JP4431921B2 - Epoxy resin composition and electronic component device - Google Patents
Epoxy resin composition and electronic component device Download PDFInfo
- Publication number
- JP4431921B2 JP4431921B2 JP2000188283A JP2000188283A JP4431921B2 JP 4431921 B2 JP4431921 B2 JP 4431921B2 JP 2000188283 A JP2000188283 A JP 2000188283A JP 2000188283 A JP2000188283 A JP 2000188283A JP 4431921 B2 JP4431921 B2 JP 4431921B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- integer
- group
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000647 polyepoxide Polymers 0.000 title claims description 116
- 239000003822 epoxy resin Substances 0.000 title claims description 115
- 239000000203 mixture Substances 0.000 title claims description 65
- -1 quinone compound Chemical class 0.000 claims description 47
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 38
- 239000005011 phenolic resin Substances 0.000 claims description 36
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 34
- 238000007259 addition reaction Methods 0.000 claims description 20
- 239000011256 inorganic filler Substances 0.000 claims description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000001588 bifunctional effect Effects 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920003986 novolac Polymers 0.000 description 12
- 150000002989 phenols Chemical class 0.000 description 11
- 239000007983 Tris buffer Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 229940005561 1,4-benzoquinone Drugs 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 7
- 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 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000012778 molding material Substances 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000000547 substituted alkyl group Chemical group 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 150000004780 naphthols Chemical class 0.000 description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000004053 quinones Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QJIMTLTYXBDJFC-UHFFFAOYSA-N (4-methylphenyl)-diphenylphosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJIMTLTYXBDJFC-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
- ZEGDFCCYTFPECB-UHFFFAOYSA-N 2,3-dimethoxy-1,4-benzoquinone Natural products C1=CC=C2C(=O)C(OC)=C(OC)C(=O)C2=C1 ZEGDFCCYTFPECB-UHFFFAOYSA-N 0.000 description 2
- MYKLQMNSFPAPLZ-UHFFFAOYSA-N 2,5-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=CC1=O MYKLQMNSFPAPLZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- RLQZIECDMISZHS-UHFFFAOYSA-N 2-phenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1 RLQZIECDMISZHS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RMMPZDDLWLALLJ-UHFFFAOYSA-N Thermophillin Chemical compound COC1=CC(=O)C(OC)=CC1=O RMMPZDDLWLALLJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- 150000004057 1,4-benzoquinones Chemical class 0.000 description 1
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- ZZYASVWWDLJXIM-UHFFFAOYSA-N 2,5-di-tert-Butyl-1,4-benzoquinone Chemical compound CC(C)(C)C1=CC(=O)C(C(C)(C)C)=CC1=O ZZYASVWWDLJXIM-UHFFFAOYSA-N 0.000 description 1
- ZJKWJHONFFKJHG-UHFFFAOYSA-N 2-Methoxy-1,4-benzoquinone Chemical compound COC1=CC(=O)C=CC1=O ZJKWJHONFFKJHG-UHFFFAOYSA-N 0.000 description 1
- HRSLYNJTMYIRHM-UHFFFAOYSA-N 2-[[4-[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]-2,6-dimethylphenoxy]methyl]oxirane Chemical group CC1=CC(C=2C=C(C)C(OCC3OC3)=C(C)C=2)=CC(C)=C1OCC1CO1 HRSLYNJTMYIRHM-UHFFFAOYSA-N 0.000 description 1
- OZRVXYJWUUMVOW-UHFFFAOYSA-N 2-[[4-[4-(oxiran-2-ylmethoxy)phenyl]phenoxy]methyl]oxirane Chemical group C1OC1COC(C=C1)=CC=C1C(C=C1)=CC=C1OCC1CO1 OZRVXYJWUUMVOW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- CRGRWBQSZSQVIE-UHFFFAOYSA-N diazomethylbenzene Chemical compound [N-]=[N+]=CC1=CC=CC=C1 CRGRWBQSZSQVIE-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 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
- 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
- 125000006840 diphenylmethane group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004206 montan acid ester Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DOXFBSZBACYHFY-UHFFFAOYSA-N phenol;stilbene Chemical class OC1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 DOXFBSZBACYHFY-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000012808 vapor phase Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、成形材料、積層板用又は接着剤の材料として好適なエポキシ樹脂組成物、及びこのエポキシ樹脂組成物により封止された素子を備えた電子部品装置に関する。
【０００２】
【従来の技術】
従来から、成形材料、積層板用、接着剤用材料等にエポキシ樹脂が広範囲に使用され、トランジスタ、ＩＣ等の電子部品の素子封止の分野では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。特に、オルソクレゾールノボラック型エポキシ樹脂とフェノールノボラック硬化剤の組み合わせはこれらのバランスに優れており、IC封止用成形材料のベース樹脂として主流になっている。また、硬化促進剤としては３級アミン、イミダゾール等のアミン化合物、ホスフィン類、ホスホニウム等のリン化合物が一般に使用されている。
【０００３】
【発明が解決しようとする課題】
近年、電子部品のプリント配線板への高密度実装化が進んでおり、これに伴い電子部品は従来のピン挿入型のパッケージから、表面実装型のパッケージが主流になりつつある。ＩＣ、ＬＳＩなどの表面実装型ＩＣは、実装密度を高くするために素子のパッケージに対する占有体積がしだいに大きくなり、パッケージの肉厚は非常に薄くなってきた。さらに、ピン挿入型パッケージは、ピンを配線板に挿入した後に配線板裏面からはんだ付けが行われるためパッケージが直接高温にさらされることがなかったのに対し、表面実装型ＩＣは配線板表面に仮止めを行った後、はんだバスやリフロー装置などで処理されるため、直接はんだ付け温度にさらされる。この結果、ＩＣパッケージが吸湿した場合、はんだ付け時に吸湿水分が急激に膨張しパッケージクラックに至り、これが大きな問題になっている。
【０００４】
このはんだ付け時のパッケージクラックに対する耐性、いわゆる耐リフロークラック性を改良するために、無機充填剤を多く含むエポキシ樹脂組成物が提案されている。しかし、無機充填剤量の増加は成形時の流動性の低下を招き、充填不良、ボイド発生等の成形上の障害やＩＣチップのボンディングワイヤが断線し導通不良が発生するなど、成形品の性能低下を招くため、無機充填剤の増加量には限界があり、結果として耐リフロークラック性の著しい向上が望めないという問題があった。
特にトリフェニルホスフィン等のリン系硬化促進剤や１，８−ジアザビシクロ［５．４．０］ウンデセン−７等のアミン系硬化促進剤を用いた場合、流動性が低く、耐リフロークラック性の著しい向上が望めないのが実情である。
【０００５】
このような問題点を改善するために、トリフェニルホスフィンと１，４−ベンゾキノンとの付加反応物を硬化促進剤として用いる方法が提案されている（特開平９−１５７４９７公報）が、吸湿時の硬化性及び保存安定性に問題があった。
【０００６】
本発明は、このような状況に鑑みなされたもので、保存安定性、吸湿時の硬化性、流動性及び耐リフロークラック性に優れるエポキシ樹脂組成物、及びこのエポキシ樹脂組成物により封止された素子を備えた電子部品装置を提供しようとするものである。
【課題を解決するための手段】
【０００７】
本発明者らは上記の課題を解決するために鋭意検討を重ねた結果、トリフェニルホスフィンと少なくとも一つの置換基を有するキノン化合物との付加反応物を配合することにより、保存安定性、吸湿時の硬化性、流動性及び耐リフロークラック性に優れるエポキシ樹脂組成物が得られ、上記の目的を達成しうることを見い出し、本発明を完成するに至った。
【０００８】
すなわち、本発明は、
（１）（Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂及び（Ｃ）トリフェニルホスフィンと少なくとも一つの置換基を有するキノン化合物との付加反応物を必須成分とするエポキシ樹脂組成物、
（２）少なくとも一つの置換基を有するキノン化合物が下記一般式（Ｉ）で示される化合物である上記（１）記載のエポキシ樹脂組成物、
【化５】
（３）（Ａ）エポキシ樹脂が２官能のエポキシ樹脂及び／又はエポキシ当量が１９０以上のエポキシ樹脂を含有してなる上記（１）又は（２）記載のエポキシ樹脂組成物、
（４）（Ｂ）フェノール樹脂が２官能のフェノール樹脂及び／又は水酸基当量が１５０以上のフェノール樹脂を含有してなる上記（１）〜（３）のいずれかに記載のエポキシ樹脂組成物、
（５）（Ｄ）無機充填剤をさらに含有し、その配合量がエポキシ樹脂組成物に対して５５〜９０体積％である上記（１）〜（４）のいずれかに記載のエポキシ樹脂組成物、
（６）（Ａ）エポキシ樹脂が下記一般式（II）〜（VII）のいずれかで示されるエポキシ樹脂の少なくとも１種を含有してなる上記（１）〜（５）のいずれかに記載のエポキシ樹脂組成物、及び
【化６】
（７）（Ｂ）フェノール樹脂が下記一般式（VIII）〜（XI）のいずれかで示されるフェノール樹脂の少なくとも１種を含有してなる上記（１）〜（６）のいずれかに記載のエポキシ樹脂組成物、並びに
【化８】
（８）上記（１）〜（７）のいずれかに記載のエポキシ樹脂組成物により封止された素子を備えた電子部品装置
に関する。
【０００９】
【発明の実施の形態】
本発明において用いられる（Ａ）エポキシ樹脂としては特に制限はないが、例えば、一般に使用されている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、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂をはじめとするフェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール類及び／又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、アルキル置換又は非置換のビフェノール、スチルベン系フェノール類等のジグリシジルエーテル、ブタンジオ一ル、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテル、フタル酸、イソフタル酸、テトラヒドロフタル酸等のカルボン酸類のグリシジルエステル、アニリン、イソシアヌール酸等の窒素原子に結合した活性水素をグリシジル基で置換したもの等のグリシジル型またはメチルグリシジル型のエポキシ樹脂、分子内のオレフィン結合をエポキシ化して得られるビニルシクロヘキセンジエポキシド、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、２−（３，４−エポキシ）シクロヘキシル−５，５−スピロ（３，４−エポキシ）シクロヘキサン−ｍ−ジオキサン等の脂環型エポキシ樹脂、パラキシリレン及び／又はメタキシリレン変性フェノール樹脂のグリシジルエーテル、テルペン変性フェノール樹脂のグリシジルエーテル、ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテル、シクロペンタジエン変性フェノール樹脂のグリシジルエーテル、多環芳香環変性フェノール樹脂のグリシジルエーテル、ナフタレン環含有フェノール樹脂のグリシジルエーテル、ビフェニル型エポキシ樹脂、ハロゲン化フェノールノボラック型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。これらのエポキシ樹脂の中で、２官能のエポキシ樹脂が流動性及び耐リフロークラック性の点で好ましく、エポキシ当量が１９０以上のエポキシ樹脂が耐リフロークラック性の点で好ましい。中でも、下記一般式（II）〜（VII）のいずれかで示されるエポキシ樹脂が耐リフロークラック性及び流動性の点で好ましく、特に耐リフロークラック性の観点からは４，４'−ビス（２，３−エポキシプロポキシ）−３，３'，５，５'−テトラメチルビフェニルがより好ましく、成形性及び耐熱性の観点からは４，４'−ビス（２，３−エポキシプロポキシ）−ビフェニルがより好ましい。これら一般式（II）〜（VII）のいずれかで示されるエポキシ樹脂は、いずれか１種を単独で用いても２種以上を組み合わせて用いてもよいが、その性能を発揮するために、（Ａ）成分のエポキシ樹脂全量に対して、合わせて３０重量％以上使用することが好ましく、５０重量％以上使用することがより好ましい。
【００１０】
【化９】
上記一般式（II）〜（VII）中のＲ4〜Ｒ13について、それぞれ全てが同一でも異なっていてもよいの意味は、例えば式（II）中の８個のＲ4の全てが同一でも異なっていてもよいの意味である。他のＲ5〜Ｒ13についても式中に含まれるそれぞれの個数について全てが同一でも異なっていてもよいとの意味である。また、Ｒ4〜Ｒ13はそれぞれが同一でも異なっていてもよい。例えばＲ4とＲ5の全てについて同一でも異なっていてもよい。
上記一般式（Ｖ）で示されるエポキシ樹脂としては、ｌ個の構成単位及びｍ個の構成単位をランダムに含むランダム共重合体、交互に含む交互共重合体、規則的に含む共重合体、ブロック状に含むブロック共重合体が挙げられ、これらのいずれか１種を単独で用いても、２種以上を組み合わせて用いてもよい。
【００１１】
本発明において用いられる（Ｂ）フェノール樹脂としては特に制限はないが、例えば、一般に使用されている１分子中に２個以上のフェノール性水酸基を有するフェノール樹脂で、フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール類及び／又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド類とを酸性触媒下で縮合又は共縮合させて得られる樹脂、フェノール類及び／又はナフトール類とジメトキシパラキシレンやビス（メトキシメチル）ビフェニルから合成されるフェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等のアラルキル型フェノール樹脂、パラキシリレン及び／又はメタキシリレン変性フェノール樹脂、メラミン変性フェノール樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、シクロペンタジエン変性フェノール樹脂、多環芳香環変性フェノール樹脂などが挙げられ、これらを単独で用いても２種以上を組み合わせて用いてもよい。これらのフェノール樹脂の中で、２官能のフェノール樹脂が耐リフロークラック性及び流動性の点で好ましく、水酸基当量が１５０以上のフェノール樹脂が耐リフロークラック性の点で好ましい。中でも、耐リフロークラック性の観点からは下記一般式（VIII）〜（XI）のいずれかで示されるフェノール樹脂がより好ましい。これら一般式（VIII）〜（XI）のいずれかで示されるフェノール樹脂は、いずれか１種を単独で用いても２種以上を組み合わせて用いてもよいが、その性能を発揮するためには、（Ｂ）成分のフェノール樹脂全量に対して合わせて３０重量％以上使用することが好ましく、５０重量％以上使用することがより好ましい。
【００１２】
【化１１】
上記一般式（VIII）〜（XI）中のＲ14〜Ｒ21について、それぞれ全てが同一でも異なっていてもよいの意味は、例えば式（IX）中のｉ個のＲ14の全てが同一でも相互に異なっていてもよいの意味である。他のＲ15〜Ｒ21についても式中に含まれるそれぞれの個数について全てが同一でも相互に異なっていてもよいとの意味である。また、Ｒ14〜Ｒ21はそれぞれが同一でも異なっていてもよい。例えばＲ14とＲ15の全てについて同一でも異なっていてもよく、Ｒ16とＲ19の全てについて同一でも異なっていてもよい。
上記一般式（VIII）〜（XI）中のｎは０〜１０の範囲であることが必要で、１０を超えた場合は（Ｂ）成分の溶融粘度が高くなるため、エポキシ樹脂組成物の溶融成形時の粘度も高くなり、未充填不良やボンディングワイヤ（素子とリードを接続する金線）の変形を引き起こしやすくなる。１分子中の平均ｎは１〜４の範囲に設定されることが好ましい。
【００１３】
本発明において（Ａ）エポキシ樹脂と（Ｂ）フェノール樹脂との配合比率は、全エポキシ樹脂のエポキシ当量に対する全フェノール樹脂の水酸基当量の比率（フェノール樹脂中の水酸基数／エポキシ樹脂中のエポキシ基数）で０．５〜２．０の範囲に設定されることが好ましく、０．７〜１．５がより好ましく、０．８〜１．３がさらに好ましい。この比率が０．５未満ではエポキシ樹脂の硬化が不充分となり、硬化物の耐熱性、耐湿性及び電気特性が劣る傾向があり、２．０を超えるとフェノール樹脂成分が過剰なため硬化が不充分となったり、硬化樹脂中に多量のフェノール性水酸基が残るため電気特性及び耐湿性が悪くなったりする傾向がある。
【００１４】
本発明において用いられる（Ｃ）トリフェニルホスフィンと少なくとも１つの置換基を有するキノン化合物との付加反応物としては、硬化促進剤として働くものであれば特に制限されるものではないが、中でも、硬化性の観点からトリフェニルホスフィンと下記一般式（Ｉ）で示されるキノン化合物との付加反応物が好ましい。
【化１２】
【００１５】
上記一般式（Ｉ）中のＲ1〜Ｒ3は、水素原子又は炭素数１〜１２の炭化水素基を示すが、炭素数１〜１２の炭化水素基としては特に制限はなく、例えば、炭素数１〜１２の置換又は非置換の脂肪族炭化水素基、炭素数１〜１２の置換又は非置換の脂環式炭化水素基、炭素数１〜１２の置換又は非置換の芳香族炭化水素基等が挙げられる。
炭素数１〜１２の置換又は非置換の脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ-ブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、オクチル基、デキル基、ドデキル基等のアルキル基、アリル基、メトキシ基、エトキシ基、プロポキシル基、ｎ-ブトキシ基、tert-ブトキシ基等のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基等のアルキルアミノ基、メチルチオ基、エチルチオ基、ブチルチオ基、ドデキルチオ基等のアルキルチオ基、アミノ基置換アルキル基、アルコキシ置換アルキル基、水酸基置換アルキル基、アリール基置換アルキル基等の置換アルキル基、アミノ基置換アルコキシ基、水酸基置換アルコキシ基、アリール基置換アルコキシ基等の置換アルコキシ基などが挙げられる。
炭素数１〜１２の置換又は非置換の脂環式炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等及びこれらにアルキル基、アルコキシ基、アリール基、水酸基、アミノ基、ハロゲン等が置換したものなどが挙げられる。
炭素数１〜１２の置換又は非置換の芳香族炭化水素基としては、例えば、フェニル基、トリル基等のアリール基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、ｔ-ブチルフェニル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、ｔ-ブトキシフェニル基等のアルコキシ基置換アリール基、フェノキシ基、クレゾキシ基等のアリーロキシ基、フェニルチオ基、トリルチオ基、ジフェニルアミノ基など、及びこれらにアミノ基、ハロゲン等が置換したもの等が挙げられる。
【００１６】
また、上記一般式（Ｉ）で示されるキノン化合物は、Ｒ1とＲ2が結合し環状構造となっていてもよい。本発明において用いられる、Ｒ1とＲ2が結合して環状構造をとる多環式のキノン化合物としては、特に制限はないが、例えば、置換したテトラメチレン基、テトラメチン基等が結合した下記一般式（XII）〜（XIV）のいずれかで示される多環式キノン化合物等が挙げられる。
【化１３】
上記一般式（Ｉ）で示されるキノン化合物の中でも、吸湿時の硬化性の観点からは、２，３−ジメトキシ−１，４ベンゾキノン、２，５−ジメトキシ−１，４−ベンゾキノン、メトキシ−１，４−ベンゾキノン等のアルコキシ基置換１，４−ベンゾキノン、及び２，３−ジメチル−１，４−ベンゾキノン、２，５−ジメチル−１，４−ベンゾキノン、メチル−１，４−ベンゾキノン等のアルキル基置換１，４−ベンゾキノンが好ましく、保存安定性の観点からは、２，５−ジ−t−ブチル−１，４−ベンゾキノン、t−ブチル−１，４−ベンゾキノン、フェニル−１，４−ベンゾキノンが好ましい。
【００１８】
トリフェニルホスフィンと上記一般式（Ｉ）で示されるキノン化合物との付加反応物の構造としては、例えば、下記一般式（XV）で示される化合物が挙げられる。
【化１４】
【００１９】
（Ｃ）トリフェニルホスフィンと少なくとも１つの置換基を有するキノン化合物との付加反応物の製造方法としては特に制限はないが、例えば、原料として用いられるトリフェニルホスフィンとキノン化合物とを両者が溶解する有機溶媒中で付加反応させて単離する方法、（Ｂ）成分のフェノール樹脂中で付加反応させる方法等が挙げられ、後者の方法においては単離せずにそのままフェノール樹脂中に溶解した状態で、エポキシ樹脂組成物の配合成分として用いることができる。
（Ｃ）トリフェニルホスフィンと少なくとも１つの置換基を有するキノン化合物との付加反応物は、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。
【００２０】
また、本発明のエポキシ樹脂組成物には、（Ｃ）成分以外に、エポキシ樹脂とフェノール樹脂との硬化反応を促進する硬化促進剤として一般に用いられているものを１種以上併用することができる。併用する硬化促進剤としては、例えば、１，５−ジアザビシクロ［４．３．０］ノネン−５、１，８−ジアザビシクロ［５．４．０］ウンデセン−７等のジアザビシクロアルケンなどのシクロアミジン化合物、その誘導体、それらのフェノールノボラック塩及びこれらの化合物に無水マレイン酸、１，４−ベンゾキノン、２，５−トルキノン、１，４−ナフトキノン、２，３−ジメチルベンゾキノン、２，６−ジメチルベンゾキノン、２，３−ジメトキシ−５−メチル−１，４−ベンゾキノン、２，３−ジメトキシ−１，４−ベンゾキノン、フェニル−１，４−ベンゾキノン等のキノン化合物、ジアゾフェニルメタンなどのπ結合をもつ化合物を付加してなる分子内分極を有する化合物、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類及びこれらの誘導体、２−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、２−ヘプタデシルイミダゾール等のイミダゾール類、テトラフェニルホスホニウム・テトラフェニルボレート等のテトラ置換ホスホニウム・テトラ置換ボレート、２−エチル−４−メチルイミダゾール・テトラフェニルボレート、Ｎ−メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩、トリフェニルホスフィン、ジフェニル（ｐ−トリル）ホスフィン、トリス（アルキルフェニル）ホスフィン、トリス（アルコキシフェニル）ホスフィン、トリス（アルキル・アルコキシフェニル）ホスフィン、トリス（ジアルキルフェニル）ホスフィン、トリス（トリアルキルフェニル）ホスフィン、トリス（テトラアルキルフェニル）ホスフィン、トリス（ジアルコキシフェニル）ホスフィン、トリス（トリアルコキシフェニル）ホスフィン、トリス（テトラアルコキシフェニル）ホスフィン、トリアルキルホスフィン、ジアルキルアリールホスフィン、アルキルジアリールホスフィン等の有機ホスフィン類、又はこれら有機ホスフィン類と有機ボロン類との錯体やこれら有機ホスフィン類と１，４−ベンゾキノン等の非置換のキノン化合物とのベタイン型付加反応物などが挙げられる。
【００２１】
これらの硬化促進剤を併用する場合、（Ｃ）成分の配合量は、全硬化促進剤に対して３０重量％以上が好ましく、より好ましくは５０重量％以上である。（Ｃ）成分の配合量が３０重量％未満であると吸湿時の硬化性又は流動性が低下し、本発明の効果が少なくなる傾向がある。
（Ｃ）成分を含む全硬化促進剤の合計配合量は、硬化促進効果が得られれば特に制限はないが、吸湿時硬化性及び流動性の観点からは（Ａ）エポキシ樹脂と（Ｂ）フェノール樹脂の合計１００重量部に対して０．１〜１０重量部が好ましく、１〜７．０重量部がより好ましい。０．１重量部未満では短時間で硬化させることが困難で、１０重量部を超えると硬化速度が速すぎて良好な成形品が得られない場合が生じる傾向がある。
【００２２】
本発明のエポキシ樹脂組成物には、（Ｄ）無機充填剤を必要に応じてさらに配合することができる。特にエポキシ樹脂組成物を封止用成形材料として用いる場合には、（Ｄ）無機充填剤を配合することが好ましい。本発明において用いられる（Ｄ）無機充填剤としては、一般に封止用成形材料に用いられるもので特に限定はないが、例えば、溶融シリカ、結晶シリカ、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカ等の微粉未、又はこれらを球形化したビーズなどが挙げられる。さらに、難燃効果のある無機充填剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。中でも、線膨張係数低減の観点からは溶融シリカが、高熱伝導性の観点からはアルミナが好ましい。これらの無機充填剤は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。
【００２３】
（Ｄ）無機充填剤の配合量は、本発明の効果が得られれば特に制限はないが、エポキシ樹脂組成物に対して５５〜９０体積％の範囲であることが好ましい。これら無機充填剤は硬化物の熱膨張係数、熱伝導率、弾性率等の改良を目的に配合するものであり、配合量が５５体積％未満ではこれらの特性の改良が不十分となる傾向があり、９０体積％を超えるとエポキシ樹脂組成物の粘度が上昇して流動性が低下し成形が困難になる傾向がある。
また、（Ｄ）無機充填剤の平均粒径は１〜５０μｍが好ましく、１０〜３０μｍがより好ましい。１μｍ未満ではエポキシ樹脂組成物の粘度が上昇しやすく、５０μｍを超えると樹脂成分と無機充墳剤とが分離しやすくなり、硬化物が不均一になったり硬化物特性がばらついたり、狭い隙間への充填性が低下したりする傾向がある。
流動性の観点からは、（Ｄ）無機充填剤の粒子形状は角形より球形が好ましく、（Ｄ）無機充填剤の粒度分布は広範囲に分布したものが好ましい。例えば、無機充填剤を７５体積％以上配合する場合、その７０重量％以上を球状粒子とし、０．１〜８０μｍという広範囲に分布したものが好ましい。このような無機充填剤は最密充填構造をとりやすいため配合量を増加させても材料の粘度上昇が少なく、流動性に優れたエポキシ樹脂組成物を得ることができる。
【００２４】
本発明のエポキシ樹脂組成物には、陰イオン交換体を必要に応じて配合することができる。特にエポキシ樹脂組成物を封止用成形材料として用いる場合には、封止される素子を備える電子部品装置の耐湿性及び高温放置特性を向上させる観点から、陰イオン交換体を配合することが好ましい。本発明において用いられる陰イオン交換体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、例えば、ハイドロタルサイト類や、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマスから選ばれる元素の含水酸化物等が挙げられ、これらを単独で又は２種以上を組み合わせて用いることができる。中でも、下記一般式（XVI）で示されるハイドロタルサイトが好ましい。
【化１５】
Ｍｇ1-XＡｌX（ＯＨ）2（ＣＯ3）X/2・ｍＨ2Ｏ ……（XVI）
（０＜Ｘ≦０．５、ｍは正の整数）
これらの陰イオン交換体の配合量は、ハロゲンイオンなどの陰イオンを捕捉できる十分量であれば特に制限はないが、（Ａ）エポキシ樹脂に対して０．1〜３０重量％の範囲が好ましく、１〜５重量％がより好ましい。
【００２５】
本発明のエポキシ樹脂組成物には、樹脂成分と無機充項剤との接着性を高めるためのカップリング剤として、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等の各種シラン系化合物、チタン系化合物、アルミニウムキレート類、アルミニウム／ジルコニウム系化合物等の公知の添加剤を必要に応じて配合することができる。また、カーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を配合しても良い。
【００２６】
本発明のエポキシ樹脂組成物には、成形時に金型との良好な離型性を持たせるため離型剤を配合してもよい。本発明において用いられる離型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、例えば、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックス等が挙げられ、これらの１種を単独で用いても２種以上を組み合わせて用いてもよい。中でも、酸化型又は非酸化型のポリオレフィン系ワックスが好ましく、その配合量としては（Ａ）エポキシ樹脂に対して０.０１〜１０重量％が好ましく、０．１〜５重量％がより好ましい。ポリオレフィン系ワックスの配合量が０.０１重量％未満では離型性が不十分な傾向があり、１０重量％を超えると接着性が阻害されるおそれがある。ポリオレフィン系ワックスとしては、例えば市販品ではヘキスト社製のＨ４、ＰＥ、ＰＥＤシリーズ等の数平均分子量が５００〜１００００程度の低分子量ポリエチレンなどが挙げられる。また、ポリオレフィン系ワックスに他の離型剤を併用する場合、その配合量は（Ａ）エポキシ樹脂に対して０.１〜１０重量％が好ましく、０.５〜３重量％がより好ましい。
【００２７】
本発明のエポキシ樹脂組成物には、難燃性を付与するために必要に応じて難燃剤を配合することができる。本発明において用いられる難燃剤としては特に制限はなく、例えば、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む公知の有機若しくは無機の化合物、金属水酸化物などが挙げられ、これらの１種を単独で用いても２種以上を組み合わせて用いてもよい。難燃剤の配合量は、難燃効果が達成されれば特に制限はないが、（Ａ）エポキシ樹脂に対して１〜３０重量％が好ましく、２〜１５重量％がより好ましい。
さらに、本発明のエポキシ樹脂組成物には、その他の添加剤として、シリコーンオイル、シリコーンゴム粉末等の応力緩和剤などを必要に応じて配合することができる。
【００２８】
本発明のエポキシ樹脂組成物は、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ミキサー等によって十分混合した後、ミキシングロール、押出機等によって溶融混練した後、冷却、粉砕する方法を挙げることができる。例えば、上述した成分の所定量を均一に撹拌、混合し、予め７０〜１４０℃に加熱してあるニーダー、ロール、エクストルーダー等で混練、冷却し、粉砕するなどの方法で得ることができる。成形条件に合うような寸法及び重量でタブレット化すると使いやすい。
【００２９】
本発明で得られるエポキシ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、配線板、ガラス、シリコンウエハ等の支持部材に、半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子、コンデンサ、抵抗体、コイル等の受動素子等の素子を搭載し、必要な部分を本発明のエポキシ樹脂組成物で封止した、電子部品装置などが挙げられる。このような電子部品装置としては、例えば、リードフレーム上に半導体素子を固定し、ボンディングパッド等の素子の端子部とリード部をワイヤボンディングやバンプで接続した後、本発明のエポキシ樹脂組成物を用いてトランスファ成形などにより封止してなる、ＤＩＰ（Dual Inline Package）、ＰＬＣＣ（Plastic Leaded Chip Carrier）、ＱＦＰ（Quad Flat Package）、ＳＯＰ（Small Outline Package）、ＳＯＪ（Small Outline J-lead package）、ＴＳＯＰ（Thin Small Outline Package）、ＴＱＦＰ（Thin Quad Flat Package）等の一般的な樹脂封止型ＩＣ、テープキャリアにバンプで接続した半導体チップを、本発明のエポキシ樹脂組成物で封止したＴＣＰ（Tape Carrier Package）、配線板やガラス上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子及び／又はコンデンサ、抵抗体、コイル等の受動素子を、本発明のエポキシ樹脂組成物で封止したＣＯＢ（Chip On Board）モジュール、ハイブリッドＩＣ、マルチチップモジュール、裏面に配線板接続用の端子を形成した有機基板の表面に素子を搭載し、バンプまたはワイヤボンディングにより素子と有機基板に形成された配線を接続した後、本発明のエポキシ樹脂組成物で素子を封止したＢＧＡ（Ball Grid Array）、ＣＳＰ（Chip Size Package）などが挙げられる。また、プリント回路板にも本発明のエポキシ樹脂組成物は有効に使用できる。
【００３０】
本発明のエポキシ樹脂組成物を用いて、電子部品装置を封止する方法としては、低圧トランスファー成形法が最も一般的であるが、インジェクション成形法、圧縮成形法等を用いてもよい。
【００３１】
【実施例】
次に実施例により本発明を説明するが、本発明の範囲はこれらの実施例に限定されるものではない。
実施例１〜４９、比較例１〜４９
エポキシ樹脂としてはエポキシ当量１９６、融点１０６℃のビフェニル骨格型エポキシ樹脂（エポキシ樹脂１：油化シェルエポキシ株式会社製商品名ＹＸ−４０００Ｈ）、エポキシ当量２１０、融点１２０℃のスチルベン型エポキシ樹脂（エポキシ樹脂２：住友化学工業株式会社製商品名ＥＳＬＶ−２１０）、エポキシ当量１９２、融点７９℃のジフェニルメタン骨格型エポキシ樹脂（エポキシ樹脂３：新日鐡化学株式会社製商品名ＹＳＬＶ−８０ＸＹ）、エポキシ当量２１７、軟化点６４℃のナフトールオルトクレゾールノボラック型エポキシ樹脂（エポキシ樹脂４：日本化薬株式会社製商品名ＮＣ−７３００Ｌ）、エポキシ当量２６４、軟化点６４℃のジシクロペンタジエン変性フェノールノボラック型エポキシ樹脂（エポキシ樹脂５：大日本インキ化学工業株式会社製商品名ＨＰ−７２００）、エポキシ当量１９５、軟化点６２℃のオルトクレゾールノボラック型エポキシ樹脂（エポキシ樹脂６：住友化学工業株式会社製商品名ＥＳＣＮ−１９０−２）、硬化剤としては水酸基当量１７６、軟化点７０℃のフェノールアラルキル樹脂（硬化剤１：三井化学株式会社製商品名ミレックスＸＬ−２２５）、水酸基当量１９９、軟化点８９℃のビフェニル骨格型フェノール樹脂（硬化剤２：明和化成株式会社製商品名ＭＥＨ−７８５１）、水酸基当量１８３、軟化点７９℃のナフトールアラルキル樹脂（硬化剤３：新日鐵化学株式会社製商品名ＳＮ−１７０）、水酸基当量１７０、軟化点９３℃のジシクロペンタジエン変性フェノールノボラック樹脂（硬化剤４：日本石油化学株式会社製商品名ＤＰＰ）、実施例の硬化促進剤としてはトリフェニルホスフィンとメチル−１，４−ベンゾキノンとの付加反応物（硬化促進剤１）、トリフェニルホスフィンと２，３−ジメチル−１，４−ベンゾキノンとの付加反応物（硬化促進剤２）、トリフェニルホスフィンとフェニル−１，４−ベンゾキノンとの付加反応物（硬化促進剤３）、トリフェニルホスフィンとｔ-ブチル−１，４−ベンゾキノンとの付加反応物（硬化促進剤４）、トリフェニルホスフィンとメトキシ−１，４−ベンゾキノンとの付加反応物（硬化促進剤５）、比較例の硬化促進剤としてはトリフェニルホスフィン（硬化促進剤Ａ）、トリフェニルホスフィンと１，４−ベンゾキノンとの付加反応物（硬化促進剤Ｂ）、トリ−ｐ−トリルホスフィンと１，４−ベンゾキノンとの付加反応物（硬化促進剤Ｃ）、ジフェニル−ｐ−トリルホスフィンと１，４−ベンゾキノンとの付加反応物（硬化促進剤Ｄ）、ＤＢＵのフェノールノボラック塩（硬化促進剤Ｅ：サンアプロ株式会社製商品名ＳＡ−８４１）、無機充填剤としては平均粒径１７．５μｍ、比表面積３．８ｍ2／ｇの球状溶融シリカを用い、その他の添加成分としては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、着色剤としてカーボンブラック（三菱化学株式会社製商品名ＭＡ−１００）、離型剤としてカルナバワックス（株式会社セラリカＮＯＤＡ製）、難燃剤として三酸化アンチモン及びエポキシ当量３９３、軟化点８０℃、臭素含有量４８重量％の臭素化ビスフェノールＡ型エポキシ樹脂（臭素化エポキシ樹脂）を用い、表１〜表６に示す重量部で配合し、混練温度８０℃、混練時間１５分の条件でロール混練を行い、実施例１〜４９、比較例１〜４９のエポキシ樹脂組成物を得た。
【００３２】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
実施例、比較例のエポキシ樹脂組成物を、次の各試験により評価した。評価結果を表７〜表１２に示す。
なお、エポキシ樹脂組成物の成形は、トランスファ成形機により、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で行った。また、後硬化は１７５℃で６時間行った。
（１）スパイラルフロー（流動性の指標）
ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型を用いて、上記条件でエポキシ樹脂組成物を成形して流動距離（ｃｍ）を測定した。
（２）保存安定性
上記（１）で成形したエポキシ樹脂組成物を２５℃で７２時間保存後、流動距離（ｃｍ）を測定し、保存前の値と比較して、流動距離の保持率（％）で評価した。
（３）熱時硬度
エポキシ樹脂組成物を上記条件で直径５０ｍｍ×厚さ３ｍｍの円板に成形し、成形後直ちにショアＤ型硬度計を用いて測定した。
（４）吸湿時熱時硬度
上記（３）で成形したエポキシ樹脂組成物を２５℃／５０％ＲＨの条件で７２時間放置後、ショアＤ型硬度計を用いて測定した。
（５）耐リフロークラック性
４２アロイフレームに寸法８×１０×０．４ｍｍのテスト用シリコンチップを銀ペーストを用いて搭載した、外形寸法１４×２０×２．０ｍｍのＱＦＰ８０ピンのパッケージを、エポキシ樹脂組成物を用いて上記条件で成形、後硬化して作製し、８５℃、６０％ＲＨの条件で１６８時間吸湿させた後、ベーパーフェーズリフロー装置により、２１５℃、９０秒の条件でリフロー処理を行って、クラックの発生の有無を確認し、試験パッケージ数（５）に対するクラック発生パッケージ数で評価した。
【００３９】
【表７】
【表８】
【表９】
【表１０】
【表１１】
【表１２】
実施例１〜４９は、いずれも流動性、保存安定性、熱時硬度、吸湿時熱時硬度及び耐リフロークラック性に優れる。
これに対して、本発明の（Ｃ）成分を含まない比較例１〜４９では、同じ樹脂組成の実施例と比較して、流動性、吸湿時熱時硬度及び保存安定性の少なくともいずれかに劣っている。
【００４６】
【発明の効果】
本発明になるエポキシ樹脂組成物は、流動性、保存安定性、吸湿時の硬化性、に優れ、このエポキシ樹脂組成物を用いてＩＣ、ＬＳＩ等の電子部品を封止すれば、実施例で示したように耐リフロークラック性が良好で、信頼性に優れる電子部品装置を得ることができるので、その工業的価値は大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an epoxy resin composition suitable as a molding material, a laminated plate material or an adhesive material, and an electronic component device including an element sealed with the epoxy resin composition.
[0002]
[Prior art]
Conventionally, epoxy resins have been widely used for molding materials, laminates, adhesive materials, and the like, and epoxy resin compositions have been widely used in the field of device sealing of electronic components such as transistors and ICs. This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, the combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance between these, and has become the mainstream as a base resin for molding materials for IC sealing. As the curing accelerator, amine compounds such as tertiary amines and imidazoles, and phosphorus compounds such as phosphines and phosphonium are generally used.
[0003]
[Problems to be solved by the invention]
In recent years, high-density mounting of electronic components on printed wiring boards has progressed, and along with this, electronic components are becoming mainstream from conventional pin insertion type packages to surface mount type packages. In surface mount ICs such as ICs and LSIs, the volume occupied by the element package gradually increases in order to increase the mounting density, and the thickness of the package has become very thin. Furthermore, since the pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, the package was not directly exposed to high temperature, whereas the surface mount type IC is not attached to the surface of the wiring board. After being temporarily fixed, it is exposed to the soldering temperature directly because it is processed by a solder bath or a reflow device. As a result, when the IC package absorbs moisture, the moisture absorption moisture rapidly expands at the time of soldering and leads to a package crack, which is a big problem.
[0004]
In order to improve the resistance against package cracks during soldering, so-called reflow crack resistance, an epoxy resin composition containing a large amount of an inorganic filler has been proposed. However, an increase in the amount of inorganic fillers leads to a decrease in fluidity during molding, and molding performance such as defective filling and voiding, and IC chip bonding wires are broken, resulting in poor continuity. Since the decrease causes an increase in the amount of the inorganic filler, there is a limit, and as a result, there is a problem that a remarkable improvement in reflow crack resistance cannot be expected.
In particular, when a phosphorus curing accelerator such as triphenylphosphine or an amine curing accelerator such as 1,8-diazabicyclo [5.4.0] undecene-7 is used, the fluidity is low and the reflow crack resistance is remarkable. The fact is that improvement cannot be expected.
[0005]
In order to improve such problems, a method using an addition reaction product of triphenylphosphine and 1,4-benzoquinone as a curing accelerator has been proposed (Japanese Patent Laid-Open No. 9-157497). There were problems with curability and storage stability.
[0006]
The present invention was made in view of such a situation, and was sealed by an epoxy resin composition excellent in storage stability, curability at the time of moisture absorption, fluidity and reflow crack resistance, and this epoxy resin composition. An electronic component device provided with an element is to be provided.
[Means for Solving the Problems]
[0007]
As a result of intensive studies in order to solve the above problems, the present inventors have blended an addition reaction product of triphenylphosphine and a quinone compound having at least one substituent, whereby storage stability, when moisture is absorbed. An epoxy resin composition having excellent curability, fluidity and reflow crack resistance was obtained, and it was found that the above object could be achieved, and the present invention was completed.
[0008]
That is, the present invention
(1) An epoxy resin composition comprising, as an essential component, an addition reaction product of (A) an epoxy resin, (B) a phenol resin, and (C) triphenylphosphine and a quinone compound having at least one substituent,
(2) The epoxy resin composition according to the above (1), wherein the quinone compound having at least one substituent is a compound represented by the following general formula (I):
[Chemical formula 5]
(3) The epoxy resin composition according to the above (1) or (2), wherein (A) the epoxy resin contains a bifunctional epoxy resin and / or an epoxy resin having an epoxy equivalent of 190 or more,
(4) The epoxy resin composition according to any one of (1) to (3) above, wherein the (B) phenol resin contains a bifunctional phenol resin and / or a phenol resin having a hydroxyl equivalent weight of 150 or more,
(5) The epoxy resin composition according to any one of the above (1) to (4), further comprising (D) an inorganic filler, the amount of which is 55 to 90% by volume based on the epoxy resin composition. ,
(6) (A) The epoxy resin according to any one of (1) to (5) above, wherein the epoxy resin contains at least one epoxy resin represented by any one of the following general formulas (II) to (VII) An epoxy resin composition, and
[Chemical 6]
(7) (B) The phenol resin according to any one of the above (1) to (6), wherein the phenol resin contains at least one phenol resin represented by any one of the following general formulas (VIII) to (XI): Epoxy resin composition, and
[Chemical 8]
(8) Electronic component device including an element sealed with the epoxy resin composition according to any one of (1) to (7)
About.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The (A) epoxy resin used in the present invention is not particularly limited. For example, a generally used epoxy resin having two or more epoxy groups in one molecule, such as a phenol novolac type epoxy resin or an orthocresol novolak. Phenols such as epoxy resin, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde Epoxidized novolak resin obtained by condensation or cocondensation with a compound having an aldehyde group such as benzaldehyde, salicylaldehyde, etc. under an acidic catalyst, bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenols, diglycidyl ethers such as stilbene phenols, glycidyl ethers of alcohols such as butanediol, polyethylene glycol, polypropylene glycol, phthalic acid, isophthalic acid, tetrahydrophthalic acid Glycidyl type or methyl glycidyl type epoxy resin such as glycidyl group substituted active hydrogen bonded to nitrogen atom such as glycidyl ester of carboxylic acid, aniline, isocyanuric acid, etc., and olefin bond in the molecule is epoxidized The resulting vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4 Poxy) Cyclohexane-m-dioxane and other alicyclic epoxy resins, paraxylylene and / or metaxylylene modified phenolic resin glycidyl ether, terpene modified phenolic resin glycidyl ether, dicyclopentadiene modified phenolic resin glycidyl ether, cyclopentadiene modified phenolic resin Glycidyl ether, polycyclic aromatic ring-modified phenolic resin glycidyl ether, naphthalene ring-containing phenolic resin glycidyl ether, biphenyl type epoxy resin, halogenated phenol novolak type epoxy resin, etc. A combination of the above may also be used. Among these epoxy resins, bifunctional epoxy resins are preferable in terms of fluidity and reflow crack resistance, and epoxy resins having an epoxy equivalent of 190 or more are preferable in terms of reflow crack resistance. Among these, an epoxy resin represented by any one of the following general formulas (II) to (VII) is preferable from the viewpoint of reflow crack resistance and fluidity, and particularly from the viewpoint of reflow crack resistance, 4,4′-bis (2 , 3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is more preferable, and 4,4′-bis (2,3-epoxypropoxy) -biphenyl is preferable from the viewpoint of moldability and heat resistance. More preferred. The epoxy resin represented by any one of these general formulas (II) to (VII) may be used alone or in combination of two or more, but in order to exhibit its performance, (A) It is preferable to use 30 weight% or more in total with respect to the total amount of the epoxy resin of the component, and it is more preferable to use 50 weight% or more.
[0010]
[Chemical 9]
R in the above general formulas (II) to (VII) Four ~ R 13 Meaning that all may be the same or different, for example, 8 R in formula (II) Four This means that all of may be the same or different. Other R Five ~ R 13 Also means that all of the numbers contained in the formula may be the same or different. R Four ~ R 13 May be the same or different. For example R Four And R Five All of these may be the same or different.
As the epoxy resin represented by the general formula (V), a random copolymer randomly including 1 structural unit and m structural units, an alternating copolymer including alternately, a copolymer including regularly, The block copolymer contained in a block shape is mentioned, Any one of these may be used independently or may be used in combination of 2 or more type.
[0011]
The (B) phenol resin used in the present invention is not particularly limited. For example, a phenol resin having two or more phenolic hydroxyl groups in one molecule generally used, such as phenol, cresol, xylenol, resorcin, Phenols such as catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Phenol synthesized from resins, phenols and / or naphthols, and dimethoxyparaxylene or bis (methoxymethyl) biphenyl obtained by condensation or cocondensation of Ar-aralkyl resins such as le-aralkyl resins, naphthol-aralkyl resins, paraxylylene and / or metaxylylene-modified phenol resins, melamine-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, cyclopentadiene-modified phenol resins, polycyclic Aromatic ring-modified phenol resins and the like can be mentioned, and these may be used alone or in combination of two or more. Among these phenol resins, a bifunctional phenol resin is preferable in terms of reflow crack resistance and fluidity, and a phenol resin having a hydroxyl group equivalent of 150 or more is preferable in terms of reflow crack resistance. Among these, from the viewpoint of reflow crack resistance, a phenol resin represented by any one of the following general formulas (VIII) to (XI) is more preferable. The phenol resin represented by any one of these general formulas (VIII) to (XI) may be used alone or in combination of two or more, but in order to exhibit its performance It is preferable to use 30% by weight or more, and more preferably 50% by weight or more, based on the total amount of the phenol resin of component (B).
[0012]
Embedded image
R in the above general formulas (VIII) to (XI) 14 ~ R twenty one Meaning that all may be the same or different, for example, i R in formula (IX) 14 This means that all of may be the same or different from each other. Other R 15 ~ R twenty one This means that all of the numbers included in the formula may be the same or different from each other. R 14 ~ R twenty one May be the same or different. For example R 14 And R 15 All may be the same or different and R 16 And R 19 All of these may be the same or different.
In the above general formulas (VIII) to (XI), n must be in the range of 0 to 10, and if it exceeds 10, the melt viscosity of the component (B) becomes high, so that the melting of the epoxy resin composition Viscosity at the time of molding is also increased, and unfilled defects and bonding wires (gold wires connecting elements and leads) are likely to be deformed. The average n per molecule is preferably set in the range of 1-4.
[0013]
In the present invention, the blending ratio of (A) epoxy resin and (B) phenol resin is the ratio of the hydroxyl equivalent of all phenol resins to the epoxy equivalent of all epoxy resins (number of hydroxyl groups in phenol resin / number of epoxy groups in epoxy resin). Is preferably set in the range of 0.5 to 2.0, more preferably 0.7 to 1.5, and still more preferably 0.8 to 1.3. If this ratio is less than 0.5, the epoxy resin is not sufficiently cured, and the heat resistance, moisture resistance and electrical properties of the cured product tend to be inferior. If it exceeds 2.0, the phenol resin component is excessive and curing is insufficient. There is a tendency that electrical properties and moisture resistance are deteriorated because of a sufficient amount of phenolic hydroxyl groups remaining in the cured resin.
[0014]
The addition reaction product of (C) triphenylphosphine and a quinone compound having at least one substituent used in the present invention is not particularly limited as long as it functions as a curing accelerator. From the viewpoint of properties, an addition reaction product of triphenylphosphine and a quinone compound represented by the following general formula (I) is preferable.
Embedded image
[0015]
R in the above general formula (I) 1 ~ R Three Represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, but the hydrocarbon group having 1 to 12 carbon atoms is not particularly limited, for example, a substituted or unsubstituted aliphatic carbon atom having 1 to 12 carbon atoms. Examples thereof include a hydrogen group, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms.
Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. , Alkyl groups such as hexyl group, octyl group, decyl group, dodecyl group, allyl group, methoxy group, ethoxy group, propoxyl group, n-butoxy group, alkoxy group such as tert-butoxy group, dimethylamino group, diethylamino group Alkylamino groups such as methylthio group, ethylthio group, butylthio group, dodecylthio group and other alkylthio groups, amino group substituted alkyl groups, alkoxy substituted alkyl groups, hydroxyl group substituted alkyl groups, substituted alkyl groups such as aryl group substituted alkyl groups, amino Substituted alkoxy groups such as group-substituted alkoxy groups, hydroxyl group-substituted alkoxy groups, aryl group-substituted alkoxy groups, etc. And so on.
Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, and an aryl group. Examples thereof include those substituted with a group, a hydroxyl group, an amino group, halogen and the like.
Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, and t-butylphenyl group. Alkyl group-substituted aryl group, alkoxy group-substituted aryl group such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, aryloxy group such as phenoxy group, crezoxy group, phenylthio group, tolylthio group, diphenylamino group And those substituted with an amino group, halogen or the like.
[0016]
The quinone compound represented by the general formula (I) is R 1 And R 2 May be combined to form a ring structure. R used in the present invention 1 And R 2 There are no particular limitations on the polycyclic quinone compound having a cyclic structure by bonding to each other. For example, any one of the following general formulas (XII) to (XIV) in which a substituted tetramethylene group, tetramethine group or the like is bonded. The polycyclic quinone compound etc. which are shown by these are mentioned.
Embedded image
Among the quinone compounds represented by the above general formula (I), 2,3-dimethoxy-1,4benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, methoxy-1 from the viewpoint of curability at the time of moisture absorption. 1,4-benzoquinone such as 1,4-benzoquinone and alkyl such as 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone and methyl-1,4-benzoquinone A group-substituted 1,4-benzoquinone is preferable, and 2,5-di-t-butyl-1,4-benzoquinone, t-butyl-1,4-benzoquinone, phenyl-1,4- is preferable from the viewpoint of storage stability. Benzoquinone is preferred.
[0018]
Examples of the structure of the addition reaction product of triphenylphosphine and the quinone compound represented by the above general formula (I) include compounds represented by the following general formula (XV).
Embedded image
[0019]
(C) Although there is no restriction | limiting in particular as a manufacturing method of the addition reaction product of a triphenylphosphine and a quinone compound which has at least 1 substituent, For example, both triphenylphosphine and a quinone compound used as a raw material melt | dissolve. Examples include a method of isolation by addition reaction in an organic solvent, a method of addition reaction in the phenol resin of the component (B), etc. In the latter method, in the state dissolved in the phenol resin as it is without isolation, It can be used as a compounding component of an epoxy resin composition.
(C) The addition reaction product of triphenylphosphine and a quinone compound having at least one substituent may be used alone or in combination of two or more.
[0020]
In addition to the component (C), the epoxy resin composition of the present invention can be used in combination with one or more kinds commonly used as a curing accelerator that accelerates the curing reaction between the epoxy resin and the phenol resin. . Examples of the curing accelerator used in combination include cyclohexane such as diazabicycloalkene such as 1,5-diazabicyclo [4.3.0] nonene-5, 1,8-diazabicyclo [5.4.0] undecene-7. Amidine compounds, derivatives thereof, phenol novolac salts thereof and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethyl Π bonds such as benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, quinone compounds such as phenyl-1,4-benzoquinone, and diazophenylmethane. A compound with intramolecular polarization formed by adding a compound having triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and their derivatives, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Imidazoles, tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, tri Phenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phos Fins, Tris (dialkylphenyl) phosphine, Tris (trialkylphenyl) phosphine, Tris (tetraalkylphenyl) phosphine, Tris (dialkoxyphenyl) phosphine, Tris (trialkoxyphenyl) phosphine, Tris (tetraalkoxyphenyl) phosphine, Tris Organic phosphines such as alkyl phosphines, dialkyl aryl phosphines, alkyl diaryl phosphines, etc., complexes of these organic phosphines and organic borons, and betaine types of these organic phosphines and unsubstituted quinone compounds such as 1,4-benzoquinone Examples include addition reaction products.
[0021]
When these curing accelerators are used in combination, the blending amount of the component (C) is preferably 30% by weight or more, more preferably 50% by weight or more with respect to the total curing accelerator. When the blending amount of the component (C) is less than 30% by weight, the curability or fluidity at the time of moisture absorption is lowered and the effect of the present invention tends to be reduced.
The total blending amount of all curing accelerators including the component (C) is not particularly limited as long as a curing acceleration effect can be obtained, but from the viewpoint of curability during moisture absorption and fluidity, (A) an epoxy resin and (B) phenol. 0.1-10 weight part is preferable with respect to a total of 100 weight part of resin, and 1-7.0 weight part is more preferable. If it is less than 0.1 parts by weight, it is difficult to cure in a short time, and if it exceeds 10 parts by weight, the curing rate tends to be too high and a good molded product tends not to be obtained.
[0022]
(D) An inorganic filler can be further mix | blended with the epoxy resin composition of this invention as needed. In particular, when the epoxy resin composition is used as a molding material for sealing, it is preferable to blend (D) an inorganic filler. The inorganic filler (D) used in the present invention is not particularly limited as it is generally used for a molding material for sealing. For example, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, Calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica, etc. Can be mentioned. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxide of magnesium and zinc, and zinc borate. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.
[0023]
(D) Although there will be no restriction | limiting in particular if the compounding quantity of an inorganic filler will acquire the effect of this invention, It is preferable that it is the range of 55-90 volume% with respect to an epoxy resin composition. These inorganic fillers are blended for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the blending amount is less than 55% by volume, these properties tend to be insufficiently improved. If it exceeds 90% by volume, the viscosity of the epoxy resin composition is increased, the fluidity is lowered, and molding tends to be difficult.
Moreover, 1-50 micrometers is preferable and, as for the average particle diameter of (D) inorganic filler, 10-30 micrometers is more preferable. If it is less than 1 μm, the viscosity of the epoxy resin composition tends to increase, and if it exceeds 50 μm, the resin component and the inorganic filler are easily separated, resulting in unevenness of the cured product and variations in the properties of the cured product. There is a tendency for the fillability of the to decrease.
From the viewpoint of fluidity, the particle shape of (D) inorganic filler is preferably spherical rather than rectangular, and (D) the particle size distribution of inorganic filler is preferably distributed over a wide range. For example, when blending 75% by volume or more of the inorganic filler, it is preferable that 70% by weight or more of the filler be spherical particles and distributed over a wide range of 0.1 to 80 μm. Since such an inorganic filler can easily have a close-packed structure, even if the amount is increased, an increase in the viscosity of the material is small, and an epoxy resin composition excellent in fluidity can be obtained.
[0024]
An anion exchanger can be mix | blended with the epoxy resin composition of this invention as needed. In particular, when an epoxy resin composition is used as a molding material for sealing, it is preferable to blend an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature standing characteristics of an electronic component device including an element to be sealed. . The anion exchanger used in the present invention is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcite, water content of an element selected from magnesium, aluminum, titanium, zirconium and bismuth can be used. An oxide etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, hydrotalcite represented by the following general formula (XVI) is preferable.
Embedded image
Mg 1-X Al X (OH) 2 (CO Three ) X / 2 ・ MH 2 O ...... (XVI)
(0 <X ≦ 0.5, m is a positive integer)
The amount of these anion exchangers is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but is preferably in the range of 0.1 to 30% by weight based on (A) the epoxy resin. 1 to 5% by weight is more preferable.
[0025]
The epoxy resin composition of the present invention includes various silanes such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, and vinyl silane as a coupling agent for enhancing the adhesion between the resin component and the inorganic filler. Known additives such as compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be blended as necessary. Moreover, you may mix | blend well-known colorants, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara.
[0026]
In the epoxy resin composition of the present invention, a mold release agent may be blended in order to give good mold releasability from the mold during molding. The release agent used in the present invention is not particularly limited and conventionally known release agents can be used. For example, higher fatty acids such as carnauba wax, montanic acid, stearic acid, higher fatty acid metal salts, montanic acid esters, etc. Examples thereof include polyolefin waxes such as ester wax, oxidized polyethylene and non-oxidized polyethylene, and these may be used alone or in combination of two or more. Among these, oxidized or non-oxidized polyolefin-based waxes are preferable, and the blending amount thereof is preferably 0.01 to 10% by weight and more preferably 0.1 to 5% by weight with respect to (A) the epoxy resin. If the blending amount of the polyolefin wax is less than 0.01% by weight, the releasability tends to be insufficient, and if it exceeds 10% by weight, the adhesion may be hindered. Examples of the polyolefin-based wax include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Moreover, when using another mold release agent together with a polyolefin-type wax, 0.1 to 10 weight% is preferable with respect to (A) epoxy resin, and 0.5 to 3 weight% is more preferable.
[0027]
In the epoxy resin composition of the present invention, a flame retardant can be blended as necessary to impart flame retardancy. There is no restriction | limiting in particular as a flame retardant used in this invention, For example, the well-known organic or inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, etc. are mentioned, These 1 type May be used alone or in combination of two or more. Although there will be no restriction | limiting in particular if the flame-retardant effect is achieved, the compounding quantity of a flame retardant is 1-30 weight% with respect to (A) epoxy resin, and 2-15 weight% is more preferable.
Furthermore, in the epoxy resin composition of the present invention, a stress relaxation agent such as silicone oil or silicone rubber powder can be blended as necessary as other additives.
[0028]
The epoxy resin composition of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed, but as a general method, components of a predetermined blending amount are sufficiently mixed by a mixer or the like. Thereafter, a method of melting and kneading with a mixing roll, an extruder or the like, followed by cooling and pulverization can be mentioned. For example, a predetermined amount of the above-described components can be uniformly stirred and mixed, and can be obtained by a method such as kneading, cooling, and pulverizing with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C. in advance. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.
[0029]
An electronic component device obtained by sealing an element with the epoxy resin composition obtained in the present invention includes a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, a semiconductor chip, a transistor An electronic component device in which active elements such as diodes and thyristors, passive elements such as capacitors, resistors, and coils are mounted and necessary portions are sealed with the epoxy resin composition of the present invention. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, the terminal part of the element such as a bonding pad and the lead part are connected by wire bonding or bump, and then the epoxy resin composition of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package) TCP in which a semiconductor chip connected to a tape carrier with bumps on a general resin-encapsulated IC such as TSOP (Thin Small Outline Package) and TQFP (Thin Quad Flat Package) is encapsulated with the epoxy resin composition of the present invention (Tape Carrier Package), connected to wiring formed on wiring boards and glass by wire bonding, flip chip bonding, soldering, etc. COB (Chip On Board) module, hybrid IC, in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc. are sealed with the epoxy resin composition of the present invention After mounting the element on the surface of the organic substrate having the terminal for connecting the wiring board formed on the back surface of the multichip module and connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the epoxy resin composition of the present invention Examples include BGA (Ball Grid Array) and CSP (Chip Size Package) in which an element is sealed with an object. The epoxy resin composition of the present invention can also be used effectively for printed circuit boards.
[0030]
As a method for sealing an electronic component device using the epoxy resin composition of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.
[0031]
【Example】
EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
Examples 1-49, Comparative Examples 1-49
As an epoxy resin, an epoxy equivalent of 196 and a melting point of 106 ° C. biphenyl skeleton type epoxy resin (epoxy resin 1: YY-4000H manufactured by Yuka Shell Epoxy Co., Ltd.), an epoxy equivalent of 210 and a melting point of 120 ° C. stilbene type epoxy resin (epoxy) Resin 2: Sumitomo Chemical Co., Ltd. trade name ESLV-210), epoxy equivalent 192, melting point 79 ° C. diphenylmethane skeleton epoxy resin (epoxy resin 3: Nippon Steel Chemical Co., Ltd. trade name YSLV-80XY), epoxy equivalent 217, naphthol orthocresol novolak type epoxy resin having a softening point of 64 ° C. (epoxy resin 4: product name NC-7300L manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 264, dicyclopentadiene-modified phenol novolac type epoxy resin having a softening point of 64 ° C. (Epoxy resin 5: Nippon Ink Chemical Co., Ltd., trade name HP-7200), epoxy equivalent 195, orthocresol novolak type epoxy resin having a softening point of 62 ° C. (epoxy resin 6: trade name ESCN-190-2, manufactured by Sumitomo Chemical Co., Ltd.), curing Examples of the agent include a phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (curing agent 1: trade name Milex XL-225 manufactured by Mitsui Chemicals), a biphenyl skeleton type phenol resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. 2: Meiwa Kasei Co., Ltd. trade name MEH-7851), hydroxyl equivalent 183, naphthol aralkyl resin having a softening point of 79 ° C. (curing agent 3: Nippon Steel Chemical Co., Ltd. trade name SN-170), hydroxyl equivalent 170, softening Dicyclopentadiene-modified phenol novolak resin with a point of 93 ° C (curing agent 4: Nippon Petrochemical Co., Ltd.) Co., Ltd., trade name DPP), examples of curing accelerators include addition reaction product of triphenylphosphine and methyl-1,4-benzoquinone (curing accelerator 1), triphenylphosphine and 2,3-dimethyl-1, Addition reaction product of 4-benzoquinone (curing accelerator 2), addition reaction product of triphenylphosphine and phenyl-1,4-benzoquinone (curing accelerator 3), triphenylphosphine and t-butyl-1,4- Addition reaction product with benzoquinone (curing accelerator 4), addition reaction product of triphenylphosphine and methoxy-1,4-benzoquinone (curing accelerator 5), and as a curing accelerator of a comparative example, triphenylphosphine (curing acceleration) Agent A), addition reaction product of triphenylphosphine and 1,4-benzoquinone (curing accelerator B), tri-p-tolylphosphine and 1,4-ben Addition reaction product with quinone (curing accelerator C), addition reaction product of diphenyl-p-tolylphosphine and 1,4-benzoquinone (curing accelerator D), phenol novolak salt of DBU (curing accelerator E: San Apro Corporation) Company product name SA-841), the inorganic filler has an average particle size of 17.5 μm, specific surface area of 3.8 m 2 / G spherical fused silica, as other additive components, γ-glycidoxypropyltrimethoxysilane as a coupling agent, carbon black as a colorant (trade name MA-100 manufactured by Mitsubishi Chemical Corporation), mold release agent Carnauba wax (manufactured by Celerica NODA Co., Ltd.), antimony trioxide and epoxy equivalent 393 as a flame retardant, brominated bisphenol A type epoxy resin (brominated epoxy resin) having a softening point of 80 ° C. and a bromine content of 48% by weight, It mix | blended by the weight part shown in Table 1-Table 6, and roll knead | mixing on the conditions of kneading | mixing temperature 80 degreeC and kneading | mixing time 15 minutes, and obtained the epoxy resin composition of Examples 1-49 and Comparative Examples 1-49.
[0032]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
The epoxy resin compositions of Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Tables 7 to 12.
The epoxy resin composition was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.
(1) Spiral flow (fluidity index)
An epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was measured.
(2) Storage stability
After storing the epoxy resin composition molded in the above (1) at 25 ° C. for 72 hours, the flow distance (cm) was measured and compared with the value before storage, and evaluated by the retention rate (%) of the flow distance.
(3) Heat hardness
The epoxy resin composition was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and was measured immediately after molding using a Shore D type hardness meter.
(4) Hardness during heat absorption
The epoxy resin composition molded in the above (3) was allowed to stand for 72 hours under the condition of 25 ° C./50% RH, and then measured using a Shore D type hardness meter.
(5) Reflow crack resistance
A QFP80 pin package having an outer dimension of 14 × 20 × 2.0 mm, in which a test silicon chip having a size of 8 × 10 × 0.4 mm is mounted on a 42 alloy frame using a silver paste, is formed using the epoxy resin composition. Molding and post-curing under conditions, absorbing moisture for 168 hours at 85 ° C. and 60% RH, and then performing reflow treatment at 215 ° C. for 90 seconds with a vapor phase reflow device to generate cracks The number of crack generation packages with respect to the number of test packages (5) was evaluated.
[0039]
[Table 7]
[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
Examples 1 to 49 are all excellent in fluidity, storage stability, hot hardness, hot moisture hardness and reflow crack resistance.
On the other hand, in Comparative Examples 1 to 49, which does not contain the component (C) of the present invention, compared with Examples having the same resin composition, at least one of fluidity, hardness at the time of moisture absorption and storage stability. Inferior.
[0046]
【The invention's effect】
The epoxy resin composition according to the present invention is excellent in fluidity, storage stability, and curability at the time of moisture absorption. By using this epoxy resin composition to seal electronic parts such as ICs and LSIs, As shown, since an electronic component device having good reflow crack resistance and excellent reliability can be obtained, its industrial value is great.
Claims (8)
（Ｂ）フェノール樹脂、及び
（Ｃ）トリフェニルホスフィンと少なくとも一つの置換基を有するキノン化合物との付加反応物
を必須成分とするエポキシ樹脂組成物。(A) epoxy resin,
(B) An epoxy resin composition comprising, as an essential component, an addition reaction product of (B) a phenol resin and (C) triphenylphosphine and a quinone compound having at least one substituent.
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| JP2000188283A JP4431921B2 (en) | 2000-05-16 | 2000-06-22 | Epoxy resin composition and electronic component device |
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| JP4341247B2 (en) * | 2003-01-07 | 2009-10-07 | 住友ベークライト株式会社 | Curing accelerator for epoxy resin composition, epoxy resin composition and semiconductor device |
| JP2004231800A (en) * | 2003-01-30 | 2004-08-19 | Sumitomo Bakelite Co Ltd | Anionic catalyst, epoxy resin composition and semiconductor device |
| JP2005041928A (en) * | 2003-07-23 | 2005-02-17 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP5281280B2 (en) | 2007-12-25 | 2013-09-04 | パナソニック株式会社 | Epoxy resin composition, prepreg, metal-clad laminate, multilayer printed wiring board |
| JP2012214743A (en) * | 2011-04-01 | 2012-11-08 | Hitachi Chemical Co Ltd | Solid sealing resin composition for compression molding, and semiconductor device |
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