JP4692885B2 - Epoxy resin composition and semiconductor device - Google Patents
Epoxy resin composition and semiconductor device Download PDFInfo
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- JP4692885B2 JP4692885B2 JP2005502690A JP2005502690A JP4692885B2 JP 4692885 B2 JP4692885 B2 JP 4692885B2 JP 2005502690 A JP2005502690 A JP 2005502690A JP 2005502690 A JP2005502690 A JP 2005502690A JP 4692885 B2 JP4692885 B2 JP 4692885B2
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- Prior art keywords
- epoxy resin
- resin composition
- general formula
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- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims description 69
- 239000003822 epoxy resin Substances 0.000 title claims description 68
- 239000000203 mixture Substances 0.000 title claims description 39
- 239000004065 semiconductor Substances 0.000 title claims description 28
- 239000005011 phenolic resin Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000007822 coupling agent Substances 0.000 description 19
- 229910000679 solder Inorganic materials 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001721 transfer moulding Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 150000001463 antimony compounds Chemical class 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- -1 amine compounds Chemical class 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- PBLVLXGAPMEPKW-UHFFFAOYSA-N CC(C)(NC)OC Chemical compound CC(C)(NC)OC PBLVLXGAPMEPKW-UHFFFAOYSA-N 0.000 description 2
- OWRANONYOLPEGA-UHFFFAOYSA-N C[O](C1CCCCC1)=C Chemical compound C[O](C1CCCCC1)=C OWRANONYOLPEGA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 2
- 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 2
- 239000001993 wax Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- GHXRKGHKMRZBJH-UHFFFAOYSA-N boric acid Chemical class OB(O)O.OB(O)O GHXRKGHKMRZBJH-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 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
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 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
- 239000006082 mold release agent Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 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 compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-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
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/72—Fillers; Inorganic pigments; Reinforcing additives
Description
【技術分野】
【０００１】
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。
【背景技術】
【０００２】
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。
【０００３】
通常、エポキシ樹脂組成物中には、難燃性を付与するために、臭素含有有機化合物及び三酸化アンチモン、四酸化アンチモン等のアンチモン化合物が配合されているが、環境・衛生の点から好ましくない。そこで臭素含有有機化合物及びアンチモン化合物を使用しなくても難燃性に優れたエポキシ樹脂組成物として、構造中に多数の芳香環を持つ樹脂を使用する手法がある（例えば、特開平１１−１４０２７７号公報第２〜１１頁参照）。しかし多数の芳香環を持つために、粘度が上昇してしまうという欠点があった。
【０００４】
また、半導体装置をプリント回路基板への実装時する際、鉛を含有する半田（スズ−鉛合金）が使用されてきたが、同様に環境・衛生の点から鉛を含有する半田（スズ−鉛合金）を使用しないことが望まれている。鉛を含有する半田（スズ−鉛合金）の融点は１８３℃で、実装時の半田処理の温度は２２０〜２４０℃であるのに対し、スズ−銀合金に代表される鉛を含有しない半田では融点が高く、半田処理時の温度が２６０℃程度となる。そのため、半導体装置が半田浸漬或いは半田リフロー工程でかかる応力が増大し、半導体装置内、特に半導体素子、リードフレーム、インナーリード上の金メッキや銀メッキ等の各種メッキされた各接合部分とエポキシ樹脂組成物の硬化物の界面で剥離が生じたりして、信頼性が著しく低下してしまう。
【０００５】
半田処理による信頼性低下を改善するために、エポキシ樹脂組成物中の無機質充填材の充填量を増加させることで低吸湿化、高強度化、低熱膨張化を達成し耐半田クラック性を向上させ、低溶融粘度の樹脂を使用して、成形時に低粘度で高流動性を維持させる手法がある（例えば、特開昭６４−６５１１６号公報第２〜７頁参照。）。この手法を用いることにより耐半田クラック性がかなり改良されるが、無機充填材の充填割合の増加と共に、流動性が犠牲になりパッケージ内に空隙が生じやすくなる欠点があった。そこでアミノシラン等の各種カップリング剤を添加して流動性と耐半田クラック性の両立を図る手法も提案されている（例えば、特開平２−２１８７３５号公報第１〜９頁参照。）が、金メッキや銀メッキ等各種メッキされた各接合部分とエポキシ樹脂組成物の硬化物の界面での剥離は抑えられず、十分に良好な耐半田クラック性を備えた半導体封止用エポキシ樹脂組成物は得られるには至らなかった。
【発明の開示】
【発明が解決しようとする課題】
【０００６】
本発明は、流動性、耐半田クラック性に優れた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ものである。
【課題を解決するための手段】
【０００７】
本発明は、
［１］ （Ａ）一般式（１）で表されるエポキシ樹脂、（Ｂ）一般式（２）で表されるフェノール樹脂、（Ｃ）硬化促進剤、（Ｄ）無機充填材、（Ｅ）一般式（３）で表されるシランカップリング剤、及び（Ｆ）一般式（４）で表されるシランカップリング剤を必須成分とする半導体封止用エポキシ樹脂組成物、
【０００８】
【化１】
【０００９】
【化２】
【００１０】
【化３】
【００１１】
【化４】
【００１２】
［２］ 第［１］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。
【００１３】
（発明の実施の形態）
本発明で用いられる一般式（１）で表されるエポキシ樹脂は、エポキシ基間に疎水性で剛直なビフェニレン骨格を有しており、これを用いたエポキシ樹脂組成物の硬化物は吸湿率が低く、ガラス転移温度（以下、Ｔｇという）を越えた高温域での弾性率が低く、半導体素子、有機基板、及び金属基板との密着性に優れる。また架橋密度が低い割には耐熱性が高いという特徴を有している。
【００１４】
一般式（１）中のｎは平均値で、１〜５の正数、好ましくは１〜３である。ｎが下限値を下回るとエポキシ樹脂組成物の硬化性が低下する可能性がある。ｎが上限値を越えると粘度が高くなりエポキシ樹脂組成物の流動性が低下する可能性がある。一般式（１）で表されるエポキシ樹脂は、１種類を単独で用いても２種類以上を併用してもよい。
【００１５】
一般式（１）で表されるエポキシ樹脂の内では、式（５）で表されるエポキシ樹脂が特に好ましい。
【００１６】
【化５】
【化６】
一般式（１）で表されるエポキシ樹脂の本来の特性を損なわない範囲で、他のエポキシ樹脂を併用してもよい。併用する場合は、分子中にエポキシ基を有するモノマー、オリゴマー、ポリマー全般で、極力低粘度のものを使用することが望ましく、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、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、トリフェノールメタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂（フェニレン骨格を有する）、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、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等が挙げられ、これらは１種類を単独で用いても２種類以上を併用してもよい。
【００１９】
一般式（１）で表されるエポキシ樹脂の使用量は、全エポキシ樹脂中に３０重量％以上含むことが好ましく、特に５０重量％以上が好ましい。下限値を下回ると、難燃性が不十分となる可能性がある。
【００２０】
本発明で用いられる一般式（２）で表されるフェノール樹脂は、フェノール性水酸基間に疎水性で剛直なビフェニレン骨格を有しており、これを用いたエポキシ樹脂組成物の硬化物は吸湿率が低く、Ｔｇを越えた高温域での弾性率が低く、半導体素子、有機基板、及び金属基板との密着性に優れる。また架橋密度が低い割には耐熱性が高いという特徴を有している。
【００２１】
一般式（２）中のｎは平均値で、１〜５の正数、好ましくは１〜３である。ｎが下限値を下回るとエポキシ樹脂組成物の硬化性が低下する可能性がある。ｎが上限値を越えると、粘度が高くなりエポキシ樹脂組成物の流動性が低下する可能性がある。一般式（２）で表されるフェノール樹脂は、１種類を単独で用いても２種類以上を併用してもよい。
【００２２】
一般式（２）で表されるフェノール樹脂の内では、式（６）で表されるフェノール樹脂が特に好ましい。
【００２３】
【化７】
【化８】
本発明で用いられる一般式（２）で表されるフェノール樹脂の特性を損なわない範囲で他のフェノール樹脂を併用してもよい。併用する場合は、分子中にフェノール性水酸基を有するモノマー、オリゴマー、ポリマー全般で、極力低粘度のものを使用することが望ましく、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、フェノールアラルキル樹脂（フェニレン骨格を有する）、ナフトールアラルキル樹脂、トリフェノールメタン樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂等が挙げられ、これらは１種類を単独で用いても２種類以上を併用してもよい。
【００２６】
一般式（２）で表されるフェノール樹脂の使用量は、全フェノール樹脂中に３０重量％以上含むことが好ましく、特に５０重量％以上が好ましい。下限値を下回ると、難燃性が不十分となる可能性がある。
【００２７】
全エポキシ樹脂のエポキシ基と全フェノール樹脂のフェノール性水酸基の当量比としては、好ましくは０．５〜２であり、特に０．７〜１．５がより好ましい。上記範囲を外れると、耐湿性、硬化性等が低下する可能性がある。
【００２８】
本発明で用いる無機充填材の種類については特に限定しないが、例えば、溶融破砕シリカ、溶融球状シリカ、結晶シリカ、２次凝集シリカ、アルミナ、チタンホワイト、水酸化アルミニウム、水酸化マグネシウム、ほう酸亜鉛、モリブデン酸亜鉛等が挙げられ、特に溶融球状シリカが好ましい。溶融球状シリカの形状としては、流動性改善のために限りなく真球状であり、かつ粒度分布がブロードであることが好ましい。
【００２９】
無機充填材及び必要に応じて添加する金属水酸化物、無機イオン交換耐等を含めた全無機物の含有量としては、特に規定されないが、全エポキシ樹脂組成物中に８４重量％以上、９４重量％以下が好ましい。下限値を下回ると、エポキシ樹脂組成物の硬化物の低吸湿性が得られず耐半田クラック性が不十分となる可能性がある。また、上限値を越えると、エポキシ樹脂組成物の流動性が低下し、成形時に充填不良等が生じたり、高粘度化により半導体装置内の金線変形等の不都合が生じる可能性がある。
【００３０】
本発明は、臭素含有有機化合物及びアンチモン化合物を使用せずに難燃性を達成するものである。本発明における全エポキシ樹脂組成物中の臭素原子及びアンチモン原子は、それぞれ０．０５重量％以下となっている。これは経済上の理由から原料や製造段階において混入する微量の成分以外には、臭素原子及びアンチモン原子を添加しないことを意味している。
【００３１】
本発明に用いる無機充填材は、予め十分に混合しておくことが好ましい。また必要に応じて無機充填材をカップリング剤やエポキシ樹脂あるいはフェノール樹脂で予め被覆処理して用いてもよく、被覆処理の方法としては、溶剤を用いて混合した後に溶媒を除去する方法や直接無機充填材に添加し、混合機を用いて混合する方法等が挙げられる。
【００３２】
本発明で用いられる硬化促進剤としては、エポキシ基とフェノール性水酸基の反応を促進するものであれば特に限定しないが、例えば、１，８−ジアザビシクロ（５，４，０）ウンデセン−７等のジアザビシクロアルケン及びその誘導体、トリブチルアミン、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種類を単独で用いても２種類以上を併用してもよい。
【００３３】
本発明において一般式（３）で表されるシランカップリング剤は必須である。一般式（３）で表されるシランカップリング剤は１種類を単独で使用しても２種類以上を併用してもよい。また配合量は、特に限定されないが、全エポキシ樹脂組成物中０．０１〜３重量％が望ましく、より好ましくは０.０５〜１重量％である。下限値を下回ると十分な流動性が得られない可能性があり、上限値を超えると硬化性が低下する可能性がある。
【００３４】
【化９】
本発明において一般式（４）で表されるシランカップリング剤は必須である。一般式（４）で表されるシランカップリング剤は１種類を単独で使用しても２種類以上を併用してもよい。また配合量は、特に限定されないが、全エポキシ樹脂組成物中０．０１〜３重量％が望ましく、より好ましくは０.０５〜１重量％である。下限値を下回ると十分な密着性が得られない可能性があり、上限値を超えると硬化性が低下する可能性がある。
【００３６】
【化１０】
本発明において一般式（３）で表されるシランカップリング剤と、一般式（４）で表されるシランカップリング剤は併用することが必須であり、どちらか一方だけ配合していても、流動性及び耐半田クラック性が十分でない。
【００３８】
本発明のエポキシ樹脂組成物は、必要に応じて、一般式（３）で表される以外のアミノシラン、一般式（４）で表される以外のメルカプトシラン、エポキシシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシランカップリング剤や、チタネートカップリング剤、アルミニウムカップリング剤、アルミニウム／ジルコニウムカップリング剤等のカップリング剤、カーボンブラック等の着色剤、天然ワックス、合成ワックス等の離型剤及び、ゴム等の低応力添加剤を適宜配合しても差し支えない。
【００３９】
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。
【００４０】
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形すればよい。
【００４１】
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。
【００４２】
なお、実施例、及び比較例で用いたカップリング剤及び化合物について、以下に示す。
【００４３】
カップリング剤１：式（７）で示されるカップリング剤（信越化学（株）製、ＫＢＭ−５７３）
【００４４】
【化１１】
【００４５】
【化１２】
【００４６】
【化１３】
【００４７】
【化１４】
【００４８】
エポキシ樹脂１：式（５）で示されるエポキシ樹脂（日本化薬（株）製、ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３、以下、Ｅ−１という）
４９重量部
【００４９】
【化１５】
４２重量部
【００５０】
【化１６】
５重量部
溶融球状シリカ（平均粒径２１μｍ） ８７０重量部
カップリング剤１ ３重量部
カップリング剤２ ３重量部
カーボンブラック ３重量部
カルナバワックス ５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。結果を表１に示す。
【００５１】
評価方法
スパイラルフロー：ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型を用いて、金型温度１７５℃、圧力６．９ＭＰa、硬化時間１２０秒で測定した。単位はｃｍ。
【００５２】
密着性：トランスファー成形機を用いて、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒の条件で、リードフレーム上に２ｍｍ×２ｍｍ×２ｍｍの密着強度試験片を成形した。リードフレームには銅フレームに銀メッキしたもの（フレーム１）とＮｉＰｄ合金フレームに金メッキしたもの（フレーム２）の２種類を用いた。その後、自動せん断強度測定装置（ＤＡＧＥ社製、ＰＣ２４００）を用いて、エポキシ樹脂組成物の硬化物とフレームとのせん断強度を測定した。単位はＮ／ｍｍ２。
【００５３】
耐半田クラック性：低圧トランスファー成形機を用いて、成形温度１７５℃、圧力８．３ＭＰａ、硬化時間１２０秒で、８０ｐＱＦＰ（ＮｉＰｄ合金フレームに金メッキしたフレーム、チップサイズ６．０ｍｍ×６．０ｍｍ）を成形し、アフターベークとして１７５℃、８時間加熱処理した後、８５℃、相対湿度８５％で１２０時間の加湿処理を行った後、２６０℃のＩＲリフロー処理をした。パッケージ内部の剥離とクラックを超音波探傷機で確認した。１０個のパッケージ中の不良パッケージ数を示す。
【００５４】
難燃性：トランスファー成形機を用いて、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間１２０秒で長さ１２７ｍｍ、幅１２．７ｍｍ、厚さ１．６ｍｍの成形品を成形し、ポストキュアとして１７５℃で８時間加熱処理した後、得られた成形品を２３℃、相対湿度５０％の環境下で４８時間加湿処理し、ＵＬ−９４に準じて難燃性試験を行った。
【００５５】
実施例２〜５、比較例１〜５
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。
【００５６】
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：式（１１）を主成分とするエポキシ樹脂（ジャパンエポキシレジン（株）製、ＹＸ−４０００、エポキシ当量１９０ｇ／ｅｑ、融点１０５℃、以下、Ｅ−２という）
【００５７】
【化１７】
【００５８】
【化１８】
【表１】
実施例１と比較例１，２を比べると、カップリング剤１，２をそれぞれ単独で用いるのではなく併用することにより、流動性、密着性ともに大きくなっている。その効果は、比較例３のようにカップリング剤３，４を併用した時には現れず、また、比較例４のように他の樹脂を使用した場合にも現れない、特有のものである。
【００６１】
【産業上の利用可能性】
本発明に従うと、臭素含有有機化合物、アンチモン化合物を使用せずとも良好な難燃性が得られ、かつ良好な流動性、基板との良好な密着性を有するエポキシ樹脂組成物が得られ、これを用いた半導体装置は耐半田クラック性に優れている。【Technical field】
[0001]
The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device using the same.
[Background]
[0002]
As a sealing method for semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is suitable for mass production at low cost and has been adopted for a long time, and a phenol resin that is an epoxy resin or a curing agent in terms 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.
[0003]
Usually, an epoxy resin composition contains a bromine-containing organic compound and an antimony compound such as antimony trioxide and antimony tetroxide in order to impart flame retardancy, which is not preferable from the viewpoint of environment and hygiene. . Therefore, as an epoxy resin composition excellent in flame retardancy without using bromine-containing organic compounds and antimony compounds, there is a method of using a resin having a large number of aromatic rings in its structure (for example, JP-A-11-140277). No. 2-11). However, since it has a large number of aromatic rings, there is a drawback that the viscosity increases.
[0004]
In addition, when mounting a semiconductor device on a printed circuit board, lead-containing solder (tin-lead alloy) has been used. Similarly, lead-containing solder (tin-lead) It is desired not to use an alloy. The melting point of lead-containing solder (tin-lead alloy) is 183 ° C., and the soldering temperature during mounting is 220-240 ° C., whereas in the case of solder not containing lead typified by tin-silver alloy The melting point is high, and the temperature during soldering is about 260 ° C. For this reason, the stress applied to the semiconductor device by the solder dipping or solder reflow process increases, and various plated joint portions such as gold plating and silver plating on the semiconductor device, particularly the semiconductor element, the lead frame, and the inner lead, and the epoxy resin composition Separation occurs at the interface of the cured product, resulting in a significant decrease in reliability.
[0005]
In order to improve reliability degradation due to solder processing, increase the amount of inorganic filler in the epoxy resin composition to achieve low moisture absorption, high strength, low thermal expansion, and improve solder crack resistance. There is a technique in which a low melt viscosity resin is used to maintain a low viscosity and high fluidity during molding (see, for example, JP-A No. 64-65116, pages 2 to 7). By using this method, the solder crack resistance is considerably improved. However, as the filling rate of the inorganic filler is increased, the fluidity is sacrificed and voids are easily generated in the package. In view of this, there has also been proposed a method of adding various coupling agents such as aminosilane to achieve both fluidity and solder crack resistance (see, for example, JP-A-2-218735, pages 1 to 9). Separation at the interface between each plated joint such as silver or silver plating and the cured product of the epoxy resin composition is not suppressed, and an epoxy resin composition for semiconductor encapsulation with sufficiently good solder crack resistance is obtained. It was not reached.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0006]
The present invention provides an epoxy resin composition for semiconductor encapsulation excellent in fluidity and solder crack resistance, and a semiconductor device using the same.
[Means for Solving the Problems]
[0007]
The present invention
[1] (A) Epoxy resin represented by general formula (1), (B) phenol resin represented by general formula (2), (C) curing accelerator, (D) inorganic filler, (E) A silane coupling agent represented by the general formula (3), and (F) an epoxy resin composition for encapsulating a semiconductor containing the silane coupling agent represented by the general formula (4) as essential components,
[0008]
[Chemical 1]
[0009]
[Chemical 2]
[0010]
[Chemical 3]
[0011]
[Formula 4]
[0012]
[2] A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor encapsulation according to [1],
It is.
[0013]
(Embodiment of the Invention)
The epoxy resin represented by the general formula (1) used in the present invention has a hydrophobic and rigid biphenylene skeleton between epoxy groups, and a cured product of an epoxy resin composition using the epoxy resin has a moisture absorption rate. It has a low elastic modulus in a high temperature range exceeding the glass transition temperature (hereinafter referred to as Tg), and is excellent in adhesion to a semiconductor element, an organic substrate, and a metal substrate. Moreover, it has the characteristic that heat resistance is high although a crosslinking density is low.
[0014]
N in the general formula (1) is an average value and is a positive number of 1 to 5, preferably 1 to 3. When n is less than the lower limit, the curability of the epoxy resin composition may be lowered. When n exceeds the upper limit, the viscosity increases and the fluidity of the epoxy resin composition may be reduced. The epoxy resin represented by General formula (1) may be used individually by 1 type, or may use 2 or more types together.
[0015]
Among the epoxy resins represented by the general formula (1), the epoxy resin represented by the formula (5) is particularly preferable.
[0016]
[Chemical formula 5]
[Chemical 6]
You may use another epoxy resin together in the range which does not impair the original characteristic of the epoxy resin represented by General formula (1). When used in combination, it is desirable to use monomers, oligomers, and polymers having an epoxy group in the molecule as low as possible in general. For example, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins Bisphenol type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, phenol aralkyl type epoxy resin (with phenylene skeleton), naphthol type epoxy resin, naphthalene type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine Examples thereof include a nucleus-containing epoxy resin and a dicyclopentadiene-modified phenol type epoxy resin, and these may be used alone or in combination of two or more.
[0019]
The amount of the epoxy resin represented by the general formula (1) is preferably 30% by weight or more, and particularly preferably 50% by weight or more in the total epoxy resin. Below the lower limit, the flame retardancy may be insufficient.
[0020]
The phenol resin represented by the general formula (2) used in the present invention has a hydrophobic and rigid biphenylene skeleton between phenolic hydroxyl groups, and a cured product of an epoxy resin composition using the phenol resin has a moisture absorption rate. The elastic modulus is low in a high temperature range exceeding Tg, and the adhesiveness with a semiconductor element, an organic substrate, and a metal substrate is excellent. Moreover, it has the characteristic that heat resistance is high although a crosslinking density is low.
[0021]
In the general formula (2), n is an average value and is a positive number of 1 to 5, preferably 1 to 3. When n is less than the lower limit, the curability of the epoxy resin composition may be lowered. When n exceeds the upper limit, the viscosity becomes high and the fluidity of the epoxy resin composition may be lowered. The phenol resin represented by General formula (2) may be used individually by 1 type, or may use 2 or more types together.
[0022]
Among the phenol resins represented by the general formula (2), the phenol resin represented by the formula (6) is particularly preferable.
[0023]
[Chemical 7]
[Chemical 8]
You may use together other phenol resin in the range which does not impair the characteristic of the phenol resin represented by General formula (2) used by this invention. When used in combination, it is desirable to use monomers, oligomers, and polymers having a phenolic hydroxyl group in the molecule, and those having as low a viscosity as possible. For example, phenol novolak resins, cresol novolak resins, phenol aralkyl resins (phenylene skeletons) Naphthol aralkyl resin, triphenol methane resin, terpene-modified phenol resin, dicyclopentadiene-modified phenol resin, and the like. These may be used alone or in combination of two or more.
[0026]
The use amount of the phenol resin represented by the general formula (2) is preferably 30% by weight or more, and particularly preferably 50% by weight or more in the total phenol resin. Below the lower limit, the flame retardancy may be insufficient.
[0027]
The equivalent ratio of the epoxy groups of all epoxy resins to the phenolic hydroxyl groups of all phenol resins is preferably 0.5 to 2, and more preferably 0.7 to 1.5. If it is out of the above range, moisture resistance, curability and the like may be lowered.
[0028]
Although it does not specifically limit about the kind of inorganic filler used by this invention, For example, fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, magnesium hydroxide, zinc borate, Examples thereof include zinc molybdate, and fused spherical silica is particularly preferable. The shape of the fused spherical silica is preferably infinitely spherical to improve fluidity and has a broad particle size distribution.
[0029]
The content of the total inorganic material including the inorganic filler and the metal hydroxide to be added as necessary, inorganic ion exchange resistance, etc. is not particularly specified, but is 84% by weight or more and 94% by weight in the total epoxy resin composition. % Or less is preferable. If the lower limit is not reached, the low hygroscopicity of the cured product of the epoxy resin composition may not be obtained, and the solder crack resistance may be insufficient. On the other hand, if the upper limit is exceeded, the fluidity of the epoxy resin composition may decrease, resulting in poor filling during molding, or inconveniences such as deformation of the gold wire in the semiconductor device due to increased viscosity.
[0030]
The present invention achieves flame retardancy without using bromine-containing organic compounds and antimony compounds. The bromine atom and antimony atom in the total epoxy resin composition in the present invention are each 0.05% by weight or less. This means that for economic reasons, bromine atoms and antimony atoms are not added in addition to the trace amounts of components mixed in the raw materials and the manufacturing stage.
[0031]
The inorganic filler used in the present invention is preferably mixed well in advance. In addition, if necessary, the inorganic filler may be pre-coated with a coupling agent, an epoxy resin or a phenol resin, and the coating method may be a method of removing the solvent after mixing with a solvent or directly. Examples of the method include adding to an inorganic filler and mixing using a mixer.
[0032]
The curing accelerator used in the present invention is not particularly limited as long as it accelerates the reaction between an epoxy group and a phenolic hydroxyl group. For example, 1,8-diazabicyclo (5,4,0) undecene-7 is used. Diazabicycloalkene and its derivatives, amine compounds such as tributylamine and benzyldimethylamine, imidazole compounds such as 2-methylimidazole, organic phosphines such as triphenylphosphine and methyldiphenylphosphine, tetraphenylphosphonium tetraphenylborate, Tetraphenylphosphonium ・ tetrabenzoic acid borate, tetraphenylphosphonium ・ tetranaphthoic acid borate, tetraphenylphosphonium ・ tetranaphthoyloxyborate, tetraphenylphosphonium ・ tetranaphthyloxy Tetra-substituted phosphonium tetra-substituted borate borate, and the like. These may be used in combination of two or more be used one kind alone.
[0033]
In the present invention, the silane coupling agent represented by the general formula (3) is essential. The silane coupling agent represented by the general formula (3) may be used alone or in combination of two or more. Moreover, although a compounding quantity is not specifically limited, 0.01 to 3 weight% is desirable in all the epoxy resin compositions, More preferably, it is 0.05 to 1 weight%. If the lower limit is not reached, sufficient fluidity may not be obtained, and if it exceeds the upper limit, curability may be lowered.
[0034]
[Chemical 9]
In the present invention, the silane coupling agent represented by the general formula (4) is essential. The silane coupling agent represented by General formula (4) may be used individually by 1 type, or may use 2 or more types together. Moreover, although a compounding quantity is not specifically limited, 0.01 to 3 weight% is desirable in all the epoxy resin compositions, More preferably, it is 0.05 to 1 weight%. If the lower limit is not reached, sufficient adhesion may not be obtained, and if it exceeds the upper limit, curability may be lowered.
[0036]
Embedded image
In the present invention, it is essential to use the silane coupling agent represented by the general formula (3) and the silane coupling agent represented by the general formula (4) in combination, The fluidity and solder crack resistance are not sufficient.
[0038]
If necessary, the epoxy resin composition of the present invention may be an aminosilane other than that represented by the general formula (3), a mercaptosilane other than that represented by the general formula (4), an epoxysilane, an alkylsilane, a ureidosilane, Silane coupling agents such as vinyl silane, titanate coupling agents, aluminum coupling agents, coupling agents such as aluminum / zirconium coupling agents, colorants such as carbon black, mold release agents such as natural wax and synthetic wax, and A low stress additive such as rubber may be appropriately blended.
[0039]
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.
[0040]
The epoxy resin composition of the present invention is used to encapsulate various electronic components such as semiconductor elements, and to manufacture semiconductor devices by conventional molding methods such as transfer molding, compression molding, and injection molding. do it.
[0041]
Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
[0042]
In addition, it shows below about the coupling agent and compound which were used by the Example and the comparative example.
[0043]
Coupling agent 1: coupling agent represented by formula (7) (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)
[0044]
Embedded image
[0045]
Embedded image
[0046]
Embedded image
[0047]
Embedded image
[0048]
Epoxy resin 1: epoxy resin represented by formula (5) (Nippon Kayaku Co., Ltd., NC3000P, softening point 58 ° C., epoxy equivalent 273, hereinafter referred to as E-1)
49 parts by weight
Embedded image
42 parts by weight [0050]
Embedded image
5 parts by weight Fused spherical silica (average particle size 21 μm) 870 parts by weight Coupling agent 1 3 parts by weight Coupling agent 2 3 parts by weight Carbon black 3 parts by weight Carnauba wax 5 parts by weight are mixed in a mixer and a hot roll is used. The mixture was kneaded at 95 ° C. for 8 minutes, cooled and pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.
[0051]
Evaluation method Spiral flow: Using a spiral flow measurement mold according to EMMI-1-66, measurement was performed at a mold temperature of 175 ° C., a pressure of 6.9 MPa, and a curing time of 120 seconds. The unit is cm.
[0052]
Adhesiveness: Using a transfer molding machine, a 2 mm × 2 mm × 2 mm adhesion strength test piece was molded on a lead frame under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds. Two types of lead frames were used: a silver plated copper frame (frame 1) and a gold plated NiPd alloy frame (frame 2). Thereafter, the shear strength between the cured product of the epoxy resin composition and the frame was measured using an automatic shear strength measuring apparatus (manufactured by DAGE, PC2400). The unit is N / mm 2 .
[0053]
Resistance to solder cracking: Using a low-pressure transfer molding machine, with a molding temperature of 175 ° C., a pressure of 8.3 MPa, and a curing time of 120 seconds, 80 pQFP (a NiPd alloy frame gold-plated frame, chip size 6.0 mm × 6.0 mm) After forming and heat-treating at 175 ° C. for 8 hours as an afterbake, a humidification treatment was performed at 85 ° C. and a relative humidity of 85% for 120 hours, followed by an IR reflow treatment at 260 ° C. Peeling and cracks inside the package were confirmed with an ultrasonic flaw detector. The number of defective packages among the 10 packages is shown.
[0054]
Flame retardancy: Using a transfer molding machine, a molded product having a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, a curing time of 120 seconds, a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm is molded. After curing as a cure at 175 ° C. for 8 hours, the obtained molded product was humidified for 48 hours in an environment of 23 ° C. and a relative humidity of 50%, and a flame retardancy test was performed according to UL-94.
[0055]
Examples 2-5, Comparative Examples 1-5
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.
[0056]
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: epoxy resin mainly composed of formula (11) (manufactured by Japan Epoxy Resin Co., Ltd., YX-4000, epoxy equivalent 190 g / eq, melting point 105 ° C., hereinafter referred to as E-2)
[0057]
Embedded image
[0058]
Embedded image
[Table 1]
When Example 1 and Comparative Examples 1 and 2 are compared, both the fluidity and the adhesiveness are increased by using the coupling agents 1 and 2 in combination rather than individually. The effect is unique when it does not appear when the coupling agents 3 and 4 are used together as in Comparative Example 3 and does not appear when other resins are used as in Comparative Example 4.
[0061]
[Industrial applicability]
According to the present invention, an epoxy resin composition having good flame retardancy without using a bromine-containing organic compound or antimony compound and having good fluidity and good adhesion to a substrate is obtained. The semiconductor device using is excellent in solder crack resistance.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005502690A JP4692885B2 (en) | 2003-02-18 | 2004-02-13 | Epoxy resin composition and semiconductor device |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003039620 | 2003-02-18 | ||
| JP2003039620 | 2003-02-18 | ||
| JP2005502690A JP4692885B2 (en) | 2003-02-18 | 2004-02-13 | Epoxy resin composition and semiconductor device |
| PCT/JP2004/001569 WO2004074344A1 (en) | 2003-02-18 | 2004-02-13 | Epoxy resin composition and semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2004074344A1 JPWO2004074344A1 (en) | 2006-06-01 |
| JP4692885B2 true JP4692885B2 (en) | 2011-06-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2005502690A Expired - Fee Related JP4692885B2 (en) | 2003-02-18 | 2004-02-13 | Epoxy resin composition and semiconductor device |
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| Country | Link |
|---|---|
| JP (1) | JP4692885B2 (en) |
| KR (1) | KR100982123B1 (en) |
| CN (1) | CN1315905C (en) |
| MY (1) | MY146460A (en) |
| TW (1) | TWI320421B (en) |
| WO (1) | WO2004074344A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2813510A1 (en) | 2013-06-12 | 2014-12-17 | Shin-Etsu Chemical Co., Ltd. | Thiocarbamatoalky-silanoles as adhesion improvers |
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| JP2006206696A (en) * | 2005-01-26 | 2006-08-10 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2006328360A (en) * | 2005-04-28 | 2006-12-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP5062714B2 (en) * | 2006-01-19 | 2012-10-31 | 日本化薬株式会社 | Active energy ray-curable resin composition and use thereof |
| KR100699191B1 (en) * | 2006-03-13 | 2007-03-23 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor device and the semiconductor device using thereof |
| JP4984722B2 (en) * | 2006-07-28 | 2012-07-25 | 住友ベークライト株式会社 | Epoxy resin composition, epoxy resin molding material and semiconductor device |
| KR100834351B1 (en) * | 2006-11-24 | 2008-06-02 | 제일모직주식회사 | Epoxy Resin Composition for Encapsulating Multichip?Package and the Multichip?Package using the same |
| KR100798675B1 (en) | 2006-12-12 | 2008-01-28 | 제일모직주식회사 | Epoxy resin composition for encapsulating semiconductor device and the semiconductor device using the??same |
| JP5473196B2 (en) * | 2007-05-16 | 2014-04-16 | 東レ・ダウコーニング株式会社 | Curable epoxy resin composition and cured product thereof |
| KR100934558B1 (en) * | 2007-10-08 | 2009-12-29 | 제일모직주식회사 | Adhesive film composition for semiconductor assembly comprising phenol type curable resin reacted with silane coupling agent and adhesive film |
| KR101023241B1 (en) * | 2009-12-28 | 2011-03-21 | 제일모직주식회사 | Adhensive composition for semiconductor device and adhensive film using the same |
| JP5423402B2 (en) * | 2010-01-06 | 2014-02-19 | 住友ベークライト株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device |
| CN102372899A (en) * | 2010-08-11 | 2012-03-14 | 江苏中鹏新材料股份有限公司 | Flame-retarding green epoxy molding compound |
| CN101967266A (en) * | 2010-09-25 | 2011-02-09 | 江苏中鹏新材料股份有限公司 | Halogen-free fire-retarding epoxy resin composition |
| CN101962466B (en) * | 2010-09-25 | 2012-01-04 | 江苏中鹏新材料股份有限公司 | Intrinsic flame-retardant epoxy resin composition for semiconductor package |
| JP2013108024A (en) * | 2011-11-24 | 2013-06-06 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing and electronic component device |
| SG11201405065PA (en) * | 2012-03-01 | 2014-10-30 | Sumitomo Bakelite Co | Resin composition for rotor fixing, rotor, and automotive vehicle |
| JP2013234303A (en) * | 2012-05-11 | 2013-11-21 | Panasonic Corp | Epoxy resin composition for sealing semiconductor and semiconductor device |
| CN106592281B (en) * | 2016-12-15 | 2019-05-28 | 武汉纺织大学 | A method of improving coating and is impregnated with efficiency |
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| JP2003040981A (en) * | 2001-07-30 | 2003-02-13 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP2003252961A (en) * | 2002-03-05 | 2003-09-10 | Toray Ind Inc | Epoxy-based resin composition and semiconductor device using the composition |
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| EP2813510A1 (en) | 2013-06-12 | 2014-12-17 | Shin-Etsu Chemical Co., Ltd. | Thiocarbamatoalky-silanoles as adhesion improvers |
| US9120828B2 (en) | 2013-06-12 | 2015-09-01 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compounds, making methods, and adhesion improver |
| US9238663B2 (en) | 2013-06-12 | 2016-01-19 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compounds, making methods, and adhesion improver |
| US9243005B2 (en) | 2013-06-12 | 2016-01-26 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compounds, making methods, and adhesion improver |
| EP3424933A1 (en) | 2013-06-12 | 2019-01-09 | Shin-Etsu Chemical Co., Ltd. | Thiocarbamatoalkyl-substituted 2,4,6-trioxo-1,3,5-triazines as adhesion improvers |
| EP3428172A1 (en) | 2013-06-12 | 2019-01-16 | Shin-Etsu Chemical Co., Ltd. | Thiocarbamatoalkyl-silanoles as adhesion improvers |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI320421B (en) | 2010-02-11 |
| JPWO2004074344A1 (en) | 2006-06-01 |
| KR100982123B1 (en) | 2010-09-14 |
| MY146460A (en) | 2012-08-15 |
| CN1315905C (en) | 2007-05-16 |
| WO2004074344A1 (en) | 2004-09-02 |
| TW200420658A (en) | 2004-10-16 |
| KR20050107416A (en) | 2005-11-11 |
| CN1745119A (en) | 2006-03-08 |
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