compositions, More preferably, it is 0.05 to 0.8 weight%. Within the above range, good viscosity characteristics and flow characteristics can be obtained, and curable In addition, these silane coupling agents may be used by hydrolysis with addition of water or an acid or alkali as required, or may be previously treated with an inorganic filler. May be.
本発明のエポキシ樹脂組成物には必要に応じて芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物を使用することができる。使用できる化合物として、例えば、カテコール、ピロガロール、没食子酸、没食子酸エステル、１，２−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン及びこれらの誘導体が挙げられる。これらのうちカテコール、ピロガロール、１，２−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレンが好ましい。これらの化合物は１種類を単独で使用しても２種以上併用してもよい。これらの化合物の配合量は全エポキシ樹脂組成物中０．０１重量％以上、１重量％以下が望ましく、より好ましくは０．０２重量％以上、０．８重量％以下である。上記範囲内であると、良好な粘度特性及び流動特性が得られ、また硬化性の低下や硬化物物性の低下を抑えることができる。 In the epoxy resin composition of the present invention, a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used as necessary. Examples of the compound that can be used include catechol, pyrogallol, gallic acid, gallic acid ester, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Of these, catechol, pyrogallol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are preferable. These compounds may be used alone or in combination of two or more. The compounding amount of these compounds is desirably 0.01% by weight or more and 1% by weight or less, more preferably 0.02% by weight or more and 0.8% by weight or less in the total epoxy resin composition. Within the above range, good viscosity characteristics and flow characteristics can be obtained, and a decrease in curability and a decrease in physical properties of the cured product can be suppressed.
本発明に用いることができる芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物は、前記シランカップリング剤との相乗効果により、低粘度化と流動性向上を図ることができるため、着色剤の凝集物等が粗大粒子としてインナーリード間、ワイヤー間に挟まるのを抑える効果も有している。 A compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring that can be used in the present invention is intended to reduce viscosity and improve fluidity by a synergistic effect with the silane coupling agent. Therefore, the colorant aggregates and the like can be prevented from being caught as coarse particles between the inner leads and between the wires.
本発明のエポキシ樹脂組成物には必要に応じて離型剤を用いることができる。使用できる離型剤としては、従来公知のものを用いることができるが、例えば、高級脂肪酸、高級脂肪酸金属塩、エステル系ワックス、ポリエチレン系ワックス等が挙げられ、これらは１種類単独でも２種以上併用しても構わない。これらのうちポリエチレン系ワックス、モンタン酸エステル系ワックスが離型性に優れ、着色剤が凝集し難いという点で好ましい。
離型剤の配合量は特に制限されないが、全エポキシ樹脂組成物中０．０５重量％以上、３重量％以下が望ましく、より好ましくは０.１重量％以上、１重量％以下である。
A release agent can be used in the epoxy resin composition of the present invention as necessary. As the release agent that can be used, conventionally known release agents can be used, and examples thereof include higher fatty acids, higher fatty acid metal salts, ester waxes, polyethylene waxes, and the like. You may use together. Of these, polyethylene waxes and montanic acid ester waxes are preferred in that they are excellent in releasability and the colorant hardly aggregates.
The compounding amount of the release agent is not particularly limited, but is preferably 0.05% by weight or more and 3% by weight or less, more preferably 0.1% by weight or more and 1% by weight or less in the total epoxy resin composition.
本発明のエポキシ樹脂組成物は、エポキシ樹脂、フェノール樹脂、無機充填材、硬化促進剤、着色剤が必須であり、更に必要に応じて、シランカップリング剤、芳香環を構成する２個以上の隣接する炭素原子にそれぞれ水酸基が結合した化合物、離型剤を用いるが、これ以外に、ハイドロタルサイト類やマグネシウム、アルミニウム、ビスマス、チタン、ジルコニウムから選ばれる元素の含水酸化物等のイオントラップ剤、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シランカップリング剤以外のカップリング剤、シリコーンオイル、ゴム等の低応力添加剤、チアゾリン、ジアゾール、トリアゾール、トリアジン、ピリミジン等の密着付与剤、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、ほう酸亜鉛、モリブデン酸亜鉛、フォスファゼン等の難燃剤等の添加剤を適宜配合しても差し支えない。 In the epoxy resin composition of the present invention, an epoxy resin, a phenol resin, an inorganic filler, a curing accelerator, and a colorant are essential, and if necessary, a silane coupling agent and two or more constituting an aromatic ring. A compound in which a hydroxyl group is bonded to each adjacent carbon atom and a release agent are used, but in addition to this, ion trapping agents such as hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium and zirconium , Titanate coupling agents, aluminum coupling agents, coupling agents other than silane coupling agents such as aluminum / zirconium coupling agents, low-stress additives such as silicone oil, rubber, thiazoline, diazole, triazole, triazine, pyrimidine, etc. Adhesion promoter, brominated epoxy resin and ammonium trioxide Mon, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, be suitably blended additives such as flame retardants such as phosphazene no problem.
また、本発明のエポキシ樹脂組成物は、ミキサー等を用いて原料を充分に均一に混合した後、更に熱ロール又はニーダー等で溶融混練し、冷却後粉砕して得られる。
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、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型すればよい。
The epoxy resin composition of the present invention can be obtained by mixing the raw materials sufficiently uniformly using a mixer or the like, then melt-kneading with a hot roll or a kneader, cooling and pulverizing.
The epoxy resin composition of the present invention is used to encapsulate various electronic components such as semiconductor elements and to manufacture a semiconductor device by a conventional molding method such as transfer molding, compression molding, injection molding, etc. do it.
以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。配合割合は重量部とする。
なお、実施例及び比較例で用いた着色剤の内容について以下に示す。
着色剤１：黒色系酸化チタン、Ｔｉ４Ｏ７、体積抵抗率７．３×１０４Ω・ｃｍ
着色剤２：黒色系酸化チタン、Ｔｉ６Ｏ１１、体積抵抗率２．５×１０７Ω・ｃｍ
着色剤３：黒色系酸化チタン、Ｔｉ２Ｏ３、体積抵抗率１．３×１０１Ω・ｃｍ
Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
In addition, it shows below about the content of the coloring agent used by the Example and the comparative example.
Colorant 1: Black titanium oxide, Ti 4 O 7 , volume resistivity 7.3 × 10 4 Ω · cm
Colorant 2: Black titanium oxide, Ti 6 O 11 , volume resistivity 2.5 × 10 7 Ω · cm
Colorant 3: Black titanium oxide, Ti 2 O 3 , volume resistivity 1.3 × 10 1 Ω · cm
実施例１
エポキシ樹脂１：下記式（１）で表される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（日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３） ８５重量部
Epoxy resin 1: phenol aralkyl type epoxy resin having a biphenylene skeleton represented by the following formula (1) (manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000P, softening point: 58 ° C., epoxy equivalent: 273) 85 parts by weight
フェノール樹脂１：下記式（２）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点１０７℃、水酸基当量２０４） ５３重量部
溶融球状シリカ１：（平均粒径２８μｍ、比表面積３．２ｍ２／ｇ） ７５０重量部
溶融球状シリカ２：（平均粒径０．５μｍ、比表面積６．０ｍ２／ｇ） ８８重量部
硬化促進剤１：トリフェニルホスフィンと１，４−ベンゾキノンとの付加物
３重量部
着色剤１ １５重量部
カップリング剤１：Ｎ−フェニルγ−アミノプロピルトリメトキシシラン（信越化学（株）製、商品名ＫＢＭ−５７３） ２重量部
カップリング剤２：γ−メルカプトプロピルトリメトキシシラン（信越化学（株）製、商品名ＫＢＭ−８０３） １重量部
２，３−ジヒドロキシナフタレン（関東化学（株）製、試薬） １重量部
離型剤：モンタン酸エステル系ワックス（クラリアントジャパン（株）製、商品名リコルブＷＥ−４） ２重量部
をミキサーにて混合し、熱ロールを用いて、９５℃で８分間混練して冷却後粉砕し、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。また、高温リーク試験においては、上記成分から着色剤１のみを除いた成分を、上記と同様にミキサーにて混合し、熱ロールを用いて、９５℃で８分間混練して冷却後粉砕したものを、評価に用いた。結果を表１に示す。
Fused spherical silica 1: (average particle size 28 μm, specific surface area 3.2 m 2 / g) 750 parts by weight Fused spherical silica 2: (average particle size 0.5 μm, specific surface area 6.0 m 2 / g) 88 parts by weight Curing acceleration Agent 1: Adduct of triphenylphosphine and 1,4-benzoquinone
3 parts by weight Colorant 1 15 parts by weight Coupling agent 1: N-phenyl γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-573) 2 parts by weight Coupling agent 2: γ-mercaptopropyl Trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-803) 1 part by weight 2,3-dihydroxynaphthalene (manufactured by Kanto Chemical Co., Ltd., reagent) 1 part by weight Release agent: Montanate ester wax (Clariant 2 parts by weight of Japan Co., Ltd., trade name Recolve WE-4) were mixed with a mixer, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. In addition, in the high temperature leak test, the component obtained by removing only the colorant 1 from the above components was mixed with a mixer in the same manner as described above, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized. Was used for evaluation. The results are shown in Table 1.
評価方法
スパイラルフロー：低圧トランスファー成形機を用いて、ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型に、金型温度１７５℃、注入圧力６．９ＭＰa、硬化時間１２０秒の条件で、エポキシ樹脂組成物を注入し、流動長を測定した。
Evaluation method Spiral flow: Using a low-pressure transfer molding machine, a spiral flow measurement mold conforming to EMMI-1-66, with a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. The resin composition was injected and the flow length was measured.
硬化性: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IVＰＳ型）を用い、１７５℃、６０秒後のトルク値を３００秒後のトルク値で除した値で示した。この値の大きい方が硬化性は良好である。 Curability: Using a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IVPS type), the torque value after 60 seconds at 175 ° C. was divided by the torque value after 300 seconds. The larger this value, the better the curability.
外観（硬化物の色）：低圧トランスファー成形機を用いて、金型温度１７５℃、注入圧力６．９ＭＰａ、硬化時間７０秒で、８０ｐＱＦＰ（１４×２０×２．０ｍｍ厚）を成形し、１２個のパッケージを得た。外観（硬化物の色）のチェックは目視にて観察を行った。 Appearance (color of cured product): Using a low-pressure transfer molding machine, 80 pQFP (14 × 20 × 2.0 mm thickness) was molded at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 70 seconds. Got packages. The appearance (color of the cured product) was checked visually.
ＹＡＧレーザーマーキング性：低圧トランスファー成形機を用いて、金型温度１７５℃、注入圧力６．９ＭＰａ、保圧時間１２０秒で、８０ｐＱＦＰ（２．７ｍｍ厚）を成形し、更に１７５℃、８時間でポストキュアした。次に、日本電気（株）・製のマスクタイプのＹＡＧレーザー捺印機（印加電圧２．４ｋＶ、パルス幅１２０μｓの条件）でマーキングし、印字の視認性（ＹＡＧレーザーマーキング性）を評価した。良好であれば○、使用可能範囲であれば△、使用不可能であれば×と表示した。 YAG laser marking property: Using a low-pressure transfer molding machine, 80pQFP (2.7 mm thickness) was molded at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a holding time of 120 seconds, and further at 175 ° C. for 8 hours. Post cure. Next, marking was performed using a mask type YAG laser stamping machine (applied voltage 2.4 kV, pulse width 120 μs) manufactured by NEC Corporation, and printing visibility (YAG laser marking property) was evaluated. If it was good, it was indicated as ◯, if it was usable, Δ, and if it was not usable, it was indicated as x.
凝集物：低圧トランスファー成形機を用いて、金型温度１７５℃、注入圧力６．９ＭＰａ、保圧時間１２０秒で、１００ｍｍφの円板を成形した。着色剤が酸化チタンである場合は、この表面を研磨し研磨面をまずＳＥＭ−ＥＤＳにてマッピングしてチタン元素濃度が高い場所を特定し、その後金属顕微鏡にてその部分を観察した。着色剤がカーボンブラックである場合は、表面を研磨した後、蛍光顕微鏡（オリンパス（株）製・ＢＸ５１Ｍ−５３ＭＦ）にて観察した。２５μｍ以上の着色剤凝集物個数を測定した。 Aggregate: A 100 mmφ disk was molded using a low-pressure transfer molding machine at a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a holding time of 120 seconds. When the colorant was titanium oxide, this surface was polished and the polished surface was first mapped with SEM-EDS to identify a place where the titanium element concentration was high, and then that portion was observed with a metal microscope. When the colorant was carbon black, the surface was polished and then observed with a fluorescence microscope (Olympus Co., Ltd., BX51M-53MF). The number of colorant aggregates of 25 μm or more was measured.
高温リーク：実施例１の樹脂組成物並びに実施例１において着色剤１のみを除いた成分から得た樹脂組成物について、低圧トランスファー成形機を用いて、金型温度１７５℃、注入圧力７．８ＭＰａ、保圧時間９０秒で、６０μｍピッチのテスト用チップに径３０μｍの金線を施した１４４ｐＴＱＦＰを１００個封止成形した。次に、ＡＤＶＡＮＴＥＳＴ製の微少電流計８２４０Ａを用いてリーク電流を測定した。判断基準は１７５℃においてリーク電流が着色剤１のみを除いた樹脂組成物の場合におけるメジアン値と比較して、１オーダーを超えて高い値を示すものが１個でもあった場合を△、２オーダーを超えて高い値を示すものが１個でもあった場合を×とした。 High-temperature leak: For the resin composition obtained in Example 1 and the resin composition obtained from the components excluding only the colorant 1 in Example 1, using a low-pressure transfer molding machine, the mold temperature was 175 ° C. and the injection pressure was 7.8 MPa. Then, 100 pieces of 144pTQFP in which a gold wire with a diameter of 30 μm was applied to a test chip with a pitch of 60 μm was sealed and molded in a holding time of 90 seconds. Next, leakage current was measured using a microammeter 8240A manufactured by ADVANTEST. Judgment criteria are △, 2 when the leakage current at 175 ° C. is one that shows a high value exceeding one order compared to the median value in the case of the resin composition excluding only colorant 1. The case where there was even one that showed a high value exceeding the order was rated as x.
実施例２〜４、比較例１〜２
表１の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得て、実施例１と同様にして評価した。結果を表１に示す。
実施例１以外で用いた原材料を以下に示す。
エポキシ樹脂２：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、商品名ＹＸ−４０００、エポキシ当量１９０、融点１０５℃）
According to the composition of Table 1, an epoxy resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name YX-4000, epoxy equivalent 190, melting point 105 ° C.)
フェノール樹脂２：フェノールアラルキル樹脂（三井化学（株）製、商品名ＸＬＣ−ＬＬ、水酸基当量１６５、軟化点７９℃）
硬化促進剤２：トリフェニルホスフィン（ケイ・アイ化成（株）製、商品名ＰＰ−３６０）
カーボンブラック：（三菱化学（株）製、商品名＃５、体積抵抗率０．８Ω・ｃｍ）
Curing accelerator 2: Triphenylphosphine (manufactured by Kay Kasei Co., Ltd., trade name PP-360)
Carbon black: (Mitsubishi Chemical Corporation, trade name # 5, volume resistivity 0.8 Ω · cm)
本発明に従うと、半導体素子等の封止成形時において良好な流動性、硬化性を有し、かつ配線のショート、リーク不良等の電気不良を生ずることのない半導体封止用エポキシ樹脂組成物が得られるので、特に表面実装型の半導体装置の製造用として好適に用いることができる。 According to the present invention, there is provided an epoxy resin composition for semiconductor encapsulation that has good fluidity and curability at the time of sealing molding of a semiconductor element and the like and does not cause electrical defects such as wiring shorts and leakage defects. Since it is obtained, it can be suitably used particularly for the production of a surface-mount type semiconductor device.
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| JP4483655B2 true JP4483655B2 (en) | 2010-06-16 |
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| KR100827949B1 (en) | 2006-12-27 | 2008-05-08 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor device which has excellent laser marking property and the semiconductor device using the same |
| JP4894554B2 (en) * | 2007-02-23 | 2012-03-14 | パナソニック電工株式会社 | Resin composition for optical semiconductor encapsulation and optical semiconductor device |
| JP2014152302A (en) * | 2013-02-13 | 2014-08-25 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor, method for manufacturing semiconductor device, and semiconductor device |
| FR3019179B1 (en) * | 2014-03-28 | 2017-11-24 | Saint Gobain Ct Recherches | POLYMER-CERAMIC COMPOSITES |
| KR20170036975A (en) * | 2015-09-24 | 2017-04-04 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same |
| JP2018053111A (en) * | 2016-09-29 | 2018-04-05 | 株式会社ノリタケカンパニーリミテド | Thermosetting insulating composition |
| WO2019098026A1 (en) * | 2017-11-14 | 2019-05-23 | パナソニックＩｐマネジメント株式会社 | Semiconductor encapsulation resin composition and semiconductor package |
| KR102171971B1 (en) * | 2018-02-06 | 2020-10-30 | 스미또모 베이크라이트 가부시키가이샤 | Resin composition for semiconductor encapsulation, semiconductor device, and method for producing a resin composition for semiconductor encapsulation |
| JP7170240B2 (en) * | 2018-07-27 | 2022-11-14 | パナソニックＩｐマネジメント株式会社 | Resin composition for semiconductor encapsulation, semiconductor device, and method for manufacturing semiconductor device |
| JP2020132750A (en) * | 2019-02-19 | 2020-08-31 | 住友ベークライト株式会社 | Sealing resin composition and electronic device using the same |
| EP4029896A4 (en) * | 2019-09-09 | 2023-07-05 | Adeka Corporation | Curable resin composition |
| CN115298261A (en) * | 2020-03-27 | 2022-11-04 | 京瓷株式会社 | Epoxy resin composition and ignition coil |
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