JP2003327791A - Sealing epoxy resin molding material and electronic component device - Google Patents
Sealing epoxy resin molding material and electronic component deviceInfo
- Publication number
- JP2003327791A JP2003327791A JP2002140919A JP2002140919A JP2003327791A JP 2003327791 A JP2003327791 A JP 2003327791A JP 2002140919 A JP2002140919 A JP 2002140919A JP 2002140919 A JP2002140919 A JP 2002140919A JP 2003327791 A JP2003327791 A JP 2003327791A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- molding material
- resin molding
- group
- metal hydroxide
- 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.)
- Withdrawn
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 182
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 181
- 239000012778 molding material Substances 0.000 title claims abstract description 76
- 238000007789 sealing Methods 0.000 title claims abstract description 38
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 62
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 45
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 45
- 150000007824 aliphatic compounds Chemical class 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005011 phenolic resin Substances 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 32
- -1 phosphine compound Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000005538 encapsulation Methods 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 229920003986 novolac Polymers 0.000 claims description 23
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 claims description 23
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 20
- 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 claims description 17
- 239000004305 biphenyl Substances 0.000 claims description 16
- 235000010290 biphenyl Nutrition 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000003495 polar organic solvent Substances 0.000 claims description 16
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 10
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 10
- 235000021286 stilbenes Nutrition 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- 235000013872 montan acid ester Nutrition 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 claims 1
- 150000003333 secondary alcohols Chemical class 0.000 claims 1
- 101150035983 str1 gene Proteins 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 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 12
- 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 12
- 229920001568 phenolic resin Polymers 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 11
- 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 description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 10
- 239000003063 flame retardant Substances 0.000 description 10
- 230000017525 heat dissipation Effects 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000005350 fused silica glass Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 229910002026 crystalline silica Inorganic materials 0.000 description 4
- 238000005040 ion trap Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004780 naphthols Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010680 novolac-type phenolic resin Substances 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 2
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- QIRPHBPKRGXMJD-UHFFFAOYSA-N 4-[2-(3-tert-butyl-4-hydroxy-5-methylphenyl)ethenyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C=CC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QIRPHBPKRGXMJD-UHFFFAOYSA-N 0.000 description 2
- WTWMJYNGYCJIGR-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)ethenyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C=CC=2C=C(C)C(O)=C(C)C=2)=C1 WTWMJYNGYCJIGR-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZKHOYAKAFALNQD-UHFFFAOYSA-N Octacosanoic acid methyl ester Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)OC ZKHOYAKAFALNQD-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- CRGRWBQSZSQVIE-UHFFFAOYSA-N diazomethylbenzene Chemical compound [N-]=[N+]=CC1=CC=CC=C1 CRGRWBQSZSQVIE-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- DOXFBSZBACYHFY-UHFFFAOYSA-N phenol;stilbene Chemical class OC1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 DOXFBSZBACYHFY-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、封止用エポキシ樹
脂成形材料、特に環境対応の観点から要求されるノンハ
ロゲンかつノンアンチモンの難燃性や高放熱性を要求さ
れる成形材料であり、厳しい信頼性を要求されるＶＬＳ
Ｉ等の素子の封止用に好適な封止用エポキシ樹脂成形材
料及びこの成形材料で封止した素子を備えた電子部品装
置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing epoxy resin molding material, particularly a molding material which is required to have non-halogen and antimony flame retardancy and high heat dissipation required from the viewpoint of environmental friendliness. VLS that requires reliability
The present invention relates to a sealing epoxy resin molding material suitable for sealing an element such as I and an electronic component device including an element sealed with this molding material.
【０００２】[0002]
【従来の技術】従来から、トランジスタ、ＩＣ等の電子
部品装置の素子封止の分野では生産性、コスト等の面か
ら樹脂封止が主流となり、エポキシ樹脂成形材料が広く
用いられている。この理由としては、エポキシ樹脂が電
気特性、耐湿性、耐熱性、機械特性、インサート品との
接着性などの諸特性にバランスがとれている為である。
これらの封止用エポキシ樹脂成形材料の難燃化は主にテ
トラブロモビスフェノールＡのジグリシジルエーテル等
のブロム化樹脂と酸化アンチモンの組合せにより行われ
ているが、近年、環境保護の観点からダイオキシン問題
に端を発し、デカブロムをはじめとするハロゲン化樹脂
やアンチモン化合物に量規制の動きがあり、封止用エポ
キシ樹脂成形材料についてもノンハロゲン化（ノンブロ
ム化）及びノンアンチモン化の要求が出てきている。ま
た、プラスチック封止ＩＣの高温放置特性にブロム化合
物が悪影響を及ぼすことが知られており、この観点から
もブロム化樹脂量の低減が望まれている。ブロム化樹脂
や酸化アンチモンを用いずに難燃化を達成する手法の一
つとしては、金属水酸化物を用いる方法（特開平９−２
４１４８３号公報）、金属水酸化物と金属酸化物を併用
する方法（特開平９−１００３３７号公報）等を挙げる
ことができる。近年はまた、半導体素子の発熱量の増大
に伴い、封止用エポキシ樹脂成形材料への放熱性の要求
も高まっており、特に高放熱性の要求が強いパッケージ
に対しては、封止用エポキシ樹脂成形材料の無機充填剤
に一般的に用いられる溶融シリカの他に、結晶性シリカ
や、さらに放熱性の高いアルミナ（酸化アルミニウム）
等を併用する等の手法が用いられている。2. Description of the Related Art Conventionally, resin encapsulation has been the mainstream in the field of element encapsulation of electronic component devices such as transistors and ICs from the viewpoint of productivity and cost, and epoxy resin molding materials have been widely used. The reason for this is that the epoxy resin is well balanced in various characteristics such as electric characteristics, humidity resistance, heat resistance, mechanical characteristics, and adhesiveness with insert products.
Flame retardation of these encapsulating epoxy resin molding materials is mainly carried out by a combination of brominated resin such as diglycidyl ether of tetrabromobisphenol A and antimony oxide, but in recent years, from the viewpoint of environmental protection, there is a problem of dioxins. The amount of halogenated resins such as decabrom and antimony compounds are being regulated, and demand for non-halogenated (non-bromed) and non-antimony compounds for epoxy resin molding materials for encapsulation is increasing. . Further, it is known that the bromine compound has an adverse effect on the high temperature storage property of the plastic encapsulation IC, and from this viewpoint, it is desired to reduce the amount of the brominating resin. As one of the methods for achieving flame retardancy without using a brominated resin or antimony oxide, a method using a metal hydroxide (JP-A-9-2
No. 41483), a method of using a metal hydroxide and a metal oxide in combination (JP-A-9-100337), and the like. In recent years, as the amount of heat generated by semiconductor elements has increased, the demand for heat dissipation from epoxy resin molding compounds for sealing has increased. In addition to fused silica, which is generally used as an inorganic filler for resin molding materials, crystalline silica and alumina (aluminum oxide) with high heat dissipation
Techniques such as the combined use of the above are used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、封止用
エポキシ樹脂成形材料に、難燃剤として金属水酸化物、
金属酸化物を用いた場合や、高放熱性実現の為にアルミ
ナ等を用いた場合、流動性の低下や、成形装置内のゲー
ト残り発生等による連続成形性の低下といった、特に成
形性上の問題が発生し、難燃剤としてブロム化樹脂と酸
化アンチモンを併用した封止用エポキシ樹脂成形材料、
あるいは無機充填剤として溶融シリカや結晶シリカのみ
を用いた封止用エポキシ樹脂成形材料と同等の成形性、
信頼性を得るに至っていない。本発明はかかる状況に鑑
みなされたもので、金属酸化物又は金属水酸化物を含有
し、成形性に優れた封止用エポキシ樹脂材料、及びこれ
により封止した素子を備えた電子部品装置を提供しよう
とするものである。However, the epoxy resin molding material for encapsulation contains metal hydroxide as a flame retardant,
When metal oxide is used or alumina is used to achieve high heat dissipation, there is a decrease in fluidity and continuous moldability due to the generation of gate residue in the molding equipment. A problem occurs, epoxy resin molding material for encapsulation that uses brominated resin and antimony oxide together as a flame retardant,
Or moldability equivalent to the epoxy resin molding material for sealing using only fused silica or crystalline silica as the inorganic filler,
It has not yet gained credibility. The present invention has been made in view of the above circumstances, and includes a sealing epoxy resin material containing a metal oxide or a metal hydroxide and excellent in moldability, and an electronic component device including an element sealed by the sealing epoxy resin material. It is the one we are trying to provide.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記の課題
を解決するために鋭意検討を重ねた結果、金属酸化物又
は金属水酸化物を、有機溶媒下、特定の構造を有する離
型剤で前処理を行った後に成形材料の配合を行うことに
よって得られる封止用エポキシ樹脂成形材料により上記
の目的を達成しうることを見い出し、本発明を完成する
に至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a metal oxide or a metal hydroxide is released from a mold having a specific structure in an organic solvent. It was found that the above-mentioned object can be achieved by the epoxy resin molding material for encapsulation obtained by performing the pretreatment with the agent and then compounding the molding material, and completed the present invention.
【０００５】すなわち、本発明は（１） （Ａ）エポキ
シ樹脂、（Ｂ）硬化剤、（Ｃ）離型剤で処理された金属
酸化物又は金属水酸化物を必須成分とし、前記離型剤
が、炭素数が２５以上の高級脂肪族化合物である封止用
エポキシ樹脂成形材料に関する。また、本発明は（２）
（Ｃ）成分に用いられる離型剤が、高級脂肪酸又はそ
のエステルであって、炭素数２５〜５７の化合物である
（１）に記載の封止用エポキシ樹脂成形材料、（３）
（Ｃ）成分に用いられる離型剤が、モンタン酸又は炭素
数５７以下のモンタン酸エステルである（１）または
（２）に記載の封止用エポキシ樹脂成形材料に関する。
さらに、本発明は（４） （Ｃ）成分が有機溶媒を用い
て離型剤で処理されたものである（１）〜（３）いずれ
かに記載の封止用エポキシ樹脂成形材料、（５） 有機
溶媒が、１種以上の極性有機溶媒を含む（４）に記載の
封止用エポキシ樹脂成形材料、（６） 極性有機溶媒
が、炭素数６以下の、１級、２級、又は３級のアルコー
ル又はグリコールを含む（５）に記載の封止用エポキシ
樹脂成形材料、（７） さらに、(Ｄ)無機充填剤を含有
する（１）〜（６）のいずれかに記載の封止用エポキシ
樹脂成形材料に関する。本発明は、さらにまた、（８）
（Ａ）エポキシ樹脂が、ビフェニル型エポキシ樹脂、
スチルベン型エポキシ樹脂、硫黄原子含有エポキシ樹
脂、ノボラック型エポキシ樹脂、ジシクロペンタジエン
型エポキシ樹脂、ナフタレン型エポキシ樹脂及びトリフ
ェニルメタン型エポキシ樹脂の少なくとも１種を含有す
る（１）〜（７）のいずれかに記載の封止用エポキシ樹
脂成形材料、（９） （Ｂ）硬化剤がビフェニル型フェ
ノール樹脂、アラルキル型フェノール樹脂、ジシクロペ
ンタジエン型フェノール樹脂、トリフェニルメタン型フ
ェノール樹脂及びノボラック型フェノール樹脂の少なく
とも１種を含有する（１）〜（８）のいずれかに記載の
封止用エポキシ樹脂成形材料、（１０） さらに（Ｅ）
硬化促進剤を含有する（１）〜（９）のいずれかに記載
の封止用エポキシ樹脂成形材料、（１１） （Ｅ）硬化
促進剤が、ホスフィン化合物とキノン化合物との付加物
を含有する（１０）に記載の封止用エポキシ樹脂成形材
料、（１２） （Ｃ）成分が、離型剤で処理された複合
金属水酸化物である（１）〜（１１）のいずれか記載の
封止用エポキシ樹脂成形材料、（１３） 複合金属水酸
化物が、下記一般式（Ｉ）で表される（１２）に記載の
封止用エポキシ樹脂成形材料に関する。That is, the present invention comprises (1) (A) an epoxy resin, (B) a curing agent, and (C) a release agent-treated metal oxide or metal hydroxide as an essential component. Relates to an epoxy resin molding material for sealing, which is a higher aliphatic compound having 25 or more carbon atoms. The present invention also provides (2)
The mold releasing agent used in the component (C) is a higher fatty acid or its ester, which is a compound having 25 to 57 carbon atoms, and the epoxy resin molding material for sealing according to (1), (3).
The mold releasing agent used as the component (C) relates to the epoxy resin molding material for encapsulation according to (1) or (2), which is montanic acid or a montanic acid ester having 57 or less carbon atoms.
Furthermore, the present invention provides (4) the epoxy resin molding material for encapsulation according to any one of (1) to (3), wherein the component (C) is treated with a release agent using an organic solvent, (5) ) The organic solvent contains one or more kinds of polar organic solvents, the epoxy resin molding material for closure as described in (4), (6) The polar organic solvent has a carbon number of 6 or less, primary, secondary, or 3 The epoxy resin molding material for sealing according to (5), which contains a high-grade alcohol or glycol, (7) The sealing according to any one of (1) to (6), which further contains (D) an inorganic filler. For epoxy resin molding materials for automobiles. The present invention also provides (8)
(A) The epoxy resin is a biphenyl type epoxy resin,
Any of (1) to (7) containing at least one of stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin. The epoxy resin molding material for encapsulation according to (9), wherein (B) the curing agent is a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a triphenylmethane type phenol resin, or a novolac type phenol resin. The encapsulating epoxy resin molding material according to any one of (1) to (8), which contains at least one kind, (10), and (E).
The encapsulating epoxy resin molding material according to any one of (1) to (9) containing a curing accelerator, and (11) the curing accelerator (E) contains an adduct of a phosphine compound and a quinone compound. The sealing epoxy resin molding material according to (10), (12) the seal according to any one of (1) to (11), wherein the component (C) is a composite metal hydroxide treated with a release agent. Stopping epoxy resin molding material, (13) The composite metal hydroxide relates to the sealing epoxy resin molding material according to (12) represented by the following general formula (I).
【化２】
ｐ(Ｍ1 aＯb)・ｑ(Ｍ2 cＯd)・ｒ(Ｍ3 eＯf)・ｍＨ2Ｏ （Ｉ）
（ここで、Ｍ1、Ｍ2及びＭ3は互いに異なる金属元素を
示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｐ、ｑ及びｍは正の
数、ｒは０又は正の数を示す。）
また、本発明は、（１４） （１）〜（１３）のいずれ
かに記載の封止用エポキシ樹脂成形材料で封止された素
子を備えた電子部品装置に関する。## STR2 ## p (M 1 a O b) · q (M 2 c O d) · r (M 3 e O f) · mH 2 O (I) ( wherein, M 1, M 2 and M 3 are Indicating different metal elements from each other, a, b, c, d, e, f, p, q and m are positive numbers, and r is 0 or a positive number.) The present invention also provides (14) ( The present invention relates to an electronic component device including an element sealed with the epoxy resin molding material for sealing according to any one of 1) to 13).
【０００６】[0006]
【発明の実施の形態】本発明において用いられる（Ａ）
エポキシ樹脂は、封止用エポキシ樹脂成形材料に一般に
使用されているもので特に制限はない。たとえば、フェ
ノールノボラック型エポキシ樹脂、オルソクレゾールノ
ボラック型エポキシ樹脂、トリフェニルメタン骨格を有
するエポキシ樹脂をはじめとするフェノール、クレゾー
ル、キシレノール、レゾルシン、カテコール、ビスフェ
ノールＡ、ビスフェノールＦ等のフェノール類及び／又
はα−ナフトール、β−ナフトール、ジヒドロキシナフ
タレン等のナフトール類とホルムアルデヒド、アセトア
ルデヒド、プロピオンアルデヒド、ベンズアルデヒド、
サリチルアルデヒド等のアルデヒド基を有する化合物と
を酸性触媒下で縮合又は共縮合させて得られるノボラッ
ク樹脂をエポキシ化したノボラック型エポキシ樹脂；ビ
スフェノールＡ、ビスフェノールＦ、ビスフェノールＳ
等のビスフェノールのジグリシジルエーテル（ビスフェ
ノール型エポキシ樹脂）；アルキル置換又は非置換のビ
フェノール等のジグリシジルエーテル（ビフェニル型エ
ポキシ樹脂）；スチルベン型エポキシ樹脂；ハイドロキ
ノン型エポキシ樹脂；フタル酸、ダイマー酸等の多塩基
酸とエピクロルヒドリンの反応により得られるグリシジ
ルエステル型エポキシ樹脂；ジアミノジフェニルメタ
ン、イソシアヌル酸等のポリアミンとエピクロルヒドリ
ンの反応により得られるグリシジルアミン型エポキシ樹
脂；ジシクロペンタジエンとフェノール類の共縮合樹脂
のエポキシ化物（ジシクロペンタジエン型エポキシ樹
脂）；ナフタレン環を有するエポキシ樹脂（ナフタレン
型エポキシ樹脂）；フェノール・アラルキル樹脂、ナフ
トール・アラルキル樹脂等のアラルキル型フェノール樹
脂のエポキシ化物；トリメチロールプロパン型エポキシ
樹脂；テルペン変性エポキシ樹脂；オレフィン結合を過
酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹
脂；脂環族エポキシ樹脂；硫黄原子含有エポキシ樹脂等
が挙げられる。これらを単独で用いても２種以上を組み
合わせて用いてもよい。なかでも、耐リフロー性の観点
からはビフェニル型エポキシ樹脂、スチルベン型エポキ
シ樹脂及び硫黄原子含有エポキシ樹脂が好ましく、硬化
性の観点からはノボラック型エポキシ樹脂が好ましく、
低吸湿性の観点からはジシクロペンタジエン型エポキシ
樹脂が好ましく、耐熱性及び低反り性の観点からはナフ
タレン型エポキシ樹脂及びトリフェニルメタン型エポキ
シ樹脂が好ましく、これらのエポキシ樹脂の少なくとも
１種を含有していることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION (A) Used in the Present Invention
The epoxy resin is generally used as a sealing epoxy resin molding material and is not particularly limited. For example, phenols such as phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin, epoxy resin having a triphenylmethane skeleton, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol A, and / or α and the like. -Naphthols such as naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde,
A novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation with a compound having an aldehyde group such as salicylaldehyde under an acidic catalyst; bisphenol A, bisphenol F, bisphenol S
Such as diglycidyl ether of bisphenol (bisphenol type epoxy resin); diglycidyl ether such as alkyl-substituted or unsubstituted biphenol (biphenyl type epoxy resin); stilbene type epoxy resin; hydroquinone type epoxy resin; phthalic acid, dimer acid, etc. Glycidyl ester type epoxy resin obtained by reaction of polybasic acid and epichlorohydrin; glycidyl amine type epoxy resin obtained by reaction of polyamine such as diaminodiphenylmethane, isocyanuric acid and epichlorohydrin; epoxidized product of co-condensation resin of dicyclopentadiene and phenols (Dicyclopentadiene type epoxy resin); Epoxy resin having naphthalene ring (naphthalene type epoxy resin); Phenol / aralkyl resin, naphthol / aralkyl resin Epoxidized aralkyl type phenolic resin such as; trimethylolpropane type epoxy resin; terpene modified epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; alicyclic epoxy resin; Examples thereof include sulfur atom-containing epoxy resins. These may be used alone or in combination of two or more. Among them, biphenyl type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of reflow resistance, and novolac type epoxy resin is preferable from the viewpoint of curability,
Dicyclopentadiene type epoxy resin is preferable from the viewpoint of low hygroscopicity, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable from the viewpoint of heat resistance and low warpage, and contains at least one of these epoxy resins. It is preferable that
【０００７】ビフェニル型エポキシ樹脂としてはたとえ
ば下記一般式（II）で示されるエポキシ樹脂等が挙げら
れ、スチルベン型エポキシ樹脂としてはたとえば下記一
般式（III）で示されるエポキシ樹脂等が挙げられ、硫
黄原子含有エポキシ樹脂としてはたとえば下記一般式
（IV）で示されるエポキシ樹脂等が挙げられる。The biphenyl type epoxy resin includes, for example, an epoxy resin represented by the following general formula (II), and the stilbene type epoxy resin includes, for example, an epoxy resin represented by the following general formula (III), and sulfur. Examples of atom-containing epoxy resins include epoxy resins represented by the following general formula (IV).
【化３】
（ここで、Ｒ1〜Ｒ8は水素原子及び炭素数１〜１０の置
換又は非置換の一価の炭化水素基から選ばれ、これらは
全てが同一でも異なっていてもよい。ｎは０〜３の整数
を示す。）[Chemical 3] (Here, R 1 to R 8 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, all of which may be the same or different. N is 0 to 0. Indicates an integer of 3.)
【化４】
（ここで、Ｒ1〜Ｒ8は水素原子及び炭素数１〜５の置換
又は非置換の一価の炭化水素基から選ばれ、これらは全
てが同一でも異なっていてもよい。ｎは０〜１０の整数
を示す。）[Chemical 4] (Here, R 1 to R 8 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms, all of which may be the same or different. N is 0 to 0. Indicates an integer of 10.)
【化５】
（ここで、Ｒ1〜Ｒ8は水素原子、置換又は非置換の炭素
数１〜１０のアルキル基及び置換又は非置換の炭素数１
〜１０のアルコキシ基から選ばれ、これらは全てが同一
でも異なっていてもよい。ｎは０〜３の整数を示す。）
上記一般式（II）で示されるビフェニル型エポキシ樹脂
としては、たとえば、４，４´−ビス（２，３−エポキ
シプロポキシ）ビフェニル又は４，４´−ビス（２，３
−エポキシプロポキシ）−３，３´，５，５´−テトラ
メチルビフェニルを主成分とするエポキシ樹脂、エピク
ロルヒドリンと４，４´−ビフェノール又は４，４´−
（３，３´，５，５´−テトラメチル）ビフェノールと
を反応させて得られるエポキシ樹脂等が挙げられる。な
かでも４，４´−ビス（２，３−エポキシプロポキシ）
−３，３´，５，５´−テトラメチルビフェニルを主成
分とするエポキシ樹脂が好ましい。上記一般式（III）
で示されるスチルベン型エポキシ樹脂は、原料であるス
チルベン系フェノール類とエピクロルヒドリンとを塩基
性物質存在下で反応させて得ることができる。この原料
であるスチルベン系フェノール類としては、たとえば３
−ｔ−ブチル−４，４′−ジヒドロキシ−３′，５，
５′−トリメチルスチルベン、３−ｔ−ブチル−４，
４′−ジヒドロキシ−３′，５′，６−トリメチルスチ
ルベン、４，４´−ジヒドロキシ−３，３´，５，５´
−テトラメチルスチルベン、４，４´−ジヒドロキシ−
３，３´−ジ−ｔ−ブチル−５，５´−ジメチルスチル
ベン、４，４´−ジヒドロキシ−３，３´−ジ−ｔ−ブ
チル−６，６´−ジメチルスチルベン等が挙げられ、な
かでも３−ｔ−ブチル−４，４′−ジヒドロキシ−
３′，５，５′−トリメチルスチルベン、及び４，４´
−ジヒドロキシ−３，３´，５，５´−テトラメチルス
チルベンが好ましい。これらのスチルベン型フェノール
類は単独で用いても２種以上を組み合わせて用いてもよ
い。上記一般式（IV）で示される硫黄原子含有エポキシ
樹脂のなかでも、Ｒ1〜Ｒ8が水素原子、置換又は非置換
の炭素数１〜１０のアルキル基及び置換又は非置換の炭
素数１〜１０のアルコキシ基から選ばれるエポキシ樹脂
が好ましく、Ｒ1、Ｒ4、Ｒ5及びＲ8が水素原子で、
Ｒ2、Ｒ3、Ｒ6及びＲ7がアルキル基であるエポキシ樹脂
がより好ましく、Ｒ1、Ｒ4、Ｒ5及びＲ8が水素原子で、
Ｒ2及びＲ7がメチル基で、Ｒ3及びＲ6がｔ−ブチル基で
あるエポキシ樹脂がさらに好ましい。このような化合物
としては、ＹＳＬＶ−１２０ＴＥ(新日鐵化学社製商品
名)等が市販品として入手可能である。これらのエポキ
シ樹脂はいずれか１種を単独で用いても２種以上を組合
わせて用いてもよいが、その配合量は、その性能を発揮
するためにエポキシ樹脂全量に対して合わせて２０重量
％以上とすることが好ましく、３０重量％以上がより好
ましく、５０重量％以上とすることがさらに好ましい。[Chemical 5] (Here, R 1 to R 8 are a hydrogen atom, a substituted or unsubstituted C 1-10 alkyl group, and a substituted or unsubstituted C 1
10 to 10 alkoxy groups, all of which may be the same or different. n shows the integer of 0-3. ) Examples of the biphenyl type epoxy resin represented by the above general formula (II) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3).
-Epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl-based epoxy resin, epichlorohydrin and 4,4'-biphenol or 4,4'-
Examples thereof include epoxy resins obtained by reacting with (3,3 ′, 5,5′-tetramethyl) biphenol. Among them, 4,4'-bis (2,3-epoxypropoxy)
An epoxy resin containing -3,3 ', 5,5'-tetramethylbiphenyl as a main component is preferable. The above general formula (III)
The stilbene type epoxy resin represented by can be obtained by reacting the starting stilbene phenols with epichlorohydrin in the presence of a basic substance. Examples of the stilbene-based phenols as the raw material include 3
-T-butyl-4,4'-dihydroxy-3 ', 5,
5'-trimethylstilbene, 3-t-butyl-4,
4'-dihydroxy-3 ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'
-Tetramethylstilbene, 4,4'-dihydroxy-
3,3'-di-t-butyl-5,5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene and the like are mentioned. But 3-t-butyl-4,4'-dihydroxy-
3 ', 5,5'-trimethylstilbene, and 4,4'
-Dihydroxy-3,3 ', 5,5'-tetramethylstilbene is preferred. These stilbene type phenols may be used alone or in combination of two or more kinds. Among the sulfur atom-containing epoxy resins represented by the general formula (IV), R 1 to R 8 are hydrogen atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted carbon atom 1 to 1 An epoxy resin selected from the alkoxy groups of 10 is preferable, and R 1 , R 4 , R 5 and R 8 are hydrogen atoms,
More preferred is an epoxy resin in which R 2 , R 3 , R 6 and R 7 are alkyl groups, and R 1 , R 4 , R 5 and R 8 are hydrogen atoms,
An epoxy resin in which R 2 and R 7 are methyl groups and R 3 and R 6 are t-butyl groups is more preferable. As such a compound, YSLV-120TE (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available. These epoxy resins may be used alone or in combination of two or more, but the compounding amount thereof is 20% by weight based on the total amount of the epoxy resin in order to exert its performance. % Or more, preferably 30% by weight or more, more preferably 50% by weight or more.
【０００８】ノボラック型エポキシ樹脂としては、たと
えば下記一般式（Ｖ）で示されるエポキシ樹脂等が挙げ
られる。Examples of the novolac type epoxy resin include epoxy resins represented by the following general formula (V).
【化６】
（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は
非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の
整数を示す。）
上記一般式（Ｖ）で示されるノボラック型エポキシ樹脂
は、ノボラック型フェノール樹脂にエピクロルヒドリン
を反応させることによって容易に得られる。なかでも、
一般式（Ｖ）中のＲとしては、メチル基、エチル基、プ
ロピル基、ブチル基、イソプロピル基、イソブチル基等
の炭素数１〜１０のアルキル基、メトキシ基、エトキシ
基、プロポキシ基、ブトキシ基等の炭素数１〜１０のア
ルコキシル基が好ましく、水素原子又はメチル基がより
好ましい。ｎは０〜３の整数が好ましい。上記一般式
（Ｖ）で示されるノボラック型エポキシ樹脂のなかで
も、オルトクレゾールノボラック型エポキシ樹脂が好ま
しい。ノボラック型エポキシ樹脂を使用する場合、その
配合量は、その性能を発揮するためにエポキシ樹脂全量
に対して２０重量％以上とすることが好ましく、３０重
量％以上がより好ましい。[Chemical 6] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10.) Represented by the general formula (V). The novolac type epoxy resin is easily obtained by reacting novolac type phenol resin with epichlorohydrin. Above all,
R in the general formula (V) is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. And the like, an alkoxyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolac type epoxy resins represented by the general formula (V), orthocresol novolac type epoxy resins are preferable. When a novolac type epoxy resin is used, its content is preferably 20% by weight or more, more preferably 30% by weight or more based on the total amount of the epoxy resin in order to exert its performance.
【０００９】ジシクロペンタジエン型エポキシ樹脂とし
ては、たとえば下記一般式（VI）で示されるエポキシ樹
脂等が挙げられる。Examples of the dicyclopentadiene type epoxy resin include epoxy resins represented by the following general formula (VI).
【化７】
（ここで、Ｒ1及びＲ2は水素原子及び炭素数１〜１０の
置換又は非置換の一価の炭化水素基からそれぞれ独立し
て選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整
数を示す。）
上記一般式（VI）中のＲ1としては、たとえば、水素原
子、メチル基、エチル基、プロピル基、ブチル基、イソ
プロピル基、ｔ−ブチル基等のアルキル基、ビニル基、
アリル基、ブテニル基等のアルケニル基、ハロゲン化ア
ルキル基、アミノ基置換アルキル基、メルカプト基置換
アルキル基などの炭素数１〜１０の置換又は非置換の一
価の炭化水素基が挙げられ、なかでもメチル基、エチル
基等のアルキル基及び水素原子が好ましく、メチル基及
び水素原子がより好ましい。Ｒ2としては、たとえば、
水素原子、メチル基、エチル基、プロピル基、ブチル
基、イソプロピル基、ｔ−ブチル基等のアルキル基、ビ
ニル基、アリル基、ブテニル基等のアルケニル基、ハロ
ゲン化アルキル基、アミノ基置換アルキル基、メルカプ
ト基置換アルキル基などの炭素数１〜１０の置換又は非
置換の一価の炭化水素基が挙げられ、なかでも水素原子
が好ましい。ジシクロペンタジエン型エポキシ樹脂を使
用する場合、その配合量は、その性能を発揮するために
エポキシ樹脂全量に対して２０重量％以上とすることが
好ましく、３０重量％以上がより好ましい。[Chemical 7] (Here, R 1 and R 2 are independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is It represents an integer of 0 to 6.) Examples of R 1 in the general formula (VI) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group. , Vinyl group,
Examples thereof include alkenyl groups such as allyl group and butenyl group, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups and other substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. However, an alkyl group such as a methyl group and an ethyl group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. As R 2 , for example,
Alkyl group such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, t-butyl group, alkenyl group such as vinyl group, allyl group, butenyl group, halogenated alkyl group, amino group-substituted alkyl group And a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms such as a mercapto group-substituted alkyl group, and a hydrogen atom is preferable. When a dicyclopentadiene type epoxy resin is used, its content is preferably 20% by weight or more, and more preferably 30% by weight or more based on the total amount of the epoxy resin in order to exert its performance.
【００１０】ナフタレン型エポキシ樹脂としてはたとえ
ば下記一般式（VII）で示されるエポキシ樹脂等が挙げ
られ、トリフェニルメタン型エポキシ樹脂としてはたと
えば下記一般式（VIII）で示されるエポキシ樹脂等が挙
げられる。下記一般式（VII）で示されるナフタレン型
エポキシ樹脂としては、１個の構成単位及びｍ個の構成
単位をランダムに含むランダム共重合体、交互に含む交
互共重合体、規則的に含む共重合体、ブロック状に含む
ブロック共重合体が挙げられ、これらのいずれか１種を
単独で用いても、２種以上を組み合わせて用いてもよ
い。また、下記一般式（VIII）で示されるトリフェニル
メタン型エポキシ樹脂としては特に制限はないが、サリ
チルアルデヒド型エポキシ樹脂が好ましい。The naphthalene type epoxy resin includes, for example, an epoxy resin represented by the following general formula (VII), and the triphenylmethane type epoxy resin includes, for example, an epoxy resin represented by the following general formula (VIII). . The naphthalene-type epoxy resin represented by the following general formula (VII) includes a random copolymer randomly containing one constitutional unit and m constitutional units, an alternating copolymer containing alternating units, and a copolymer containing regular units. Examples thereof include a block copolymer and a block copolymer containing a block. Any one of these may be used alone, or two or more thereof may be used in combination. The triphenylmethane type epoxy resin represented by the following general formula (VIII) is not particularly limited, but salicylaldehyde type epoxy resin is preferable.
【化８】
（ここで、Ｒ1〜Ｒ3は水素原子及び置換又は非置換の炭
素数１〜１２の一価の炭化水素基から選ばれ、これらは
全てが同一でも異なっていてもよい。ｐは１又は０で、
ｌ、ｍはそれぞれ０〜１１の整数であって、（ｌ＋ｍ）
が１〜１１の整数でかつ（ｌ＋ｐ）が１〜１２の整数と
なるよう選ばれる。ｉは０〜３の整数、ｊは０〜２の整
数、ｋは０〜４の整数を示す。）[Chemical 8] (Here, R 1 to R 3 are selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, all of which may be the same or different. P is 1 or 0,
l and m are each an integer of 0 to 11, and (l + m)
Is an integer from 1 to 11 and (l + p) is an integer from 1 to 12. i is an integer of 0 to 3, j is an integer of 0 to 2, and k is an integer of 0 to 4. )
【化９】
（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は
非置換の一価の炭化水素基から選ばれ、ｎは１〜１０の
整数を示す。）
これらのエポキシ樹脂はいずれか１種を単独で用いても
両者を組合わせて用いてもよいが、その配合量は、その
性能を発揮するためにエポキシ樹脂全量に対して合わせ
て２０重量％以上とすることが好ましく、３０重量％以
上がより好ましく、５０重量％以上とすることがさらに
好ましい。[Chemical 9] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.) One of these epoxy resins is used. May be used alone or in combination with each other, but the compounding amount thereof is preferably 20% by weight or more in total with respect to the total amount of the epoxy resin in order to exert its performance, and 30% by weight is preferable. The above is more preferable, and 50% by weight or more is further preferable.
【００１１】上記のビフェニル型エポキシ樹脂、スチル
ベン型エポキシ樹脂、硫黄原子含有エポキシ樹脂、ノボ
ラック型エポキシ樹脂、ジシクロペンタジエン型エポキ
シ樹脂、ナフタレン型エポキシ樹脂及びトリフェニルメ
タン型エポキシ樹脂は、いずれか１種を単独で用いても
２種以上を組合わせて用いてもよいが、その配合量はエ
ポキシ樹脂全量に対して合わせて５０重量％以上とする
ことが好ましく、６０重量％以上がより好ましく、８０
重量％以上がさらに好ましい。Any one of the above-mentioned biphenyl type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin may be used. May be used alone or in combination of two or more kinds, but the compounding amount thereof is preferably 50% by weight or more, more preferably 60% by weight or more, more preferably 80% by weight in total with respect to the total amount of the epoxy resin.
It is more preferably at least wt%.
【００１２】本発明において用いられる（Ｂ）硬化剤
は、封止用エポキシ樹脂成形材料に一般に使用されてい
るもので特に制限はない。たとえば、フェノール、クレ
ゾール、レゾルシン、カテコール、ビスフェノールＡ、
ビスフェノールＦ、フェニルフェノール、アミノフェノ
ール等のフェノール類及び／又はα−ナフトール、β−
ナフトール、ジヒドロキシナフタレン等のナフトール類
とホルムアルデヒド、アセトアルデヒド、プロピオンア
ルデヒド、ベンズアルデヒド、サリチルアルデヒド等の
アルデヒド基を有する化合物とを酸性触媒下で縮合又は
共縮合させて得られるノボラック型フェノール樹脂；フ
ェノール類及び／又はナフトール類とジメトキシパラキ
シレン又はビス（メトキシメチル）ビフェニルから合成
されるフェノール・アラルキル樹脂、ナフトール・アラ
ルキル樹脂等のアラルキル型フェノール樹脂；フェノー
ル類及び／又はナフトール類とジシクロペンタジエンか
ら共重合により合成される、ジシクロペンタジエン型フ
ェノール樹脂、ジシクロペンタジエン型ナフトール樹
脂；テルペン変性フェノール樹脂；ビフェニル型フェノ
ール樹脂；トリフェニルメタン型フェノール樹脂などが
挙げられ、これらを単独で用いても２種以上を組合わせ
て用いてもよい。なかでも、難燃性の観点からはビフェ
ニル型フェノール樹脂が好ましく、耐リフロー性及び硬
化性の観点からはアラルキル型フェノール樹脂が好まし
く、低吸湿性の観点からはジシクロペンタジエン型フェ
ノール樹脂が好ましく、耐熱性、低膨張率及び低そり性
の観点からはトリフェニルメタン型フェノール樹脂が好
ましく、硬化性の観点からはノボラック型フェノール樹
脂が好ましく、これらのフェノール樹脂の少なくとも１
種を含有していることが好ましい。The curing agent (B) used in the present invention is generally used for epoxy resin molding materials for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A,
Phenols such as bisphenol F, phenylphenol, aminophenol and / or α-naphthol, β-
Novolac phenolic resins obtained by condensation or co-condensation of naphthols such as naphthol and dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde under acidic catalyst; phenols and / Or aralkyl type phenol resin such as phenol / aralkyl resin, naphthol / aralkyl resin, etc. synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; synthesized by copolymerization from phenols and / or naphthols and dicyclopentadiene Dicyclopentadiene type phenolic resin, dicyclopentadiene type naphthol resin; terpene modified phenolic resin; biphenyl type phenolic resin; trife Such Rumetan type phenolic resin. These may be used in combination of two or more even with these alone. Among them, the biphenyl type phenol resin is preferable from the viewpoint of flame retardancy, the aralkyl type phenol resin is preferable from the viewpoint of reflow resistance and curability, and the dicyclopentadiene type phenol resin is preferable from the viewpoint of low hygroscopicity, From the viewpoint of heat resistance, low expansion coefficient and low warpage, triphenylmethane type phenolic resin is preferable, and from the viewpoint of curability, novolac type phenolic resin is preferable, and at least one of these phenolic resins is preferable.
It is preferable to contain a seed.
【００１３】ビフェニル型フェノール樹脂としては、た
とえば下記一般式（IX）で示されるフェノール樹脂等が
挙げられる。Examples of the biphenyl type phenol resin include a phenol resin represented by the following general formula (IX).
【化１０】
上記一般式（IX）中のＲ1〜Ｒ9は全てが同一でも異なっ
ていてもよく、水素原子、メチル基、エチル基、プロピ
ル基、ブチル基、イソプロピル基、イソブチル基等の炭
素数１〜１０のアルキル基、メトキシ基、エトキシ基、
プロポキシ基、ブトキシ基等の炭素数１〜１０のアルコ
キシル基、フェニル基、トリル基、キシリル基等の炭素
数６〜１０のアリール基、及び、ベンジル基、フェネチ
ル基等の炭素数６〜１０のアラルキル基から選ばれ、な
かでも水素原子とメチル基が好ましい。ｎは０〜１０の
整数を示す。上記一般式（IX）で示されるビフェニル型
フェノール樹脂としては、たとえばＲ1〜Ｒ9が全て水素
原子である化合物等が挙げられ、なかでも溶融粘度の観
点から、ｎが１以上の縮合体を５０重量％以上含む縮合
体の混合物が好ましい。このような化合物としては、Ｍ
ＥＨ−７８５１（明和化成株式会社製商品名）が市販品
として入手可能である。ビフェニル型フェノール樹脂を
使用する場合、その配合量は、その性能を発揮するため
に硬化剤全量に対して３０重量％以上とすることが好ま
しく、５０重量％以上がより好ましく、６０重量％以上
がさらに好ましい。[Chemical 10] All of R 1 to R 9 in the above general formula (IX) may be the same or different and have 1 to 1 carbon atoms such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group. 10 alkyl groups, methoxy groups, ethoxy groups,
Propoxy group, butoxy group, etc., C1-C10 alkoxyl group, phenyl group, tolyl group, xylyl group, etc., C6-C10 aryl group, and benzyl group, phenethyl group, etc., C6-C10 It is selected from an aralkyl group, and among them, a hydrogen atom and a methyl group are preferable. n shows the integer of 0-10. Examples of the biphenyl type phenolic resin represented by the general formula (IX) include compounds in which R 1 to R 9 are all hydrogen atoms, and among them, a condensate having n of 1 or more is selected from the viewpoint of melt viscosity. A mixture of condensates containing 50% by weight or more is preferred. Such compounds include M
EH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) is commercially available. When a biphenyl type phenol resin is used, its content is preferably 30% by weight or more, more preferably 50% by weight or more, and more preferably 60% by weight or more based on the total amount of the curing agent in order to exert its performance. More preferable.
【００１４】アラルキル型フェノール樹脂としては、た
とえばフェノール・アラルキル樹脂、ナフトール・アラ
ルキル樹脂等が挙げられ、下記一般式（Ｘ）で示される
フェノール・アラルキル樹脂が好ましく、一般式（Ｘ）
中のＲが水素原子で、ｎの平均値が０〜８であるフェノ
ール・アラルキル樹脂がより好ましい。具体例として
は、ｐ−キシリレン型フェノール・アラルキル樹脂、ｍ
−キシリレン型フェノール・アラルキル樹脂等が挙げら
れる。これらのアラルキル型フェノール樹脂を用いる場
合、その配合量は、その性能を発揮するために硬化剤全
量に対して３０重量％以上とすることが好ましく、５０
重量％以上がより好ましい。The aralkyl type phenol resin includes, for example, phenol / aralkyl resin, naphthol / aralkyl resin and the like, and the phenol / aralkyl resin represented by the following general formula (X) is preferable, and the general formula (X) is preferable.
A phenol / aralkyl resin in which R is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resin, m
Examples include xylylene type phenol and aralkyl resin. When these aralkyl type phenol resins are used, the compounding amount thereof is preferably 30% by weight or more with respect to the total amount of the curing agent in order to exert its performance,
It is more preferably at least wt%.
【化１１】
（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は
非置換の一価の炭化水素基から選ばれ、ｎは０〜１０の
整数を示す。）[Chemical 11] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.)
【００１５】ジシクロペンタジエン型フェノール樹脂と
しては、たとえば下記一般式（XI）で示されるフェノー
ル樹脂等が挙げられる。Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XI).
【化１２】
（ここで、Ｒ1及びＲ2は水素原子及び炭素数１〜１０の
置換又は非置換の一価の炭化水素基からそれぞれ独立し
て選ばれ、ｎは０〜１０の整数を示し、ｍは０〜６の整
数を示す。）
ジシクロペンタジエン型フェノール樹脂を用いる場合、
その配合量は、その性能を発揮するために硬化剤全量に
対して３０重量％以上とすることが好ましく、５０重量
％以上がより好ましい。[Chemical 12] (Here, R 1 and R 2 are independently selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is Indicates an integer of 0 to 6.) When using a dicyclopentadiene type phenol resin,
The blending amount thereof is preferably 30% by weight or more and more preferably 50% by weight or more based on the total amount of the curing agent in order to exert its performance.
【００１６】トリフェニルメタン型フェノール樹脂とし
ては、たとえば下記一般式（XII）で示されるフェノー
ル樹脂等が挙げられる。下記一般式（XII）で示される
トリフェニルメタン型フェノール樹脂としては特に制限
はないが、たとえば、サリチルアルデヒド型フェノール
樹脂、ｏ−ヒドロキシベンズアルデヒド型フェノール樹
脂、ｍ−ヒドロキシベンズアルデヒド型フェノール樹脂
等が挙げられ、これらの１種を単独で用いても２種以上
を組合わせて用いてもよい。なかでもサリチルアルデヒ
ド型フェノール樹脂が好ましい。Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XII). The triphenylmethane type phenolic resin represented by the following general formula (XII) is not particularly limited, and examples thereof include salicylaldehyde type phenolic resin, o-hydroxybenzaldehyde type phenolic resin, m-hydroxybenzaldehyde type phenolic resin and the like. , One of these may be used alone, or two or more thereof may be used in combination. Of these, salicylaldehyde type phenol resin is preferable.
【化１３】
（ここで、Ｒは水素原子及び炭素数１〜１０の置換又は
非置換の一価の炭化水素基から選ばれ、ｎは１〜１０の
整数を示す。）
トリフェニルメタン型フェノール樹脂を用いる場合、そ
の配合量は、その性能を発揮するために硬化剤全量に対
して３０重量％以上とすることが好ましく、５０重量％
以上がより好ましい。ノボラック型フェノール樹脂とし
ては、たと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、ナフトールノボラック樹脂等が挙げら
れ、なかでもフェノールノボラック樹脂が好ましい。ノ
ボラック型フェノール樹脂を用いる場合、その配合量
は、その性能を発揮するために硬化剤全量に対して３０
重量％以上とすることが好ましく、５０重量％以上がよ
り好ましい。[Chemical 13] (Here, R is selected from a hydrogen atom and a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 10.) When using a triphenylmethane type phenol resin In order to exert its performance, its content is preferably 30% by weight or more, and 50% by weight based on the total amount of the curing agent.
The above is more preferable. Examples of the novolac type phenolic resin include phenol novolac resin, cresol novolac resin, naphthol novolac resin, and the like, of which phenol novolac resin is preferable. When using a novolac type phenolic resin, its compounding amount is 30 with respect to the total amount of the curing agent in order to exert its performance.
It is preferably at least 50% by weight, more preferably at least 50% by weight.
【００１７】上記のビフェニル型フェノール樹脂、アラ
ルキル型フェノール樹脂、ジシクロペンタジエン型フェ
ノール樹脂、トリフェニルメタン型フェノール樹脂及び
ノボラック型フェノール樹脂は、いずれか１種を単独で
用いても２種以上を組合わせて用いてもよいが、その配
合量は硬化剤全量に対して合わせて６０重量％以上とす
ることが好ましく、８０重量％以上がより好ましい。The above biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolak type phenol resin may be used alone or in combination of two or more kinds. Although they may be used together, the total amount thereof is preferably 60% by weight or more, more preferably 80% by weight or more, based on the total amount of the curing agent.
【００１８】（Ａ）エポキシ樹脂と（Ｂ）硬化剤との当
量比、すなわち、エポキシ樹脂中のエポキシ基数に対す
る硬化剤中の水酸基数の比（硬化剤中の水酸基数／エポ
キシ樹脂中のエポキシ基数）は、特に制限はないが、そ
れぞれの未反応分を少なく抑えるために０．５〜２の範
囲に設定されることが好ましく、０．６〜１．３がより
好ましい。成形性及び耐リフロー性に優れる封止用エポ
キシ樹脂成形材料を得るためには０．８〜１．２の範囲
に設定されることがさらに好ましい。The equivalent ratio of (A) epoxy resin to (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (the number of hydroxyl groups in the curing agent / the number of epoxy groups in the epoxy resin). ) Is not particularly limited, but is preferably set in the range of 0.5 to 2 and more preferably 0.6 to 1.3 in order to suppress the unreacted content of each. In order to obtain an epoxy resin molding material for sealing which is excellent in moldability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.
【００１９】本発明において用いられる（Ｃ）離型剤で
処理された金属酸化物又は金属水酸化物は、難燃剤、も
しくは高放熱剤として作用する。まず、金属水酸化物に
ついて説明する。金属水酸化物は、本発明の効果が得ら
れれば特に制限はないが、成形性の観点からは複合金属
水酸化物を用いることが好ましく、特に、下記一般式
（Ｉ）で示される化合物が難燃性向上の点で好ましい。The metal oxide or metal hydroxide treated with the releasing agent (C) used in the present invention acts as a flame retardant or a high heat dissipation agent. First, the metal hydroxide will be described. The metal hydroxide is not particularly limited as long as the effects of the present invention can be obtained, but from the viewpoint of moldability, it is preferable to use a composite metal hydroxide, and particularly, a compound represented by the following general formula (I) is used. It is preferable in terms of improving flame retardancy.
【化１４】
ｐ(Ｍ1 aＯb)・ｑ(Ｍ2 cＯd)・ｒ(Ｍ3 eＯf)・ｍＨ2Ｏ （Ｉ）
（ここで、Ｍ1、Ｍ2及びＭ3は互いに異なる金属元素を
示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｐ、ｑ及びｍは正の
数、ｒは０又は正の数を示す。）
上記一般式（Ｉ）中のＭ1、Ｍ2及びＭ3は互いに異なる
金属元素であれば特に制限はないが、難燃性の観点から
は、Ｍ1が第３周期の金属元素、IIＡ族のアルカリ土類
金属元素、IVＢ族、IIＢ族、VIII族、ＩＢ族、IIIＡ族
及びIVＡ族に属する金属元素から選ばれ、Ｍ2がIIIＢ〜
IIＢ族の遷移金属元素から選ばれることが好ましく、Ｍ
1がマグネシウム、カルシウム、アルミニウム、スズ、
チタン、鉄、コバルト、ニッケル、銅及び亜鉛から選ば
れ、Ｍ2が鉄、コバルト、ニッケル、銅及び亜鉛から選
ばれることがより好ましい。さらに、流動性の観点から
は、Ｍ1がマグネシウム、Ｍ2が亜鉛又はニッケルで、ｒ
＝０のものが好ましい。Ｍ 1 aＯb、Ｍ2 cＯd及びＭ3 eＯf
のモル比のｐ、ｑ及びｒの比は特に制限はないが、ｒ＝
０で、ｐ／ｑが１／９９〜１／１であることが好まし
い。市販品としては、例えば、上記一般式（Ｉ）中のＭ
1がマグネシウム、Ｍ2が亜鉛で、ｐが７、ｑが３、ｍが
１０で、ａ、ｂ、ｃ及びｄが１で、ｒが０である水酸化
マグネシウム・亜鉛固溶体複合金属水酸化物（タテホ化
学工業株式会社製商品名エコーマグＺ−１０）を使用で
きる。なお、金属元素とは半金属元素といわれるものも
含めるものとし、非金属元素を除く全ての元素をさす。
金属元素の分類は、典型元素をＡ亜族、遷移元素をＢ亜
族とする長周期型の周期律表（出典：共立出版株式会社
発行「化学大辞典４」１９８７年２月１５日縮刷版第３
０刷）に基づいて行った。複合金属水酸化物以外の金属
水酸化物としては、マグネシウム、アルミニウム、チタ
ン、ジルコニウム、ビスマス、カルシウム、バリウムか
ら選ばれる元素の水酸化物等が挙げられ、なかでも、水
酸化アルミニウム、水酸化マグネシウムが好ましい。こ
れら金属水酸化物は単独で用いても２種以上を組み合わ
せて用いてもよい。[Chemical 14]
p (M1 aOb) ・ Q (M2 cOd) ・ R (M3 eOf) ・ MH2O (I)
(Where M1, M2And M3Are different metal elements
, A, b, c, d, e, f, p, q and m are positive
The number r is 0 or a positive number. )
M in the general formula (I)1, M2And M3Are different from each other
There is no particular limitation as long as it is a metal element, but from the viewpoint of flame retardancy
Is M1Is the third period metal element, Group IIA alkaline earth
Metal element, IVB group, IIB group, VIII group, IB group, IIIA group
And metal elements belonging to Group IVA, M2Is IIIB ~
It is preferably selected from the group IIB transition metal elements, and M
1Is magnesium, calcium, aluminum, tin,
Select from titanium, iron, cobalt, nickel, copper and zinc
M2Is selected from iron, cobalt, nickel, copper and zinc
It is more preferable to be exposed. Furthermore, from the perspective of liquidity
Is M1Is magnesium, M2Is zinc or nickel, and
= 0 is preferable. M 1 aOb, M2 cOdAnd M3 eOf
The molar ratio of p, q and r is not particularly limited, but r =
0, p / q is preferably 1/99 to 1/1
Yes. Examples of commercially available products include M in the general formula (I).
1Is magnesium, M2Is zinc, p is 7, q is 3, and m is
10, hydroxylation in which a, b, c and d are 1 and r is 0
Magnesium / Zinc solid solution composite metal hydroxide (Tateho)
Gaku Kogyo Co., Ltd. product name Echo Mag Z-10)
Wear. Some metal elements are called metalloid elements.
Included and refers to all elements except non-metallic elements.
As for the classification of metallic elements, typical elements are group A and transition elements are group B.
Periodic table of long period type as a tribe (Source: Kyoritsu Publishing Co., Ltd.
Published "Chemical Dictionary 4" February 15, 1987, reduced edition, third edition
0 printing). Metals other than complex metal hydroxides
As hydroxides, magnesium, aluminum, titanium
, Zirconium, bismuth, calcium, barium
Examples include hydroxides of elements selected from
Aluminum oxide and magnesium hydroxide are preferred. This
These metal hydroxides can be used alone or in combination of two or more.
You may use it.
【００２０】次に金属酸化物について説明する。金属酸
化物は、本発明の効果が得られれば特に制限はないが、
酸化ナトリウム、酸化カリウム等のアルカリ金属酸化
物、酸化マグネシウム、酸化カルシウム等のアルカリ土
類金属酸化物の他、酸化アルミニウム、酸化亜鉛等が挙
げられる。これらを単独で用いても２種以上を組み合わ
せて用いてもよい。特に、高放熱性の観点からは酸化ア
ルミニウム等が好適に用いられ、難燃性の観点からは酸
化マグネシウム、酸化カルシウム等のアルカリ土類金属
などが好適に用いられる。金属水酸化物と金属酸化物と
は、それぞれ単独で使用してもよいし、両者を併用して
も良い。両者を併用する場合、上記金属水酸化物と金属
酸化物との複合金属水酸化物も使用できる。本発明の
（Ｃ）成分に用いるものとして、成形性、難燃性等の観
点からは金属水酸化物、特に複合金属水酸化物が好まし
い。Next, the metal oxide will be described. The metal oxide is not particularly limited as long as the effects of the present invention can be obtained,
Examples thereof include alkali metal oxides such as sodium oxide and potassium oxide, alkaline earth metal oxides such as magnesium oxide and calcium oxide, and aluminum oxide and zinc oxide. These may be used alone or in combination of two or more. In particular, aluminum oxide and the like are preferably used from the viewpoint of high heat dissipation, and alkaline earth metals such as magnesium oxide and calcium oxide are preferably used from the viewpoint of flame retardancy. The metal hydroxide and the metal oxide may be used alone or in combination. When both are used in combination, a composite metal hydroxide of the above metal hydroxide and metal oxide can also be used. As the component (C) of the present invention, a metal hydroxide, particularly a composite metal hydroxide, is preferable from the viewpoint of moldability, flame retardancy and the like.
【００２１】（Ｃ）成分に用いる金属酸化物又は金属水
酸化物の形状は特に制限はないが、流動性の観点から
は、平板状より、適度の厚みを有する多面体形状が好ま
しい。また、形状は鋭角が少ないものが好ましく、粒径
は、最大粒径が１００μｍ以下が好ましく、７５μｍ以
下がより好ましい。平均粒径は１〜３０μｍが好まし
い。（Ｃ）成分に用いる金属酸化物および金属水酸化物
の配合量は特に制限はないが、難燃剤として用いる場合
には封止用エポキシ樹脂成形材料に対して０．５〜２０
重量％が好ましく、０．７〜１５重量％がより好まし
く、１．４〜１２重量％がさらに好ましい。０．５重量
％未満では難燃性が不十分となる傾向があり、２０重量
％を超えると流動性及び耐リフロー性が低下する傾向が
ある。また、高放熱剤として使用する場合には封止用エ
ポキシ樹脂成形材料に対して１０〜９８重量％が好まし
く、２０〜９５重量％がより好ましく、２５〜９２重量
％がさらに好ましい。１０重量％未満では高放熱性が不
十分となる傾向があり、９８重量％を超えると流動性が
著しく低下する傾向がある。The shape of the metal oxide or metal hydroxide used as the component (C) is not particularly limited, but from the viewpoint of fluidity, a polyhedral shape having an appropriate thickness is preferable to a flat plate shape. Further, the shape is preferably one having a small acute angle, and the particle diameter is preferably the maximum particle diameter of 100 μm or less, more preferably 75 μm or less. The average particle size is preferably 1 to 30 μm. The amount of the metal oxide and the metal hydroxide used as the component (C) is not particularly limited, but when used as a flame retardant, it is 0.5 to 20 relative to the epoxy resin molding material for sealing.
Weight% is preferable, 0.7-15 weight% is more preferable, 1.4-12 weight% is still more preferable. If it is less than 0.5% by weight, flame retardancy tends to be insufficient, and if it exceeds 20% by weight, fluidity and reflow resistance tend to be lowered. When it is used as a high heat dissipation agent, it is preferably 10 to 98% by weight, more preferably 20 to 95% by weight, still more preferably 25 to 92% by weight, based on the epoxy resin molding material for sealing. If it is less than 10% by weight, the high heat dissipation tends to be insufficient, and if it exceeds 98% by weight, the fluidity tends to be remarkably lowered.
【００２２】（Ｃ）成分における金属酸化物又は金属水
酸化物の処理に用いる離型剤は、炭素数２５以上の高級
脂肪族化合物である必要があり、成形性の改善効果とい
った観点からは、炭素数２８以上の高級脂肪族化合物が
より好ましい。炭素数２５未満の化合物では、金属酸化
物又は金属水酸化物の表面改質効果が低く、成形性向上
効果が不十分となる場合がある。また、耐リフロー性、
耐湿性等の信頼性の観点からは炭素数が５７以下の高級
脂肪族化合物であることが好ましく、炭素数５０以下の
高級脂肪族化合物がより好ましい。炭素数５７より多い
高級脂肪族化合物を用いた場合、密着性の低下から上記
信頼性の低下を招き易くなる傾向がある。本発明に用い
られる離型剤は、金属酸化物又は金属水酸化物と反応性
を有する官能基を持っていることが好ましく、中でもカ
ルボキシル基やカルボン酸エステルを持つ化合物が特に
好ましい。金属酸化物又は金属水酸化物との反応性を有
する官能基を持たない化合物では、表面改質効果が不十
分となる傾向にある。上記した条件を満たす高級脂肪族
化合物としては、例えば高級脂肪酸およびそのエステル
等が挙げられ、そのうちで炭素数２５〜５７の化合物で
あることが好ましく、さらに、炭素数２８〜５０の化合
物であるのが好ましい。より好ましくは、例えば炭素数
２８の高級脂肪酸であるモンタン酸や、モンタン酸メチ
ル、モンタン酸エチル等の炭素数５７以下のモンタン酸
エステルを挙げることができる。このような化合物のう
ち１種を単独で用いても２種以上を組み合わせて用いて
もよい。The release agent used for the treatment of the metal oxide or metal hydroxide in the component (C) must be a higher aliphatic compound having 25 or more carbon atoms, and from the viewpoint of the effect of improving moldability, Higher aliphatic compounds having 28 or more carbon atoms are more preferable. If the compound has less than 25 carbon atoms, the effect of surface modification of the metal oxide or metal hydroxide is low, and the effect of improving moldability may be insufficient. Also, reflow resistance,
From the viewpoint of reliability such as moisture resistance, a higher aliphatic compound having 57 or less carbon atoms is preferable, and a higher aliphatic compound having 50 or less carbon atoms is more preferable. When a higher aliphatic compound having more than 57 carbon atoms is used, the adhesion tends to deteriorate and the reliability tends to decrease. The release agent used in the present invention preferably has a functional group reactive with a metal oxide or a metal hydroxide, and a compound having a carboxyl group or a carboxylic acid ester is particularly preferable. A compound having no functional group reactive with a metal oxide or a metal hydroxide tends to have an insufficient surface modifying effect. Examples of the higher aliphatic compounds that satisfy the above conditions include higher fatty acids and their esters, and among them, compounds having 25 to 57 carbon atoms are preferable, and compounds having 28 to 50 carbon atoms are more preferable. Is preferred. More preferred are montanic acid, which is a higher fatty acid having 28 carbon atoms, and montanic acid ester having 57 or less carbon atoms, such as methyl montanate and ethyl montanate. Of these compounds, one kind may be used alone, or two or more kinds may be used in combination.
【００２３】（Ｃ）成分における金属酸化物又は金属水
酸化物を離型剤で処理する際には、有機溶媒を用いるの
が好ましい。この有機溶媒は、本発明の効果が得られれ
ば特に制限はないが、分子内に極性を有する有機溶媒
（極性有機溶媒）を１種以上含むことが好ましい。極性
有機溶媒にはメタノール、エタノール、ｎ-プロパノー
ル、iso‐プロパノール等のアルコール類、エチレング
リコール等のグリコール類、メチルアミン、エチルアミ
ン等のアミン類、ギ酸、酢酸等の有機酸類等を挙げるこ
とができるが、中でも、炭素数６以下の、１級、２級、
又は３級のアルコール又はグリコールを１種以上使用す
ることが好ましく、炭素数の少ない１級アルコール、例
えばメタノール、エタノール等を使用することがより好
ましい。なお、ここで、「極性有機溶媒」とは、成分原
子の電気陰性度の差異から分子内の電子雲の分布に偏り
が生じ、分子内に双極子を形成するような化合物、具体
的には、酸素原子、窒素原子、ハロゲン族原子を含む有
機溶媒を指す。When the metal oxide or metal hydroxide in the component (C) is treated with a release agent, it is preferable to use an organic solvent. The organic solvent is not particularly limited as long as the effects of the present invention can be obtained, but it is preferable to include one or more polar organic solvents (polar organic solvents) in the molecule. Examples of polar organic solvents include alcohols such as methanol, ethanol, n-propanol and iso-propanol, glycols such as ethylene glycol, amines such as methylamine and ethylamine, organic acids such as formic acid and acetic acid. However, among them, primary, secondary, and
Alternatively, it is preferable to use one or more tertiary alcohols or glycols, and it is more preferable to use a primary alcohol having a small number of carbon atoms, such as methanol or ethanol. The term “polar organic solvent” as used herein means a compound that causes a bias in the distribution of electron clouds in the molecule due to the difference in electronegativity of component atoms, and specifically a compound that forms a dipole in the molecule. , An organic solvent containing an oxygen atom, a nitrogen atom, and a halogen atom.
【００２４】（Ｃ）成分における金属酸化物又は金属水
酸化物を離型剤で処理する際に用いる有機溶媒には、上
記アルコール類等の極性有機溶媒とともに、１種以上の
非極性有機溶媒を併用するのが好ましい。ここで、「非
極性有機溶媒」とは、成分原子の電気陰性度の差異から
生じる分子内の電子雲の分布に偏りが全くないか、又は
非常に小さい化合物を指し、具体的には、酸素原子、窒
素原子、ハロゲン族原子を含まない有機化合物を指す。
非極性有機溶媒の例として、ベンゼン、トルエン、キシ
レン等を挙げることができ、特にベンゼン環を有する非
極性溶媒が好ましい。As the organic solvent used when the metal oxide or metal hydroxide in the component (C) is treated with a release agent, one or more non-polar organic solvents may be used together with the polar organic solvent such as the above alcohols. It is preferable to use them in combination. Here, the "nonpolar organic solvent" refers to a compound having no or very small distribution of electron clouds in the molecule resulting from the difference in electronegativity of component atoms, and specifically, oxygen. Refers to organic compounds containing no atoms, nitrogen atoms, or halogen atoms.
Examples of the non-polar organic solvent include benzene, toluene, xylene and the like, and the non-polar solvent having a benzene ring is particularly preferable.
【００２５】（Ｃ）成分において、金属酸化物又は金属
水酸化物を、１種以上の有機溶媒を用いて離型剤処理す
る方法については、本発明の効果が得られれば特に制限
はないが、例えば、予め離型剤を溶解させた有機溶媒中
に金属酸化物、又は金属水酸化物を浸し、室温下、もし
くは加熱還流条件下、それらを一定時間攪拌後、加熱乾
燥により残存溶媒を除去する方法、また、予め離型剤を
溶解させた有機溶媒を、金属酸化物又は金属水酸化物に
直接噴霧した後に残存する有機溶媒を除去する等の方法
が挙げられる。金属酸化物及び金属水酸化物と離型剤の
比率は特に制限するものではないが、本発明の効果を充
分得る為には、金属酸化物及び金属水酸化物１００に対
し、離型剤０．１〜１０の重量比率が好ましく、０．５
〜５の重量比率がより好ましい。また、極性有機溶媒と
非極性有機溶媒とを併用する場合の両者の比率について
も特に制限するものではないが、本発明の効果を充分得
る為には、極性有機溶媒１に対し、非極性有機溶媒０．
１〜５の体積比率が好ましく、０．２〜２の体積比率が
特に好ましい。さらに、有機溶媒の量については、やは
り特に制限するものではないが、本発明の効果を充分得
る為には、極性有機溶媒と非極性有機溶媒の合計が金属
酸化物及び金属水酸化物の体積と同体積以上であること
が好ましく、加熱乾燥作業を考慮した場合、３体積倍以
下であることが好ましい。攪拌時間については、やはり
特に制限するものではないが、本発明の効果を充分得る
為には０．３〜３時間程度が好ましく、０．５〜２時間
程度がより好ましい。処理温度については、特に制限す
るものではなく、２５℃程度の室温から１５０℃程度の
温度範囲を任意に選べば良い。In the component (C), the method of treating the metal oxide or the metal hydroxide with the release agent using at least one organic solvent is not particularly limited as long as the effects of the present invention can be obtained. , For example, soaking the metal oxide or metal hydroxide in an organic solvent in which a release agent is dissolved in advance, stirring them for a certain period of time at room temperature or under the condition of heating under reflux, and then removing the residual solvent by heating and drying. And the method of removing the remaining organic solvent after directly spraying the organic solvent in which the release agent is dissolved onto the metal oxide or the metal hydroxide. The ratio of the metal oxide and the metal hydroxide to the release agent is not particularly limited, but in order to obtain the effects of the present invention sufficiently, 100 parts of the metal oxide and the metal hydroxide are mixed with 0 parts of the release agent. A weight ratio of 1 to 10 is preferable and 0.5
A weight ratio of ~ 5 is more preferred. Further, when the polar organic solvent and the non-polar organic solvent are used in combination, the ratio of both is not particularly limited, but in order to sufficiently obtain the effect of the present invention, the polar organic solvent is added to the non-polar organic solvent. Solvent 0.
A volume ratio of 1 to 5 is preferable, and a volume ratio of 0.2 to 2 is particularly preferable. Further, the amount of the organic solvent is not particularly limited, but in order to sufficiently obtain the effect of the present invention, the total amount of the polar organic solvent and the nonpolar organic solvent is the volume of the metal oxide and the metal hydroxide. Is preferably equal to or more than the same volume, and is preferably 3 times or less by volume in consideration of the heating and drying work. Although the stirring time is not particularly limited, it is preferably about 0.3 to 3 hours, more preferably about 0.5 to 2 hours in order to sufficiently obtain the effects of the present invention. The treatment temperature is not particularly limited, and a temperature range of about 25 ° C. to 150 ° C. may be arbitrarily selected.
【００２６】本発明の封止用エポキシ樹脂成形材料に
は、（Ｃ）成分の金属酸化物又は金属水酸化物に加え、
難燃剤として使用する場合には、ノンハロゲン、ノンア
ンチモンの難燃剤を必要に応じて併用することができる
し、高放熱剤として使用する場合には、溶融シリカ等の
無機充填剤を必要に応じて併用することができる。難燃
剤として使用する場合の併用相手としては、たとえば、
被覆又は無被覆の赤リン等のリン化合物、メラミン、メ
ラミン誘導体、メラミン変性フェノール樹脂、トリアジ
ン環を有する化合物、シアヌル酸誘導体、イソシアヌル
酸誘導体等の窒素含有化合物、シクロホスファゼン等の
リン及び窒素含有化合物などが挙げられ、これらの１種
を単独で用いても２種以上を組合わせて用いてもよい。
高放熱剤として使用する場合の併用相手としては、前記
溶融シリカの他に結晶性シリカ、金属又は非金属の窒化
物等が挙げられ、これらは１種を単独で用いても２種以
上を組み合わせて用いてもよい。In the epoxy resin molding material for sealing of the present invention, in addition to the metal oxide or metal hydroxide of the component (C),
When used as a flame retardant, a non-halogen or non-antimony flame retardant can be used in combination as required, and when used as a high heat dissipation agent, an inorganic filler such as fused silica is optionally added. Can be used together. As a combination partner when used as a flame retardant, for example,
Phosphorus compounds such as coated or uncoated red phosphorus, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives, isocyanuric acid derivatives, and phosphorus- and nitrogen-containing compounds such as cyclophosphazene And the like. These may be used alone or in combination of two or more.
In the case of being used as a high heat dissipation agent, in addition to the fused silica, crystalline silica, a metal or non-metal nitride, etc. may be mentioned as a combination partner. These may be used alone or in combination of two or more. You may use it.
【００２７】本発明の封止用エポキシ樹脂成形材料に
は、必要に応じて（Ｄ）無機充填剤を配合することがで
きる。（Ｄ）無機充填剤は、吸湿性、線膨張係数低減、
熱伝導性向上及び強度向上のために配合されるものであ
り、封止用エポキシ樹脂成形材料に一般に使用されるも
ので特に制限はないが、たとえば、溶融シリカ、結晶シ
リカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カル
シウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化
アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコ
ン、フォステライト、ステアタイト、スピネル、ムライ
ト、チタニア等の粉体、又はこれらを球形化したビー
ズ、ガラス繊維などが挙げられ、これらを単独で用いて
も２種以上を組み合わせて用いてもよい。なかでも、線
膨張係数低減の観点からは溶融シリカが、高熱伝導性の
観点からはアルミナが好ましく、充填剤形状は成形時の
流動性及び金型摩耗性の点から球形が好ましい。（Ｄ）
無機充填剤の配合量は、難燃性、成形性、吸湿性、線膨
張係数低減及び強度向上の観点から、封止用エポキシ樹
脂成形材料に対して６０重量％以上が好ましく、７０〜
９５重量％がより好ましく、７５〜９２重量％がさらに
好ましい。６０重量％未満では難燃性及び耐リフロー性
が低下する傾向があり、９５重量％を超えると流動性が
不足する傾向がある。The sealing epoxy resin molding material of the present invention may optionally contain (D) an inorganic filler. (D) The inorganic filler is hygroscopic, has a reduced linear expansion coefficient,
It is blended to improve thermal conductivity and strength, and is generally used for epoxy resin molding materials for encapsulation and is not particularly limited. For example, fused silica, crystalline silica, alumina, zircon, silicic acid. Powder of calcium, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc. , Glass fiber, etc., and these may be used alone or in combination of two or more kinds. Of these, fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity during molding and wear of the mold. (D)
From the viewpoint of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement, the amount of the inorganic filler compounded is preferably 60% by weight or more, and 70 to 70% by weight based on the epoxy resin molding material for sealing.
95 wt% is more preferable, and 75 to 92 wt% is further preferable. If it is less than 60% by weight, flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by weight, fluidity tends to be insufficient.
【００２８】本発明の封止用エポキシ樹脂成形材料に
は、必要に応じて（Ｅ）硬化促進剤を用いることができ
る。（Ｅ）硬化促進剤としては、封止用エポキシ樹脂成
形材料に一般に使用されているもので特に制限はない
が、たとえば、１，８−ジアザ−ビシクロ（５，４，
０）ウンデセン−７、１，５−ジアザ−ビシクロ（４，
３，０）ノネン、５、６−ジブチルアミノ−１，８−ジ
アザ−ビシクロ（５，４，０）ウンデセン−７等のシク
ロアミジン化合物及びこれらの化合物に無水マレイン
酸、１，４−ベンゾキノン、２，５−トルキノン、１，
４−ナフトキノン、２，３−ジメチルベンゾキノン、
２，６−ジメチルベンゾキノン、２，３−ジメトキシ−
５−メチル−１，４−ベンゾキノン、２，３−ジメトキ
シ−１，４−ベンゾキノン、フェニル−１，４−ベンゾ
キノン等のキノン化合物、ジアゾフェニルメタン、フェ
ノール樹脂等のπ結合をもつ化合物を付加してなる分子
内分極を有する化合物、ベンジルジメチルアミン、トリ
エタノールアミン、ジメチルアミノエタノール、トリス
（ジメチルアミノメチル）フェノール等の３級アミン類
及びこれらの誘導体、２−メチルイミダゾール、２−フ
ェニルイミダゾール、２−フェニル−４−メチルイミダ
ゾール等のイミダゾール類及びこれらの誘導体、トリブ
チルホスフィン、メチルジフェニルホスフィン、トリフ
ェニルホスフィン、トリス（４−メチルフェニル）ホス
フィン、ジフェニルホスフィン、フェニルホスフィン等
のホスフィン化合物及びこれらのホスフィン化合物に無
水マレイン酸、上記キノン化合物、ジアゾフェニルメタ
ン、フェノール樹脂等のπ結合をもつ化合物を付加して
なる分子内分極を有するリン化合物、テトラフェニルホ
スホニウムテトラフェニルボレート、トリフェニルホス
フィンテトラフェニルボレート、２−エチル−４−メチ
ルイミダゾールテトラフェニルボレート、Ｎ−メチルモ
ルホリンテトラフェニルボレート等のテトラフェニルボ
ロン塩及びこれらの誘導体などが挙げられ、これらを単
独で用いても２種以上を組み合わせて用いてもよい。な
かでも、硬化性及び流動性の観点からは、ホスフィン化
合物及びホスフィン化合物とキノン化合物との付加物が
好ましく、トリフェニルホスフィン等の第三ホスフィン
化合物及びトリフェニルホスフィンとキノン化合物との
付加物がより好ましい。第三ホスフィン化合物を用いる
場合にはキノン化合物をさらに含有することが好まし
い。If necessary, a curing accelerator (E) can be used in the epoxy resin molding material for sealing of the present invention. The curing accelerator (E) is generally used in epoxy resin molding materials for encapsulation and is not particularly limited, but, for example, 1,8-diaza-bicyclo (5,4,4).
0) undecene-7,1,5-diaza-bicyclo (4,
3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 and other cycloamidine compounds, and these compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,
4-naphthoquinone, 2,3-dimethylbenzoquinone,
2,6-dimethylbenzoquinone, 2,3-dimethoxy-
Add quinone compounds such as 5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane and phenol resin. Compounds having intramolecular polarization, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tertiary amines such as tris (dimethylaminomethyl) phenol and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole and other imidazoles and derivatives thereof, phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine and phenylphosphine And a phosphorus compound having an intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, and a phenol resin to these phosphine compounds, tetraphenylphosphonium tetraphenylborate, triphenylphosphine Tetraphenylboron, 2-ethyl-4-methylimidazole tetraphenylborate, tetraphenylboron salts such as N-methylmorpholine tetraphenylborate and derivatives thereof, and the like can be mentioned. Even if these are used alone, two or more kinds are combined. You may use it. Among them, from the viewpoint of curability and fluidity, a phosphine compound and an adduct of a phosphine compound and a quinone compound are preferable, and a third phosphine compound such as triphenylphosphine and an adduct of a triphenylphosphine and a quinone compound are more preferable. preferable. When a third phosphine compound is used, it is preferable to further contain a quinone compound.
【００２９】（Ｅ）硬化促進剤の配合量は、硬化促進効
果が達成される量であれば特に制限されるものではない
が、封止用エポキシ樹脂成形材料に対して０．００５〜
２重量％が好ましく、０．０１〜０．５重量％がより好
ましい。０．００５重量％未満では短時間での硬化性に
劣る傾向があり、２重量％を超えると硬化速度が速すぎ
て良好な成形品を得ることが困難になる傾向がある。The compounding amount of the (E) curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is 0.005 to the epoxy resin molding material for sealing.
2 wt% is preferable, and 0.01 to 0.5 wt% is more preferable. If it is less than 0.005% by weight, the curability in a short time tends to be inferior, and if it exceeds 2% by weight, the curing rate tends to be too fast, and it tends to be difficult to obtain a good molded product.
【００３０】本発明の封止用エポキシ樹脂成形材料に
は、ＩＣ等の半導体素子の耐湿性及び高温放置特性を向
上させる観点から、必要に応じて（Ｆ）イオントラップ
剤をさらに配合することができる。（Ｆ）イオントラッ
プ剤としては特に制限はなく、従来公知のものを用いる
ことができるが、たとえば、ハイドロタルサイト類や、
マグネシウム、アルミニウム、チタン、ジルコニウム及
びビスマスから選ばれる元素の含水酸化物等が挙げら
れ、これらを単独で用いても２種以上を組み合わせて用
いてもよい。なかでも、下記一般式（XIII）で示される
ハイドロタルサイトが好ましい。From the viewpoint of improving the moisture resistance and high-temperature storage characteristics of semiconductor elements such as ICs, the encapsulating epoxy resin molding material of the present invention may further contain (F) an ion trap agent, if necessary. it can. The ion trap agent (F) is not particularly limited, and conventionally known ones can be used. For example, hydrotalcites and
Examples thereof include hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth, and these may be used alone or in combination of two or more kinds. Among them, hydrotalcite represented by the following general formula (XIII) is preferable.
【化１５】
Ｍｇ1-XＡｌX（ＯＨ）2（ＣＯ3）X/2・ｍＨ2Ｏ ……（XIII）
（０＜Ｘ≦０.５、ｍは正の数）
（Ｆ）イオントラップ剤の配合量は、ハロゲンイオンな
どの陰イオンを捕捉できる十分量であれば特に制限はな
いが、成形性、耐湿性及び高温放置特性の観点から、
（Ａ）エポキシ樹脂に対して０．1〜３０重量％が好ま
しく、０．５〜１０重量％がより好ましく、１〜５重量
％がさらに好ましい。Embedded image Mg 1-X Al X (OH) 2 (CO 3 ) X / 2 · mH 2 O (XIII) (0 <X ≦ 0.5, m is a positive number) (F) Ion trap The blending amount of the agent is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions, but from the viewpoint of moldability, moisture resistance and high temperature storage characteristics,
The amount of the epoxy resin (A) is preferably 0.1 to 30% by weight, more preferably 0.5 to 10% by weight, still more preferably 1 to 5% by weight.
【００３１】また、本発明の封止用エポキシ樹脂成形材
料には、樹脂成分と無機充填剤との接着性を高めるため
に、必要に応じて、エポキシシラン、メルカプトシラ
ン、アミノシラン、アルキルシラン、ウレイドシラン、
ビニルシラン等の各種シラン系化合物、チタン系化合
物、アルミニウムキレート類、アルミニウム／ジルコニ
ウム系化合物等の公知のカップリング剤を添加すること
ができる。これらを例示すると、ビニルトリクロロシラ
ン、ビニルトリエトキシシラン、ビニルトリス（β−メ
トキシエトキシ）シラン、γ−メタクリロキシプロピル
トリメトキシシラン、β−（３，４−エポキシシクロヘ
キシル）エチルトリメトキシシラン、γ−グリシドキシ
プロピルトリメトキシシラン、γ−グリシドキシプロピ
ルメチルジメトキシシラン、ビニルトリアセトキシシラ
ン、γ−メルカプトプロピルトリメトキシシラン、γ−
アミノプロピルトリエトキシシラン、γ-アニリノプロ
ピルトリメトキシシラン、γ-アニリノプロピルメチル
ジメトキシシラン、γ−［ビス（β−ヒドロキシエチ
ル）］アミノプロピルトリエトキシシラン、Ｎ−β−
（アミノエチル）−γ−アミノプロピルトリメトキシシ
ラン、γ−（β−アミノエチル）アミノプロピルジメト
キシメチルシラン、Ｎ−（トリメトキシシリルプロピ
ル）エチレンジアミン、Ｎ−（ジメトキシメチルシリル
イソプロピル）エチレンジアミン、メチルトリメトキシ
シラン、ジメチルジメトキシシラン、メチルトリエトキ
シシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチ
ル）−γ−アミノプロピルトリメトキシシラン、γ−ク
ロロプロピルトリメトキシシラン、ヘキサメチルジシラ
ン、ビニルトリメトキシシラン、γ−メルカプトプロピ
ルメチルジメトキシシラン等のシラン系カップリング
剤、イソプロピルトリイソステアロイルチタネート、イ
ソプロピルトリス（ジオクチルパイロホスフェート）チ
タネート、イソプロピルトリ（Ｎ−アミノエチル−アミ
ノエチル）チタネート、テトラオクチルビス（ジトリデ
シルホスファイト）チタネート、テトラ（２，２−ジア
リルオキシメチル−１−ブチル）ビス（ジトリデシル）
ホスファイトチタネート、ビス（ジオクチルパイロホス
フェート）オキシアセテートチタネート、ビス（ジオク
チルパイロホスフェート）エチレンチタネート、イソプ
ロピルトリオクタノイルチタネート、イソプロピルジメ
タクリルイソステアロイルチタネート、イソプロピルト
リドデシルベンゼンスルホニルチタネート、イソプロピ
ルイソステアロイルジアクリルチタネート、イソプロピ
ルトリ（ジオクチルホスフェート）チタネート、イソプ
ロピルトリクミルフェニルチタネート、テトライソプロ
ピルビス（ジオクチルホスファイト）チタネート等のチ
タネート系カップリング剤などが挙げられ、これらを単
独で用いても２種以上を組み合わせて用いてもよい。上
記カップリング剤の配合量は、（Ｄ）無機充填剤に対し
て０．０５〜５重量％であることが好ましく、０．１〜
２．５重量％がより好ましい。０．０５重量％未満では
フレームとの接着性が低下する傾向があり、５重量％を
超えるとパッケージの成形性が低下する傾向がある。Further, in the epoxy resin molding material for encapsulation of the present invention, in order to enhance the adhesiveness between the resin component and the inorganic filler, if necessary, epoxysilane, mercaptosilane, aminosilane, alkylsilane and ureido are used. Silane,
Known coupling agents such as various silane compounds such as vinylsilane, titanium compounds, aluminum chelates, aluminum / zirconium compounds and the like can be added. Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycine. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxy Silane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ -A silane coupling agent such as mercaptopropylmethyldimethoxysilane, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri N- aminoethyl - aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyl-1-butyl) bis (ditridecyl)
Phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl isostearoyl diacrylic titanate, Examples of titanate coupling agents such as isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. can be used alone or in combination of two or more. Good. The compounding amount of the coupling agent is preferably 0.05 to 5% by weight with respect to the inorganic filler (D), and is 0.1 to 5.
2.5% by weight is more preferred. If it is less than 0.05% by weight, the adhesiveness to the frame tends to decrease, and if it exceeds 5% by weight, the moldability of the package tends to decrease.
【００３２】さらに、本発明の封止用エポキシ樹脂成形
材料には、その他の添加剤として、高級脂肪酸、高級脂
肪酸金属塩、エステル系ワックス、ポリオレフィン系ワ
ックス、ポリエチレン、酸化ポリエチレン等の離型剤、
カーボンブラック等の着色剤、シリコーンオイル、シリ
コーンゴム粉末等の応力緩和剤などを必要に応じて配合
することができる。Further, in the epoxy resin molding material for encapsulation of the present invention, as other additives, a release agent such as higher fatty acid, higher fatty acid metal salt, ester wax, polyolefin wax, polyethylene, or polyethylene oxide,
A coloring agent such as carbon black, a stress relieving agent such as silicone oil or silicone rubber powder, and the like can be blended as necessary.
【００３３】本発明の封止用エポキシ樹脂成形材料は、
各種原材料を均一に分散混合できるのであれば、いかな
る手法を用いても調製できるが、一般的な手法として、
所定の配合量の原材料をミキサー等によって十分混合し
た後、ミキシングロール、押出機等によって溶融混練し
た後、冷却、粉砕する方法を挙げることができる。成形
条件に合うような寸法及び重量でタブレット化すると使
いやすい。The encapsulating epoxy resin molding material of the present invention is
As long as various raw materials can be uniformly dispersed and mixed, it can be prepared by any method, but as a general method,
A method may be mentioned in which a predetermined amount of raw materials are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, and then cooled and pulverized. It is easy to use if it is made into a tablet with dimensions and weight that match the molding conditions.
【００３４】本発明で得られる封止用エポキシ樹脂成形
材料により封止した素子を備えた電子部品装置として
は、リードフレーム、配線済みのテープキャリア、配線
板、ガラス、シリコンウエハ等の支持部材に、半導体チ
ップ、トランジスタ、ダイオード、サイリスタ等の能動
素子、コンデンサ、抵抗体、コイル等の受動素子等の素
子を搭載し、必要な部分を本発明の封止用エポキシ樹脂
成形材料で封止した、電子部品装置などが挙げられる。
このような電子部品装置としては、たとえば、リードフ
レーム上に半導体素子を固定し、ボンディングパッド等
の素子の端子部とリード部をワイヤボンディングやバン
プで接続した後、本発明の封止用エポキシ樹脂成形材料
を用いてトランスファ成形等により封止してなる、ＤＩ
Ｐ（Dual Inline Package）、ＰＬＣＣ（Plastic Leade
d Chip Carrier）、ＱＦＰ（Quad Flat Package）、Ｓ
ＯＰ（Small Outline Package）、ＳＯＪ（Small Outli
ne J-lead package）、ＴＳＯＰ（Thin Small Outline
Package）、ＴＱＦＰ（Thin Quad Flat Package）等の
一般的な樹脂封止型ＩＣ、テープキャリアにバンプで接
続した半導体チップを、本発明の封止用エポキシ樹脂成
形材料で封止したＴＣＰ（Tape Carrier Package）、配
線板やガラス上に形成した配線に、ワイヤボンディン
グ、フリップチップボンディング、はんだ等で接続した
半導体チップ、トランジスタ、ダイオード、サイリスタ
等の能動素子及び／又はコンデンサ、抵抗体、コイル等
の受動素子を、本発明の封止用エポキシ樹脂成形材料で
封止したＣＯＢ（Chip On Board）モジュール、ハイブ
リッドＩＣ、マルチチップモジュール、裏面に配線板接
続用の端子を形成した有機基板の表面に素子を搭載し、
バンプまたはワイヤボンディングにより素子と有機基板
に形成された配線を接続した後、本発明の封止用エポキ
シ樹脂成形材料で素子を封止したＢＧＡ（Ball Grid Ar
ray）、ＣＳＰ（Chip Size Package）などが挙げられ
る。また、プリント回路板にも本発明の封止用エポキシ
樹脂成形材料は有効に使用できる。The electronic component device provided with the element encapsulated by the encapsulating epoxy resin molding material obtained in the present invention can be used as a supporting member such as a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, or the like. , Semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors, elements such as passive elements such as coils are mounted, and necessary parts are sealed with the epoxy resin molding material for sealing of the present invention, Examples include electronic component devices.
As such an electronic component device, for example, after fixing a semiconductor element on a lead frame and connecting the terminal portion of the element such as a bonding pad and the lead portion by wire bonding or bump, the sealing epoxy resin of the present invention is used. DI formed by transfer molding using a molding material
P (Dual Inline Package), PLCC (Plastic Leade)
d Chip Carrier), QFP (Quad Flat Package), S
OP (Small Outline Package), SOJ (Small Outli
ne J-lead package), TSOP (Thin Small Outline)
Package), TQFP (Thin Quad Flat Package), and other general resin-sealed ICs, TCP (Tape Carrier) in which a semiconductor chip connected to a tape carrier by bumps is encapsulated with the encapsulating epoxy resin molding material of the present invention. Package), active elements such as semiconductor chips, transistors, diodes, thyristors, etc. that are connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. and / or passive elements such as capacitors, resistors and coils. A device is formed on the surface of a COB (Chip On Board) module, a hybrid IC, a multi-chip module in which an element is encapsulated with the encapsulating epoxy resin molding material of the present invention, and an organic substrate on which terminals for connecting wiring boards are formed on the back surface. Equipped with,
BGA (Ball Grid Ar) in which the element and the wiring formed on the organic substrate are connected by bumps or wire bonding and then the element is encapsulated by the encapsulating epoxy resin molding material of the present invention.
ray), CSP (Chip Size Package), and the like. Further, the epoxy resin molding material for sealing of the present invention can be effectively used for printed circuit boards.
【００３５】本発明の封止用エポキシ樹脂成形材料を用
いて素子を封止する方法としては、低圧トランスファ成
形法が最も一般的であるが、インジェクション成形法、
圧縮成形法等を用いてもよい。As a method of encapsulating an element using the encapsulating epoxy resin molding material of the present invention, the low pressure transfer molding method is the most general method.
A compression molding method or the like may be used.
【００３６】[0036]
【実施例】次に実施例により本発明を説明するが、本発
明の範囲はこれらの実施例に限定されるものではない。
（離型剤で処理した金属酸化物の作製例）平均粒径２０
μｍの不定形酸化アルミニウム（昭和電工株式会社製商
品名ＡＳ‐２０）６００ｇを、メタノール／キシレン＝
１／１（体積比）溶媒４００ｍｌにモンタン酸（炭素数
２８。クラリアントジャパン株式会社製商品名ＨＷ‐Ｓ
Ｗ）１２ｇを溶解させた懸濁液に注ぎ、還流下１００℃
で１時間撹拌した後、取り出して吸引濾過し、１５０℃
で１時間乾燥を行い、金属酸化物１を作製した。また、
モンタン酸を、モンタン酸とエチレングリコールのジエ
ステル化物（炭素数５８。クラリアントジャパン株式会
社製商品名ＨＷ−Ｅ）とした以外は金属酸化物１と同様
にして処理を行い、金属酸化物２を作製した。比較のた
めに、モンタン酸を、α−オレフィン（炭素数２０）と
無水マレイン酸との１：１共重合体（日本油脂株式会社
製商品名ニッサンエレクトールＤ１２１）とした以外は
金属酸化物１と同様にして処理を行い、比較金属酸化物
１を作製した。無処理の前記酸化アルミニウムを比較金
属酸化物２とした。The present invention will now be described with reference to examples, but the scope of the present invention is not limited to these examples. (Production Example of Metal Oxide Treated with Release Agent) Average Particle Size 20
600 g of μm amorphous aluminum oxide (trade name AS-20 manufactured by Showa Denko KK) was added to methanol / xylene =
In 1/1 (volume ratio) solvent 400 ml, montanic acid (carbon number 28. Product name HW-S manufactured by Clariant Japan Co., Ltd.
W) Pour into a suspension in which 12 g is dissolved and reflux at 100 ° C.
After stirring for 1 hour, remove and filter with suction to 150 ° C.
And dried for 1 hour to prepare metal oxide 1. Also,
A metal oxide 2 was prepared by performing the same treatment as the metal oxide 1 except that montanic acid was changed to a diester of montanic acid and ethylene glycol (carbon number 58; trade name HW-E manufactured by Clariant Japan Co., Ltd.). did. For comparison, a metal oxide 1 except that montanic acid was a 1: 1 copolymer of α-olefin (having 20 carbon atoms) and maleic anhydride (trade name: Nissan Electol D121, manufactured by NOF CORPORATION) Comparative Metal Oxide 1 was prepared by treating in the same manner as above. The untreated aluminum oxide was designated as Comparative Metal Oxide 2.
【００３７】（離型剤で処理した金属水酸化物の作製
例）上記組成式（Ｉ）中のＭ1がマグネシウム、Ｍ2が亜
鉛で、ｐが７、ｑが３、ｍが１０で、ａ、ｂ、ｃ及びｄ
が１で、ｒが０である水酸化マグネシウム・亜鉛固溶体
複合金属水酸化物（タテホ化学工業株式会社製商品名エ
コーマグＺ−１０）１３５ｇを、メタノール／キシレン
＝１／１（体積比）溶媒２８０ｍｌに前記モンタン酸
１．８ｇを溶解させた懸濁液に注ぎ、還流下１００℃で
１時間撹拌した後、取り出して吸引濾過し、１５０℃で
１時間乾燥を行い、金属水酸化物１を作製した。モンタ
ン酸を前記モンタン酸ジエステルとした以外は金属水酸
化物１と同様にして処理を行い、金属水酸化物２を作製
した。メタノール／キシレン＝１／１（体積比）溶媒を
キシレンとした以外は金属水酸化物１と同様にして処理
を行い、金属水酸化物３を作製した。さらに、水酸化マ
グネシウム（協和化学工業株式会社製商品名キスマＳ
２）６７．５ｇを、メタノール／キシレン＝１／１（体
積比）溶媒１５０ｍｌに前記モンタン酸０．９ｇを溶解
させた懸濁液に注ぎ、還流下１００℃で１時間撹拌した
後、取り出して吸引濾過し、１５０℃で１時間乾燥を行
い、金属水酸化物４を作製した。比較のために、モンタ
ン酸を、前記α−オレフィンと無水マレイン酸との１：
１共重合体とした以外は金属水酸化物１と同様にして処
理を行い、比較金属水酸化物１を作製した。無処理の前
記水酸化マグネシウム・亜鉛固溶体を比較金属水酸化物
２とした。無処理の前記水酸化マグネシウムを比較金属
水酸化物３とした。(Production Example of Metal Hydroxide Treated with Release Agent) In the above composition formula (I), M 1 is magnesium, M 2 is zinc, p is 7, q is 3, and m is 10, a, b, c and d
Is 1 and r is 0, 135 g of magnesium hydroxide / zinc solid solution composite metal hydroxide (trade name Echomag Z-10 manufactured by Tateho Chemical Industry Co., Ltd.), 280 ml of methanol / xylene = 1/1 (volume ratio) solvent Was poured into a suspension in which 1.8 g of the above-mentioned montanic acid was dissolved, stirred at reflux at 100 ° C. for 1 hour, taken out, suction-filtered, and dried at 150 ° C. for 1 hour to prepare metal hydroxide 1. did. A metal hydroxide 2 was prepared by treating in the same manner as the metal hydroxide 1 except that the montanic acid diester was used as the montanic acid. Methanol / xylene = 1/1 (volume ratio) Metal hydroxide 3 was prepared by the same treatment as metal hydroxide 1 except that xylene was used as the solvent. Furthermore, magnesium hydroxide (Kyowa Chemical Industry Co., Ltd. product name Kisuma S
2) 67.5 g was poured into a suspension prepared by dissolving 0.9 g of montanic acid in 150 ml of a solvent of methanol / xylene = 1/1 (volume ratio), and the mixture was stirred under reflux at 100 ° C. for 1 hour, and then taken out. It was suction filtered and dried at 150 ° C. for 1 hour to prepare metal hydroxide 4. For comparison, montanic acid was prepared by mixing 1 part of the above α-olefin with maleic anhydride.
Comparative metal hydroxide 1 was prepared by treating in the same manner as metal hydroxide 1 except that the 1-copolymer was used. The untreated magnesium hydroxide / zinc solid solution was designated as Comparative Metal Hydroxide 2. The untreated magnesium hydroxide was used as a comparative metal hydroxide 3.
【００３８】（実施例１〜８、比較例１〜５）エポキシ
樹脂として、エポキシ当量１９２、融点１０５℃のビフ
ェニル型エポキシ樹脂（エポキシ樹脂１：ジャパンエポ
キシレジン株式会社製商品名エピコートＹＸ−４０００
Ｈ）、エポキシ当量２１０、軟化点１３０℃のスチルベ
ン型エポキシ樹脂（エポキシ樹脂２：住友化学工業株式
会社製商品名ＥＳＬＶ−２１０）、エポキシ当量１９
５、軟化点６５℃のｏ−クレゾールノボラック型エポキ
シ樹脂（エポキシ樹脂３：住友化学工業株式会社製商品
名ＥＳＣＮ−１９０）、エポキシ当量２４４、融点１１
８℃の硫黄原子含有エポキシ樹脂（エポキシ樹脂４：新
日鐵化学株式会社製商品名ＹＳＬＶ−１２０ＴＥ）、硬
化剤として、水酸基当量１７２、軟化点７０℃のフェノ
ール・アラルキル樹脂（三井化学株式会社製商品名ミレ
ックスＸＬ−２２５）、本発明で規定する離型剤で処理
した金属酸化物又は金属水酸化物として、上記で作製し
た金属酸化物１〜２及び金属水酸化物１〜４、規定外の
離型剤で処理した金属酸化物又は金属水酸化物として、
上記で作製した比較金属酸化物１及び比較金属水酸化物
１、未処理の金属酸化物又は金属水酸化物として、上記
の比較金属酸化物２、比較金属水酸化物２〜３、その他
の添加物として、難燃剤として三酸化アンチモン、ビス
フェノールＡ型ブロム化エポキシ樹脂（住友化学工業株
式会社製商品名ＥＳＢ−４００Ｔ、エポキシ当量３７
５、臭素含有４８重量％）、無機充填剤として平均粒子
径１７．５μｍ、比表面積３．８ｍ2／ｇの球状溶融シ
リカ、硬化促進剤としてトリフェニルホスフィンと１，
４−ベンゾキノンとの付加物、イオントラップ剤として
ハイドロタルサイト（協和化学工業株式会社製商品名Ｄ
ＨＴ−４Ａ）、エポキシシランカップリング剤（信越化
学工業株式会社製商品名ＫＢＭ４０３）、カルナバワッ
クス（クラリアントジャパン株式会社製）、及びカーボ
ンブラック（三菱化学株式会社製商品名ＭＡ−１００）
をそれぞれ表１に示す重量部で配合し、混練温度８０
℃、混練時間１０分の条件でロール混練を行って、実施
例１〜８及び比較例１〜５の封止用エポキシ樹脂成形材
料を作製した。(Examples 1 to 8 and Comparative Examples 1 to 5) As an epoxy resin, a biphenyl type epoxy resin having an epoxy equivalent of 192 and a melting point of 105 ° C (epoxy resin 1: manufactured by Japan Epoxy Resin Co., Ltd., trade name Epicoat YX-4000).
H), epoxy equivalent 210, stilbene type epoxy resin having a softening point of 130 ° C. (epoxy resin 2: Sumitomo Chemical Co., Ltd. trade name ESLV-210), epoxy equivalent 19
5, o-cresol novolac type epoxy resin having a softening point of 65 ° C. (epoxy resin 3: trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.), epoxy equivalent 244, melting point 11
Sulfur atom-containing epoxy resin at 8 ° C (epoxy resin 4: product name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.), as a curing agent, a hydroxyl equivalent 172, and a phenol / aralkyl resin having a softening point of 70 ° C (manufactured by Mitsui Chemicals, Inc.) Trade name Milex XL-225), the metal oxides 1 and 2 and the metal hydroxides 1 to 4 produced above as metal oxides or metal hydroxides treated with the release agent specified in the present invention, not specified. As a metal oxide or metal hydroxide treated with a release agent,
Comparative metal oxide 1 and comparative metal hydroxide 1 produced above, as untreated metal oxides or metal hydroxides, the above comparative metal oxide 2, comparative metal hydroxides 2-3, and other additions As a flame retardant, antimony trioxide, bisphenol A type brominated epoxy resin (trade name ESB-400T manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 37
5, bromine-containing 48% by weight), as an inorganic filler, spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m 2 / g, triphenylphosphine and 1, as a curing accelerator.
Hydrotalcite (product name D manufactured by Kyowa Chemical Industry Co., Ltd. as an adduct with 4-benzoquinone, an ion trap agent
HT-4A), epoxy silane coupling agent (trade name KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (manufactured by Clariant Japan Co., Ltd.), and carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Co., Ltd.).
At a kneading temperature of 80
Roll kneading was performed under conditions of a temperature of 10 minutes and a kneading time of 10 minutes to prepare epoxy resin molding materials for sealing of Examples 1 to 8 and Comparative Examples 1 to 5.
【００３９】[0039]
【表１】 [Table 1]
【００４０】作製した実施例及び比較例の封止用エポキ
シ樹脂成形材料を、次の各試験により評価した。結果を
表１に併記する。なお、封止用エポキシ樹脂成形材料の
成形は、トランスファ成形機により、金型温度１８０
℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で行
った。また、後硬化は１８０℃で５時間行った。
（１）スパイラルフロー（流動性の指標）
ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金
型を用いて、封止用エポキシ樹脂成形材料を上記条件で
成形し、流動距離（ｃｍ）を求めた。
（２）熱時硬度
封止用エポキシ樹脂成形材料を上記条件で直径５０ｍｍ
×厚さ３ｍｍの円板に成形し、成形後直ちにショアＤ型
硬度計を用いて測定した。
（３）難燃性
厚さ１／１６インチの試験片を成形する金型を用いて、
封止用エポキシ樹脂成形材料を上記条件で成形して後硬
化を行い、ＵＬ−９４試験法に従って難燃性を評価し
た。
（４）耐リフロー性
８ｍｍ×１０ｍｍ×０．４ｍｍのシリコーンチップを搭
載した外形寸法２０ｍｍ×１４ｍｍ×２ｍｍの８０ピン
フラットパッケージ（ＱＦＰ）を、封止用エポキシ樹脂
成形材料を用いて上記条件で成形、後硬化して作製し、
８５℃、８５％ＲＨの条件で９６時間の加湿を行った
後、２４０℃、１０秒の条件でリフロー処理を行い、ク
ラックの有無を観察し、試験パッケージ数（５）に対す
るクラック発生パッケージ数で評価した。
（５）耐湿性
５μｍ厚の酸化膜上に線幅１０μｍ、厚さ１μｍのアル
ミ配線を施した６ｍｍ×６ｍｍ×０．４ｍｍのテスト用
シリコーンチップを搭載した外形寸法２０ｍｍ×１４ｍ
ｍ×２．７ｍｍの８０ピンフラットパッケージ（ＱＦ
Ｐ）を、封止用エポキシ樹脂成形材料を用いて上記条件
で成形、後硬化して作製し、前処理を行った後加湿し、
５００時間後のアルミ配線腐食による断線不良を調べ、
試験パッケージ数（１０）に対する不良パッケージ数で
評価した。なお、前処理は８５℃、８５％ＲＨ、７２時
間の条件でフラットパッケージを加湿後、２１５℃、９
０秒間のベーパーフェーズリフロー処理を行った。その
後の加湿は０．２ＭＰａ、１２１℃の条件で行った。
（６）ゲート残り性
最小断面積０．８ｍｍ2のゲート（成形樹脂が各パッケ
ージに流れ込む流入路）を持った２０×１４×２．０ｍ
ｍの８０ピンフラットパッケージ（ＱＦＰ）金型を用い
て１０ショットの連続成形を行った後、成形品のゲート
を金属顕微鏡で観察し、ゲート残りの有無を判定した。
成形条件は、クリーニング材（三菱ガス化学株式会社
製）を３ショット（１８０秒成形）、離型回復材を１シ
ョット（１２０秒成形）成形後、作製サンプルを７０秒
で成形した。ゲートの観察には、１ショットあたり１０
ヶのパッケージを用いた。全パッケージ数１００ヶ（１
０パッケージ／ショット×１０ショット）に対する、ゲ
ート残りの発生したパッケージ数で評価した。The produced epoxy resin molding materials for encapsulation of Examples and Comparative Examples were evaluated by the following tests. The results are also shown in Table 1. The epoxy resin molding material for sealing is molded by a transfer molding machine at a mold temperature of 180.
C., the molding pressure was 6.9 MPa, and the curing time was 90 seconds. Further, post-curing was performed at 180 ° C. for 5 hours. (1) Spiral flow (index of fluidity) Using a mold for spiral flow measurement according to EMMI-1-66, an epoxy resin molding material for sealing is molded under the above conditions, and a flow distance (cm) is determined. It was (2) Epoxy resin molding material for hot hardness sealing with a diameter of 50 mm under the above conditions
C. A disk having a thickness of 3 mm was molded and measured immediately after molding using a Shore D hardness meter. (3) Flame-retardant Using a mold for molding a test piece having a thickness of 1/16 inch,
The epoxy resin molding material for sealing was molded under the above conditions, post-cured, and evaluated for flame retardancy according to the UL-94 test method. (4) Molding an 80-pin flat package (QFP) of 20 mm x 14 mm x 2 mm in external dimensions, in which a silicone chip of 8 mm x 10 mm x 0.4 mm with reflow resistance is mounted, using the epoxy resin molding material for sealing under the above conditions. After curing,
After performing humidification for 96 hours at 85 ° C. and 85% RH, reflow treatment is performed at 240 ° C. for 10 seconds, and the presence or absence of cracks is observed. evaluated. (5) Moisture resistance External dimensions of 20 mm x 14 m equipped with a 6 mm x 6 mm x 0.4 mm test silicone chip with aluminum wiring having a line width of 10 μm and a thickness of 1 μm on an oxide film with a thickness of 5 μm
mx 2.7 mm 80-pin flat package (QF
P) is molded by using an epoxy resin molding material for encapsulation under the above conditions and post-cured to be pre-treated, and then moistened,
Checking for disconnection defects due to aluminum wiring corrosion after 500 hours,
The number of defective packages to the number of test packages (10) was evaluated. The pretreatment was performed at 85 ° C., 85% RH and 72 hours for 72 hours at 215 ° C. after humidifying the flat package.
A vapor phase reflow treatment for 0 seconds was performed. The subsequent humidification was performed under the conditions of 0.2 MPa and 121 ° C. (6) Gate remnant 20 x 14 x 2.0 m with a gate (inflow path through which molding resin flows into each package) with a minimum cross-sectional area of 0.8 mm 2.
After performing continuous molding for 10 shots using an 80-pin flat package (QFP) mold of m, the gate of the molded product was observed with a metallurgical microscope to determine the presence or absence of a gate residue.
As for molding conditions, a cleaning material (manufactured by Mitsubishi Gas Chemical Co., Inc.) was molded for 3 shots (180 seconds molding), a release recovery material was molded for 1 shot (120 seconds molding), and then a sample was molded in 70 seconds. 10 per shot for gate observation
I used a package. 100 packages (1
The evaluation was made by the number of packages in which the remaining gate was generated for 0 package / shot × 10 shots.
【００４１】炭素数が本発明の規定量より少ない離型剤
で処理された金属酸化物又は金属水酸化物を用いた比較
例１および３、金属酸化物又は金属水酸化物を全く処理
を施さずに用いた比較例２、４、５は流動性及び熱時硬
度、若しくはゲート残り性といった成形性が不十分であ
る。なお、比較例２は成形不良によりスパイラルフロー
及び熱時硬度以外の項目は測定できなかった。これに対
して、本発明の（Ａ）〜（Ｃ）成分を全て含み、かつ、
(Ｃ)成分における離型剤の炭素数が規定範囲内である実
施例は、流動性、熱時硬度、ゲート残り性といった成形
性が良好であり、（Ｃ）成分を難燃剤として用いた場合
にもＵＬ−９４試験でＶ−０を達成し良好な難燃性を示
す。なお、金属酸化物または金属水酸化物を離型剤で処
理する際に、還流下１００℃で１時間撹拌する替わり
に、室温で１時間〜１．５時間撹拌した場合も、還流下
８０℃、１１０℃又は１２０℃で１時間〜１．５時間撹
拌した場合も同様の結果が得られた。Comparative Examples 1 and 3 using a metal oxide or a metal hydroxide treated with a release agent having a carbon number smaller than the specified amount of the present invention, the metal oxide or the metal hydroxide was treated at all. Comparative Examples 2, 4 and 5 which were used as they were, had insufficient moldability such as fluidity and hot hardness, or gate residual property. In Comparative Example 2, items other than spiral flow and hot hardness could not be measured due to defective molding. On the other hand, including all the components (A) to (C) of the present invention, and
In the examples in which the carbon number of the release agent in the component (C) is within the specified range, the moldability such as fluidity, heat hardness and gate residual property is good, and when the component (C) is used as a flame retardant. Also, it achieved V-0 in the UL-94 test and showed good flame retardancy. When treating a metal oxide or a metal hydroxide with a release agent, instead of stirring at 100 ° C. under reflux for 1 hour, when stirring at room temperature for 1 hour to 1.5 hours, 80 ° C. under reflux. Similar results were obtained when stirring at 110 ° C. or 120 ° C. for 1 to 1.5 hours.
【００４２】[0042]
【発明の効果】本発明になる封止用エポキシ樹脂成形材
料は、実施例で示したように、金属酸化物又は金属水酸
化物を含有してなお、良好な成形性を示し、これを用い
てＩＣ、ＬＳＩ等の電子部品を封止すれば良好に製品を
得ることができ、その工業的価値は大である。The encapsulating epoxy resin molding material of the present invention contains a metal oxide or a metal hydroxide as shown in the examples and still exhibits good moldability. A good product can be obtained by sealing electronic parts such as IC and LSI, and its industrial value is great.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｌ 23/31 (72)発明者 山田 慎也 茨城県結城市大字鹿窪1772―１ 日立化成 工業株式会社下館事業所内 (72)発明者 石黒 正 茨城県結城市大字鹿窪1772―１ 日立化成 工業株式会社下館事業所内 Ｆターム(参考） 4J002 CC04X CC05X CC06X CC07X CD02W CD03W CD04W CD05W CD06W CD07W CD10W CD11W CD13W CD20W CE00X DA117 DE067 DE076 DE086 DE096 DE097 DE106 DE116 DE136 DE146 DE147 DE187 DE237 DF017 DJ007 DJ017 DK007 DL007 EN028 EN108 EU098 EU118 EW018 EW178 FA047 FA087 FB236 FB246 FD017 FD090 FD136 FD158 FD160 FD200 GQ00 4J036 AB02 AC02 AC05 AD07 AD08 AD10 AD21 AE05 AE07 AF05 AF06 AF08 AF15 AF16 AF19 AF34 AF36 AG05 AG07 AH07 AH15 DB06 DB11 DC05 DC10 DC12 DC13 DC41 DC46 DD07 FA01 FA03 FA05 FB06 FB07 FB08 GA06 GA23 JA07 4M109 AA01 CA21 EB07 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI Theme Coat (reference) H01L 23/31 (72) Inventor Shinya Yamada 1721 Kagoku, Yuki City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Shimodate Project In-house (72) Inventor Tadashi Ishiguro Yuki-shi, Ibaraki 1722, Kagoku, Hitachi Chemical Co., Ltd. Shimodate Works F-term (reference) 4J002 CC04X CC05X CC06X CC07X CD02W CD03W CD04W CD05W CD06W CD07W CD10W CD11W CD13W CD20W CE67X DE76 DE DE 117 DE096 DE097 DE106 DE116 DE136 DE146 DE147 DE187 DE237 DF017 DJ007 DJ017 DK007 DL007 EN028 EN108 EU098 EU118 EW018 EW178 FA047 FA087 FB236 FB246 FD017 FD090 FD136 FD158 FD160 FD200 GQ00 4J036 AB02 AC02 AC05 AF15 AF06 AF05 AF07 AF05 AF07 AD05 AF05 AD07 AD05 AD10 AD05 AD05 AD07 AD05 AD10 AD05 AD05 AD07 AF05 AD10 AD05 AD07 AD05 AF05 AD07 AF05 AD07 AD05 AD05 AD07 AF05 AD07 AD05 AD05 AD07 AF05 AD07 AF05 AD07 AD05 AD07 AF05 AD07 AF05 AD07 AD05 AD05 AD05 AD05 AF05 AG07 AH07 AH15 DB06 DB11 DC05 DC10 DC12 DC13 DC41 DC46 DD07 FA01 FA0 3 FA05 FB06 FB07 FB08 GA06 GA23 JA07 4M109 AA01 CA21 EB07
Claims (14)
（Ｃ）離型剤で処理された金属酸化物又は金属水酸化物
を必須成分とし、前記離型剤が、炭素数が２５以上の高
級脂肪族化合物である封止用エポキシ樹脂成形材料。1. An epoxy resin (A), a curing agent (B),
(C) An epoxy resin molding material for encapsulation, which contains a metal oxide or a metal hydroxide treated with a release agent as an essential component, and the release agent is a higher aliphatic compound having 25 or more carbon atoms.
脂肪酸又はそのエステルであって、炭素数２５〜５７の
化合物である請求項１に記載の封止用エポキシ樹脂成形
材料。2. The epoxy resin molding material for encapsulation according to claim 1, wherein the release agent used in the component (C) is a higher fatty acid or its ester, which is a compound having 25 to 57 carbon atoms.
タン酸又は炭素数５７以下のモンタン酸エステルである
請求項１または２に記載の封止用エポキシ樹脂成形材
料。3. The epoxy resin molding material for encapsulation according to claim 1, wherein the release agent used in the component (C) is montanic acid or a montanic acid ester having 57 or less carbon atoms.
処理されたものである請求項１〜３いずれかに記載の封
止用エポキシ樹脂成形材料。4. The encapsulating epoxy resin molding material according to claim 1, wherein the component (C) is treated with a release agent using an organic solvent.
含む請求項４に記載の封止用エポキシ樹脂成形材料。5. The encapsulating epoxy resin molding material according to claim 4, wherein the organic solvent contains one or more polar organic solvents.
級、２級、又は３級のアルコール又はグリコールを含む
請求項５に記載の封止用エポキシ樹脂成形材料。6. The polar organic solvent is 1 having a carbon number of 6 or less.
The epoxy resin molding material for encapsulation according to claim 5, which contains a grade 2, secondary or tertiary alcohol or glycol.
項１〜６のいずれかに記載の封止用エポキシ樹脂成形材
料。7. The epoxy resin molding material for sealing according to claim 1, further comprising (D) an inorganic filler.
ポキシ樹脂、スチルベン型エポキシ樹脂、硫黄原子含有
エポキシ樹脂、ノボラック型エポキシ樹脂、ジシクロペ
ンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂
及びトリフェニルメタン型エポキシ樹脂の少なくとも１
種を含有する請求項１〜７のいずれかに記載の封止用エ
ポキシ樹脂成形材料。8. The (A) epoxy resin is a biphenyl type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin and a triphenylmethane type epoxy resin. At least one of the resins
The encapsulating epoxy resin molding material according to any one of claims 1 to 7, further comprising a seed.
樹脂、アラルキル型フェノール樹脂、ジシクロペンタジ
エン型フェノール樹脂、トリフェニルメタン型フェノー
ル樹脂及びノボラック型フェノール樹脂の少なくとも１
種を含有する請求項１〜８のいずれかに記載の封止用エ
ポキシ樹脂成形材料。9. The (B) curing agent is at least one of biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin.
The epoxy resin molding material for encapsulation according to claim 1, further comprising a seed.
求項１〜９のいずれかに記載の封止用エポキシ樹脂成形
材料。10. The epoxy resin molding material for encapsulation according to claim 1, further comprising (E) a curing accelerator.
物とキノン化合物との付加物を含有する請求項１０に記
載の封止用エポキシ樹脂成形材料。11. The encapsulating epoxy resin molding material according to claim 10, wherein the curing accelerator (E) contains an adduct of a phosphine compound and a quinone compound.
合金属水酸化物である請求項１〜１１のいずれか記載の
封止用エポキシ樹脂成形材料。12. The epoxy resin molding material for encapsulation according to claim 1, wherein the component (C) is a composite metal hydroxide treated with a release agent.
（Ｉ）で表される請求項１２に記載の封止用エポキシ樹
脂成形材料。 【化１】 ｐ(Ｍ1 aＯb)・ｑ(Ｍ2 cＯd)・ｒ(Ｍ3 eＯf)・ｍＨ2Ｏ （Ｉ） （ここで、Ｍ1、Ｍ2及びＭ3は互いに異なる金属元素を
示し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｐ、ｑ及びｍは正の
数、ｒは０又は正の数を示す。）13. The encapsulating epoxy resin molding material according to claim 12, wherein the composite metal hydroxide is represented by the following general formula (I). ## STR1 ## p (M 1 a O b) · q (M 2 c O d) · r (M 3 e O f) · mH 2 O (I) ( wherein, M 1, M 2 and M 3 are A metal element different from each other is shown, and a, b, c, d, e, f, p, q and m are positive numbers, and r is 0 or a positive number.)
止用エポキシ樹脂成形材料で封止された素子を備えた電
子部品装置。14. An electronic component device comprising an element encapsulated with the epoxy resin molding material for encapsulation according to any one of claims 1 to 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002140919A JP2003327791A (en) | 2002-05-16 | 2002-05-16 | Sealing epoxy resin molding material and electronic component device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002140919A JP2003327791A (en) | 2002-05-16 | 2002-05-16 | Sealing epoxy resin molding material and electronic component device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003327791A true JP2003327791A (en) | 2003-11-19 |
Family
ID=29701646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002140919A Withdrawn JP2003327791A (en) | 2002-05-16 | 2002-05-16 | Sealing epoxy resin molding material and electronic component device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003327791A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006249377A (en) * | 2005-03-14 | 2006-09-21 | Nitto Denko Corp | Resin composition for sealing semiconductor and semiconductor device using the same |
| 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 |
-
2002
- 2002-05-16 JP JP2002140919A patent/JP2003327791A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US7846998B2 (en) | 2004-03-03 | 2010-12-07 | Hitachi Chemical Co., Ltd. | Sealant epoxy-resin molding material, and electronic component device |
| JP2006249377A (en) * | 2005-03-14 | 2006-09-21 | Nitto Denko Corp | Resin composition for sealing semiconductor and semiconductor device using the same |
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