JP4237600B2 - Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same - Google Patents
Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same Download PDFInfo
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- JP4237600B2 JP4237600B2 JP2003352233A JP2003352233A JP4237600B2 JP 4237600 B2 JP4237600 B2 JP 4237600B2 JP 2003352233 A JP2003352233 A JP 2003352233A JP 2003352233 A JP2003352233 A JP 2003352233A JP 4237600 B2 JP4237600 B2 JP 4237600B2
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- JP
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- Prior art keywords
- epoxy resin
- resin composition
- semiconductor
- mass
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003822 epoxy resin Substances 0.000 title claims description 140
- 229920000647 polyepoxide Polymers 0.000 title claims description 140
- 239000000203 mixture Substances 0.000 title claims description 81
- 239000004065 semiconductor Substances 0.000 title claims description 63
- 238000005538 encapsulation Methods 0.000 title claims description 30
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- 238000001723 curing Methods 0.000 claims description 32
- 229920003986 novolac Polymers 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000003063 flame retardant Substances 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000005011 phenolic resin Substances 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 150000001463 antimony compounds Chemical class 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 10
- 150000002366 halogen compounds Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- -1 phosphate ester compound Chemical class 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- 238000000034 method Methods 0.000 description 20
- 239000004593 Epoxy Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 235000013824 polyphenols Nutrition 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 150000002989 phenols Chemical class 0.000 description 11
- 229910000679 solder Inorganic materials 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 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 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 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
- 239000003921 oil Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical class CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- YTIPFUNXZCIVBV-UHFFFAOYSA-N 1-butyl-1,2,3,3-tetramethylguanidine Chemical compound CCCCN(C)C(=NC)N(C)C YTIPFUNXZCIVBV-UHFFFAOYSA-N 0.000 description 1
- ZUZAETTVAMCNTO-UHFFFAOYSA-N 2,3-dibutylbenzene-1,4-diol Chemical compound CCCCC1=C(O)C=CC(O)=C1CCCC ZUZAETTVAMCNTO-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-O 2-methyl-1h-imidazol-3-ium Chemical compound CC=1NC=C[NH+]=1 LXBGSDVWAMZHDD-UHFFFAOYSA-O 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- WINNTJDLRWGRLM-UHFFFAOYSA-N 3,4,5-trihydroxy-6-methoxybenzene-1,2-dicarboperoxoic acid Chemical compound COC1=C(C(C(=O)OO)=C(C(=C1O)O)O)C(=O)OO WINNTJDLRWGRLM-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CHZAMJVESILJGH-UHFFFAOYSA-N 3-[bis(2-cyanoethyl)phosphanyl]propanenitrile Chemical compound N#CCCP(CCC#N)CCC#N CHZAMJVESILJGH-UHFFFAOYSA-N 0.000 description 1
- YICAEXQYKBMDNH-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)phosphanyl]propan-1-ol Chemical compound OCCCP(CCCO)CCCO YICAEXQYKBMDNH-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- VMBUUPYAGAQZMM-UHFFFAOYSA-N OC1=CC=CCC1 Chemical compound OC1=CC=CCC1 VMBUUPYAGAQZMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
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- 238000007429 general method Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- PRQMIJVEENXPNQ-UHFFFAOYSA-N n,n-dimethyl-3,4-dihydro-2h-pyrrol-5-amine Chemical compound CN(C)C1=NCCC1 PRQMIJVEENXPNQ-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
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- PADOFXALCIVUFS-UHFFFAOYSA-N tris(2,3-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(P(C=2C(=C(OC)C=CC=2)OC)C=2C(=C(OC)C=CC=2)OC)=C1OC PADOFXALCIVUFS-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加すること無しに、優れた難燃性を有する硬化物を与え、さらに低粘度であるため流動性に優れ、低吸湿性であるため耐クラック性に優れる半導体封止用エポキシ樹脂組成物及びそ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及び／又は半導体集積回路を封止した半導体装置に関する。 The present invention provides a cured product having excellent flame retardancy without adding a halogen compound or an antimony compound as a flame retardant imparting component, and also has excellent fluidity and low hygroscopicity due to its low viscosity. The present invention relates to an epoxy resin composition for semiconductor encapsulation excellent in crack resistance and a semiconductor device in which a semiconductor element and / or a semiconductor integrated circuit are sealed using the epoxy resin composition for semiconductor encapsulation.
半導体素子の封止には、信頼性、生産性及びコストの面から、エポキシ樹脂組成物が広く用いられている。一般のプラスチック材料と同じく、これら組成物にも難燃性が要求されており、そのために主成分とは別に難燃付与成分として、テトラブロモビスフェノールＡ型エポキシ樹脂や臭素化フェノールノボラック型エポキシ樹脂などの臭素化エポキシ樹脂と酸化アンチモンが組み合わせて配合されている。 For sealing semiconductor elements, epoxy resin compositions are widely used in terms of reliability, productivity, and cost. Like general plastic materials, these compositions are also required to have flame retardancy. For this reason, as a flame retardant component other than the main component, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, etc. A brominated epoxy resin and antimony oxide are combined.
近年、環境保護の観点からダイオキシン類似化合物を発生する危惧のある含ハロゲン化合物や毒性の高いアンチモン化合物の使用を量規制する動きが高まっており、半導体封止用組成物に関しては、上述の臭素化エポキシ樹脂をはじめとするハロゲン化合物や酸化アンチモンを使用することなしに難燃性を達成させる技術が検討されるようになった。例えば、赤リンを配合する方法（特許文献１）、リン酸エステル化合物を配合する方法（特許文献２）、ホスファゼン化合物を配合する方法（特許文献３）、金属水酸化物を配合する方法（特許文献４）などのハロゲン化合物や酸化アンチモンに代わる難燃剤を配合する手法及び充填剤の配合割合を高くする手法（特許文献５）などが検討されている。 In recent years, from the viewpoint of environmental protection, there is an increasing movement to regulate the use of halogen-containing compounds that are likely to generate dioxin-like compounds and highly toxic antimony compounds. Techniques for achieving flame retardancy without using epoxy compounds and other halogen compounds and antimony oxide have been studied. For example, a method of blending red phosphorus (Patent Document 1), a method of blending a phosphate ester compound (Patent Document 2), a method of blending a phosphazene compound (Patent Document 3), a method of blending a metal hydroxide (Patent Document 3) A method of blending a halogen compound such as literature 4) or a flame retardant in place of antimony oxide and a method of increasing the blending ratio of the filler (Patent Literature 5) have been studied.
しかし、半導体封止用エポキシ組成物に赤リンを用いた場合は耐湿信頼性の低下や赤リンの打撃発火性に起因する安全性の問題、リン酸エステルやホスファゼン化合物を用いた場合は可塑化による成形性の低下や耐湿信頼性の低下の問題、金属水酸化物を用いた場合や充填剤の配合割合を高くした場合は流動性の低下の問題がそれぞれにあり、いずれの場合も臭素化エポキシ樹脂と酸化アンチモンを併用した封止用エポキシ樹脂組成物と同等の成形性、信頼性を得るに至っていない。 However, when red phosphorus is used in the epoxy composition for semiconductor encapsulation, the moisture resistance reliability is reduced and the safety problem due to the impact ignition property of red phosphorus, and plasticization is achieved when using phosphate ester or phosphazene compound. There is a problem of decrease in formability and moisture resistance reliability due to aging, and there is a problem of decrease in fluidity when using a metal hydroxide or when the filler content is increased. The moldability and reliability equivalent to those of an epoxy resin composition for sealing using an epoxy resin and antimony oxide in combination have not been achieved.
一方で、近年の高度に複雑化した実装方式に対応するため、封止用エポキシ樹脂組成物には、なお一層の耐ハンダクラック性が要求されており、これらを達成するためには、充填剤の高配合を実現できる組成物の流動性及び硬化後の低吸湿性に十分配慮する必要がある。 On the other hand, in order to cope with recent highly complicated mounting methods, the epoxy resin composition for sealing is required to have further solder crack resistance, and in order to achieve these, a filler is used. Therefore, sufficient consideration must be given to the fluidity of the composition capable of realizing a high blending ratio and the low hygroscopicity after curing.
これらの要求を満足させるために、低溶融粘度であるテトラメチルビフェノール型エポキシ樹脂と非極性の置換基を有するフェノールアラルキル樹脂などのフェノール樹脂からなる組成物を用い、流動性の確保と低吸湿性を両立させる技術（特許文献６）、吸湿性を改善するために嵩高い置換基を有するジシクロペンタジエンフェノールを原料とするエポキシ樹脂を主成分に用いる技術（特許文献７）など、種々の検討が提案されている。しかし、どの提案も環境に配慮した提案とは言えず、難燃剤としてハロゲン化合物やアンチモン化合物を用いないと十分な難燃性を達成できない。
本発明は、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加すること無しに、優れた難燃性を有するとともに、低粘度であるため流動性に優れ、低吸湿性であるために耐ハンダクラック性に優れた硬化物を与える半導体封止用エポキシ樹脂組成物及びそれを用いて半導体素子を封止した半導体装置を提供しようとするものである。 The present invention has excellent flame retardancy without adding a halogen compound or antimony compound as a flame retardant imparting component, and also has excellent fluidity due to low viscosity and solder crack resistance due to low moisture absorption. It is an object of the present invention to provide an epoxy resin composition for encapsulating a semiconductor that provides a cured product having excellent properties and a semiconductor device in which a semiconductor element is encapsulated using the epoxy resin composition.
本発明者等は、前記の課題を解決するために鋭意研究を重ねた結果、特定のエポキシ樹脂を配合した封止用エポキシ樹脂組成物により、上記の目的を達成することができることを見出し、本発明を完成するに至った。
すなわち、本発明は、以下の各発明を包含する。
As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by an epoxy resin composition for sealing containing a specific epoxy resin. The invention has been completed.
That is, the present invention includes the following inventions.
（１）(a) 下記組成のエポキシ樹脂
(a-1)一般式（１）で表されるエポキシ樹脂５〜１００質量％
(a-2) (a-1)以外のエポキシ樹脂０〜９５質量％
(b) １分子中に２個以上のフェノール性水酸基をもつフェノール性硬化剤
(c) 無機充填剤
(d) 硬化促進剤
を必須成分とする半導体封止用エポキシ樹脂組成物。
(1) (a) Epoxy resin with the following composition
(a-1) 5 to 100% by mass of the epoxy resin represented by the general formula (1)
(a-2) Epoxy resin other than (a-1) 0 to 95% by mass
(b) A phenolic curing agent having two or more phenolic hydroxyl groups in one molecule
(c) Inorganic filler
(d) An epoxy resin composition for semiconductor encapsulation containing a curing accelerator as an essential component.
（２）前記（a-1）エポキシ樹脂が、前記一般式（１）においてＲ1〜Ｒ10が水素原子、又はＲ3，Ｒ4がメチル基かつ他のＲが水素原子である、エポキシ樹脂であることを特徴とする、（１）項記載の半導体封止用エポキシ樹脂組成物。 (2) The epoxy resin (a-1) is an epoxy resin in which R 1 to R 10 are hydrogen atoms, or R 3 and R 4 are methyl groups and the other R is a hydrogen atom in the general formula (1). The epoxy resin composition for semiconductor encapsulation according to item (1), wherein
（３）前記(b)フェノール性硬化剤が、フェノールノボラック樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂、ナフトールアラルキル樹脂から選ばれた少なくとも一種類のフェノール樹脂である（１）項又は（２）項のいずれか１項に記載の半導体封止用エポキシ樹脂組成物。 (3) The item (1) or (2), wherein the (b) phenolic curing agent is at least one phenol resin selected from a phenol novolak resin, a phenol aralkyl resin, a naphthol novolak resin, and a naphthol aralkyl resin. The epoxy resin composition for semiconductor encapsulation according to any one of the above.
（４）前記(c)無機充填剤として、組成物全体の６０〜９５質量％の破砕型及び／又は球状の、溶融及び／又は結晶シリカ粉末充填剤を配合することを特徴とする（１）項〜（３）項のいずれか１項に記載の半導体封止用エポキシ樹脂組成物。 (4) The above-mentioned (c) inorganic filler is blended with 60 to 95% by mass of the crushed mold and / or spherical fused and / or crystalline silica powder filler (1) Item 3. An epoxy resin composition for sealing a semiconductor according to any one of Items 3 to 3.
（５）前記（a）〜（d）を必須成分とし、難燃付与成分としてハロゲン化合物及び／又はアンチモン化合物を含まず、かつその硬化物がＵＬ−９４規格のＶ−０を満足する難燃性を有することを特徴とする（１）項〜（４）項のいずれか１項に記載の半導体封止用エポキシ樹脂組成物。 (5) Flame retardant comprising (a) to (d) as essential components, containing no halogen compound and / or antimony compound as a flame retardant imparting component, and a cured product satisfying V-0 of UL-94 standard The epoxy resin composition for semiconductor encapsulation according to any one of the items (1) to (4), which has a property.
（６）前記（a）と（b）の当量混合物の１５０℃における溶融粘度が、コーンプレート型回転粘度計で測定した値で１０〜２００ｍＰａ・ｓである、（１）項〜（５）項のいずれか１項に記載の半導体封止用エポキシ樹脂組成物。 (6) Item (1) to Item (5), wherein the melt viscosity at 150 ° C. of the equivalent mixture of (a) and (b) is 10 to 200 mPa · s as measured by a cone plate type rotational viscometer. The epoxy resin composition for semiconductor encapsulation according to any one of the above.
（７）加熱硬化後の吸湿率が０．１〜０．５％である（１）項〜（６）項のいずれか１項に記載の半導体封止用エポキシ樹脂組成物。
ただし、吸湿率＝〔（８５℃、８５％ＲＨの恒温恒湿槽に７２時間処理後の試験片の質量−処理前の試験片の質量）／（処理前の試験片の質量）〕×１００
(7) The epoxy resin composition for semiconductor encapsulation according to any one of (1) to (6), wherein the moisture absorption after heat curing is 0.1 to 0.5%.
However, moisture absorption rate = [(mass of test piece after treatment for 72 hours in constant temperature and humidity chamber of 85 ° C., 85% RH−mass of test piece before treatment) / (mass of test piece before treatment)] × 100
（８）半導体素子及び／又は半導体集積回路が、（１）項〜（７）項のいずれか１項に記載の半導体封止用エポキシ樹脂組成物の硬化物で封止されている半導体装置。 (8) A semiconductor device in which a semiconductor element and / or a semiconductor integrated circuit are sealed with a cured product of the epoxy resin composition for semiconductor sealing according to any one of (1) to (7).
本発明のエポキシ樹脂組成物は、難燃付与成分としてハロゲン化合物、アンチモン化合物を添加すること無しに、優れた難燃性を有するとともに、低粘度であるため流動性に優れ、低吸湿性であるために耐ハンダクラック性に優れた硬化物を与えるので半導体封止用エポキシ樹脂組成物として有用である。また、これを用いて封止した半導体装置はハロゲン化合物、アンチモン化合物を含まなくても難燃性を保持するので環境配慮型の半導体装置として有用である。 The epoxy resin composition of the present invention has excellent flame retardancy without adding a halogen compound or antimony compound as a flame retardant imparting component, and has excellent fluidity and low hygroscopicity due to its low viscosity. Therefore, it provides a cured product excellent in solder crack resistance, and is useful as an epoxy resin composition for semiconductor encapsulation. In addition, a semiconductor device encapsulated using this is useful as an environmentally friendly semiconductor device because it retains flame retardancy even without containing a halogen compound or an antimony compound.
本発明に用いられる(a-1)エポキシ樹脂の製造については、一般式（２）で表されるジヒドロアントラハイドロキノン化合物とエピハロヒドリンとの反応を公知の方法で行えるが、代表的な製造例を以下に詳述する。 Regarding the production of the (a-1) epoxy resin used in the present invention, the reaction between the dihydroanthrahydroquinone compound represented by the general formula (2) and the epihalohydrin can be carried out by a known method. It will be described in detail.
まず、不活性ガス気流下、ジヒドロアントラハイドロキノン化合物１モル当たり４〜４０モルに相当する量のエピハロヒドリンに溶解させて均一な溶液とする。ついで、その溶液を撹拌しながら、これにジヒドロアントラハイドロキノン化合物１モル当たり１．８〜５モル量のアルカリ金属水酸化物を固体又は水溶液で加えて反応させる。この反応は、常圧下又は減圧下で行わせることができ、反応温度は通常、常圧下の反応の場合は３０〜１２０℃であり、減圧下の反応の場合は３０〜８０℃である。反応は必要に応じて所定の温度を保持しながら反応液を共沸させ、揮発する蒸気を冷却して得られた凝縮液を油／水分離し、水分を除いた油分を反応系へ戻す方法により脱水することができる。アルカリ金属水酸化物の添加は、急激な反応を抑えるために、１〜８時間かけて少量ずつを断続的もしくは連続的に添加する。その全反応時間は通常、１〜１０時間である。なお、反応が終了するまで系内は不活性ガス雰囲気であることが望ましい。反応終了後、不溶性の副生塩を濾別して除くか、水洗により除去した後、未反応のエピハロヒドリンを減圧留去して除くと、目的のエポキシ樹脂が得られる。 First, in an inert gas stream, it is dissolved in an amount of epihalohydrin corresponding to 4 to 40 moles per mole of dihydroanthrahydroquinone compound to obtain a uniform solution. Next, while stirring the solution, an alkali metal hydroxide in an amount of 1.8 to 5 mol per mol of the dihydroanthrahydroquinone compound is added as a solid or an aqueous solution, and reacted. This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is usually 30 to 120 ° C. in the case of reaction under normal pressure and 30 to 80 ° C. in the case of reaction under reduced pressure. In the reaction, the reaction liquid is azeotroped while maintaining a predetermined temperature as required, the condensed liquid obtained by cooling the vaporized vapor is separated into oil / water, and the oil component excluding moisture is returned to the reaction system. Can be dehydrated. Addition of the alkali metal hydroxide is intermittently or continuously added little by little over 1 to 8 hours in order to suppress a rapid reaction. The total reaction time is usually 1 to 10 hours. In addition, it is desirable that the inside of the system is an inert gas atmosphere until the reaction is completed. After completion of the reaction, the insoluble by-product salt is removed by filtration or removed by washing with water, and then the unreacted epihalohydrin is removed by distillation under reduced pressure to obtain the desired epoxy resin.
この反応におけるエピハロヒドリンとしては、通常、エピクロルヒドリン又はエピブロモヒドリンが用いられる。アルカリ金属水酸化物としては、通常、水酸化ナトリウム又は水酸化カリウムが用いられる。また、不活性ガスとしては、通常、窒素、アルゴンが用いられる。 As epihalohydrin in this reaction, epichlorohydrin or epibromohydrin is usually used. As the alkali metal hydroxide, sodium hydroxide or potassium hydroxide is usually used. Moreover, nitrogen and argon are usually used as the inert gas.
また、この反応においては、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムブロミドなどの第四級アンモニウム塩；ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノールなどの第三級アミン；２−エチル−４−メチルイミダゾール、２−フェニルイミダゾールなどのイミダゾール類；エチルトリフェニルホスホニウムアイオダイドなどのホスホニウム塩；トリフェニルホスフィンなどのホスフィン類等の触媒を用いても良い。さらにこの反応においては、エタノール、イソプロパノールなどのアルコール類；アセトン、メチルエチルケトンなどのケトン類；ジオキサン、エチレングリコールジメチルエーテルなどのエーテル類；メトキシプロパノールなどのグリコールエーテル類；ジメチルスルホキシド、ジメチルホルムアミドなどの非プロトン性極性溶媒等の不活性な有機溶媒を使用しても良い。 In this reaction, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; 2-ethyl Catalysts such as imidazoles such as -4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine may be used. Further, in this reaction, alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; aprotic such as dimethyl sulfoxide and dimethylformamide An inert organic solvent such as a polar solvent may be used.
上記のようにして得られたエポキシ樹脂の可鹸化ハロゲン量が多すぎる場合は、再処理して十分に可鹸化ハロゲン量が低下した精製エポキシ樹脂を得ることができる。つまり、その粗製エポキシ樹脂を、２−プロパノール、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、ジオキサン、メトキシプロパノール、ジメチルスルホキシドなどの不活性な有機溶媒に再溶解し、アルカリ金属水酸化物を固体又は水溶液で加えて、約３０〜１２０℃の温度で０．５〜８時間再閉環反応を行った後、水洗等の方法で過剰のアルカリ金属水酸化物や副性塩を除去し、さらに有機溶媒を減圧留去して除くと、精製されたエポキシ樹脂が得られる。 When the amount of saponifiable halogen in the epoxy resin obtained as described above is too large, a purified epoxy resin having a sufficiently reduced amount of saponifiable halogen can be obtained by reprocessing. That is, the crude epoxy resin is redissolved in an inert organic solvent such as 2-propanol, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dioxane, methoxypropanol, dimethyl sulfoxide, and the alkali metal hydroxide is dissolved in a solid or aqueous solution. In addition, after re-ringing reaction at a temperature of about 30 to 120 ° C. for 0.5 to 8 hours, excess alkali metal hydroxide and secondary salts are removed by a method such as washing with water, and an organic solvent is further removed. When removed under reduced pressure, a purified epoxy resin is obtained.
上記一般式（１）において、ｎは０以上の整数であり、この値はエポキシ樹脂の製造時にジヒドロアントラハイドロキノン化合物に対するエピハロヒドリンのモル比で制御することができるが、ｎが０のものが５０％以上含まれることが好ましい。ｎが０のものが５０％より低い場合は溶融粘度の低いエポキシ樹脂が得られず、本発明の特性が十分に発揮されない。ジヒドロアントラハイドロキノン化合物１モルに対するエピハロヒドリンのモル比は、好ましくは４〜４０モル、より好ましくは８〜２０モルである。このモル比が４より低いと、上述のようにｎが０のものが少なくなるのでエポキシ樹脂の溶融粘度が高くなり、４０より高くてもエポキシ樹脂の粘度はそれ以上低くならないばかりか、未反応のエピハロヒドリンの留去に手間がかかり非効率的である。 In the above general formula (1), n is an integer of 0 or more, and this value can be controlled by the molar ratio of epihalohydrin to the dihydroanthrahydroquinone compound during the production of the epoxy resin. It is preferable to be contained above. When n is less than 50%, an epoxy resin having a low melt viscosity cannot be obtained, and the characteristics of the present invention are not sufficiently exhibited. The molar ratio of epihalohydrin to 1 mol of dihydroanthrahydroquinone compound is preferably 4 to 40 mol, more preferably 8 to 20 mol. If this molar ratio is lower than 4, the number of n = 0 is reduced as described above, so that the melt viscosity of the epoxy resin is increased, and even if it is higher than 40, the viscosity of the epoxy resin does not decrease any more and is not reacted. This is inefficient because it takes time to distill off the epihalohydrin.
また、「(a-1)エポキシ樹脂」はあらかじめ調製したジヒドロアントラハイドロキノン化合物のアルカリ金属塩をエピハロヒドリンと反応させて製造することもできる。この場合、ジヒドロアントラハイドロキノン化合物のアルカリ金属塩はそのまま、あるいは、水溶液でエピハロヒドリン中に添加するが、急激な反応を防ぐために、少量づつ分割して系内へ添加することが望ましい。水溶液として供給した場合は、閉環反応を十分に進行させるために、途中で系内の水を除去した後、アルカリ金属水酸化物を固形又は水溶液で添加してエポキシ化率を上げることが望ましい。 The “(a-1) epoxy resin” can also be produced by reacting a previously prepared alkali metal salt of a dihydroanthrahydroquinone compound with epihalohydrin. In this case, the alkali metal salt of the dihydroanthrahydroquinone compound is added to the epihalohydrin as it is or in an aqueous solution, but in order to prevent a rapid reaction, it is desirable to add it into the system in small portions. When supplied as an aqueous solution, it is desirable to increase the epoxidation rate by removing the water in the system on the way and then adding an alkali metal hydroxide as a solid or an aqueous solution in order to sufficiently advance the ring closure reaction.
また、そのジヒドロアントラハイドロキノン化合物のアルカリ金属塩水溶液の濃度は５〜５０質量％、好ましくは１５〜３０質量％である。５質量％より低濃度では、系内に持ち込む水の量が増え、エポキシ化反応の進行を阻害することがある。５０質量％より多いと、水溶液の流動性が低下し、装置の配管を閉塞するなどのおそれがあるのでよくない。また、ジヒドロアントラハイドロキノン化合物のアルカリ金属塩水溶液は、安定化のために、塩を形成させるに必要な当量以上のアルカリ金属水酸化物を含むことができる。この水溶液には、その安定性を損なわないのであれば、他の有機溶媒、例えばアルコール類を添加しても差し支えない。 Moreover, the density | concentration of the alkali metal salt aqueous solution of the dihydroanthrahydroquinone compound is 5-50 mass%, Preferably it is 15-30 mass%. When the concentration is lower than 5% by mass, the amount of water brought into the system increases, which may inhibit the progress of the epoxidation reaction. If it is more than 50% by mass, the fluidity of the aqueous solution is lowered, and there is a possibility that the piping of the apparatus may be clogged. Moreover, the alkali metal salt aqueous solution of a dihydroanthrahydroquinone compound can contain an alkali metal hydroxide in an equivalent amount or more necessary for forming a salt for stabilization. If this aqueous solution does not impair its stability, other organic solvents such as alcohols may be added.
ジヒドロアントラハイドロキノン化合物のアルカリ金属塩あるいはその水溶液を出発物質とする場合も、前記ジヒドロアントラハイドロキノン化合物のエポキシ化反応と同様な各種条件、各種反応触媒、各種有機溶剤及び操作を用いてエポキシ樹脂を得ることができる。また、粗エポキシ樹脂を精製エポキシ樹脂にする場合も、前述の方法が適用できる。 Even when an alkali metal salt of a dihydroanthrahydroquinone compound or an aqueous solution thereof is used as a starting material, an epoxy resin is obtained using various conditions, various reaction catalysts, various organic solvents and operations similar to the epoxidation reaction of the dihydroanthrahydroquinone compound. be able to. The above-described method can also be applied when a crude epoxy resin is used as a purified epoxy resin.
「(a-1)エポキシ樹脂」の原料である、ジヒドロアントラハイドロキノン及びジヒドロアントラハイドロキノンのアルカリ金属塩（又はその水溶液）は公知の方法で製造できる（特開昭５４−１２２２６３号公報）。また、前記一般式（２）においてＲ1〜Ｒ10が水素原子である、１，４−ジヒドロアントラハイドロキノンのジナトリウム塩の水溶液は、すでにパルプ蒸解助剤などの用途に世界で広く使用されているので、これをそのまま使用することもできる。 Dihydroanthrahydroquinone and alkali metal salt of dihydroanthrahydroquinone (or an aqueous solution thereof), which are raw materials of “(a-1) epoxy resin”, can be produced by a known method (Japanese Patent Laid-Open No. Sho 54-122263). In addition, an aqueous solution of disodium salt of 1,4-dihydroanthrahydroquinone in which R 1 to R 10 are hydrogen atoms in the general formula (2) has already been widely used in the world for applications such as pulp cooking aids. This can be used as it is.
また、本発明のエポキシ樹脂組成物の難燃性や低溶融粘度性を考慮すると、一般式（２）においてＲ1〜Ｒ10が水素原子である化合物（１，４−ジヒドロアントラハイドロキノン）又は、Ｒ3、Ｒ4がメチル基かつ他のＲが水素原子である化合物（２，３−ジメチル−１，４−ジヒドロアントラハイドロキノン）を原料とするエポキシ樹脂を用いることが好ましい。これらのエポキシ樹脂を下式（３）及び（４）に示す。なお、各式中、ｎは０以上の整数を示す。 In consideration of the flame retardancy and low melt viscosity of the epoxy resin composition of the present invention, a compound (1,4-dihydroanthrahydroquinone) in which R 1 to R 10 are hydrogen atoms in the general formula (2), or It is preferable to use an epoxy resin made from a compound (2,3-dimethyl-1,4-dihydroanthrahydroquinone) in which R 3 and R 4 are methyl groups and the other R is a hydrogen atom. These epoxy resins are shown in the following formulas (3) and (4). In each formula, n represents an integer of 0 or more.
本発明に用いられる「(a-2) (a-1)エポキシ樹脂以外のエポキシ樹脂」については、「(a-1)エポキシ樹脂」と別に製造した後、「(a-1)エポキシ樹脂」と混合しても良いし、「(a-2) (a-1)エポキシ樹脂以外のエポキシ樹脂」の原料である化合物を「(a-1)エポキシ樹脂」の原料である化合物と混合使用してエピハロヒドリンと反応させ、両エポキシ樹脂化合物の混合エポキシ樹脂として同時に製造しても良い。 For the "(a-2) (a-1) epoxy resin other than the epoxy resin" used in the present invention, after being manufactured separately from the "(a-1) epoxy resin", the "(a-1) epoxy resin" The compound that is the raw material of “(a-2) (a-1) epoxy resin other than epoxy resin” may be mixed with the compound that is the raw material of “(a-1) epoxy resin”. It is possible to react with epihalohydrin to produce a mixed epoxy resin of both epoxy resin compounds at the same time.
「(a-1)エポキシ樹脂」と混合することができる「(a-2) (a-1)エポキシ樹脂以外のエポキシ樹脂」としては、公知のものが使用できるが、具体例としては、多価フェノール類あるいはフェノール樹脂とエピハロヒドリンから製造されるエポキシ樹脂；例えば、ビスフェノールＦ、ビスフェノールＡＤ、ビフェノール、テトラメチルビフェノール、ビス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシフェニル）プロパン、テルペンジフェノール、ハイドロキノン、メチルハイドロキノン、ジブチルハイドロキノン、レゾルシン、メチルレゾルシン、、ビスフェノールＳ、チオジフェノール、ジヒドロキシジフェニルエーテル、ジヒドロキシナフタレン、フェノールノボラック樹脂、オルソ−クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエンフェノール樹脂、テルペンフェノール樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂などの種々の多価フェノール類や、種々のフェノール類と、ベンズアルデヒド、ヒドロキシベンズアルデヒド、クロトンアルデヒド、グリオキザールなどの種々のアルデヒド類との縮合反応で得られるフェノール樹脂等の各種のフェノール化合物及びフェノール変性キシレン樹脂など、とエピハロヒドリンとから製造されるエポキシ樹脂や、アミン化合物とエピハロヒドリンとから製造されるエポキシ樹脂；例えば、ジアミノジフェニルメタン、アミノフェノール、キシレンジアミンなどとエピハロヒドリンとから製造されるエポキシ樹脂、及び、カルボン酸類とエピハロヒドリンとから製造されるエポキシ樹脂；例えば、メチルヘキサヒドロキシフタル酸、ダイマー酸などのアミン化合物とエピハロヒドリンとから製造されるエポキシ樹脂などが挙げられ、これらは２種以上併用しても良い。 As “(a-2) (a-1) epoxy resin other than epoxy resin” that can be mixed with “(a-1) epoxy resin”, known ones can be used. Epoxy resins produced from polyhydric phenols or phenol resins and epihalohydrins; for example, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, terpene diphenol , Hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, bisphenol S, thiodiphenol, dihydroxydiphenyl ether, dihydroxynaphthalene, phenol novolac resin, ortho-cresol novolac resin, bisphenol Various polyphenols such as novolak resin, dicyclopentadiene phenol resin, terpene phenol resin, phenol aralkyl resin, naphthol novolak resin, various phenols, and various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal Epoxy resins produced from various phenolic compounds such as phenolic resins obtained by condensation reactions with phenols and phenol-modified xylene resins, and epihalohydrins, and epoxy resins produced from amine compounds and epihalohydrins; for example, diaminodiphenylmethane , Epoxy resin produced from aminophenol, xylenediamine, etc. and epihalohydrin, and epoxy resin produced from carboxylic acid and epihalohydrin. Poxy resin; for example, an epoxy resin produced from an amine compound such as methylhexahydroxyphthalic acid or dimer acid and epihalohydrin may be used, and these may be used in combination of two or more.
本発明に用いられる「(a-1)エポキシ樹脂」と「(a-2) (a-1)以外のエポキシ樹脂」の混合割合は「(a-1)エポキシ樹脂」５質量％以上１００質量％以下に対して、「(a-2) (a-1)以外のエポキシ樹脂」０質量％以上９５質量％以下であり、好ましくは「(a-1)エポキシ樹脂」１５質量％以上１００質量％以下に対して、(a-1)以外のエポキシ樹脂０質量％以上８５質量％以下であり、より好ましくは(a-1)エポキシ樹脂４０質量％以上１００質量％以下に対して、「(a-2) (a-1)以外のエポキシ樹脂」０質量％以上６０質量％以下である。「(a-1)エポキシ樹脂」の混合割合が少なすぎると、本発明のエポキシ樹脂組成物に十分な性能を付与することができない。 The mixing ratio of “(a-1) epoxy resin” and “(a-2) epoxy resin other than (a-1)” used in the present invention is “(a-1) epoxy resin” 5 mass% to 100 mass. % Of epoxy resin other than (a-2) (a-1) ”is 0% by mass to 95% by mass, preferably“ (a-1) epoxy resin ”is 15% by mass to 100% by mass. % Of epoxy resin other than (a-1) is 0% by mass or more and 85% by mass or less, and more preferably (a-1) epoxy resin is 40% by mass or more and 100% by mass or less. a-2) Epoxy resin other than (a-1) ”is 0 to 60% by mass. If the mixing ratio of “(a-1) epoxy resin” is too small, sufficient performance cannot be imparted to the epoxy resin composition of the present invention.
本発明の半導体封止用エポキシ樹脂組成物において必須成分として使用される「(b)１分子中に２個以上のフェノール性水酸基を持つフェノール性硬化剤」としては公知のものが使用できる。具体例としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、チオジフェノール、ハイドロキノン、レゾルシン、ビフェノール、テトラメチルビフェノール、ジヒドロキシナフタレン、ジヒドロキシジフェニルエーテル、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、ナフトールノボラック樹脂などの種々の多価フェノール類や、種々のフェノール類とベンズアルデヒド、ヒドロキシベンズアルデヒド、クロトンアルデヒド、グリオキザールなどの種々のアルデヒド類との縮合反応で得られる多価フェノール樹脂等の各種のフェノール樹脂類、フェノールアラルキル樹脂、フェノールテルペン樹脂、ジシクロペンタジエンフェノール樹脂、重質油類又はピッチ類とフェノール類とアルデヒド化合物とを重縮合反応させて得られた変性フェノール樹脂等が挙げられる。 As the “(b) phenolic curing agent having two or more phenolic hydroxyl groups in one molecule” used as an essential component in the epoxy resin composition for semiconductor encapsulation of the present invention, known ones can be used. Specific examples include bisphenol A, bisphenol F, bisphenol S, thiodiphenol, hydroquinone, resorcin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, phenol novolac resin, cresol novolac resin, bisphenol A novolak resin, naphthol novolak resin. Various phenolic resins such as polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal, phenol Aralkyl resins, phenol terpene resins, dicyclopentadiene phenol resins, heavy oils or pitches and phenols Modified phenol resins obtained an aldehyde compound by polycondensation reaction.
組成物の硬化後の低吸湿性や難燃性などの観点から、上記フェノール性硬化剤のなかで、フェノールノボラック樹脂〔例えば、下式（５）〕、フェノールアラルキル樹脂〔例えば、下式（６）及び（７）〕、ナフトールノボラック樹脂〔例えば、下式（８）〕及びナフトールアラルキル樹脂〔例えば、下式（９）〕が特に好ましい。なお、各式中、ｎは０以上の整数を示す。 From the viewpoint of low hygroscopicity and flame retardancy after curing of the composition, among the phenolic curing agents, phenol novolac resins [for example, the following formula (5)], phenol aralkyl resins [for example, the following formula (6) ) And (7)], naphthol novolak resins [for example, the following formula (8)] and naphthol aralkyl resins [for example, the following formula (9)] are particularly preferable. In each formula, n represents an integer of 0 or more.
これらの「(b)フェノール性硬化剤」は、１種単独でも、２種以上併用しても良い。これらの各種フェノール性硬化剤は市販品として入手でき、フェノールアラルキル樹脂としては、例えば、明和化成社製ＭＥＨ７８００〔式（６）に相当する〕などや明和化成社製ＭＥＨ７８５１〔式（７）に相当する〕などが、ナフトールノボラック樹脂としては、例えば、群栄化学社製ＮＣ−３０〔式（８）に相当する〕などが、ナフトールアラルキル樹脂としては、例えば、明和化成社製ＭＥＨ７８１０〔式（９）に相当する〕などが挙げられる。 These “(b) phenolic curing agents” may be used alone or in combination of two or more. These various phenolic curing agents are available as commercial products, and examples of the phenol aralkyl resin include MEH7800 manufactured by Meiwa Kasei Co., Ltd. [corresponding to formula (6)] and MEH7851 manufactured by Meiwa Kasei Co., Ltd. [corresponding to formula (7). As the naphthol novolak resin, for example, NC-30 manufactured by Gunei Chemical Co., Ltd. (corresponding to the formula (8)) and the like, as the naphthol aralkyl resin, for example, Mehka Kasei Co., Ltd. MEH7810 [formula (9 And the like)].
本発明の半導体用エポキシ樹脂組成物には、「(b)フェノール性硬化剤」以外の硬化剤を混合使用することができる。その混合使用することのできる硬化剤としてはメチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水ピロメリット酸、メチルナジック酸等の酸無水物類、ジエチレントリアミン、イソホロンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジシアンジアミド等のアミン類及び、前記「(b)フェノール性硬化剤」の具体例として挙げた各種のフェノール化合物のフェノール性水酸基の全部もしくは一部をベンゾエート化あるいはアセテート化などのエステル化することによって得られる活性エステル化合物、などが挙げられる。 In the epoxy resin composition for semiconductors of the present invention, a curing agent other than “(b) phenolic curing agent” can be mixed and used. Curing agents that can be used in combination are methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, acid anhydrides such as methyl nadic acid, diethylenetriamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide. And all or part of the phenolic hydroxyl groups of the various phenol compounds mentioned as specific examples of the “(b) phenolic curing agent” can be obtained by esterification such as benzoate or acetate. Active ester compounds, and the like.
これら硬化剤の各成分は、あらかじめ混合して混合硬化剤を調製してから使用しても良いし、エポキシ樹脂組成物の製造時に各種の成分を混合する際にエポキシ樹脂用硬化剤の各成分をそれぞれ別々に添加して同時に混合しても良い。使用される硬化剤の使用量は、全エポキシ樹脂成分中のエポキシ基１モルに対して、全硬化剤中のエポキシ基と反応する基が０.５〜２.０モルになる量が好ましく、より好ましくは０.７〜１.２モルである。 Each component of these curing agents may be used after mixing in advance to prepare a mixed curing agent, or each component of the curing agent for epoxy resin when mixing various components during the production of the epoxy resin composition May be added separately and mixed at the same time. The amount of the curing agent used is preferably such that the group reacting with the epoxy group in the total curing agent is 0.5 to 2.0 mol with respect to 1 mol of the epoxy group in the total epoxy resin component, More preferably, it is 0.7-1.2 mol.
本発明の半導体封止用エポキシ樹脂組成物には、「(c)無機充填剤」が配合される。その無機充填剤の種類としては、例えば、溶融シリカ、結晶性シリカ、ガラス粉、アルミナ、炭酸カルシウムなどが挙げられる。その形状としては、破砕型又は球状である。各種の無機充填剤は、単独で又は、２種以上混合して用いられるが、それらの中では溶融シリカ又は結晶性シリカが好ましい。その使用量は、組成物全体の６０〜９５質量％である。 “(C) Inorganic filler” is blended in the epoxy resin composition for semiconductor encapsulation of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, and calcium carbonate. The shape is crushing or spherical. Various inorganic fillers may be used alone or in combination of two or more. Among them, fused silica or crystalline silica is preferable. The usage-amount is 60-95 mass% of the whole composition.
「(c)無機充填剤」の使用量が少なすぎると、吸湿性が大きくなり、耐ハンダクラック性に悪影響を及ぼす。「(c)無機充填剤」の使用量が多すぎると、成形時の流動性が損なわれる。 When the amount of “(c) inorganic filler” used is too small, the hygroscopicity is increased and the solder crack resistance is adversely affected. If the amount of “(c) inorganic filler” used is too large, fluidity during molding is impaired.
本発明の半導体用エポキシ樹脂組成物に用いられる「(d)硬化促進剤」は、エポキシ樹脂中のエポキシ基とフェノール性硬化剤中の水酸基との硬化反応を促進する化合物である。その具体例としては、トリブチルホスフィン、トリフェニルホスフィン、トリス(ジメトキシフェニル)ホスフィン、トリス(ヒドロキシプロピル)ホスフィン、トリス(シアノエチル)ホスフィンなどのホスフィン化合物、テトラフェニルホスホニウムテトラフェニルボレート、メチルトリブチルホスホニウムテトラフェニルボレート、メチルトリシアノエチルホスホニウムテトラフェニルボレートなどのホスホニウム塩、２−メチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、１−シアノエチル−２−メチルイミダゾール、２,４−ジシアノ−６−[２−メチルイミダゾリル−(１)]−エチル−Ｓ−トリアジン、２,４−ジシアノ−６−[２−ウンデシルイミダゾリル-(１)]−エチル−Ｓ−トリアジンなどのイミダゾール類、１−シアノエチル−２−ウンデシルイミダゾリウムトリメリテート、２−メチルイミダゾリウムイソシアヌレート、２−エチル−４−メチルイミダゾリウムテトラフェニルボレート、２−エチル-１,４-ジメチルイミダゾリウムテトラフェニルボレートなどのイミダゾリウム塩、２,４,６−トリス(ジメチルアミノメチル)フェノール、ベンジルジメチルアミン、テトラメチルブチルグアニジン、Ｎ−メチルピペラジン、２−ジメチルアミノ−１−ピロリンなどのアミン類、トリエチルアンモニウムテトラフェニルボレートなどのアンモニウム塩、１,５−ジアザビシクロ(５,５,０)−７−ウンデセン、１,５−ジアザビシクロ(４,３,０)−５−ノネン、１,４−ジアザビシクロ(２,２,２)−オクタンなどのジアザビシクロ化合物、それらジアザビシクロ化合物のテトラフェニルボレート、フェノール塩、フェノールノボラック塩、２−エチルヘキサン酸塩などが挙げられる。 The “(d) curing accelerator” used in the epoxy resin composition for semiconductors of the present invention is a compound that accelerates the curing reaction between the epoxy group in the epoxy resin and the hydroxyl group in the phenolic curing agent. Specific examples thereof include phosphine compounds such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate. Phosphonium salts such as methyltricyanoethylphosphonium tetraphenylborate, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4 -Dicyano-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-dicyano-6- [2-undecylimidazolyl- (1)]-ethyl Imidazoles such as S-triazine, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-ethyl-4-methylimidazolium tetraphenylborate, 2-ethyl-1,4 -Imidazolium salts such as dimethylimidazolium tetraphenylborate, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, tetramethylbutylguanidine, N-methylpiperazine, 2-dimethylamino-1-pyrroline, etc. Amines, ammonium salts such as triethylammonium tetraphenylborate, 1,5-diazabicyclo (5,5,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, 1, Diaza such as 4-diazabicyclo (2,2,2) -octane Cyclo compound, tetraphenylborate thereof diazabicyclo compounds, phenol salts, phenol novolak salts and 2-ethylhexanoic acid salts.
それらの硬化促進剤となる化合物の中では、三級アミン類、ホスフィン化合物、イミダゾール化合物、ジアザビシクロ化合物、及びそれらの塩が好ましい。それらの硬化促進剤は、単独で又は、２種以上混合して用いられ、その使用量は、本発明の組成物の全エポキシ樹脂に対して、０.１〜７質量％であり、好ましくは０．５〜５質量％であり、より好ましくは０．５〜３質量％である。硬化促進剤は組成物の硬化性や保存安定性に大きく影響することがあるので、その使う種類や使用量を、本発明の特性を損なわないように、調整することができる。 Among these compounds serving as curing accelerators, tertiary amines, phosphine compounds, imidazole compounds, diazabicyclo compounds, and salts thereof are preferable. These curing accelerators are used alone or in combination of two or more, and the amount used is 0.1 to 7% by mass with respect to the total epoxy resin of the composition of the present invention, preferably It is 0.5-5 mass%, More preferably, it is 0.5-3 mass%. Since the curing accelerator may greatly affect the curability and storage stability of the composition, the type and amount used thereof can be adjusted so as not to impair the characteristics of the present invention.
本発明の半導体封止用エポキシ樹脂組成物には、必要に応じてカップリング剤、カーボンブラック、着色剤、難燃剤、難燃助剤、離型剤、イオン補足剤、応力緩和剤等を本発明の組成物の特性を損なわない程度に適宜に配合することができる。それらの使用量は適用される半導体装置の種類により変更することができるが、一般的には全組成物に対してそれぞれ０．０１〜３質量％である。 The epoxy resin composition for semiconductor encapsulation of the present invention contains a coupling agent, carbon black, a colorant, a flame retardant, a flame retardant aid, a mold release agent, an ion scavenger, a stress relieving agent, etc. as necessary. It can mix | blend suitably to such an extent that the characteristic of the composition of invention is not impaired. Although the amount of use can be changed depending on the type of semiconductor device to be applied, it is generally 0.01 to 3% by mass with respect to the total composition.
このうち難燃剤としては、臭素化エポキシ樹脂、臭素化フェノール樹脂などのハロゲン系難燃剤、三酸化アンチモンなどのアンチモン化合物、赤リン、表面被覆化赤リン、リン酸エステル類、ホスフィン類などのリン系難燃剤、メラミン誘導体などの窒素系難燃剤及び水酸化アルミニウム、水酸化マグネシウムなどの無機系難燃剤、ホスファゼン難燃剤及び特殊シリコーン難燃剤などが挙げられる。 Of these, flame retardants include halogenated flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, red phosphorus, surface-coated red phosphorus, phosphate esters, phosphines and other phosphorus compounds. And flame retardants, nitrogen flame retardants such as melamine derivatives, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, phosphazene flame retardants and special silicone flame retardants.
しかしながら、本発明の半導体封止用エポキシ樹脂組成物の硬化物は難燃性に優れるため、上記のうち、特に環境安全性が危惧されている臭素化エポキシ樹脂、臭素化フェノール樹脂などのハロゲン系難燃剤、三酸化アンチモンなどのアンチモン化合物について、これらの難燃剤を配合する必要がないか、少量にすることができる。ただし、組成物中の各成分の種類や配合量により難燃性は変化するので、ＵＬ−９４規格のＶ−０あるいはそれに準じた難燃性を確保できるよう各成分の選択や配合量の調整をする必要がある。 However, since the cured product of the epoxy resin composition for semiconductor encapsulation of the present invention is excellent in flame retardancy, among the above, halogen-based ones such as brominated epoxy resins and brominated phenol resins which are particularly concerned about environmental safety About antimony compounds, such as a flame retardant and antimony trioxide, these flame retardants do not need to be mix | blended or can be made small. However, since flame retardancy varies depending on the type and blending amount of each component in the composition, selection of each component and adjustment of blending amount so as to ensure flame retardancy according to UL-94 V-0 or equivalent. It is necessary to do.
本発明の半導体封止用エポキシ樹脂組成物において用いられる「(a)エポキシ樹脂」と「（b）フェノール性硬化剤」の当量混合物の１５０℃における溶融粘度は、エポキシ樹脂組成物の流動性を考慮すると１０〜２００ｍＰａ・ｓ、好ましくは２０〜１２０ｍＰａ・ｓになるように「(a)エポキシ樹脂」と「（b）フェノール性硬化剤」の組み合わせを考える必要がある。溶融粘度が１０ｍＰａ・ｓより低いと、ボイド不良（成形の際、組成物が金型内で乱流を起こし空気を巻き込んだまま硬化物になる現象）が頻発するため良くない。溶融粘度が２００ｍＰａ・ｓより高いと半導体チップずれやワイヤー流れなどの不良が起きやすいので良くない。〔ここに、溶融粘度の測定は、コーンプレート型回転粘度計（例えば、マイセック社 ＣＶ−１Ｄ）を用い、プレート温：１５０℃、コーン：５ポアズ、回転数：７５０ｒｐｍ、サンプル量０．５ｇである。〕 The melt viscosity at 150 ° C. of the equivalent mixture of “(a) epoxy resin” and “(b) phenolic curing agent” used in the epoxy resin composition for semiconductor encapsulation of the present invention is the fluidity of the epoxy resin composition. In consideration, it is necessary to consider a combination of “(a) epoxy resin” and “(b) phenolic curing agent” so as to be 10 to 200 mPa · s, preferably 20 to 120 mPa · s. If the melt viscosity is lower than 10 mPa · s, void defects (a phenomenon in which the composition causes a turbulent flow in the mold and becomes a cured product while entraining air during molding) are not good. If the melt viscosity is higher than 200 mPa · s, defects such as semiconductor chip displacement and wire flow are likely to occur, which is not good. [Here, the melt viscosity is measured using a cone plate type rotational viscometer (for example, Mysek CV-1D), plate temperature: 150 ° C., cone: 5 poise, rotation speed: 750 rpm, sample amount 0.5 g. is there. ]
本発明の半導体封止用エポキシ樹脂組成物は、その加熱硬化後の硬化物の吸湿率が０．１％〜０．５％である。一般に、本用途においては吸湿率は低い程よいとされるが、０．１％より低くするには、無機充填剤の含量を極端に多くする必要があり、このような組成物の製造は現実的には不可能である。０．５％より高い場合はハンダクラックによる不良が頻発するため半導体封止の用途には不適である。本発明の半導体封止用エポキシ樹脂組成物は吸湿しにくい特性をもっているが、組成物中の各成分の種類や配合量及び必須成分以外の各種添加剤により変化するので、吸湿率が０．５％を越えないよう各成分の選択や配合量の調整をする必要がある。吸湿率は下式によって求められる。
吸湿率＝〔（８５℃、８５％ＲＨの恒温恒湿槽に７２時間処理後の試験片の質量−処理前の試験片の質量）／処理前の試験片の質量〕×１００
In the epoxy resin composition for semiconductor encapsulation of the present invention, the moisture absorption rate of the cured product after heat curing is 0.1% to 0.5%. In general, it is said that the lower the moisture absorption rate in this application, the better. However, in order to make it lower than 0.1%, it is necessary to extremely increase the content of the inorganic filler, and the production of such a composition is realistic. Is impossible. If it is higher than 0.5%, defects due to solder cracks frequently occur, so that it is unsuitable for semiconductor sealing applications. Although the epoxy resin composition for semiconductor encapsulation of the present invention has a characteristic that it is difficult to absorb moisture, the moisture absorption rate is 0.5 because it varies depending on the type and amount of each component in the composition and various additives other than essential components. It is necessary to select each component and adjust the amount so that it does not exceed%. The moisture absorption rate is obtained by the following equation.
Moisture absorption rate = [(mass of test piece after treatment for 72 hours in 85 ° C., 85% RH constant humidity−mass of test piece before treatment) / mass of test piece before treatment] × 100
本発明の半導体封止用エポキシ樹脂組成物は、必須成分及びその他の任意成分を均一に分散混合できるものであれば、その混合の方法に特に指定はないが、一般的な方法として、所定の配合量の成分をミキサー等により十分混合した後、ミキシングロールやニーダーにより、必要に応じて加熱しながら溶融混合させたものを冷却固化し粉砕する方法が挙げられる。粉砕後の組成物は成形条件に合うような大きさ及び重さで打錠機などを用いてタブレットとすることもできる。 The epoxy resin composition for semiconductor encapsulation of the present invention is not particularly specified as a mixing method as long as it can uniformly disperse and mix essential components and other optional components. There is a method in which the components of the blending amount are sufficiently mixed by a mixer or the like, and then the mixture which is melt-mixed while being heated with a mixing roll or a kneader as necessary is cooled and solidified and pulverized. The composition after pulverization can be made into a tablet with a size and weight suitable for molding conditions using a tableting machine.
本発明の半導体封止用エポキシ樹脂組成物は、常温以下で固形であり、ブロッキング性が低いなど取扱性が良好であるので、粉砕性やタブレット化性も良好である。 Since the epoxy resin composition for semiconductor encapsulation of the present invention is solid at room temperature or lower and has good handling properties such as low blocking properties, the grindability and tabletability are also good.
本発明の半導体封止装置は、上述の組成物を用いて半導体チップを封止することで製造できる。封止を行う半導体チップとしては、例えば、集積回路、大規模集積回路、トランジスタ、サイリスタ、ダイオード等で特に限定されるものではなく、半導体パッケージの形態も特に限定されない。封止の一般的な方法としては、低圧トランスファー成形法が挙げられるが、射出成形、圧縮成形、注型、ポッティング等により封止することもできる。トランスファー成形などの方法で封止された半導体装置は、そのまま、あるいは８０〜２００℃の温度で１５秒〜１０時間かけて完全硬化させた後、電子機器等に搭載される。 The semiconductor sealing device of this invention can be manufactured by sealing a semiconductor chip using the above-mentioned composition. The semiconductor chip for sealing is not particularly limited, for example, with an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, or the like, and the form of the semiconductor package is not particularly limited. As a general method of sealing, a low-pressure transfer molding method can be mentioned, but sealing can also be performed by injection molding, compression molding, casting, potting or the like. A semiconductor device sealed by a transfer molding method or the like is mounted on an electronic device or the like as it is or after being completely cured at a temperature of 80 to 200 ° C. for 15 seconds to 10 hours.
以上述べたように、本発明の半導体封止用エポキシ樹脂組成物及びそれを用いて封止した半導体装置は、環境上配慮すべきハロゲン化合物やアンチモン化合物を配合しなくても難燃性に優れ、また耐ハンダクラック性にも優れる。 As described above, the epoxy resin composition for semiconductor encapsulation of the present invention and the semiconductor device encapsulated using the same are excellent in flame retardancy even without blending environmentally-friendly halogen compounds and antimony compounds. Also, it has excellent solder crack resistance.
以下に、本発明で使用されるジヒドロアントラセン型エポキシ樹脂の製造例、本発明のエポキシ樹脂組成物の実施例及び比較例を挙げてさらに詳述する。 Below, the manufacture example of the dihydroanthracene type epoxy resin used by this invention, the Example of the epoxy resin composition of this invention, and a comparative example are given and explained in full detail.
＜エポキシ樹脂の製造＞
製造例１： 撹拌装置、還流冷却管及び温度計を備えた容量３Ｌの４つ口フラスコにエピクロルヒドリン１０５０ｇ、２−プロパノール４１０ｇを仕込み、系内を減圧窒素置換した。これに、窒素雰囲気下、１，４−ジヒドロアントラハイドロキノン２００ｇを加え４０℃に昇温して均一に溶解させた後、４８．５質量％の水酸化ナトリウム水溶液１８０ｇを９０分かけて滴下した。その間に徐々に昇温し、滴下終了後には系内が６５℃になるようにした。その後、６５℃で３０分保持し反応を完了させ、水洗により副生塩及び過剰の水酸化ナトリウムを除去した。ついで、生成物から減圧下で過剰のエピクロルヒドリンと２−プロパノールを留去して、粗製エポキシ樹脂混合物を得た。
<Manufacture of epoxy resin>
Production Example 1: 1050 g of epichlorohydrin and 410 g of 2-propanol were charged into a 3 L four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, and the system was purged with nitrogen under reduced pressure. To this, 200 g of 1,4-dihydroanthrahydroquinone was added in a nitrogen atmosphere, and the mixture was heated to 40 ° C. and dissolved uniformly. Then, 180 g of a 48.5 mass% sodium hydroxide aqueous solution was added dropwise over 90 minutes. During this time, the temperature was gradually raised, and the temperature inside the system was adjusted to 65 ° C. after the dropping was completed. Thereafter, the reaction was completed by maintaining at 65 ° C. for 30 minutes, and by-product salt and excess sodium hydroxide were removed by washing with water. Subsequently, excess epichlorohydrin and 2-propanol were distilled off from the product under reduced pressure to obtain a crude epoxy resin mixture.
この粗製エポキシ樹脂混合物をメチルイソブチルケトン４６０ｇに溶解させ、４８．５質量％の水酸化ナトリウム水溶液７ｇを加え、６５℃の温度で１時間反応させた。その後、反応液に第一リン酸水素ナトリウム水溶液を加えて、過剰の水酸化ナトリウムを中和し、水洗して副生塩を除去した。なお、水洗時は液温が６５〜９０℃になるように温度制御した。次いで、加温減圧下でメチルイソブチルケトンを完全に除去したのち、溶融状態の樹脂状物をバットに抜き出し、ガラス棒で十数回撹拌したのち、室温下にて自然冷却させた。約２時間後には全体が結晶固化しており、これを取り出し、黄色結晶状エポキシ化合物２８５ｇを得た。得られたエポキシ化合物〔前記式（３）で示される〕のエポキシ当量１７６ｇ／ｅｑ、加水分解性塩素４５０ｐｐｍ、１５０℃における溶融粘度は１６ｍＰａ・ｓ、ＤＳＣ測定による融点は１０４℃であり、ＧＰＣ測定より式（３）中のｎの平均値が０．１であった。 This crude epoxy resin mixture was dissolved in 460 g of methyl isobutyl ketone, 7 g of a 48.5 mass% sodium hydroxide aqueous solution was added, and the mixture was reacted at a temperature of 65 ° C. for 1 hour. Thereafter, an aqueous sodium hydrogen phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide, followed by washing with water to remove by-product salts. The temperature was controlled so that the liquid temperature was 65 to 90 ° C. during washing with water. Subsequently, after methyl isobutyl ketone was completely removed under heating and reduced pressure, the resinous material in a molten state was taken out into a vat, stirred with a glass rod ten times, and then naturally cooled at room temperature. About 2 hours later, the whole crystallized and was taken out to obtain 285 g of a yellow crystalline epoxy compound. Epoxy equivalent of the obtained epoxy compound [shown by the above formula (3) is 176 g / eq, hydrolyzable chlorine 450 ppm, melt viscosity at 150 ° C. is 16 mPa · s, melting point by DSC measurement is 104 ° C., GPC measurement Further, the average value of n in the formula (3) was 0.1.
製造例２： 製造例１において１，４−ジヒドロアントラハイドロキノン２００ｇの代わりに１，４−ジヒドロ−２，３−ジメチルアントラハイドロキノン２２５ｇを用い、実施例１と同様の操作を行い、前記式（４）で表されるエポキシ化合物３０６ｇを得た。得られたエポキシ化合物のエポキシ当量１９４ｇ／ｅｑ、加水分解性塩素４３５ｐｐｍ、１５０℃における溶融粘度は１７ｍＰａ・ｓ、ＤＳＣ測定による融点は９４℃であった。ＧＰＣより式（４）中、ｎの平均値が０．１であった。室温において黄色結晶性の固形であり取扱性は良好であった。 Production Example 2: In Production Example 1, 225 g of 1,4-dihydro-2,3-dimethylanthrahydroquinone was used instead of 200 g of 1,4-dihydroanthrahydroquinone, and the same operation as in Example 1 was carried out. The epoxy compound represented by 306 g was obtained. The obtained epoxy compound had an epoxy equivalent of 194 g / eq, hydrolyzable chlorine of 435 ppm, a melt viscosity at 150 ° C. of 17 mPa · s, and a melting point of 94 ° C. by DSC measurement. From GPC, the average value of n in formula (4) was 0.1. At room temperature, it was a yellow crystalline solid and handleability was good.
＜エポキシ樹脂組成物の実施例及び比較例＞
実施例１〜８及び比較例１〜３
エポキシ樹脂として製造例１及び製造例２で製造したエポキシ樹脂、オルソ−クレゾールノボラック型エポキシ樹脂、臭素化エポキシ樹脂、ビフェニル型エポキシ樹脂、硬化剤としてフェノールノボラック樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂、ナフトールアラルキル樹脂を用い、エポキシ樹脂と硬化剤を当量配合し、それぞれ加熱溶融混合したものの１５０℃における溶融粘度を測定し、表１に示した。
<Examples and Comparative Examples of Epoxy Resin Composition>
Examples 1-8 and Comparative Examples 1-3
Epoxy resin produced in Production Example 1 and Production Example 2 as an epoxy resin, ortho-cresol novolak type epoxy resin, brominated epoxy resin, biphenyl type epoxy resin, phenol novolak resin, phenol aralkyl resin, naphthol novolak resin, naphthol as curing agent Table 1 shows the melt viscosity at 150 ° C. of an aralkyl resin using an equivalent amount of an epoxy resin and a curing agent, and heated and melt-mixed.
Ｅ−１ ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコートＹＸ４０００、エポキシ当量：１８６ｇ／ｅｑ）
Ｅ−２ トリフェニルメタン型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコート１０３２Ｈ６０、エポキシ当量：１７０ｇ／ｅｑ）
Ｅ−３ クレゾ−ルノボラック型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコ−ト１８０Ｓ６２、エポキシ当量：２１０ｇ／ｅｑ）
Ｅ−４ 臭素化エポキシ樹脂（日本化薬社商品名 ＢＲＥＮ−Ｓ、エポキシ当量：３８５ｇ／ｅｑ、臭素含量：４８％）
Ｐ−１ フェノ−ルノボラック樹脂（群栄化学社商品名 レヂトップＰＳＭ４２６１、水酸基当量：１０３ｇ／ｅｑ、軟化点：８５℃）
Ｐ−２ フェノ−ルアラルキル樹脂（明和化成社商品名 ＭＥＨ−７８００Ｓ、水酸基当量：１７５ｇ／ｅｑ、軟化点：７５℃）
Ｐ−３ フェノ−ルアラルキル樹脂（明和化成社商品名 ＭＥＨ−７８５１、水酸基当量：１９８ｇ／ｅｑ、軟化点：７３℃）
Ｐ−４ ナフトールノボラック樹脂（群栄化学社商品名 ＮＣ−３０、水酸基当量：１２６ｇ／ｅｑ、軟化点８３℃）
Ｐ−５ ナフトールアラルキル樹脂（明和化成社商品名 ＭＥＨ−７８１０、水酸基当量：２１０ｇ／ｅｑ、軟化点：８６℃）
＊測定条件
コーン・プレート型粘度計（マイセック社製、ＣＶ−１Ｄ）
プレート温：１５０℃、回転数：７５０ｒｐｍ、コーン：５ポアズ用
測定手順
１）サンプル０．５ｇをプレートに１分静置し、完全溶融させる。
２）コーンを溶融したサンプルに密着させ、プレート温が１５０℃に安定したら所定の回転数にて回転させ、１０秒後の粘度を測定する。
E-1 Biphenyl type epoxy resin (Japan Epoxy Resin product name Epicoat YX4000, epoxy equivalent: 186 g / eq)
E-2 Triphenylmethane type epoxy resin (Japan Epoxy Resin product name Epicoat 1032H60, epoxy equivalent: 170 g / eq)
E-3 Cresol-novolak-type epoxy resin (trade name of Japan Epoxy Resin, Epicote 180S62, epoxy equivalent: 210 g / eq)
E-4 Brominated epoxy resin (Nippon Kayaku brand name BREN-S, epoxy equivalent: 385 g / eq, bromine content: 48%)
P-1 phenol-novolak resin (Gunei Chemical Co., Ltd. trade name Residtop PSM4261, hydroxyl equivalent: 103 g / eq, softening point: 85 ° C.)
P-2 phenol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH-7800S, hydroxyl equivalent: 175 g / eq, softening point: 75 ° C.)
P-3 phenol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH-7851, hydroxyl equivalent: 198 g / eq, softening point: 73 ° C.)
P-4 Naphthol novolak resin (Gunei Chemical Co., Ltd., trade name NC-30, hydroxyl group equivalent: 126 g / eq, softening point 83 ° C.)
P-5 naphthol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH-7810, hydroxyl group equivalent: 210 g / eq, softening point: 86 ° C.)
* Measurement conditions Cone plate type viscometer (CV-1D, manufactured by MYSEC)
Plate temperature: 150 ° C., rotation speed: 750 rpm, cone: for 5 poise Measurement procedure 1) Place 0.5 g of sample on the plate for 1 minute to completely melt it.
2) The cone is brought into close contact with the melted sample. When the plate temperature is stabilized at 150 ° C., the cone is rotated at a predetermined rotation speed, and the viscosity after 10 seconds is measured.
実施例９〜１６及び比較例４〜６
上記エポキシ樹脂及び硬化剤さらに無機充填剤として溶融シリカ粉末、硬化促進剤としてトリフェニルホスフィン、難燃剤として臭素化フェノールノボラック型エポキシ樹脂、難燃助剤として三酸化アンチモン、離型剤としてカルナバワックス、シランカップリング剤としてエポキシシランを用いて、各半導体封止用エポキシ樹脂組成物を配合した。
各配合物をミキシングロールを用いて７０〜１３０℃の温度で５分間溶融混合し、得られた各溶融混合物をシート状に取り出し、２０〜２５℃で冷却固化した後、粉砕して各成形材料を得た。
これらの各成形材料を用い、低圧トランスファー成形機で金型温度１７５℃、成形時間９０秒で成形して、各試験片及び１６０ピンＴＱＦＰ型樹脂封止半導体装置を得、さらに１７５℃で５時間ポストキュアさせた。
Examples 9-16 and Comparative Examples 4-6
Fused silica powder as an inorganic filler, triphenylphosphine as a curing accelerator, brominated phenol novolac type epoxy resin as a flame retardant, antimony trioxide as a flame retardant, carnauba wax as a release agent, Each epoxy resin composition for semiconductor encapsulation was blended using epoxy silane as the silane coupling agent.
Each compound is melt-mixed at a temperature of 70 to 130 ° C. for 5 minutes using a mixing roll, and the resulting molten mixture is taken out in a sheet form, cooled and solidified at 20 to 25 ° C., and then pulverized to form each molding material. Got.
Using each of these molding materials, molding was performed with a low pressure transfer molding machine at a mold temperature of 175 ° C. and a molding time of 90 seconds to obtain each test piece and a 160-pin TQFP type resin-encapsulated semiconductor device, and further at 175 ° C. for 5 hours. Post-cure.
各成形材料の成形性の指標となる硬化性及び流動性を調べるために、それぞれ、脱型熱時硬度及びスパイラルフローをそれぞれ測定した。また、各成形材料のポストキュア後のガラス転移温度、吸湿率、難燃性を試験した結果を表２に示した。さらに各樹脂封止型半導体装置の吸湿後の耐ハンダクラック性を試験した。それらの結果を表２に示した。 In order to examine the curability and fluidity, which are indicators of moldability of each molding material, the demolding heat hardness and spiral flow were measured, respectively. Table 2 shows the results of testing the glass transition temperature, moisture absorption rate, and flame retardancy of each molding material after post-cure. Furthermore, the solder crack resistance after moisture absorption of each resin-encapsulated semiconductor device was tested. The results are shown in Table 2.
表中の配合量はすべて質量部である。
Ｅ−１ ビフェニル型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコートＹＸ４０００、エポキシ当量：１８６ｇ／ｅｑ）
Ｅ−２ トリフェニルメタン型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコート１０３２Ｈ６０、エポキシ当量：１７０ｇ／ｅｑ）
Ｅ−３ クレゾ−ルノボラック型エポキシ樹脂（ジャパンエポキシレジン社商品名 エピコ−ト１８０Ｓ６２、エポキシ当量：２１０ｇ／ｅｑ）
Ｅ−４ 臭素化エポキシ樹脂（日本化薬社商品名 ＢＲＥＮ−Ｓ、エポキシ当量：３８５ｇ／ｅｑ、臭素含量：４８％）
Ｐ−１ フェノ−ルノボラック樹脂（群栄化学社商品名 レヂトップＰＳＭ４２６１、水酸基当量：１０３ｇ／ｅｑ、軟化点：８５℃）
Ｐ−２ フェノ−ルアラルキル樹脂（明和化成社商品名 ＭＥＨ−７８００Ｓ、水酸基当量：１７５ｇ／ｅｑ、軟化点：７５℃）
Ｐ−３ フェノ−ルアラルキル樹脂（明和化成社商品名 ＭＥＨ−７８５１、水酸基当量：１９８ｇ／ｅｑ、軟化点：７３℃）
Ｐ−４ ナフトールノボラック樹脂（群栄化学社商品名 ＮＣ−３０、水酸基当量：１２６ｇ／ｅｑ、軟化点８３℃）
Ｐ−５ ナフトールアラルキル樹脂（明和化成社商品名 ＭＥＨ７８１０、水酸基当量：２１０ｇ／ｅｑ、軟化点：８６℃）
*１： 球状シリカ粉末
*２： エポキシシラン（信越化学工業社商品名 ＫＢＭ−４０３）
*３： ＡＳＴＭ Ｓｈｏｒｅ Ｄ の値
*４： ８５℃、８５％ＲＨ、７２時間後の吸湿率
*５： ＴＭＡ法
*６： １６０ピンＴＱＦＰ１６個を８５℃、８５％ＲＨにおいて７２時間吸湿後、２６０℃ハンダ浴に１０秒間浸漬し、クラックの発生した個数を求めた。
*７： ＵＬ９４
All the compounding quantities in a table | surface are a mass part.
E-1 Biphenyl type epoxy resin (Japan Epoxy Resin product name Epicoat YX4000, epoxy equivalent: 186 g / eq)
E-2 Triphenylmethane type epoxy resin (Japan Epoxy Resin product name Epicoat 1032H60, epoxy equivalent: 170 g / eq)
E-3 Cresol-novolak-type epoxy resin (trade name of Japan Epoxy Resin, Epicote 180S62, epoxy equivalent: 210 g / eq)
E-4 Brominated epoxy resin (Nippon Kayaku brand name BREN-S, epoxy equivalent: 385 g / eq, bromine content: 48%)
P-1 phenol-novolak resin (Gunei Chemical Co., Ltd. trade name Residtop PSM4261, hydroxyl equivalent: 103 g / eq, softening point: 85 ° C.)
P-2 phenol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH-7800S, hydroxyl equivalent: 175 g / eq, softening point: 75 ° C.)
P-3 phenol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH-7851, hydroxyl equivalent: 198 g / eq, softening point: 73 ° C.)
P-4 Naphthol novolak resin (Gunei Chemical Co., Ltd., trade name NC-30, hydroxyl group equivalent: 126 g / eq, softening point 83 ° C.)
P-5 naphthol aralkyl resin (Maywa Kasei Co., Ltd. trade name MEH7810, hydroxyl equivalent: 210 g / eq, softening point: 86 ° C.)
* 1: Spherical silica powder
* 2: Epoxy silane (trade name KBM-403, Shin-Etsu Chemical Co., Ltd.)
* 3: ASTM Shore D value
* 4: Moisture absorption rate after 85 hours at 85 ° C, 85% RH
* 5: TMA method
* 6: Sixteen 160-pin TQFPs were absorbed for 72 hours at 85 ° C. and 85% RH, and then immersed in a 260 ° C. solder bath for 10 seconds to determine the number of cracks.
* 7: UL94
実施例８〜１６の各組成物は、比較例４〜６の組成物に較べて、難燃剤としてハロゲン化合物（臭素化フェノールノボラック型エポキシ樹脂）及びアンチモン化合物（三酸化アンチモン）を含まなくても難燃性に優れると同時に低粘度で流動性に優れ、吸湿性が低かった。また、それらを用いて封止した半導体装置は耐ハンダクラック性に優れていた。 Each composition of Examples 8-16 does not contain a halogen compound (brominated phenol novolac type epoxy resin) and an antimony compound (antimony trioxide) as a flame retardant compared with the composition of Comparative Examples 4-6. Excellent flame retardancy, low viscosity, excellent fluidity, and low hygroscopicity. Moreover, the semiconductor device sealed using them was excellent in solder crack resistance.
Claims (8)
(a-1) 一般式（１)で表されるエポキシ樹脂５〜１００質量％
(a-2) (a-1)以外のエポキシ樹脂０〜９５質量％
(b) １分子中に２個以上のフェノール性水酸基をもつフェノール性硬化剤
(c) 無機充填剤
(d) 硬化促進剤
を必須成分とする半導体封止用エポキシ樹脂組成物。 (a) Epoxy resin with the following composition
(a-1) 5 to 100% by mass of the epoxy resin represented by the general formula (1)
(a-2) Epoxy resin other than (a-1) 0 to 95% by mass
(b) A phenolic curing agent having two or more phenolic hydroxyl groups in one molecule
(c) Inorganic filler
(d) An epoxy resin composition for semiconductor encapsulation containing a curing accelerator as an essential component.
ただし、吸湿率＝〔（８５℃、８５％ＲＨの恒温恒湿槽に７２時間処理後の試験片の質量−処理前の試験片の質量）／（処理前の試験片の質量）〕×１００ The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 6, wherein the moisture absorption after heat curing is 0.1 to 0.5%.
However, moisture absorption rate = [(mass of test piece after treatment for 72 hours in constant temperature and humidity chamber of 85 ° C., 85% RH−mass of test piece before treatment) / (mass of test piece before treatment)] × 100
A semiconductor device in which a semiconductor element and / or a semiconductor integrated circuit is sealed with a cured product of the epoxy resin composition for sealing a semiconductor according to claim 1.
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| JP2003352233A JP4237600B2 (en) | 2003-10-10 | 2003-10-10 | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
| SG200405609A SG110189A1 (en) | 2003-09-26 | 2004-08-24 | Epoxy compound, preparation method thereof, and use thereof |
| US10/927,617 US7307128B2 (en) | 2003-09-26 | 2004-08-27 | Epoxy compound, preparation method thereof, and use thereof |
| TW093126225A TWI346135B (en) | 2003-09-26 | 2004-08-31 | Epoxy compound, preparation method thereof, and use thereof |
| MYPI20043785A MY138699A (en) | 2003-09-26 | 2004-09-17 | Epoxy compound, preparation method thereof, and use thereof |
| MYPI20084542A MY147157A (en) | 2003-09-26 | 2004-09-17 | Epoxy compound, preparation method thereof, and use thereof |
| KR1020040076377A KR101143131B1 (en) | 2003-09-26 | 2004-09-23 | Epoxy compound, preparation method thereof, and use thereof |
| CNB2004100851683A CN100432063C (en) | 2003-09-26 | 2004-09-24 | Epoxy compound, preparation method thereof, and use thereof |
| US11/698,184 US7304120B2 (en) | 2003-09-26 | 2007-01-26 | Epoxy compound, preparation method thereof, and use thereof |
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| JP2003352233A JP4237600B2 (en) | 2003-10-10 | 2003-10-10 | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005255813A (en) * | 2004-03-11 | 2005-09-22 | Japan Epoxy Resin Kk | Epoxy resin composition and its cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPWO2005085316A1 (en) * | 2004-03-03 | 2007-08-09 | 日立化成工業株式会社 | Epoxy resin molding material for sealing and electronic component device |
| JP4946440B2 (en) * | 2004-07-22 | 2012-06-06 | 住友ベークライト株式会社 | Semiconductor sealing resin composition and semiconductor device |
| JP2006249145A (en) * | 2005-03-08 | 2006-09-21 | Japan Epoxy Resin Kk | Epoxy resin, its manufacturing method and epoxy resin composition |
| JP4742625B2 (en) * | 2005-03-08 | 2011-08-10 | 三菱化学株式会社 | Hydrogenated epoxy resin, method for producing the same, and epoxy resin composition |
| JP2007270126A (en) * | 2006-03-07 | 2007-10-18 | Sumitomo Bakelite Co Ltd | Resin composition for semiconductor sealing use and semiconductor device |
| JP4961856B2 (en) * | 2006-06-22 | 2012-06-27 | 川崎化成工業株式会社 | 1,4-Dihydro-9,10-anthracenediyl (meth) acrylate compound and method for producing the same |
| JP4973444B2 (en) * | 2006-10-24 | 2012-07-11 | 住友ベークライト株式会社 | Semiconductor sealing resin composition and semiconductor device |
| JPWO2019142646A1 (en) * | 2018-01-16 | 2021-01-14 | 昭和電工マテリアルズ株式会社 | Curable resin composition, semiconductor device, and method for manufacturing the semiconductor device |
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| JPS54122263A (en) * | 1978-03-13 | 1979-09-21 | Kawasaki Kasei Chem Ltd | Preparation of 1,4-dihydro-9,10-dihydroxyanthracene |
| JPH05283560A (en) * | 1991-10-04 | 1993-10-29 | Nitto Denko Corp | Semiconductor sealing epoxy resin composition and semiconductor device using it |
| JPH09216933A (en) * | 1996-02-07 | 1997-08-19 | Toshiba Chem Corp | Epoxy resin composition and sealed semiconductor device |
| JP4354242B2 (en) * | 2003-09-26 | 2009-10-28 | ジャパンエポキシレジン株式会社 | Novel crystalline epoxy resin, curable epoxy resin composition and cured product thereof |
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| JP2005255813A (en) * | 2004-03-11 | 2005-09-22 | Japan Epoxy Resin Kk | Epoxy resin composition and its cured product |
| JP4655490B2 (en) * | 2004-03-11 | 2011-03-23 | 三菱化学株式会社 | Epoxy resin composition and cured product thereof |
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