JP6386483B2 - Liquid resin composition for electronic components and electronic component device - Google Patents
Liquid resin composition for electronic components and electronic component device Download PDFInfo
- Publication number
- JP6386483B2 JP6386483B2 JP2016000194A JP2016000194A JP6386483B2 JP 6386483 B2 JP6386483 B2 JP 6386483B2 JP 2016000194 A JP2016000194 A JP 2016000194A JP 2016000194 A JP2016000194 A JP 2016000194A JP 6386483 B2 JP6386483 B2 JP 6386483B2
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- Prior art keywords
- resin composition
- liquid resin
- liquid
- epoxy resin
- electronic
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims description 110
- 239000011342 resin composition Substances 0.000 title claims description 103
- -1 cyclic acid anhydrides Chemical class 0.000 claims description 74
- 229920000647 polyepoxide Polymers 0.000 claims description 63
- 239000003822 epoxy resin Substances 0.000 claims description 61
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 150000008065 acid anhydrides Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000005040 ion trap Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000003796 beauty Effects 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 description 39
- 230000005012 migration Effects 0.000 description 31
- 238000013508 migration Methods 0.000 description 31
- 230000003078 antioxidant effect Effects 0.000 description 29
- 239000004065 semiconductor Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 16
- 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 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 230000007423 decrease Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 7
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000007973 cyanuric acids Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 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 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
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 description 2
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 2
- SBJIQJIAXGQAJD-UHFFFAOYSA-N 2-methyl-3-(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC=CC(O)=C1C SBJIQJIAXGQAJD-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 2
- AESQDCMZHBUWPN-UHFFFAOYSA-N 4h-1,3,2-dioxaphosphinine Chemical compound C1OPOC=C1 AESQDCMZHBUWPN-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method 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
- 230000007547 defect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- VTIXMGZYGRZMAW-UHFFFAOYSA-N ditridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCC VTIXMGZYGRZMAW-UHFFFAOYSA-N 0.000 description 1
- XHWQYYPUYFYELO-UHFFFAOYSA-N ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCC XHWQYYPUYFYELO-UHFFFAOYSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 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
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 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
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-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
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-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
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Wire Bonding (AREA)
Description
本発明は、電子部品の封止用に好適な電子部品用液状樹脂組成物及びこれにより封止された電子部品装置に関する。 The present invention relates to a liquid resin composition for electronic components suitable for sealing electronic components and an electronic component device sealed thereby.
従来から、トランジスタ、IC等の電子部品装置を対象とした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、エポキシ樹脂組成物が広く用いられている。この理由としては、エポキシ樹脂が作業性、成形性、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等の諸特性にバランスがとれているためである。COB(Chip on Board)、COG(Chip on Glass)、TCP(Tape Carrier Package)等のベアチップ実装した半導体装置においては電子部品用液状樹脂組成物が封止材として広く使用されている。近年では液晶等のディスプレイ駆動用ICの実装方法として、半導体素子を配線基板に直接バンプ接続する実装形態(フリップチップ接続方式)に使用されており、この実装に用いられる電子部品用液状樹脂組成物はアンダーフィル材として知られている。 Conventionally, in the field of element sealing for electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin compositions have been widely used. This is because the epoxy resin is balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. Liquid resin compositions for electronic components are widely used as sealing materials in semiconductor devices mounted on bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package). In recent years, as a method for mounting display driving ICs such as liquid crystal, it has been used in a mounting form (flip chip connection method) in which a semiconductor element is directly bump-connected to a wiring board, and a liquid resin composition for electronic components used for this mounting. Is known as an underfill material.
このアンダーフィル材は、上記フリップチップ接続方式による半導体実装方法において、バンプ間の絶縁保持および機械的強度保持のための封止を目的として、配線基板と半導体装置の間に生じる空間に充填される。従ってアンダーフィル材には、(1)常温で低粘度の液体であること、(2)充填後の樹脂の熱硬化過程においての気泡(ボイド)発生を避けるために、樹脂組成物が無溶媒であること、(3)粘度の増加、浸透性の低下を避けるためにフィラー等の固形成分の含有を可能な限り避けること、(4)固形成分を含有する場合は電子部品用液状樹脂組成物中における固形成分の均一分散性を保ち、粘度、流動性、浸透性等を損なわない粒度分布、充填量の管理をした適切な配合であること等の条件が必要な項目となっている。 The underfill material is filled in a space generated between the wiring board and the semiconductor device for the purpose of sealing for maintaining insulation between the bumps and maintaining mechanical strength in the semiconductor mounting method using the flip-chip connection method. . Therefore, the underfill material has (1) a low-viscosity liquid at room temperature, and (2) a resin composition containing no solvent in order to avoid generation of bubbles in the thermosetting process of the resin after filling. (3) Avoid the inclusion of solid components such as fillers as much as possible to avoid an increase in viscosity and a decrease in permeability. (4) In the case of containing a solid component, in the liquid resin composition for electronic components It is an item that requires conditions such as maintaining a uniform dispersibility of the solid component and maintaining a suitable particle size distribution and filling amount that do not impair the viscosity, fluidity, and permeability.
上記配線基板および半導体装置では、配線間の間隔が狭くなり、最先端のフリップチップ半導体装置では配線ピッチが30μm以下のものも出てきた。そして狭ピッチ化した配線間に高い電圧が印加されることにより、電子部品用液状樹脂組成物に対しては絶縁信頼性を損ねる不良現象の一つとしてマイグレーション現象が大きな問題になってきた。特に高温高湿下では樹脂および配線金属の劣化が促進されるため、マイグレーションが発生し易くなり、半導体装置の不良発生の懸念がさらに高まる傾向にある。 In the wiring board and the semiconductor device described above, the distance between the wirings is narrowed, and some of the most advanced flip chip semiconductor devices have a wiring pitch of 30 μm or less. When a high voltage is applied between the wirings with a narrow pitch, the migration phenomenon has become a big problem as one of the defective phenomena that impairs the insulation reliability of the liquid resin composition for electronic parts. In particular, the deterioration of the resin and the wiring metal is promoted under high temperature and high humidity, so that migration is likely to occur, and there is a tendency for further concern about the occurrence of defects in the semiconductor device.
かかる不良を回避するため、かねてより電子部品に使用される樹脂組成物に対してはマイグレーション抑制を目的とした対策がなされてきた。例えば金属イオン補足剤として、無機イオン交換体を配合した樹脂組成物(例えば、特許文献1〜4参照。)、ベンゾトリアジン、ベンゾトリアゾールやこれらのイソシアヌル酸付加物を配合した樹脂組成物(例えば、特許文献5〜10参照。)、硬化促進剤にボレート塩を含む化合物を配合した樹脂組成物(例えば、特許文献11参照。)、酸化防止剤を配合した樹脂組成物(例えば、特許文献12〜13参照。)などが、封止材、接着剤、プリプレグ等の用途に給する樹脂組成物として公知である。 In order to avoid such defects, measures have been taken for the purpose of suppressing migration of resin compositions used for electronic parts. For example, as a metal ion scavenger, a resin composition containing an inorganic ion exchanger (for example, see Patent Documents 1 to 4), a benzotriazine, a benzotriazole or a resin composition containing these isocyanuric acid adducts (for example, Patent Documents 5 to 10), a resin composition in which a compound containing a borate salt is blended in a curing accelerator (for example, see Patent Document 11), and a resin composition in which an antioxidant is blended (for example, Patent Documents 12 to 12). 13) is known as a resin composition for use in applications such as sealing materials, adhesives, and prepregs.
前記公知例のなかでも特許文献12〜13に例示した酸化防止剤を配合した樹脂組成物では、プリプレグに代表されるプリント基板用樹脂組成物において、樹脂の劣化を防止する効果に加え、耐マイグレーション性が特に優れていることが公知になっている。プリント基板用樹脂組成物では配合時にメチルエチルケトン(MEK)やトルエン等の溶媒を用いるため、一般的に常温において固形(粉末状)の各種酸化防止剤をエポキシ樹脂、硬化剤、硬化促進剤と共に混合、溶解することができ、用途や特性に応じて任意の酸化防止剤を選択することが可能である。 Among the known examples, in the resin composition containing the antioxidant exemplified in Patent Documents 12 to 13, in the resin composition for printed circuit boards represented by prepreg, in addition to the effect of preventing the deterioration of the resin, migration resistance It is known that the properties are particularly excellent. In the resin composition for printed circuit boards, since a solvent such as methyl ethyl ketone (MEK) or toluene is used at the time of blending, generally various solid (powder) antioxidants are mixed with an epoxy resin, a curing agent and a curing accelerator at room temperature. Any antioxidant can be selected depending on the application and characteristics.
これに対し、アンダーフィル材として使用する電子部品用液状樹脂組成物では、前記に述べたように充填後の樹脂の熱硬化過程において気泡(ボイド)の発生を避けるために溶媒を使用しない。このため無溶媒の電子部品用液状樹脂組成物に、従来公知の酸化防止剤を均一に溶解し、かつ低粘度性、高流動性、高浸透性や、速硬化性、低吸水性、高接着性等のアンダーフィル材として必須の諸特性を損なうことなく耐マイグレーション性に優れた電子部品用液状樹脂組成物を得ることが困難であった。 On the other hand, in the liquid resin composition for electronic parts used as the underfill material, as described above, no solvent is used in order to avoid the generation of bubbles (voids) in the thermosetting process of the resin after filling. For this reason, a conventionally known antioxidant is uniformly dissolved in a solvent-free liquid resin composition for electronic parts, and has low viscosity, high fluidity, high permeability, fast curing, low water absorption, and high adhesion. It has been difficult to obtain a liquid resin composition for electronic parts that is excellent in migration resistance without impairing various properties essential as an underfill material, such as properties.
現在は電子部品用液状樹脂組成物中の不純物を低減することで耐マイグレーション性の向上が図られている。しかし例えば細線化、狭ピッチ化の著しい代表的な半導体装置であるCOF(Chip On Film)ではさらなる耐マイグレーション性の向上が要求されており、電子部品用液状樹脂組成物の高純度化のみでは対応が困難になりつつある。 Currently, migration resistance is improved by reducing impurities in the liquid resin composition for electronic components. However, for example, COF (Chip On Film), which is a representative semiconductor device with remarkable thinning and narrowing of pitch, requires further improvement in migration resistance, and it can be handled only by increasing the purity of the liquid resin composition for electronic parts. Is becoming difficult.
本発明はかかる状況に鑑みなされたもので、耐マイグレーション性が良好であり、その他の成形性、信頼性にも優れる電子部品用液状樹脂組成物及びこれにより封止された電子部品装置を提供するものである。 The present invention has been made in view of such a situation, and provides a liquid resin composition for electronic components which has excellent migration resistance and is excellent in other moldability and reliability, and an electronic component device sealed thereby. Is.
本発明者らは上記の課題を解決するため鋭意検討を重ねた結果、半導体素子等の電子部品と配線基板との接着性が良好であり、吸水率が小さく、酸化劣化を抑制した、低粘度で流動性に優れる高純度な電子部品用液状樹脂組成物を適用することで、上記の目的を達成しうることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have good adhesion between an electronic component such as a semiconductor element and a wiring board, a low water absorption, and a low viscosity that suppresses oxidative degradation. The present inventors have found that the above object can be achieved by applying a high-purity liquid resin composition for electronic parts that is excellent in fluidity, and have completed the present invention.
本発明は以下(1)〜(14)に関する。 The present invention relates to the following (1) to (14).
(1)エポキシ樹脂、常温液体の環状酸無水物、カップリング剤、及びフェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物を含有する電子部品用液状樹脂組成物。 (1) A liquid resin composition for electronic parts comprising an epoxy resin, a normal-temperature liquid cyclic acid anhydride, a coupling agent, and a phenol compound having at least one alkyl group at the ortho position of the phenol nucleus.
(2)前記フェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物は、フェノール核のオルト位に1つのメチル基を有するフェノール化合物を含有する請求項1に記載の電子部品用液状樹脂組成物。 (2) The liquid resin composition for electronic parts according to claim 1, wherein the phenol compound having at least one alkyl group at the ortho position of the phenol nucleus contains a phenol compound having one methyl group at the ortho position of the phenol nucleus. object.
(3)前記フェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物は、ビスフェノールF型エポキシ樹脂に対する飽和溶解量が5重量%以上である(1)または(2)に記載の電子部品用液状樹脂組成物。 (3) The phenol compound having at least one alkyl group at the ortho position of the phenol nucleus has a saturated dissolution amount in a bisphenol F-type epoxy resin of 5% by weight or more, for electronic components according to (1) or (2) Liquid resin composition.
(4)エポキシ樹脂、常温液体の環状酸無水物、カップリング剤、及び酸化防止剤を含有し、前記酸化防止剤は常温で液状である酸化防止剤を含む、電子部品用液状樹脂組成物。 (4) A liquid resin composition for electronic parts comprising an epoxy resin, a cyclic acid anhydride at room temperature, a coupling agent, and an antioxidant, wherein the antioxidant comprises an antioxidant that is liquid at room temperature.
(5)さらに無機充填剤を含有し、かつ無機充填剤の配合量が10質量%以下である(1)〜(4)のいずれかに記載の電子部品用液状樹脂組成物。 (5) The liquid resin composition for electronic components according to any one of (1) to (4), further containing an inorganic filler, and the blending amount of the inorganic filler is 10% by mass or less.
(6)さらにゴム粒子を含有する(1)〜(5)のいずれかに記載の電子部品用液状樹脂組成物。 (6) The liquid resin composition for electronic parts according to any one of (1) to (5), further containing rubber particles.
(7)さらにシリコーン変性エポキシ樹脂を含有する(1)〜(6)のいずれかに記載の電子部品用液状樹脂組成物。 (7) The liquid resin composition for electronic parts according to any one of (1) to (6), further containing a silicone-modified epoxy resin.
(8)さらにイオントラップ剤を含有する(1)〜(7)のいずれかに記載の電子部品用液状樹脂組成物。 (8) The liquid resin composition for electronic parts according to any one of (1) to (7), further comprising an ion trap agent.
(9)さらに前記エポキシ樹脂と前記常温液体の環状酸無水物との反応を促進する潜在性硬化促進剤を含有する(1)〜(8)のいずれかに記載の電子部品用液状樹脂組成物。 (9) The liquid resin composition for electronic parts according to any one of (1) to (8), further comprising a latent curing accelerator that promotes the reaction between the epoxy resin and the cyclic acid anhydride of the room temperature liquid. .
(10)さらに有機溶媒含有率が1%以下であることを特徴とする(1)〜(9)のいずれかに記載の電子部品用液状樹脂組成物。 (10) The liquid resin composition for electronic parts according to any one of (1) to (9), wherein the organic solvent content is 1% or less.
(11)前記常温液体の環状酸無水物の無水酸当量が200以上であることを特徴とする(1)〜(10)のいずれかに記載の電子部品用液状樹脂組成物。 (11) The liquid resin composition for electronic parts as described in any one of (1) to (10), wherein the cyclic acid anhydride of the room temperature liquid has an acid anhydride equivalent of 200 or more.
(12)EMD型回転粘度計を用いた25℃における粘度が1.2Pa・s以下であることを特徴とする(1)〜(11)のいずれかに記載の電子部品用液状樹脂組成物。 (12) The liquid resin composition for electronic parts according to any one of (1) to (11), wherein the viscosity at 25 ° C. using an EMD type rotational viscometer is 1.2 Pa · s or less.
(13)フィルムを基材とする配線基板上に電子部品を直接バンプ接続した電子部品装置に用いられる(1)〜(12)のいずれかに記載の電子部品用液状樹脂組成物。 (13) The liquid resin composition for electronic components according to any one of (1) to (12), which is used in an electronic component device in which an electronic component is directly bump-connected on a wiring board having a film as a base material.
(14)(1)〜(13)のいずれかに記載の電子部品用液状樹脂組成物を用いて封止された電子部品装置。 (14) An electronic component device sealed with the liquid resin composition for electronic components according to any one of (1) to (13).
本発明による電子部品用液状樹脂組成物は、耐マイグレーション性が良好であり、半導体素子等の電子部品と配線基板との接着性が良好であり、吸水率が小さく、酸化劣化を抑制した、低粘度で流動性に優れる高純度な電子部品用液状樹脂組成物であるため、その工業的価値は大である。特にリジッド配線板及びフレキシブル配線板やガラス上に形成した配線に半導体素子をバンプ接続によりフリップチップボンディングした半導体装置、具体的にはフリップチップBGAやCOF等の半導体装置用のアンダーフィル材として特に有用である。 The liquid resin composition for an electronic component according to the present invention has good migration resistance, good adhesion between an electronic component such as a semiconductor element and a wiring board, a low water absorption rate, and low oxidation deterioration. Since it is a high-purity liquid resin composition for electronic parts that is excellent in viscosity and fluidity, its industrial value is great. Particularly useful as an underfill material for semiconductor devices such as flip-chip BGA and COF, in which semiconductor elements are flip-chip bonded to rigid wiring boards, flexible wiring boards, and wiring formed on glass by bump connection. It is.
本発明において用いられる(A)エポキシ樹脂は、硬化可能な1分子中に2個以上のエポキシ基を有するエポキシ樹脂であれば特に制限はなく、電子部品用液状樹脂組成物に一般に使用されているエポキシ樹脂を用いることができ、組成物が液状であれば固形、液状のどちらか一方を用いても両者を併用しても良い。たとえば、ビスフェノールA、ビスフェノールF、ビスフェノールAD、ビスフェノールS、ナフタレンジオール、水添ビスフェノールA等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ーテル型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール類とアルデヒド類とを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、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、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。 The (A) epoxy resin used in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule that can be cured, and is generally used in a liquid resin composition for electronic parts. An epoxy resin can be used. If the composition is liquid, either solid or liquid may be used, or both may be used in combination. For example, phenols and aldehydes such as glycidyl ether type epoxy resin, orthocresol novolac type epoxy resin obtained by reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin Novolak type epoxy resin obtained by epoxidizing novolak resin obtained by condensation or co-condensation with glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid, etc. Glycidylamine-type epoxy resin obtained by reaction of polyamines with epichlorohydrin, linear aliphatic epoxy obtained by oxidizing olefinic bonds with peracids such as peracetic acid Butter, and the like alicyclic epoxy resins may be used in combination of two or more even with these alone.
なかでも、低粘度化の観点からは液状エポキシ樹脂が好ましく、環状酸無水物との反応性の観点からはビスフェノール型液状エポキシ樹脂がより好ましい。 Among these, a liquid epoxy resin is preferable from the viewpoint of reducing the viscosity, and a bisphenol liquid epoxy resin is more preferable from the viewpoint of reactivity with the cyclic acid anhydride.
また、これらのエポキシ樹脂は、十分に精製されたもので、イオン性不純物が少ないものが好ましい。例えば、遊離Naイオン及び遊離Clイオンは500ppm以下であることがより好ましい。 In addition, these epoxy resins are preferably sufficiently purified and have few ionic impurities. For example, free Na ions and free Cl ions are more preferably 500 ppm or less.
本発明において用いられる(B)常温液体の環状酸無水物としては特に制限はなく、例えば無水フタル酸、無水マレイン酸、メチルハイミック酸無水物、ハイミック酸無水物、無水コハク酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、クロレンド酸無水物、メチルテトラヒドロ無水フタル酸、3−メチルヘキサヒドロ無水フタル酸、4−メチルヘキサヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸マレイン酸付加物、メチルヘキサヒドロフタル酸、ベンゾフェノンテトラカルボン酸無水物、無水トリメリット酸、無水ピロメリット酸、メチルテトラヒドロ無水フタル酸、水素化メチルナジック酸無水物、無水マレイン酸とジエン化合物からディールス・アルダー反応で得られ、複数のアルキル基を有するトリアルキルテトラヒドロ無水フタル酸、ドデセニル無水コハク酸等の各種環状酸無水物が挙げられる。 There is no particular limitation on the cyclic acid anhydride (B) used in the present invention as a normal temperature liquid cyclic acid anhydride. For example, phthalic anhydride, maleic anhydride, methyl hymic anhydride, highmic anhydride, succinic anhydride, tetrahydrophthalic anhydride Acid, hexahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, methylhexahydro It is obtained by Diels-Alder reaction from phthalic acid, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, methyltetrahydrophthalic anhydride, hydrogenated methylnadic anhydride, maleic anhydride and diene compound. Having an alkyl group of Kill tetrahydrophthalic anhydride, various cyclic acid anhydride such as dodecenyl succinic anhydride and the like.
「環状酸無水物」とは、無水フタル酸に代表されるように「−CO−O−CO−」の二個の炭素原子Cがそれぞれ他の二個の炭素原子と化学結合して環状になっているものを示す。また、「無水酸当量」は、(酸無水物の分子量)/(酸無水物分子内の無水酸基の数)で示す。 “Cyclic anhydride” means that two carbon atoms C of “—CO—O—CO—” are chemically bonded to the other two carbon atoms to form a ring as represented by phthalic anhydride. It shows what has become. The “acid anhydride equivalent” is expressed by (molecular weight of acid anhydride) / (number of hydroxyl groups in the acid anhydride molecule).
無水酸当量が200以上の化合物としては、例えば、無水酸当量が234であるジャパンエポキシレジン株式会社製商品名jERキュアYH306等が市販品として入手可能である。 As a compound having an acid anhydride equivalent of 200 or more, for example, a product name jER Cure YH306 manufactured by Japan Epoxy Resin Co., Ltd. having an acid anhydride equivalent of 234 is commercially available.
酸無水物の無水酸当量が200未満の場合、硬化物中のエステル結合が多くなるため、高温高湿下で加水分解の影響を受けやすくなり、耐湿性、特に耐マイグレーション性の低下を生じ易い。また、酸無水物の無水酸当量が200未満の場合はエステル基の影響で吸水率も高くなり、これも耐マイグレーション性の低下の原因となる。即ち、無水酸当量が大きい環状酸無水物は無水酸当量が小さい環状酸無水物よりもエステル基濃度が小さくなることから、その硬化物は吸水率が低いため、水に溶け出すCl等のイオン性不純物量を低減できる。 When the acid anhydride has an acid equivalent of less than 200, the amount of ester bonds in the cured product increases, so that it is susceptible to hydrolysis at high temperatures and high humidity, which tends to cause a decrease in moisture resistance, particularly migration resistance. . Further, when the acid anhydride equivalent of the acid anhydride is less than 200, the water absorption is also increased due to the influence of the ester group, which also causes a decrease in migration resistance. That is, since the cyclic acid anhydride having a large acid anhydride equivalent has a lower ester group concentration than the cyclic acid anhydride having a small acid equivalent equivalent, the cured product has a low water absorption rate. The amount of ionic impurities can be reduced.
無水酸当量は好ましくは200〜400であり、より好ましくは200〜300である。 The acid anhydride equivalent is preferably 200 to 400, more preferably 200 to 300.
(B)成分の環状酸無水物の構造は特に制限は無いが、耐マイグレーション性の観点から分子中に塩素、臭素などのハロゲン原子、エステル結合を含まないことが好ましい。 The structure of the cyclic acid anhydride of component (B) is not particularly limited, but it is preferable that the molecule does not contain halogen atoms such as chlorine and bromine and ester bonds from the viewpoint of migration resistance.
本発明では(B)成分以外の硬化剤を適宜使用することができ、エポキシ樹脂の硬化剤として一般に使用されているものを用いることができる。例えば、ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン、m−キシレンジアミン、トリメチルヘキサメチレンジアミン、2−メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン、イソフォロンジアミン、1,3−ビスアミノメチルシクロヘキサン、ビス(4−アミノシクロヘキシル)メタン、ノルボルネンジアミン、1,2−ジアミノシクロヘキサン、ラロミン、ジアミノジフェニルメタン、メタフェニレンジアミン、ジアミノジフェニルスルフォン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、ポリシクロヘキシルポリアミン混合物、N−アミノエチルピペラジン等のアミン化合物、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、1−(2−シアノエチル)−2−エチル−4−メチルイミダゾール、2,4−ジアミノ−6−(2−メチルイミダゾイル−(1))エチル−s−トリアジン、2−フェニルイミダゾリン、2,3−ジヒドロ−1H−ピロロ(1,2−a)ベンズイミダゾール等のイミダゾール化合物、3級アミン、DBU、ジシアンジアミド、有機酸ジヒドラジド、N,N−ジメチル尿素誘導体等が挙げられる。中でも低粘度化の観点からはアミン化合物が好ましい。 In the present invention, curing agents other than the component (B) can be used as appropriate, and those generally used as curing agents for epoxy resins can be used. For example, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4 -Aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, laromine, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine mixture, N-aminoethylpiperazine, etc. Amine compounds, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (2-cyano Til) -2-ethyl-4-methylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1)) ethyl-s-triazine, 2-phenylimidazoline, 2,3-dihydro-1H- Examples include imidazole compounds such as pyrrolo (1,2-a) benzimidazole, tertiary amines, DBU, dicyandiamide, organic acid dihydrazide, and N, N-dimethylurea derivatives. Of these, amine compounds are preferred from the viewpoint of viscosity reduction.
(B)成分の常温液体の環状酸無水物の配合量は、その性能を発揮するために(B)成分を含む硬化剤全量に対して30質量%以上が好ましく、40質量%以上がより好ましく、60質量%以上がさらに好ましい。 The blending amount of the room temperature liquid cyclic acid anhydride as the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more based on the total amount of the curing agent containing the component (B) in order to exhibit its performance. 60 mass% or more is more preferable.
(A)エポキシ樹脂と(B)成分の常温液体の環状酸無水物を含む全硬化剤との当量比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、エポキシ樹脂に対して硬化剤を0.6〜1.6当量の範囲に設定することが好ましく、0.7〜1.4当量がより好ましく、0.8〜1.2当量がさらに好ましい。0.6〜1.6当量の範囲からはずれた場合、硬化反応が不充分となり信頼性が低下する傾向がある。ここで、当量とは反応当量であり、たとえば、酸無水物の無水酸当量はエポキシ基1個に対し酸無水物基1個が反応するものとして計算され、フェノール樹脂の当量はエポキシ基1個に対しフェノール性水酸基1個が反応するものとして計算され、芳香族アミンの当量はエポキシ基1個に対しアミノ基の活性水素1個が反応するものとして計算される。 The equivalent ratio of the (A) epoxy resin and the total curing agent including the cyclic acid anhydride of the room temperature liquid of the component (B) is not particularly limited, but in order to suppress each unreacted component to a small amount, It is preferable to set a hardening | curing agent in the range of 0.6-1.6 equivalent, 0.7-1.4 equivalent is more preferable, 0.8-1.2 equivalent is further more preferable. When deviating from the range of 0.6 to 1.6 equivalents, the curing reaction is insufficient and the reliability tends to be lowered. Here, the equivalent is a reaction equivalent. For example, an acid anhydride equivalent of an acid anhydride is calculated as one acid anhydride group reacts with one epoxy group, and an equivalent of a phenol resin is one epoxy group. Is calculated as one phenolic hydroxyl group reacts, and the equivalent of aromatic amine is calculated as one amino group active hydrogen reacts with one epoxy group.
本発明において用いられる(C)カップリング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、1級及び/又は2級及び/又は3級アミノ基を有するシラン化合物、エポキシシラン、メルカプトシラン、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が挙げられる。 There is no restriction | limiting in particular as (C) coupling agent used in this invention, Although a conventionally well-known thing can be used, For example, the silane compound which has a primary and / or secondary and / or tertiary amino group, Examples thereof include various silane compounds such as epoxy silane, mercaptosilane, alkyl silane, ureido silane, vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds.
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メトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アニリノプロピルトリメトキシシラン、γ−アニリノプロピルトリエトキシシラン、γ−(N,N−ジメチル)アミノプロピルトリメトキシシラン、γ−(N,N−ジエチル)アミノプロピルトリメトキシシラン、γ−(N,N−ジブチル)アミノプロピルトリメトキシシラン、γ−(N−メチル)アニリノプロピルトリメトキシシラン、γ−(N−エチル)アニリノプロピルトリメトキシシラン、γ−(N,N−ジメチル)アミノプロピルトリエトキシシラン、γ−(N,N−ジエチル)アミノプロピルトリエトキシシラン、γ−(N,N−ジブチル)アミノプロピルトリエトキシシラン、γ−(N−メチル)アニリノプロピルトリエトキシシラン、γ−(N−エチル)アニリノプロピルトリエトキシシラン、γ−(N,N−ジメチル)アミノプロピルメチルジメトキシシラン、γ−(N,N−ジエチル)アミノプロピルメチルジメトキシシラン、γ−(N,N−ジブチル)アミノプロピルメチルジメトキシシラン、γ−(N−メチル)アニリノプロピルメチルジメトキシシラン、γ−(N−エチル)アニリノプロピルメチルジメトキシシラン、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、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る。これらの1種を単独で用いても2種類以上を組み合わせて用いてもよい。 Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, Isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, tetraisopropylbis (dioctylphosphite) titanate And titanate coupling agents such as One of these may be used alone, or two or more may be used in combination.
(C)カップリング剤の全配合量は、液状樹脂組成物に対して0.037〜5.0質量%であることが好ましく、0.05〜4.75質量%であることがより好ましく、0.1〜2.5質量%であることがさらに好ましい。0.037質量%未満では基板と液状樹脂組成物の硬化物の密着性が低下する傾向があり、5.0質量%を超えるとガラス転移温度や曲げ強度などの物性が低下する傾向がある。 (C) The total amount of coupling agent is preferably 0.037 to 5.0% by mass, more preferably 0.05 to 4.75% by mass, based on the liquid resin composition. More preferably, it is 0.1-2.5 mass%. If the amount is less than 0.037% by mass, the adhesion between the substrate and the cured product of the liquid resin composition tends to decrease, and if it exceeds 5.0% by mass, the physical properties such as glass transition temperature and bending strength tend to decrease.
本発明において用いられる(D)酸化防止剤としては従来公知のものを用いることができる。例えばフェノール化合物系酸化防止剤でフェノール核のオルト位に少なくとも1つのアルキル基を有する化合物としては、2,6−ジ−t−ブチル−4−メチルフェノール、n−オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、2,2´−メチレンビス−(4−メチル−6−t−ブチルフェノール)、3,9−ビス[2−〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ〕−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、4,4´−ブチリデンビス−(6−t−ブチル−3−メチルフェノール)、4,4´−チオビス(6−t−ブチル−3−メチルフェノール)、テトラキス[メチレン−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]メタン、2,2−チオ−ジエチレンビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、N,N´−ヘキサメチレンビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオンアミド]、イソオクチル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)ベンゼン、4,6−ビス(ドデシルチオメチル)−o−クレゾール、ビス(3,5−ジ−t−ブチル−4−ヒドロキシベンジルホスホン酸エチル)カルシウム、2,4−1ビス[(オクチルチオ)メチル]−o−クレゾール、1,6−ヘキサンジオール−ビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、6−[3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロポキシ]−2,4,8,10−テトラ−t−ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピン、2−t−ブチル−6−(3−t−ブチル−2−ヒドロキシ−5−メチルベンジル)−4−メチルフェニルアクリレート、2−[1−(2−ヒドロキシ−3,5−ジ−t−ペンチルフェニル)エチル]−4,6−ジ−t−ペンチルフェニルアクリレート、2,2´−メチレンビス−(4−エチル−6−t−ブチルフェノール)、2,6−ジ−t−ブチル−4−エチルフェノール、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−t−ブチルフェニル)ブタン、トリエチレングリコール−ビス[3−(3−t−ブチル―4−ヒドロキシ―5−メチルフェニル)プロピオネート]、トリス(3,5−ジ―t−ブチル―4ヒドロキシベンジル)イソシアヌレート、ジエチル[〔3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシフェニル〕メチル]ホスホネート、2,5,7,8−テトラメチル―2(4´,8´,12´−トリメチルトリデシル)クロマン―6―オール、2,4−ビス―(n−オクチルチオ)−6−(4−ヒドロキシ―3,5−ジ―t−ブチルアニリノ)−1,3,5−トリアジンなどが挙げられる。ジシクロヘキシルアミンとしては新日本理化株式会社製商品名D−CHA−T等が市販品として入手可能であり、その誘導体としては亜硝酸ジシクロヘキシルアミンアンモニウム、N,N−ジ(3−メチル−シクロヘキシルアミン)、N,N−ジ(2−メトキシ−シクロヘキシル)アミン、N,N−ジ(4−ブロモ−シクロヘキシル)アミンなどが挙げられる。有機硫黄化合物系酸化防止剤としてはジラウリル―3,3´−チオジプロピオネート、ジミリスチル―3,3´−チオジプロピオネート、ジステアリル―3,3´−チオジプロピオネート、ペンタエリスリチルテトラキス(3−ラウリルチオプロピオネート)、ジトリデシル―3,3´−チオジプロピオネート、2−メルカプトベンズイミダゾール、4,4´−チオビス(6−t−ブチル−3−メチルフェノール)、2,2−チオ−ジエチレンビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、4,6−ビス(ドデシルチオメチル)−o−クレゾール、2,4−1ビス[(オクチルチオ)メチル]−o−クレゾール、2,4−ビス−(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−t−ブチルアニリノ)−1,3,5−トリアジンなど、アミン化合物系酸化防止剤としてはN,N´−ジアリル−p−フェニレンジアミン、N,N´−ジ−sec−ブチル―p−フェニレンジアミン、オクチル化ジフェニルアミン、2,4−ビス−(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−t−ブチルアニリノ)−1,3,5−トリアジンなど、リン化合物系酸化防止剤としてはトリスノニルフェニルフォスファイト、トリフェニルフォスファイト、ビス(3,5−ジ−t−ブチル−4−ヒドロキシベンジルホスホン酸エチル)カルシウム、トリス(2,4−ジ−t−ブチルフェニル)フォスファイト、2−[〔2,4,8,10−テトラキス(1,1−ジメチルエ−テル)ジベンゾ[d,f][1,3,2]ジオキサフォスフェピン−6−イル〕オキシ]−N,N−ビス[2−{〔2,4,8,10−テトラキス(1,1ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサフォスフェピン−6−イル〕オキシ}−エチル]エタナミン、6−[3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロポキシ]−2,4,8,10−テトラ−t−ブチルジベンズ[d,f][1,3,2]ジオキサホスフェピン、ジエチル[〔3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシフェニル〕メチル]ホスホネートなどが挙げられる。これらの1種を単独で用いても2種類以上を組み合わせて用いてもよい。なお、前記フェノール化合物系酸化防止剤の中には、フェノール水酸基に加え、リン原子、硫黄原子、アミンのいずれかを少なくとも一つ以上同一分子中に含む化合物は重複して挙げた。 A conventionally well-known thing can be used as (D) antioxidant used in this invention. For example, as a compound having a phenol compound antioxidant and having at least one alkyl group at the ortho position of the phenol nucleus, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 3,9-bis [2- [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 4,4'-butylidenebis- (6- t-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate] methane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 4,6-bis (dodecylthiomethyl) -o-cresol, bis (3,5-di-) t-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 2,4-1bis [(octylthio) methyl] -o-cresol, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl ) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,2'-methylenebis -(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, Trier Lenglycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, diethyl [[3 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,5,7,8-tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6 -Ol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like. As dicyclohexylamine, trade name D-CHA-T manufactured by Shin Nippon Rika Co., Ltd. is available as a commercial product, and derivatives thereof include dicyclohexylamine ammonium nitrite and N, N-di (3-methyl-cyclohexylamine). N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine, and the like. Organic sulfur compound-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis (3-lauryl thiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 2,2 -Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis (dodecylthiomethyl) -o-cresol, 2,4-1bis [( Octylthio) methyl] -o-cresol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylani Lino) -1,3,5-triazine, etc. As amine compound-based antioxidants, N, N′-diallyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, octylation Tris as a phosphorus compound type antioxidant such as diphenylamine, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Nonylphenyl phosphite, triphenyl phosphite, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris (2,4-di-tert-butylphenyl) phosphite, 2- [[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] -N, N-bis [2-{[2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine -6-yl] oxy} -ethyl] ethanamine, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [ d, f] [1,3,2] dioxaphosphine, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, and the like. One of these may be used alone, or two or more may be used in combination. In addition, in the said phenol compound type antioxidant, in addition to the phenol hydroxyl group, the compound which contains at least 1 or more of a phosphorus atom, a sulfur atom, and an amine in the same molecule was mentioned repeatedly.
前記酸化防止剤の中でも、特にフェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物系酸化防止剤と、ジシクロヘキシルアミンが耐マイグレーション性向上の観点からより好ましい。フェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物系酸化防止剤では、オルト位のアルキル基が電子供与基であるため、フェノール水酸基の酸素原子の不対電子部位において電子濃度が高まり、酸化防止剤が陽極金属表面に配位し、また、ジシクロヘキシルアミンでは、アミンの窒素原子の不対電子部位が陽極金属表面に配位することで、金属表面に配位した酸化防止剤が金属の酸化劣化を抑制し、耐マイグレーション性が向上すると考えられる。 Among the antioxidants, phenol compound-based antioxidants having at least one alkyl group at the ortho position of the phenol nucleus and dicyclohexylamine are more preferable from the viewpoint of improving migration resistance. In the phenolic compound-based antioxidant having at least one alkyl group at the ortho position of the phenol nucleus, since the alkyl group at the ortho position is an electron donating group, the electron concentration is increased at the unpaired electron site of the oxygen atom of the phenol hydroxyl group, Antioxidant is coordinated to the surface of the anode metal, and in dicyclohexylamine, the unpaired electron site of the nitrogen atom of the amine is coordinated to the surface of the anode metal, so that the antioxidant coordinated to the metal surface is the metal. It is thought that oxidative degradation is suppressed and migration resistance is improved.
さらに前記フェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物系酸化防止剤では一般に固形、粉末の性状の化合物が知られているが、電子部品用液状樹脂組成物として粘度、浸透性、流動性の低下を避けるためには電子部品用液状樹脂組成物の一成分となる(A)エポキシ樹脂に対し、電子部品用液状樹脂組成物の硬化物が十分な耐マイグレーション性を有する程度に溶解することがさらに好ましい。具体的には一般のエポキシ樹脂、例えば本発明でも液状エポキシ樹脂として使用される周知のビスフェノールF型エポキシ樹脂に対する飽和溶解量が5質量%以上であることが好ましく、より好ましい範囲は10質量%以上である。この理由としては、前記好ましい範囲の飽和溶解量をもつフェノール化合物系酸化防止剤がエポキシ樹脂に溶解することにより、フェノール化合物系酸化防止剤が電子部品用液状樹脂組成物中に均一に分散することができ、耐マイグレーション性が高まるからである。ここで、前記の飽和溶解量は、液状樹脂組成物の塗布が通常は室温で行われることから、該液状組成物の安定性を考慮して、室温での値である。前記フェノール核のオルト位に少なくとも1つのアルキル基を有するフェノール化合物系酸化防止剤のうち、このような溶解性を有するフェノール化合物系酸化防止剤の例としては4,4´−ブチリデンビス−(6−t−ブチル−3−メチルフェノール)、テトラキス[メチレン−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]メタン、3,9−ビス[2−〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ〕−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、トリエチレングリコールビス〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート〕などが挙げられる。 Furthermore, in the phenolic compound-based antioxidant having at least one alkyl group at the ortho position of the phenol nucleus, a solid, powdery compound is generally known, but as a liquid resin composition for electronic parts, viscosity, permeability, In order to avoid a decrease in fluidity, the cured product of the liquid resin composition for electronic parts is dissolved to the extent that it has sufficient migration resistance with respect to the epoxy resin (A), which is a component of the liquid resin composition for electronic parts. More preferably. Specifically, the saturated dissolution amount with respect to a general epoxy resin, for example, a well-known bisphenol F type epoxy resin used as a liquid epoxy resin in the present invention is preferably 5% by mass or more, and a more preferable range is 10% by mass or more. It is. The reason for this is that the phenolic compound-based antioxidant having a saturated dissolution amount in the preferred range is dissolved in the epoxy resin, so that the phenolic compound-based antioxidant is uniformly dispersed in the liquid resin composition for electronic components. This is because migration resistance is improved. Here, the saturated dissolution amount is a value at room temperature in consideration of the stability of the liquid composition since application of the liquid resin composition is usually performed at room temperature. Among the phenolic compound antioxidants having at least one alkyl group at the ortho position of the phenol nucleus, examples of the phenolic compound antioxidants having such solubility include 4,4′-butylidenebis- (6- t-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
さらに前記エポキシ樹脂に溶解するフェノール化合物系酸化防止剤の中でも、フェノール核のオルト位に1つのメチル基を有するフェノール化合物系酸化防止剤がさらに好ましい。これは、メチル基は立体障害が少なく、かつ電子供与基であり、酸化防止剤のフェノール水酸基の不対電子がより陽極金属表面に配位しやすいためと考えられる。このようなフェノール化合物系酸化防止剤としては3,9−ビス[2−〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ〕−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン、トリエチレングリコールビス〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート〕などが挙げられる。 Furthermore, among the phenol compound antioxidants dissolved in the epoxy resin, a phenol compound antioxidant having one methyl group at the ortho position of the phenol nucleus is more preferable. This is presumably because the methyl group has little steric hindrance and is an electron donating group, and the unpaired electrons of the phenolic hydroxyl group of the antioxidant are more easily coordinated to the anode metal surface. As such a phenolic compound-based antioxidant, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
また、ジシクロヘキシルアミンでは常温における性状が液体であり、固形、粉末の酸化防止剤と比較して電子部品用液状樹脂組成物の粘度、浸透性、流動性を損なわずに均一に分散するという利点がある。 In addition, dicyclohexylamine is liquid at room temperature, and has the advantage of being uniformly dispersed without impairing the viscosity, permeability, and fluidity of the liquid resin composition for electronic components compared to solid and powder antioxidants. is there.
前記フェノール化合物系酸化防止剤の配合量は、(A)エポキシ樹脂に対して0.1〜10質量%が好ましく、より好ましくは0.5〜5.0質量%である。0.1質量%未満ではマイグレーションの抑制効果が低下し、10質量%を超えると電子部品用液状樹脂組成物の流動性が低下する傾向がある。なお、前記フェノール化合物系酸化防止剤の(A)エポキシ樹脂に対する飽和溶解量Dが5質量%<D<10質量%である場合の配合量は、0.1〜D質量%が好ましく、より好ましくは0.5〜5.0質量%である。 0.1-10 mass% is preferable with respect to (A) epoxy resin, and, as for the compounding quantity of the said phenolic compound type antioxidant, More preferably, it is 0.5-5.0 mass%. If it is less than 0.1% by mass, the effect of suppressing migration is reduced, and if it exceeds 10% by mass, the fluidity of the liquid resin composition for electronic parts tends to be reduced. In addition, 0.1-D mass% is preferable, and, as for the compounding quantity in case the saturated dissolution amount D with respect to (A) epoxy resin of the said phenolic compound type antioxidant is 5 mass% <D <10 mass%, More preferably, Is 0.5-5.0 mass%.
前記ジシクロヘキシルアミンの配合量は、(A)エポキシ樹脂に対して0.1〜30質量%が好ましく、より好ましくは0.5〜10質量%である。0.1質量%未満ではマイグレーションの抑制効果が低下し、30質量%を超えると電子部品用液状樹脂組成物の保存安定性および硬化物のガラス転移温度が低下する傾向がある。 0.1-30 mass% is preferable with respect to (A) epoxy resin, and, as for the compounding quantity of the said dicyclohexylamine, More preferably, it is 0.5-10 mass%. If the amount is less than 0.1% by mass, the effect of suppressing migration decreases, and if it exceeds 30% by mass, the storage stability of the liquid resin composition for electronic parts and the glass transition temperature of the cured product tend to decrease.
本発明の電子部品用液状樹脂組成物が適用される配線板および半導体装置の配線間もしくはバンプ間ギャップが20μm以下の場合はギャップ間の充填性や流動性を良好とするため、電子部品用液状樹脂組成物に不溶な固形の化合物の配合量は10質量%以下が好ましく、5質量%以下がより好ましい。一方、本発明の電子部品用液状樹脂組成物が適用される配線板および半導体装置の配線間もしくはバンプ間ギャップが20μmを超える場合であり、さらに耐マイグレーション性の向上が必要な場合は、配線板および半導体装置との熱膨張係数差を補うことを目的として、ギャップ間の充填性や流動性を損なわない範囲で無機充填剤を配合することが可能である。無機充填剤としては、電子部品用液状樹脂組成物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、合成シリカ等のシリカ、炭酸カルシウム、タルク、クレー、酸化アルミナ等のアルミナ、窒化珪素、炭化珪素、窒化ホウ素、珪酸カルシウム、チタン酸カリウム、窒化アルミ、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る。さらにはアルコキシド化合物の加水分解・縮合反応により得られるナノシリカ等の無機ナノ粒子を充填剤として用いることも出来る。これらの無機充填剤は単独で用いても2種以上を組み合わせて用いてもよい。 When the gap between the wiring boards and the bumps of the semiconductor device to which the liquid resin composition for electronic parts of the present invention is applied is 20 μm or less, the gap between the gaps and the fluidity are improved. The amount of the solid compound insoluble in the resin composition is preferably 10% by mass or less, and more preferably 5% by mass or less. On the other hand, the wiring board to which the liquid resin composition for electronic parts of the present invention is applied and the gap between the wirings or bumps of the semiconductor device exceed 20 μm, and further when the migration resistance needs to be improved, the wiring board For the purpose of compensating for the difference in thermal expansion coefficient with the semiconductor device, an inorganic filler can be blended within a range that does not impair the filling property and fluidity between the gaps. The inorganic filler is generally used in liquid resin compositions for electronic parts and is not particularly limited. For example, silica such as fused silica, crystalline silica, synthetic silica, calcium carbonate, talc, clay, alumina oxide, etc. Alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc. And glass fiber. Furthermore, inorganic nanoparticles such as nano silica obtained by hydrolysis / condensation reaction of an alkoxide compound can also be used as a filler. These inorganic fillers may be used alone or in combination of two or more.
無機充填剤の形状は、流動性等の成形性の観点から球形に近いことが好ましい。無機充填剤の平均粒径は、5nmから10μmの範囲が好ましい。10μmを超えるとフィラー沈降を起こしやすくなる傾向や、電子部品用液状樹脂組成物の微細間隙への浸透性・流動性が低下してボイド・未充填を招きやすくなる傾向がある。また、これらの充填剤は、必要に応じて表面をカップリング処理したものを用いてもよい。無機充填剤の配合量は、電子部品用液状樹脂組成物の10質量%以下が好ましく、5質量%以下がさらに好ましい。10質量%を超えた場合、電子部品用液状樹脂組成物の硬化物とフィルム基板を用いたフレキシブル配線板との線膨張係数差が大きくなり、両者の界面で剥離が生じやすくなる。また、無機充填剤量が多いと電子部品用液状樹脂組成物の粘度が高くなり、表面張力が上がるため、流動性が低下する傾向がある。 The shape of the inorganic filler is preferably close to a spherical shape from the viewpoint of moldability such as fluidity. The average particle size of the inorganic filler is preferably in the range of 5 nm to 10 μm. When it exceeds 10 μm, filler sedimentation tends to occur, and the permeability / fluidity of the liquid resin composition for electronic parts to the fine gaps tends to decrease, which tends to cause voids / unfilled. Moreover, you may use what carried out the coupling process of the surface as needed for these fillers. The blending amount of the inorganic filler is preferably 10% by mass or less, and more preferably 5% by mass or less of the liquid resin composition for electronic components. When it exceeds 10 mass%, the linear expansion coefficient difference of the hardened | cured material of the liquid resin composition for electronic components and the flexible wiring board using a film board | substrate will become large, and it will become easy to produce peeling in both interface. On the other hand, when the amount of the inorganic filler is large, the viscosity of the liquid resin composition for electronic parts becomes high and the surface tension increases, so that the fluidity tends to decrease.
本発明の電子部品用液状樹脂組成物には、必要に応じて(A)成分のエポキシ樹脂と(B)成分を含む硬化剤の反応を促進する硬化促進剤を用いることが好ましい。硬化促進剤としては硬化性とポットライフを両立するためには潜在性硬化促進剤が好ましい。潜在性硬化促進剤とは、ある特定の温度等の条件で硬化促進機能が発現されるもので、例えば通常の硬化促進剤が、マイクロカプセル等で保護されたり各種化合物と付加した塩の構造となっていたりするものが挙げられる。この場合、特定の温度を超えるとマイクロカプセルや付加物から硬化促進剤が開放される。 In the liquid resin composition for electronic parts of the present invention, it is preferable to use a curing accelerator that accelerates the reaction of the epoxy resin as the component (A) and the curing agent containing the component (B) as necessary. As the curing accelerator, a latent curing accelerator is preferable in order to achieve both curability and pot life. The latent curing accelerator is a substance that exhibits a curing accelerating function under conditions such as a specific temperature. For example, a normal curing accelerator is protected by microcapsules or the like, or has a structure of a salt added with various compounds. Something that has become. In this case, when a specific temperature is exceeded, the curing accelerator is released from the microcapsules and adducts.
潜在性硬化促進剤の例としては常温固体のアミノ基を有する化合物をコアとして、常温固体のエポキシ化合物のシェルを被覆してなるコア−シェル粒子が挙げられ、市販品としてアミキュア(味の素株式会社製、登録商標)や、マイクロカプセル化されたアミンをビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂に分散させたノバキュア(旭化成ケミカルズ株式会社製、登録商標)などが使用できる。 Examples of latent curing accelerators include core-shell particles formed by coating a shell of a normal temperature solid epoxy compound with a normal temperature solid amino group-containing compound as a core. Amicure (manufactured by Ajinomoto Co., Inc.) is a commercially available product. , Registered trademark) and NovaCure (registered trademark, manufactured by Asahi Kasei Chemicals Corporation) in which a microencapsulated amine is dispersed in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
さらには電子部品用液状樹脂組成物系に不溶な固体粒子で加熱成形時に解離して硬化促進作用を発現するアミン化合物またはリン化合物の塩類及びこれらに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が潜在性硬化促進剤として使用できる。 Furthermore, it is a solid particle insoluble in the liquid resin composition system for electronic parts, and it is dissociated at the time of thermoforming, and an amine compound or a phosphorus compound salt that exhibits a curing accelerating action and an intramolecular formed by adding a compound having a π bond thereto. A compound having polarization can be used as a latent curing accelerator.
これらを例示すれば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とπ結合をもつ化合物とを付加してなる分子内分極を有する化合物、トリエチレンジアミン、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)フェノール等の三級アミン化合物の誘導体、2−メチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、2−ヘプタデシルイミダゾール等のイミダゾール化合物の誘導体、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、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン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リン化合物、及びこれらの誘導体、トリフェニルホスフィントリフェニルボロン、テトラフェニルホスホニウム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、これらの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。 For example, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8- Compounds having intramolecular polarization formed by adding a cycloamidine compound such as diaza-bicyclo (5,4,0) undecene-7 and a compound having a π bond, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamino Derivatives of tertiary amine compounds such as ethanol and tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl Derivatives of imidazole compounds such as imidazole, tributylphosphine, methyldiphenyl Organic phosphine compounds such as sphin, triphenylphosphine, diphenylphosphine, phenylphosphine, maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6- Quinone compounds such as dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin, etc. Phosphorus compounds having intramolecular polarization, and their derivatives, triphenylphosphine triphenylboron, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate , N-methyl Include phenyl boronic salts and derivatives thereof, such as morpholine tetraphenyl borate, it may be used in combination of two or more even with these alone.
なかでも、保存安定性、速硬化性の観点からは、マイクロカプセル化されたアミンをビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂に分散させたものが好ましい。 Among these, from the viewpoints of storage stability and fast curability, it is preferable to disperse a microencapsulated amine in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
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、非潜在性のものも含めた全量で(A)エポキシ樹脂に対して0.1〜40質量%が好ましく、より好ましくは0.5〜30質量%である。0.1質量%未満では短時間での硬化性に劣る傾向があり、40質量%を超えると硬化速度が速すぎて制御が困難になったりポットライフ、シェルライフ等の保存安定性が劣ったりする傾向がある。 The blending amount of the curing accelerator is not particularly limited as long as the curing accelerating effect is achieved, but it is 0.1 to the total amount of (A) epoxy resin including the non-latent one. 40 mass% is preferable, More preferably, it is 0.5-30 mass%. If it is less than 0.1% by mass, it tends to be inferior in curability in a short time, and if it exceeds 40% by mass, the curing rate is too fast and it becomes difficult to control, and the storage stability such as pot life and shell life is inferior. Tend to.
本発明の電子部品用液状樹脂組成物には、エポキシ樹脂硬化物の強靭化や低弾性率化を図るために、公知の各種ゴム粒子を配合することが好ましい。該ゴム粒子はエポキシ樹脂と非相溶性のものが硬化物のガラス転移温度(耐熱性)を下げずに弾性率を下げるのに有効である。具体的には例えば、ブタジエン・アクリロニトリル・スチレン系共重合体や該重合体の末端または側鎖にエポキシ基,アミノ基,カルボキシル基、水酸基等を有する変性共重合体、末端または側鎖にエポキシ基,アミノ基,カルボキシル基,水酸基などを有する変性シリコーン系エラストマー等が挙げられる。ゴム粒子は取り扱い性や樹脂成分との分散性の点から、微粉末状で、予めエポキシ樹脂や硬化剤に細かく分散させたものを用いることが好ましい。樹脂組成物中に一様に混合できることから、常温で液状のゴム変性エポキシ樹脂(液状エポキシ樹脂とゴム粒子を加熱溶融したもの)であることが好ましい。ゴム粒子の含有によって電子部品用液状樹脂組成物の硬化物と基板等との密着性が向上し、耐高温高湿性等の信頼性向上が図られる。 In the liquid resin composition for electronic parts of the present invention, it is preferable to blend various known rubber particles in order to increase the toughness and lower elastic modulus of the cured epoxy resin. The rubber particles that are incompatible with the epoxy resin are effective in lowering the elastic modulus without lowering the glass transition temperature (heat resistance) of the cured product. Specifically, for example, a butadiene / acrylonitrile / styrene copolymer, a modified copolymer having an epoxy group, amino group, carboxyl group, hydroxyl group or the like at the terminal or side chain of the polymer, an epoxy group at the terminal or side chain , Modified silicone elastomers having amino groups, carboxyl groups, hydroxyl groups, and the like. From the viewpoint of handleability and dispersibility with the resin component, it is preferable to use rubber particles that are finely powdered and finely dispersed in an epoxy resin or a curing agent in advance. Since it can mix uniformly in a resin composition, it is preferable that it is a liquid rubber-modified epoxy resin (what melt | dissolved and heated the liquid epoxy resin and the rubber particle) at normal temperature. Inclusion of rubber particles improves the adhesion between the cured resin composition for electronic parts and the substrate, and improves reliability such as high temperature and humidity resistance.
また、本発明の電子部品用液状樹脂組成物には配線板および半導体装置への適用時における充填性や流動性を損なわない範囲で必要に応じてイオントラップ剤を耐マイグレーション性、耐湿性及び高温放置特性を向上させる観点から含有することが好ましい。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、特に下記組成式(I)で表されるハイドロタルサイトまたは(II)で表されるビスマスの含水酸化物が好ましい。 In addition, the liquid resin composition for electronic components of the present invention may be provided with an ion trap agent as migration resistance, moisture resistance and high temperature as long as it does not impair the filling property and fluidity when applied to wiring boards and semiconductor devices. It is preferably contained from the viewpoint of improving the leaving characteristics. There is no restriction | limiting in particular as an ion trap agent, A conventionally well-known thing can be used, Especially the hydrotalcite represented by the following compositional formula (I) or the hydrous oxide of bismuth represented by (II) is preferable.
(化1)
Mg1−XAlX(OH)2(CO3)X/2・mH2O (I)
(式(I)中、0<X≦0.5、mは正の数。)
(化2)
BiOx(OH)y(NO3)z(II)
(式(II)中、0.9≦x≦1.1、0.6≦y≦0.8、0.2≦z≦0.4)
これらイオントラップ剤の添加量としてはハロゲンイオンなどの陰イオンを捕捉できる十分な量であれば特に制限はないが、耐マイグレーション性の観点から電子部品用液状樹脂組成物に対して0.1〜3.0質量%が好ましく、さらに好ましくは0.3〜1.5質量%である。イオントラップ剤の平均粒径は0.1〜3.0μmが好ましく、最大粒径は10μm以下が好ましい。なお、上記式(I)の化合物は市販品として協和化学工業株式会社製商品名DHT−4Aとして入手可能である。また、上記式(II)の化合物は市販品として東亜合成株式会社製商品名IXE500として入手可能である。また必要に応じてその他のイオントラップ剤を添加することもできる。たとえば、マグネシウム、アルミニウム、チタン、ジルコニウム、アンチモン等から選ばれる元素の含水酸化物等が挙げられ、これらを単独又は2種以上を組み合わせて用いることができる。
(Chemical formula 1)
Mg 1-X Al X (OH) 2 (CO 3 ) X / 2 · mH 2 O (I)
(In formula (I), 0 <X ≦ 0.5, m is a positive number.)
(Chemical formula 2)
BiO x (OH) y (NO 3 ) z (II)
(In formula (II), 0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)
The addition amount of these ion trapping agents is not particularly limited as long as it is an amount sufficient to trap anions such as halogen ions, but from the viewpoint of migration resistance, it is 0.1 to 0.1% relative to the liquid resin composition for electronic components. 3.0 mass% is preferable, More preferably, it is 0.3-1.5 mass%. The average particle size of the ion trapping agent is preferably 0.1 to 3.0 μm, and the maximum particle size is preferably 10 μm or less. In addition, the compound of the said formula (I) is available as Kyowa Chemical Industry Co., Ltd. brand name DHT-4A as a commercial item. Moreover, the compound of the said formula (II) is available as a brand name IXE500 by Toa Gosei Co., Ltd. as a commercial item. Further, other ion trapping agents can be added as necessary. Examples thereof include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony and the like, and these can be used alone or in combination of two or more.
また、本発明の電子部品用液状樹脂組成物には、必要に応じて上記(A)エポキシ樹脂成分とは別にシリコーン変性エポキシ樹脂を添加することが好ましい。シリコーン変性エポキシ樹脂を添加することで電子部品用液状樹脂組成物のレベリング性、フィレット形成性、ボイド低減に効果が有る。シリコーン変性エポキシ樹脂はエポキシ基と反応する官能基を有するオルガノシロキサンとエポキシ樹脂との反応物として得ることができるが、常温で液状であることが好ましい。シリコーン変性エポキシ樹脂は液体の表面に局在化し、液体の表面張力を下げることができる。これにより濡れ性が高く、流動しやすくなるため、狭ギャップへの浸透性向上や巻き込みボイドの低減に効果がある。 Moreover, it is preferable to add a silicone modified epoxy resin to the liquid resin composition for electronic parts of this invention separately from the said (A) epoxy resin component as needed. Addition of the silicone-modified epoxy resin is effective in leveling properties, fillet-forming properties, and void reduction of the liquid resin composition for electronic parts. The silicone-modified epoxy resin can be obtained as a reaction product of an organosiloxane having a functional group that reacts with an epoxy group and an epoxy resin, but is preferably liquid at room temperature. The silicone-modified epoxy resin is localized on the surface of the liquid and can reduce the surface tension of the liquid. As a result, the wettability is high and the fluid is easy to flow, which is effective in improving the permeability to a narrow gap and reducing entrainment voids.
ここでエポキシ基と反応する官能基を有するオルガノシロキサンを例示すれば、アミノ基、カルボキシル基、水酸基、フェノール性水酸基、メルカプト基等を1分子中に1個以上有するジメチルシロキサン、ジフェニルシロキサン、メチルフェニルシロキサン等が挙げられる。オルガノシロキサンの重量平均分子量としては500〜5000の範囲が好ましい。この理由としては500未満では樹脂系との相溶性が良くなり過ぎて添加剤としての効果が十分に発揮されず、5000を超えると樹脂系に非相溶となるためシリコーン変性エポキシ樹脂が成形時に分離・しみ出しを発生し、接着性や外観を損なうためである。 Examples of organosiloxanes having functional groups that react with epoxy groups are dimethylsiloxane, diphenylsiloxane, methylphenyl having at least one amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, mercapto group, etc. in one molecule. Examples thereof include siloxane. The weight average molecular weight of the organosiloxane is preferably in the range of 500 to 5000. The reason for this is that if it is less than 500, the compatibility with the resin system becomes too good and the effect as an additive is not sufficiently exhibited, and if it exceeds 5000, it becomes incompatible with the resin system. This is because separation and oozing occur and the adhesiveness and appearance are impaired.
シリコーン変性エポキシ樹脂を得るためのエポキシ樹脂としては電子部品用液状樹脂組成物の樹脂系に相溶するものであれば特に制限は無く、電子部品用液状樹脂組成物に一般に使用されているエポキシ樹脂を用いることができ、たとえば、ビスフェノールA、ビスフェノールF、ビスフェノールAD、ビスフェノールS、ナフタレンジオール、水添ビスフェノールA等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ーテル型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール類とアルデヒド類とを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、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、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が、常温液状のものが好ましい。 The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the liquid resin composition for electronic parts, and is generally used for the liquid resin composition for electronic parts. For example, glycidyl ether type epoxy resins, orthocresol novolac type epoxy resins obtained by the reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin Glycidyl ester type obtained by reaction of a polybasic acid such as phthalic acid and dimer acid with epichlorohydrin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of phenols and aldehydes Glycidylamine type epoxy resin obtained by reaction of polyamine such as poxy resin, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy Resins and the like can be mentioned, and these may be used alone or in combination of two or more, but those at room temperature are preferred.
本発明の電子部品用液状樹脂組成物には、その他の添加剤として、染料、カーボンブラック、酸化チタン、鉛丹等の着色剤、難燃剤、希釈剤、他のレベリング剤、他の応力緩和剤、消泡剤、接着促進剤などを配線板および半導体装置への適用時における充填性や流動性を損なわない範囲で必要に応じて配合することができる。 In the liquid resin composition for electronic parts of the present invention, as other additives, colorants such as dyes, carbon black, titanium oxide, and lead tan, flame retardants, diluents, other leveling agents, other stress relaxation agents Further, an antifoaming agent, an adhesion promoter, and the like can be blended as necessary within a range not impairing the filling property and fluidity when applied to the wiring board and the semiconductor device.
難燃剤としては、臭素化エポキシ樹脂や三酸化アンチモンを用いることができるが、ノンハロゲン、ノンアンチモンの難燃剤を用いるのが好ましい。たとえば、赤リン、フェノール樹脂等の熱硬化性樹脂等で被覆された赤リン、リン酸エステル、酸化トリフェニルホスフィン等のリン化合物、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、ジシクロペンタジエニル鉄等の金属錯体化合物、酸化亜鉛、錫酸亜鉛、硼酸亜鉛、モリブデン酸亜鉛等の亜鉛化合物、酸化鉄、酸化モリブデン等の金属酸化物、水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物、下記組成式(III)で示される複合金属水酸化物などが挙げられる。 A brominated epoxy resin or antimony trioxide can be used as the flame retardant, but it is preferable to use a halogen-free or non-antimony flame retardant. For example, red phosphorus coated with a thermosetting resin such as red phosphorus, phenol resin, phosphorous ester, phosphorus compound such as triphenylphosphine oxide, melamine, melamine derivative, melamine modified phenolic resin, compound having triazine ring, Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, metal complex compounds such as dicyclopentadienyl iron, zinc oxide, zinc stannate, zinc borate, and zinc molybdate Examples thereof include zinc compounds, metal oxides such as iron oxide and molybdenum oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and composite metal hydroxides represented by the following composition formula (III).
(化3)
p(M1 aOb)・q(M2 cOd)・r(M3 cOd)・mH2O (III)
(組成式(III)で、M1、M2及びM3は互いに異なる金属元素を示し、a、b、c、d、p、q及びmは正の数、rは0又は正の数を示す。)
上記組成式(III)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、M1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。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。p、q及びrのモル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。なお、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に基づいて行った。上記した難燃剤は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。
(Chemical formula 3)
p (M 1 a O b) · q (M 2 c O d) · r (M 3 c O d) · mH 2 O (III)
(In the composition formula (III), M 1 , M 2 and M 3 represent different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number. Show.)
M 1 , M 2 and M 3 in the composition formula (III) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M 1 is a metal element of the third period, group IIA Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M 2 is selected from transition metal elements of groups IIIB to IIB, More preferably, M 1 is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M 2 is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M 1 is magnesium, M 2 is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. The classification of the metal elements was performed based on a long-period type periodic table in which the typical element is the A subgroup and the transition element is the B subgroup. The above flame retardants may be used alone or in combination of two or more.
希釈剤として、粘度調整のためエポキシ基を有する反応性希釈剤を混合しても良い。エポキシ基を有する反応性希釈剤としては例えばn−ブチルグリシジルエーテル、バーサティック酸グリシジルエーテル、スチレンオキサイド、エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、ブチルフェニルグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルが挙げられる。これらの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。 As a diluent, you may mix the reactive diluent which has an epoxy group for viscosity adjustment. Examples of the reactive diluent having an epoxy group include n-butyl glycidyl ether, versatic acid glycidyl ether, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neodymium Examples include pentyl glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether. One of these may be used alone, or two or more may be used in combination.
本発明の電子部品用液状樹脂組成物は、上記各種成分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、所定の配合量の成分を秤量し、らいかい機、ミキシングロール、プラネタリミキサ等を用いて混合、混練し、必要に応じて脱泡することによって得ることができる。 The liquid resin composition for electronic parts of the present invention can be prepared by any method as long as the above various components can be uniformly dispersed and mixed. However, as a general method, a component having a predetermined blending amount is weighed. It can be obtained by mixing, kneading using a raking machine, mixing roll, planetary mixer or the like, and defoaming as necessary.
本発明で得られる電子部品用液状樹脂組成物により素子を封止して得られる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、リジッド及びフレキシブル配線板、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、抵抗アレイ、コイル、スイッチ等の受動素子などの素子を搭載し、必要な部分を本発明の電子部品用液状樹脂組成物で封止して得られる電子部品装置などが挙げられる。特にフィルムを基材とする配線基板上に電子部品を直接バンプ接続した電子部品装置の封止に用いられることが好ましい。例えば、リジッド及びフレキシブル配線板やガラス上に形成した配線に半導体素子をバンプ接続によるフリップチップボンディングした半導体装置が対象となる。具体的な例としてはフリップチップBGAやCOF(Chip On Film)等の半導体装置が挙げられ、特に本発明で得られる電子部品用液状樹脂組成物は耐マイグレーション性に優れたCOF用のアンダーフィル材として好適である。また、プリント回路板にも本発明の電子部品用液状樹脂組成物は有効に使用できる。 The electronic component device obtained by sealing the element with the liquid resin composition for electronic components obtained in the present invention includes a lead frame, a wired tape carrier, a rigid and flexible wiring board, a supporting member such as glass and a silicon wafer. In addition, an active element such as a semiconductor chip, transistor, diode, thyristor, etc., an element such as a passive element such as a capacitor, a resistor, a resistor array, a coil, or a switch is mounted on the liquid resin composition for electronic components of the present invention. Examples thereof include an electronic component device obtained by sealing with an object. In particular, it is preferably used for sealing an electronic component device in which an electronic component is directly bump-connected on a wiring board having a film as a base material. For example, a semiconductor device in which a semiconductor element is flip-chip bonded by bump connection to a rigid and flexible wiring board or a wiring formed on glass is an object. Specific examples include semiconductor devices such as flip chip BGA and COF (Chip On Film). In particular, the liquid resin composition for electronic components obtained by the present invention is an underfill material for COF having excellent migration resistance. It is suitable as. Moreover, the liquid resin composition for electronic components of the present invention can also be used effectively for printed circuit boards.
本発明の電子部品用液状樹脂組成物を用いて素子を封止する方法としては、ディスペンス方式、注型方式、印刷方式等が挙げられる。 Examples of a method for sealing an element using the liquid resin composition for electronic parts of the present invention include a dispensing method, a casting method, and a printing method.
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。 EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
(実施例1〜5及び比較例)
(A)エポキシ樹脂として
エポキシ当量160のビスフェノールF型液状エポキシ樹脂(東都化成株式会社製商品名YDF−8170C)、
エポキシ当量140のナフタレン型エポキシ樹脂(大日本インキ工業株式会社製商品名HP−4032)、
ゴム粒子成分として
アクリロニトリル・ブタジエン・メタクリル酸・ジビニルベンゼン共重合物(JSR株式会社製商品名XER−91P)をビスフェノールF型液状エポキシ樹脂(YDF−8170C)に質量比1/4で予め加熱混融、微分散させたゴム変性エポキシ樹脂、
レベリング剤として
水酸基当量750のフェノール変性シリコーン(東レ・ダウコーニングシリコーン製商品名BY16−799)とビスフェノールF型液状エポキシ樹脂(YDF−8170C)を質量比1/1で加熱混融して得られたシリコーン変性エポキシ樹脂、
(B)環状酸無水物として
常温液体かつ無水酸当量234の環状酸無水物(ジャパンエポキシレジン株式会社製商品名jERキュアYH306)
(C)カップリング剤として
γ−グリシドキシプロピルトリメトキシシラン(信越化学工業株式会社製商品名KBM−403)、
(D)酸化防止剤として
4,4´−ブチリデンビス−(6−t−ブチル−3−メチルフェノール)(株式会社エーピーアイ コーポレーション製商品名ヨシノックスBB;酸化防止剤1)、テトラキス[メチレン−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]メタン(株式会社エーピーアイ コーポレーション製商品名トミノックスTT;酸化防止剤2)、
3,9−ビス[2−〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ〕−1,1−ジメチルエチル]−2,4,8,10−テトラオキサスピロ[5.5]ウンデカン(株式会社ADEKA製商品名AO−80;酸化防止剤3)、
トリエチレングリコールビス〔3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート〕(株式会社エーピーアイ コーポレーション製商品名ヨシノックス917;酸化防止剤4)、
ジシクロヘキシルアミン(新日本理化株式会社製商品名D−CHA−T;酸化防止剤5)、
硬化促進剤として
2−エチル−4−メチルイミダゾール(四国化成工業株式会社製商品名2E4MZ)、充填剤として比表面積1m2/g、平均粒径4μmの球状合成シリカを用意した。
(Examples 1-5 and comparative examples)
(A) As an epoxy resin, a bisphenol F type liquid epoxy resin having an epoxy equivalent of 160 (trade name YDF-8170C, manufactured by Toto Kasei Co., Ltd.),
Naphthalene-type epoxy resin having an epoxy equivalent of 140 (trade name HP-4032 manufactured by Dainippon Ink & Chemicals, Inc.)
As a rubber particle component, acrylonitrile / butadiene / methacrylic acid / divinylbenzene copolymer (trade name: XER-91P, manufactured by JSR Corporation) is preheated and melted into a bisphenol F type liquid epoxy resin (YDF-8170C) at a mass ratio of 1/4 in advance. , Finely dispersed rubber-modified epoxy resin,
As a leveling agent, a phenol-modified silicone having a hydroxyl equivalent weight of 750 (trade name BY16-799 manufactured by Toray Dow Corning Silicone) and a bisphenol F-type liquid epoxy resin (YDF-8170C) were heated and melted at a mass ratio of 1/1. Silicone-modified epoxy resin,
(B) A cyclic acid anhydride having a normal temperature liquid and an acid equivalent weight of 234 as a cyclic acid anhydride (trade name jER Cure YH306, manufactured by Japan Epoxy Resin Co., Ltd.)
(C) γ-glycidoxypropyltrimethoxysilane (trade name KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent,
(D) As an antioxidant, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol) (trade name Yoshinox BB manufactured by API Corporation; antioxidant 1), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name Tominox TT manufactured by API Corporation; antioxidant 2),
3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane (trade name AO-80 manufactured by ADEKA Corporation; antioxidant 3),
Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] (trade name Yoshinox 917 manufactured by API Corporation; antioxidant 4),
Dicyclohexylamine (trade name D-CHA-T manufactured by Shin Nippon Chemical Co., Ltd .; antioxidant 5),
2-ethyl-4-methylimidazole (trade name 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used as a curing accelerator, and spherical synthetic silica having a specific surface area of 1 m 2 / g and an average particle size of 4 μm was prepared as a filler.
これらをそれぞれ下記表1に示す質量部で配合し、らいかい機にて混練分散した後、真空脱泡して、実施例1〜5及び比較例の電子部品用液状樹脂組成物を作製した。 These were respectively blended in parts by mass shown in Table 1 below, kneaded and dispersed with a rough machine, and then vacuum degassed to prepare liquid resin compositions for electronic parts of Examples 1 to 5 and Comparative Example.
作製した実施例1〜5及び比較例の電子部品用液状樹脂組成物を次の各試験により評価した。評価結果を下記表2に示す。 The produced liquid resin compositions for electronic parts of Examples 1 to 5 and Comparative Example were evaluated by the following tests. The evaluation results are shown in Table 2 below.
(1)粘度
EMD型回転粘度計(株式会社トキメック製)を用い、25±1℃に保たれた電子部品用液状樹脂組成物について、実施例1〜5、比較例は100rpmで1分間回転させたときの目盛りに換算係数0.0125を乗じ、これを粘度とした。
(1) Viscosity For liquid resin compositions for electronic parts maintained at 25 ± 1 ° C. using an EMD type rotational viscometer (manufactured by Tokimec Co., Ltd.), Examples 1 to 5 and Comparative Examples were rotated at 100 rpm for 1 minute. The scale at that time was multiplied by a conversion factor of 0.0125 to obtain the viscosity.
(2)ゲル化時間
150℃の熱板上に0.1gの電子部品用液状樹脂組成物を滴下し、スパチュラで広がりすぎないようにかき混ぜた。滴下した後、電子部品用液状樹脂組成物の粘度が上がり、スパチュラを上に持ち上げたときに糸引きなく切れるまでの時間をゲル化時間とした。
(2) Gelation time 0.1 g of the liquid resin composition for electronic parts was dropped on a hot plate at 150 ° C. and stirred so as not to spread too much with a spatula. After dripping, the time until the viscosity of the liquid resin composition for electronic parts was increased and when the spatula was lifted up to break without stringing was defined as the gel time.
(3)吸水率
電子部品用液状樹脂組成物を150℃、2hの条件で硬化させ、50mm×50mm×1mmの試験片を作製した。本試験片の初期重量W1を測定した後、85℃/85%の高温高湿槽に入れ、100h後の重量W2を測定し、下式により吸水率をもとめた。
(吸水率)={(W2−W1)/W1}×100 (%)
(3) Water Absorption Rate The liquid resin composition for electronic parts was cured at 150 ° C. for 2 hours to produce a 50 mm × 50 mm × 1 mm test piece. After measuring the initial weight W 1 of this test piece, it was placed in a high-temperature and high-humidity tank at 85 ° C./85%, the weight W 2 after 100 hours was measured, and the water absorption rate was obtained by the following equation.
(Water absorption) = {(W 2 −W 1 ) / W 1 } × 100 (%)
(4)接着力
ポリイミドフィルム(東レ・デュポン株式会社商品名カプトン)上で電子部品用液状樹脂組成物を150℃、2hの条件で硬化させ、幅10mmの短冊状に切断した。これを引張試験器(島津製作所製)を用い、ポリイミドフィルムを90度上向きで剥離させるピール強度を接着力とした。
(4) Adhesive force The liquid resin composition for electronic components was cured on a polyimide film (trade name Kapton, Toray DuPont Co., Ltd.) at 150 ° C. for 2 hours, and cut into strips having a width of 10 mm. Using a tensile tester (manufactured by Shimadzu Corporation), the peel strength at which the polyimide film was peeled upward by 90 degrees was defined as the adhesive strength.
(5)侵入性
2枚のガラスで厚さ20μmのSUS製スペーサーを挟み、幅5mmの流路を作った。これを70℃のホットプレート上に水平に置いた後、電子部品用液状樹脂組成物を滴下し、ギャップ間に20mmまで侵入する時間を測定した。3分未満を良、3分以上を不良とした。
(5) Invasion A SUS spacer having a thickness of 20 μm was sandwiched between two pieces of glass to form a channel having a width of 5 mm. This was placed horizontally on a hot plate at 70 ° C., and then the liquid resin composition for electronic parts was dropped, and the time for entering to 20 mm between the gaps was measured. Less than 3 minutes was judged as good and 3 minutes or more as bad.
(6)耐マイグレーション性評価
ポリイミドフィルム上に錫メッキされた銅配線により配線幅15μm、配線間15μmの対向櫛形電極を形成したフレキシブル配線板の対向電極部に電子部品用液状樹脂組成物をディスペンス方式で塗布し、150℃、2hで硬化したものを試験片とした。この試験片を120℃/85%の高温高湿下で直流60Vの電圧をかけて抵抗値を連続的に測定し、抵抗値が106Ω以下になった時間でリークが発生したと判定した。測定は500hまで行い、抵抗値が106Ω以下にならなかった電子部品用液状樹脂組成物は>500hとした。
(6) Evaluation of migration resistance A liquid resin composition for electronic parts is dispensed on the counter electrode portion of a flexible wiring board in which a counter comb-shaped electrode having a wiring width of 15 μm and a wiring interval of 15 μm is formed by copper wiring tin-plated on a polyimide film. A test piece was prepared by coating at 150 ° C. for 2 hours. The resistance value of the test piece was continuously measured under a high temperature and high humidity of 120 ° C./85% by applying a DC voltage of 60 V, and it was determined that a leak occurred when the resistance value was 10 6 Ω or less. . The measurement was performed up to 500 h, and the liquid resin composition for electronic parts whose resistance value did not become 10 6 Ω or less was set to> 500 h.
(7)外観評価
耐マイグレーション性評価が終了した試験片を実体顕微鏡の透過光で観察し、ポリイミドフィルム上に錫メッキされた銅配線の腐食度合いを観察した。マイグレーションが発生すると、陽極配線側から配線金属が腐食し、樹脂中に溶出する現象が見られる。このため透過光で観察すると、図1に示すようにマイグレーションの進行度合いに応じ、陽極配線の幅が試験前と比較して太く見える。最も腐食している配線幅が試験前の配線幅と比較して1.0〜1.1倍であるものを◎、1.1〜1.2倍であるものを○、1.2〜1.3倍であるものを△、1.3倍以上であるものを×とした。
(7) Appearance evaluation The test piece for which the migration resistance evaluation was completed was observed with transmitted light of a stereomicroscope, and the degree of corrosion of the copper wiring tin-plated on the polyimide film was observed. When migration occurs, there is a phenomenon in which the wiring metal corrodes from the anode wiring side and is eluted into the resin. Therefore, when observed with transmitted light, as shown in FIG. 1, the width of the anode wiring appears thicker than before the test according to the progress of migration. The most corroded wiring width is 1.0 to 1.1 times the wiring width before the test, ◎, the one 1.1 to 1.2 times is ○, 1.2 to 1 .Times.3 times, and .times.1.3 times or more x.
実施例1〜5はいずれも酸化防止剤を配合した電子部品用液状樹脂組成物であるが、酸化防止剤を配合しない比較例と比較すると、粘度、ゲル化時間、吸水率、接着力、侵入性などの電子部品用液状樹脂組成物として必須となる諸特性を損なうことなく、耐マイグレーション性が向上できた。この中でもオルト位に一つのメチル基を有する酸化防止剤を用いた実施例3,4が最も絶縁信頼性、耐腐食性に優れ、それに次いでジシクロヘキシルアミンを用いた実施例5が絶縁信頼性、耐腐食性に優れており、高い耐マイグレーション性を示した。これは酸化防止剤の配合によって、高温高湿環境下における樹脂硬化物の酸化劣化が防止され、不純物イオンの生成や、絶縁性の低下が抑制されていると同時に、金属表面に作用して金属の腐食が抑制されているためと考えられる。 Examples 1 to 5 are all liquid resin compositions for electronic parts containing an antioxidant, but compared with comparative examples not containing an antioxidant, viscosity, gelation time, water absorption, adhesive strength, penetration The migration resistance could be improved without impairing various properties essential for the liquid resin composition for electronic parts such as the property. Among them, Examples 3 and 4 using an antioxidant having one methyl group at the ortho position are most excellent in insulation reliability and corrosion resistance, and then Example 5 using dicyclohexylamine is insulation reliability and resistance. Excellent corrosion resistance and high migration resistance. This combination of antioxidants prevents oxidative degradation of the cured resin under high-temperature and high-humidity environment, suppresses the generation of impurity ions and decreases in insulation, and acts on the metal surface to prevent the metal from being deteriorated. This is thought to be due to the inhibition of corrosion.
本発明になる電子部品用液状樹脂組成物は、耐マイグレーション性が良好であり、その他の成形性、信頼性にも優れる電子部品用液状樹脂組成物であり、その工業的価値は大である。特にリジッド及びフレキシブル配線板やガラス上に形成した配線に半導体素子をバンプ接続によるフリップチップボンディングした半導体装置、具体的にはフリップチップBGAやCOF等の半導体装置用のアンダーフィル材として有用である。 The liquid resin composition for electronic parts according to the present invention is a liquid resin composition for electronic parts that has good migration resistance and is excellent in other moldability and reliability, and has great industrial value. In particular, it is useful as an underfill material for a semiconductor device in which a semiconductor element is flip-chip bonded to a wiring formed on a rigid and flexible wiring board or glass by bump connection, specifically, a semiconductor device such as a flip-chip BGA or COF.
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