JP6263835B2 - Thermosetting resin molding material and electronic component device - Google Patents
Thermosetting resin molding material and electronic component device Download PDFInfo
- Publication number
- JP6263835B2 JP6263835B2 JP2012272559A JP2012272559A JP6263835B2 JP 6263835 B2 JP6263835 B2 JP 6263835B2 JP 2012272559 A JP2012272559 A JP 2012272559A JP 2012272559 A JP2012272559 A JP 2012272559A JP 6263835 B2 JP6263835 B2 JP 6263835B2
- Authority
- JP
- Japan
- Prior art keywords
- molding material
- thermosetting resin
- resin molding
- cyanate
- epoxy resin
- 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.)
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- 229920005989 resin Polymers 0.000 title claims description 144
- 239000011347 resin Substances 0.000 title claims description 144
- 239000012778 molding material Substances 0.000 title claims description 87
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 87
- 239000003822 epoxy resin Substances 0.000 claims description 99
- 229920000647 polyepoxide Polymers 0.000 claims description 99
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 71
- -1 silane compound Chemical class 0.000 claims description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 32
- 150000008366 benzophenones Chemical class 0.000 claims description 25
- 125000003700 epoxy group Chemical group 0.000 claims description 23
- 239000011256 inorganic filler Substances 0.000 claims description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000003566 sealing material Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims description 6
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 3
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- CXAYOCVHDCXPAI-UHFFFAOYSA-N naphthalen-1-yl(phenyl)methanone Chemical compound C=1C=CC2=CC=CC=C2C=1C(=O)C1=CC=CC=C1 CXAYOCVHDCXPAI-UHFFFAOYSA-N 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 description 20
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 18
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 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 11
- 239000005011 phenolic resin Substances 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 8
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 7
- 238000010292 electrical insulation Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 3
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 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 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- XEDWWPGWIXPVRQ-UHFFFAOYSA-N (2,3,4-trihydroxyphenyl)-(3,4,5-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC(O)=C(O)C(O)=C1 XEDWWPGWIXPVRQ-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- HSYUVRRTSSSDJI-UHFFFAOYSA-N 5-tert-butyl-2,4-dihydroxybenzophenone Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(=O)C=2C=CC=CC=2)=C1O HSYUVRRTSSSDJI-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 235000013872 montan acid ester Nutrition 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 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
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 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
- WQHAWOFWMDZBLB-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-phenylmethanone;(2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1.OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 WQHAWOFWMDZBLB-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SHULEACXTONYPS-UHFFFAOYSA-N (3-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 SHULEACXTONYPS-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 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
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- 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 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
- SENUUPBBLQWHMF-UHFFFAOYSA-N 2,6-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=C(C)C1=O SENUUPBBLQWHMF-UHFFFAOYSA-N 0.000 description 1
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- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- KNYWDHFOQZZIDQ-UHFFFAOYSA-N trimethoxy-(2-trimethoxysilylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1[Si](OC)(OC)OC KNYWDHFOQZZIDQ-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
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- IDXDWPWXHTXJMZ-UHFFFAOYSA-N tris(2,4,6-trimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC(C)=C1P(C=1C(=CC(C)=CC=1C)C)C1=C(C)C=C(C)C=C1C IDXDWPWXHTXJMZ-UHFFFAOYSA-N 0.000 description 1
- XDHRVAHAGMMFMC-UHFFFAOYSA-N tris(2,4-dimethylphenyl)phosphane Chemical compound CC1=CC(C)=CC=C1P(C=1C(=CC(C)=CC=1)C)C1=CC=C(C)C=C1C XDHRVAHAGMMFMC-UHFFFAOYSA-N 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- CKKFLUXMIUUGAW-UHFFFAOYSA-N tris(2-propan-2-ylphenyl)phosphane Chemical compound CC(C)C1=CC=CC=C1P(C=1C(=CC=CC=1)C(C)C)C1=CC=CC=C1C(C)C CKKFLUXMIUUGAW-UHFFFAOYSA-N 0.000 description 1
- GDKAFTKCUOBEDW-UHFFFAOYSA-N tris(2-tert-butylphenyl)phosphane Chemical compound CC(C)(C)C1=CC=CC=C1P(C=1C(=CC=CC=1)C(C)(C)C)C1=CC=CC=C1C(C)(C)C GDKAFTKCUOBEDW-UHFFFAOYSA-N 0.000 description 1
- RYXYUARTMQUYKV-UHFFFAOYSA-N tris(4-butylphenyl)phosphane Chemical compound C1=CC(CCCC)=CC=C1P(C=1C=CC(CCCC)=CC=1)C1=CC=C(CCCC)C=C1 RYXYUARTMQUYKV-UHFFFAOYSA-N 0.000 description 1
- SPNVODOGUAUMCA-UHFFFAOYSA-N tris(4-ethoxy-2,6-dimethylphenyl)phosphane Chemical compound CC1=CC(OCC)=CC(C)=C1P(C=1C(=CC(OCC)=CC=1C)C)C1=C(C)C=C(OCC)C=C1C SPNVODOGUAUMCA-UHFFFAOYSA-N 0.000 description 1
- PCCAGZSOGFNURV-UHFFFAOYSA-N tris(4-ethylphenyl)phosphane Chemical compound C1=CC(CC)=CC=C1P(C=1C=CC(CC)=CC=1)C1=CC=C(CC)C=C1 PCCAGZSOGFNURV-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- JTOQWGJGVSYTTN-UHFFFAOYSA-N tris(4-propylphenyl)phosphane Chemical compound C1=CC(CCC)=CC=C1P(C=1C=CC(CCC)=CC=1)C1=CC=C(CCC)C=C1 JTOQWGJGVSYTTN-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
- 239000011800 void material Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
本発明は、熱硬化性樹脂成形材料及び電子部品装置に関する。 The present invention relates to a thermosetting resin molding material and an electronic component device.
従来から、トランジスタ、ＩＣ等の電子部品封止の分野ではエポキシ樹脂成形材料が広く用いられている。この理由としては、エポキシ樹脂が電気特性、耐湿性、耐熱性、機械特性、インサート品との接着性等の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ノボラック型フェノール硬化剤の組合せはこれらのバランスに優れており、封止用成形材料のベース樹脂の主流になっている。近年の電子機器の小型化、軽量化及び高性能化に伴い、実装の高密度化が進み、それに伴って、電子部品の発熱が顕著となってきている。また、高温下で作動する電子部品も増加している。 Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and ICs. This is because the epoxy resin has a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesiveness with inserts, and the like. In particular, the combination of an ortho-cresol novolac type epoxy resin and a novolac type phenol curing agent has an excellent balance between these, and has become the mainstream of the base resin of the molding material for sealing. With recent miniaturization, weight reduction, and performance enhancement of electronic devices, mounting density has increased, and accordingly, heat generation of electronic components has become remarkable. In addition, electronic components that operate at high temperatures are also increasing.
特に、車載用等のパワー半導体は、長時間高温に曝されることが予想される。車載用のパワーモジュールには、ケース型の構造でゲル封止と称されるシリコーンゲルによる封止方法を適用することが主流であるが、量産性向上、耐振動性向上、耐熱温度向上等の観点から、エポキシ樹脂成形材料を用いたトランスファモールドによる封止が検討されている。更にパワー半導体では、電力損失が小さく省エネルギー性能に優れるＳｉＣデバイスの使用により動作温度は２００℃以上になるとされている。そのため、電子部品に使用される封止材成形材料には高い耐熱性が要求され、硬化物が高いガラス転移温度（Ｔｇ）を有することが要求されている。 In particular, power semiconductors for in-vehicle use are expected to be exposed to high temperatures for a long time. For power modules for in-vehicle use, it is the mainstream to apply a silicone gel sealing method called gel sealing with a case-type structure. However, such as mass production improvement, vibration resistance improvement, heat resistance temperature improvement, etc. From the viewpoint, sealing by transfer molding using an epoxy resin molding material has been studied. Furthermore, in a power semiconductor, the operating temperature is said to be 200 ° C. or higher by using a SiC device that has low power loss and excellent energy saving performance. Therefore, high heat resistance is required for the sealing material molding material used for the electronic component, and the cured product is required to have a high glass transition temperature (Tg).
エポキシ樹脂とフェノール硬化剤との組合せで高いガラス転移温度（Ｔｇ）を発現する樹脂系においては、架橋密度を高くすることが有効とされている。しかしながら、架橋密度を高くすると、架橋反応に伴って生成する２級アルコール性水酸基（ＯＨ基）の密度も高くなる。この場合、１５０℃以上の高温において封止材の電気絶縁性の確保が非常に困難になる。 In a resin system that develops a high glass transition temperature (Tg) with a combination of an epoxy resin and a phenol curing agent, it is effective to increase the crosslinking density. However, when the crosslinking density is increased, the density of the secondary alcoholic hydroxyl group (OH group) generated in association with the crosslinking reaction also increases. In this case, it becomes very difficult to ensure the electrical insulation of the sealing material at a high temperature of 150 ° C. or higher.
高耐熱性の樹脂としてシアネート樹脂が知られている。シアネート樹脂は硬化反応に伴って２級アルコール性水酸基を生成することがないため、封止用の熱硬化性樹脂成形材料として利用できれば、高温における封止材の電気絶縁性の確保につながると考えられる。しかしながら、シアネート樹脂とエポキシ樹脂との架橋反応及びシアネート基自身の３量化反応を加熱処理で完結させるには２００℃以上の温度が必要であり、シアネート樹脂の熱硬化性樹脂成形材料への適用が困難である。そのため、シアネート樹脂の硬化反応には、ナフテン酸亜鉛、ナフテン酸コバルト等の遷移金属錯体が通常用いられる（例えば、特許文献１及び２参照）。 Cyanate resin is known as a high heat resistant resin. Since cyanate resin does not generate a secondary alcoholic hydroxyl group with the curing reaction, if it can be used as a thermosetting resin molding material for sealing, it will lead to ensuring the electrical insulation of the sealing material at high temperatures. It is done. However, in order to complete the cross-linking reaction between the cyanate resin and the epoxy resin and the trimerization reaction of the cyanate group itself by heat treatment, a temperature of 200 ° C. or higher is necessary, and the application of the cyanate resin to a thermosetting resin molding material is required. Have difficulty. Therefore, transition metal complexes such as zinc naphthenate and cobalt naphthenate are usually used for the curing reaction of the cyanate resin (see, for example, Patent Documents 1 and 2).
一方、エポキシ樹脂とシアネート樹脂とを含む回路基板用樹脂組成物は高耐熱性を示すことが開示されている（例えば、特許文献３参照）。 On the other hand, it is disclosed that the resin composition for circuit boards containing an epoxy resin and cyanate resin shows high heat resistance (for example, refer patent document 3).
シアネート樹脂の短時間硬化を実現するために上記のような遷移金属錯体を添加する場合、熱硬化性樹脂成形材料中における金属イオン含有量が増大し、結果として半導体装置の信頼性低下（例えば、絶縁性の低下）につながる場合がある。よって、上記のような遷移金属錯体を用いた熱硬化性樹脂成形材料は、特に過酷な動作環境に曝されるパワー半導体用封止材料として適用することは困難である。加えて、上記の遷移金属錯体の添加量は熱硬化性樹脂成形材料中では相対的に微量であるため、材料中で均一に混錬又は分散させるのは容易でないと考えられる。また、上記の遷移金属錯体を用いる場合、僅かな添加量のずれで、その硬化挙動及び硬化物の諸特性が著しく異なる可能性があり、諸特性の再現性を生産性よく実現するのは困難と考えられる。以上のことから、上記のような遷移金属錯体を用いずにシアネート樹脂を含む熱硬化性樹脂成形材料を、パワー半導体用封止材としても適用可能な熱硬化性樹脂成形材料として提供することは困難を極め、未だ実用化には至っていない。更にパワー半導体封止用封止材には難燃性に優れることも求められている。 When a transition metal complex as described above is added to achieve a short time curing of the cyanate resin, the metal ion content in the thermosetting resin molding material increases, resulting in a decrease in reliability of the semiconductor device (for example, May lead to a decrease in insulation). Therefore, it is difficult to apply the thermosetting resin molding material using the transition metal complex as described above as a sealing material for power semiconductors that is exposed to particularly severe operating environments. In addition, since the addition amount of the transition metal complex is relatively small in the thermosetting resin molding material, it is considered that it is not easy to knead or disperse uniformly in the material. In addition, when using the above transition metal complexes, there is a possibility that the curing behavior and various properties of the cured product may be significantly different due to slight deviations in the amount added, and it is difficult to realize the reproducibility of the various properties with high productivity. it is conceivable that. From the above, it is possible to provide a thermosetting resin molding material containing a cyanate resin without using a transition metal complex as described above as a thermosetting resin molding material applicable also as a sealing material for power semiconductors. It has become extremely difficult and has not yet been put into practical use. Furthermore, the sealing material for power semiconductor sealing is also required to be excellent in flame retardancy.
本発明はかかる状況に鑑みなされたもので、優れた耐熱性及び難燃性を有し、高温における電気絶縁性に優れ、更に高温における金属との接着性に優れる硬化物を形成可能な熱硬化性樹脂成形材料及びこれにより封止された素子を備える電子部品装置を提供することを課題とする。 The present invention has been made in view of such a situation, and has excellent heat resistance and flame retardancy, is excellent in electrical insulation at high temperatures, and is capable of forming a cured product having excellent adhesion to metals at high temperatures. It is an object of the present invention to provide an electronic component device including a conductive resin molding material and an element sealed thereby.
前記課題を解決するための具体的手段は以下の通りである。
＜１＞ １分子中にエポキシ基を２個以上有するエポキシ樹脂と、１分子中にシアネート基（−ＯＣＮ）を２個以上有するシアネート樹脂と、フェノール性水酸基を有するベンゾフェノン誘導体と、を含有する熱硬化性樹脂成形材料である。
Specific means for solving the above problems are as follows.
<1> A heat containing an epoxy resin having two or more epoxy groups in one molecule, a cyanate resin having two or more cyanate groups (-OCN) in one molecule, and a benzophenone derivative having a phenolic hydroxyl group It is a curable resin molding material.
＜２＞ 前記ベンゾフェノン誘導体は、水酸基当量が５０ｇ／ｅｑ〜４００ｇ／ｅｑである前記＜１＞に記載の熱硬化性樹脂成形材料である。 <2> The benzophenone derivative is the thermosetting resin molding material according to <1>, wherein a hydroxyl group equivalent is 50 g / eq to 400 g / eq.
＜３＞ 前記ベンゾフェノン誘導体は、ベンゾフェノン、ナフチルフェニルケトン、ジナフチルケトン、キサントン、フルオレノン及びアントラキノンからなる群より選ばれる少なくとも１種の化合物の芳香環上に１個以上の水酸基が直接結合している化合物である前記＜１＞又は＜２＞に記載の熱硬化性樹脂成形材料である。 <3> In the benzophenone derivative, one or more hydroxyl groups are directly bonded to the aromatic ring of at least one compound selected from the group consisting of benzophenone, naphthyl phenyl ketone, dinaphthyl ketone, xanthone, fluorenone and anthraquinone. The thermosetting resin molding material according to <1> or <2>, which is a compound.
＜４＞ 前記エポキシ樹脂に含まれるエポキシ基数に対する前記ベンゾフェノン誘導体に含まれるフェノール性水酸基数の比が、０．１０以上０．６０以下である前記＜１＞〜＜３＞のいずれか１つに記載の熱硬化性樹脂成形材料である。 <4> The ratio of the number of phenolic hydroxyl groups contained in the benzophenone derivative to the number of epoxy groups contained in the epoxy resin is any one of the above items <1> to <3>, which is 0.10 or more and 0.60 or less. It is a thermosetting resin molding material of description.
＜５＞ 前記エポキシ樹脂に含まれるエポキシ基数に対する前記シアネート樹脂に含まれるシアネート基及び前記ベンゾフェノン誘導体に含まれるフェノール性水酸基数の総数の比が、０．７０以上３．５０以下である前記＜１＞〜＜４＞のいずれか１つに記載の熱硬化性樹脂成形材料である。 <5> The ratio of the total number of phenolic hydroxyl groups contained in the cyanate group and the benzophenone derivative contained in the cyanate resin to the number of epoxy groups contained in the epoxy resin is 0.70 or more and 3.50 or less. It is a thermosetting resin molding material as described in any one of>-<4>.
＜６＞ シラン化合物を更に含有する前記＜１＞〜＜５＞のいずれか１つに記載の熱硬化性樹脂成形材料である。 <6> The thermosetting resin molding material according to any one of <1> to <5>, further including a silane compound.
＜７＞ 硬化促進剤を更に含有する前記＜１＞〜＜６＞のいずれか１つに記載の熱硬化性樹脂成形材料である。 <7> The thermosetting resin molding material according to any one of <1> to <6>, further including a curing accelerator.
＜８＞ 無機充てん剤を更に含有する前記＜１＞〜＜７＞のいずれか１つに記載の熱硬化性樹脂成形材料である。 <8> The thermosetting resin molding material according to any one of <1> to <7>, further including an inorganic filler.
＜９＞ 素子と、前記素子を封止する前記＜１＞〜＜８＞のいずれか１つに記載の熱硬化性樹脂成形材料の硬化物と、を備える電子部品装置である。 <9> An electronic component device comprising an element and a cured product of the thermosetting resin molding material according to any one of <1> to <8>, which seals the element.
本発明によれば、優れた耐熱性及び難燃性を有し、高温における電気絶縁性に優れ、更に高温における金属との接着性に優れる硬化物を形成可能な熱硬化性樹脂成形材料及びこれにより封止された素子を備える電子部品装置を提供することができる。 According to the present invention, there is provided a thermosetting resin molding material having excellent heat resistance and flame retardancy, excellent electrical insulation at high temperatures, and capable of forming a cured product having excellent adhesion to metals at high temperatures. It is possible to provide an electronic component device including an element sealed by the above.
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。更に組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
＜熱硬化性樹脂成形材料＞
本発明の熱硬化性樹脂成形材料は、１分子中にエポキシ基を２個以上有するエポキシ樹脂の少なくとも１種と、１分子中にシアネート基（−ＯＣＮ）を２個以上有するシアネート樹脂の少なくとも１種と、フェノール性水酸基を有するベンゾフェノン誘導体の少なくとも１種と、を含有する。前記熱硬化性樹脂成形材料は、必要に応じてその他の成分を更に含んでいてもよい。前記熱硬化性樹脂成形材料は、電子部品封止に好ましく適用することができ、パワー半導体封止に、より好ましく適用できる。
<Thermosetting resin molding material>
The thermosetting resin molding material of the present invention is at least one epoxy resin having two or more epoxy groups in one molecule and at least one cyanate resin having two or more cyanate groups (—OCN) in one molecule. A seed and at least one benzophenone derivative having a phenolic hydroxyl group. The thermosetting resin molding material may further contain other components as necessary. The thermosetting resin molding material can be preferably applied to electronic component sealing, and can be more preferably applied to power semiconductor sealing.
１分子中にエポキシ基を２個以上有するエポキシ樹脂及び１分子中にシアネート基（−ＯＣＮ）を２個以上有するシアネート樹脂に加えて、フェノール性水酸基を有するベンゾフェノン誘導体を含有することで、優れた耐熱性及び難燃性を有し、高温における電気絶縁性に優れ、更に高温における金属との接着性に優れる硬化物を形成可能な電子部品封止用の熱硬化性樹脂成形材料を構成することができる。これは例えば、以下のように考えることができる。すなわち、フェノール性水酸基を有するベンゾフェノン誘導体は、ベンゾイル基を有するフェノール誘導体と見なし得る。したがって、ベンゾフェノン誘導体のフェノール性水酸基の反応活性は、ノボラック型フェノール樹脂等に比べて高くなり、これによりエポキシ樹脂及びシアネート樹脂を含む樹脂組成物の硬化反応が促進されると考えることができる。これにより、本発明の熱硬化性樹脂成形材料から形成される硬化物は、優れた耐熱性及び難燃性を有し、高温における電気絶縁性に優れ、更に高温における金属との接着性に優れると考えることができる。 In addition to an epoxy resin having two or more epoxy groups in one molecule and a cyanate resin having two or more cyanate groups (-OCN) in one molecule, it contains an excellent benzophenone derivative having a phenolic hydroxyl group. A thermosetting resin molding material for encapsulating electronic components that can form a cured product having heat resistance and flame retardancy, excellent electrical insulation at high temperatures, and excellent adhesion to metals at high temperatures. Can do. For example, this can be considered as follows. That is, a benzophenone derivative having a phenolic hydroxyl group can be regarded as a phenol derivative having a benzoyl group. Therefore, it can be considered that the reaction activity of the phenolic hydroxyl group of the benzophenone derivative is higher than that of a novolak-type phenol resin or the like, thereby promoting the curing reaction of the resin composition containing the epoxy resin and the cyanate resin. Thereby, the hardened | cured material formed from the thermosetting resin molding material of this invention has the outstanding heat resistance and a flame retardance, is excellent in the electrical insulation at high temperature, and is further excellent in the adhesiveness with the metal in high temperature. Can be considered.
（Ａ）エポキシ樹脂
熱硬化性樹脂成形材料は、１分子中にエポキシ基を２個以上有するエポキシ樹脂（以下、「多官能エポキシ樹脂」ともいう）の少なくとも１種を含有する。１分子中にエポキシ基を２個以上有するエポキシ樹脂は、熱硬化性樹脂成形材料に一般に使用されているものであれば特に制限はなく、通常用いられる多官能エポキシ樹脂から適宜選択して用いることができる。多官能エポキシ樹脂におけるエポキシ基の数は２個以上であればよく、２〜１０であることが好ましく、２〜５であることがより好ましい
(A) Epoxy resin The thermosetting resin molding material contains at least one epoxy resin having two or more epoxy groups in one molecule (hereinafter also referred to as “polyfunctional epoxy resin”). The epoxy resin having two or more epoxy groups in one molecule is not particularly limited as long as it is generally used for a thermosetting resin molding material, and is appropriately selected from commonly used polyfunctional epoxy resins. Can do. The number of epoxy groups in the polyfunctional epoxy resin may be two or more, preferably 2 to 10, and more preferably 2 to 5.
多官能エポキシ樹脂として具体的には、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、トリフェニルメタン骨格を有するエポキシ樹脂をはじめとするフェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール類及び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からなる群より選ばれる少なくとも１種と、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したノボラック型エポキシ樹脂；アルキル置換、芳香環置換又は非置換のビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ビフェノール、チオジフェノール等のジグリシジルエーテルであるエポキシ樹脂；スチルベン型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；フタル酸、ダイマー酸等の多塩基酸とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂；ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂；ジシクロペンタジエンとフェノール類の共縮合樹脂のエポキシ化物であるジシクロペンタジエン型エポキシ樹脂；ナフタレン環を有するエポキシ樹脂；フェノール類及びナフトール類の少なくとも１種とジメトキシパラキシレン又はビス（メトキシメチル）ビフェニルから合成されるフェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等のアラルキル型フェノール樹脂のエポキシ化物；トリメチロールプロパン型エポキシ樹脂；テルペン変性エポキシ樹脂；オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂；脂環族エポキシ樹脂などが挙げられる。これらは１種を単独で用いても２種以上を組み合わせて用いてもよい。 Specific examples of the polyfunctional epoxy resin include phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, epoxy resin having triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F And at least one selected from the group consisting of naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene, and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation under an acidic catalyst; alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol Epoxy resins that are diglycidyl ethers such as diol A, bisphenol F, bisphenol S, biphenol, thiodiphenol; stilbene type epoxy resins; hydroquinone type epoxy resins; obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin Glycidyl ester type epoxy resin; glycidyl amine type epoxy resin obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin; An epoxy resin having a naphthalene ring; phenol synthesized from at least one of phenols and naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl -Epoxidized aralkyl-type phenol resin such as aralkyl resin, naphthol-aralkyl resin; trimethylolpropane-type epoxy resin; terpene-modified epoxy resin; linear aliphatic epoxy obtained by oxidizing olefin bond with peracid such as peracetic acid Resin; Alicyclic epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.
中でも、１分子中にエポキシ基を２個以上有するエポキシ樹脂は、硬化性の観点からは、ノボラック型エポキシ樹脂であることが好ましい。また、耐熱性及び低反り性の観点からは、トリフェニルメタン骨格を有するノボラック型エポキシ樹脂であるトリフェニルメタン型エポキシ樹脂であることが好ましい。一方、低吸湿性及び誘電特性の観点からは、ジシクロペンタジエン型エポキシ樹脂であることが好ましい。
熱硬化性樹脂成形材料は、１分子中にエポキシ基を２個以上有するエポキシ樹脂として、ノボラック型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂からなる群より選ばれる少なくとも１種のエポキシ樹脂を含むことが好ましく、オルトクレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂からなる群より選ばれる少なくとも１種のエポキシ樹脂を含むことがより好ましい。
Especially, it is preferable that the epoxy resin which has 2 or more of epoxy groups in 1 molecule is a novolak-type epoxy resin from a sclerosing | hardenable viewpoint. Further, from the viewpoint of heat resistance and low warpage, a triphenylmethane type epoxy resin which is a novolac type epoxy resin having a triphenylmethane skeleton is preferable. On the other hand, from the viewpoint of low hygroscopicity and dielectric properties, it is preferably a dicyclopentadiene type epoxy resin.
The thermosetting resin molding material may contain at least one epoxy resin selected from the group consisting of a novolac type epoxy resin and a dicyclopentadiene type epoxy resin as an epoxy resin having two or more epoxy groups in one molecule. Preferably, it contains at least one epoxy resin selected from the group consisting of an ortho cresol novolac type epoxy resin, a triphenylmethane type epoxy resin and a dicyclopentadiene type epoxy resin.
ノボラック型エポキシ樹脂は、ノボラック型フェノール樹脂にエピクロルヒドリンを反応させることによって容易に得られる。中でも、オルソクレゾールノボラック型エポキシ樹脂及びトリフェニルメタン型エポキシ樹脂からなる群より選ばれる少なくとも１種が好ましい。
オルソクレゾールノボラック型エポキシ樹脂としては市販品としてＤＩＣ株式会社製の商品名Ｎ−６６０等として入手可能である。オルソクレゾールノボラック型エポキシ樹脂を使用する場合、その含有率は、その性能を発揮するためにエポキシ樹脂全量中に２０質量％以上とすることが好ましく、３０質量％以上がより好ましい。
トリフェニルメタン型エポキシ樹脂としては、日本化薬製の商品名ＥＰＰＮ−５０２、三菱化学株式会社製の商品名１０３２Ｈ６０等として入手可能である。トリフェニルメタン型エポキシ樹脂を使用する場合、その含有率は、その性能を発揮するためにエポキシ樹脂全量中に２０質量％以上とすることが好ましく、３０質量％以上がより好ましく、５０質量％以上とすることがさらに好ましい。
ジシクロペンタジエン型エポキシ樹脂としては、ＤＩＣ株式会社製の商品名ＨＰ−７２００等が挙げられる。ジシクロペンタジエン型エポキシ樹脂を使用する場合、その含有率は、その性能を発揮するためにエポキシ樹脂全量中に２０質量％以上とすることが好ましく、３０質量％以上がより好ましい。
A novolak type epoxy resin can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Among these, at least one selected from the group consisting of orthocresol novolac type epoxy resins and triphenylmethane type epoxy resins is preferable.
As an ortho cresol novolak type epoxy resin, it can be obtained as a commercial product under the trade name N-660 manufactured by DIC Corporation. When using an ortho-cresol novolac type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.
Triphenylmethane type epoxy resins are available as Nippon Kayaku's trade name EPPN-502, Mitsubishi Chemical Corporation's trade name 1032H60, and the like. When using a triphenylmethane type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance. More preferably.
Examples of the dicyclopentadiene type epoxy resin include trade name HP-7200 manufactured by DIC Corporation. In the case of using a dicyclopentadiene type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.
上記に挙げたオルソクレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂及びジシクロペンタジエン型エポキシ樹脂は、いずれか１種を単独で用いても２種以上を組み合わせて用いてもよい。２種以上を組み合わせて用いる場合の含有率は、エポキシ樹脂全量中に合わせて５０質量％以上とすることが好ましく、６０質量％以上がより好ましく、８０質量％以上がさらに好ましい。 The ortho-cresol novolac type epoxy resin, triphenylmethane type epoxy resin and dicyclopentadiene type epoxy resin mentioned above may be used alone or in combination of two or more. The content when two or more types are used in combination is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more, based on the total amount of the epoxy resin.
多官能エポキシ樹脂のエポキシ当量は特に制限されない。中でも成形性、耐熱性、電気的信頼等の各種特性バランスの観点から、多官能エポキシ樹脂のエポキシ当量は、１００ｇ／ｅｑ〜１０００ｇ／ｅｑであることが好ましく、１５０ｇ／ｅｑ〜５００ｇ／ｅｑであることがより好ましい。ここでエポキシ当量とは多官能エポキシ樹脂に含まれるエポキシ基１モルあたりの質量（ｇ）である。 The epoxy equivalent of the polyfunctional epoxy resin is not particularly limited. Among them, from the viewpoint of balance of various properties such as moldability, heat resistance, and electrical reliability, the epoxy equivalent of the polyfunctional epoxy resin is preferably 100 g / eq to 1000 g / eq, and is preferably 150 g / eq to 500 g / eq. It is more preferable. Here, the epoxy equivalent is the mass (g) per mole of epoxy groups contained in the polyfunctional epoxy resin.
また多官能エポキシ樹脂の軟化点又は融点は特に制限されない。中でも成形性及び耐熱性の観点から、軟化点又は融点は、４０℃〜１８０℃であることが好ましく、熱硬化性樹脂成型材料作製時における取扱い性の観点からは５０℃〜１３０℃であることがより好ましい。 The softening point or melting point of the polyfunctional epoxy resin is not particularly limited. Among these, from the viewpoint of moldability and heat resistance, the softening point or melting point is preferably 40 ° C to 180 ° C, and from the viewpoint of handleability during the production of a thermosetting resin molding material, it should be 50 ° C to 130 ° C. Is more preferable.
前記熱硬化性樹脂成形材料における多官能エポキシ樹脂の含有率は、成形性及び耐熱性の観点から、３質量％〜１５質量％であることが好ましく、５質量％〜１２質量％であることがより好ましい。 The content of the polyfunctional epoxy resin in the thermosetting resin molding material is preferably 3% by mass to 15% by mass, and preferably 5% by mass to 12% by mass from the viewpoints of moldability and heat resistance. More preferred.
（Ｂ）シアネート樹脂
熱硬化性樹脂成形材料は、１分子中にシアネート基（−ＯＣＮ）を２個以上有するシアネート樹脂（以下、「多官能シアネート樹脂」ともいう）の少なくとも１種を含有する。１分子中にシアネート基を２個以上有するシアネート樹脂は、熱硬化性樹脂成形材料に一般に使用されているものであれば特に制限はなく、通常用いられる多官能シアネート樹脂から適宜選択して用いることができる。多官能シアネート樹脂におけるシアネート基の数は２個以上であればよく、２〜６であることが好ましく、２〜４であることがより好ましい。
多官能シアネート樹脂として具体的には、２，２−ビス（４−シアナトフェニル）プロパン、ビス（４−シアナトフェニル）エタン、２，２−ビス（３，５−ジメチル−４−シアナトフェニル）メタン、α，α’−ビス（４−シアナトフェニル）−ｍ−ジイソプロピルベンゼン等のジシアネート樹脂、フェノールノボラック型シアネート樹脂、ジシクロペンタジエン型シアネート樹脂などが挙げられる。なお、ここで用いられるシアネート樹脂は、予め一部の樹脂のシアネート基が３量体を形成してオリゴマー化されていても構わない。
(B) Cyanate resin The thermosetting resin molding material contains at least one cyanate resin (hereinafter also referred to as “polyfunctional cyanate resin”) having two or more cyanate groups (—OCN) in one molecule. The cyanate resin having two or more cyanate groups in one molecule is not particularly limited as long as it is generally used in thermosetting resin molding materials, and is appropriately selected from commonly used polyfunctional cyanate resins. Can do. The number of cyanate groups in polyfunctional cyanate resin should just be two or more, it is preferable that it is 2-6, and it is more preferable that it is 2-4.
Specific examples of the polyfunctional cyanate resin include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, and 2,2-bis (3,5-dimethyl-4-cyanato). Phenyl) methane, dicyanate resins such as α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, phenol novolac-type cyanate resins, dicyclopentadiene-type cyanate resins, and the like. In addition, as for the cyanate resin used here, the cyanate group of some resin may form the trimer in advance, and may be oligomerized.
その中でも、多官能シアネート樹脂は、硬化性と流動性のバランスの観点から、ジシアネート樹脂、ジシアネート樹脂オリゴマー及びフェノールノボラック型シアネート樹脂からなる群より選ばれる少なくとも１種であることが好ましく、２，２−ビス（４−シアナトフェニル）プロパン、２，２−ビス（４−シアナトフェニル）プロパンオリゴマー及びフェノールノボラック型シアネート樹脂からなる群より選ばれる少なくとも１種であることがより好ましく、硬化性と流動性のバランスが特に良好であることから、２，２−ビス（４−シアナトフェニル）プロパンであることが更に好ましい。なお、２，２−ビス（４−シアナトフェニル）プロパンは、コスト及び生産性の点にも優れている。
またこれらの多官能シアネート樹脂は、１種類を単独で用いてもよく、２種類以上を混合して用いてもよい。
Among them, the polyfunctional cyanate resin is preferably at least one selected from the group consisting of a dicyanate resin, a dicyanate resin oligomer, and a phenol novolac type cyanate resin from the viewpoint of balance between curability and fluidity. More preferably, it is at least one selected from the group consisting of bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane oligomer and phenol novolac type cyanate resin, Since the balance of fluidity is particularly good, 2,2-bis (4-cyanatophenyl) propane is more preferable. Note that 2,2-bis (4-cyanatophenyl) propane is excellent in terms of cost and productivity.
Moreover, these polyfunctional cyanate resins may be used individually by 1 type, and may mix and use 2 or more types.
多官能シアネート樹脂のシアネート当量は特に制限されない。中でも硬化性、耐熱性、電気的信頼等の各種特性のバランスの観点から、１００ｇ／ｅｑ〜１０００ｇ／ｅｑであることが好ましく、１００ｇ／ｅｑ〜３００ｇ／ｅｑであることがより好ましい。ここでエポキシ当量とは多官能シアネート樹脂に含まれるシアネート基１モルあたりの質量（ｇ）である。 The cyanate equivalent of the polyfunctional cyanate resin is not particularly limited. Among these, from the viewpoint of balance of various properties such as curability, heat resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 100 g / eq to 300 g / eq. Here, the epoxy equivalent is the mass (g) per mole of cyanate group contained in the polyfunctional cyanate resin.
また多官能シアネート樹脂の軟化点又は融点は特に制限されない。中でも硬化性及び耐熱性の観点から、軟化点又は融点は、４０℃〜１８０℃であることが好ましく、熱硬化性樹脂成型材料作製時における取扱い性の観点からは５０℃〜１３０℃であることがより好ましい。 The softening point or melting point of the polyfunctional cyanate resin is not particularly limited. Among these, from the viewpoints of curability and heat resistance, the softening point or melting point is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing a thermosetting resin molding material, it should be 50 ° C. to 130 ° C. Is more preferable.
熱硬化性樹脂成形材料における多官能シアネート樹脂の含有率は、硬化性及び耐熱性の観点から、２質量％〜１０質量％であることが好ましく、３質量％〜８質量％であることがより好ましい。
また、熱硬化性樹脂成形材料における多官能シアネート樹脂の含有量は、硬化性及び耐熱性の観点から、エポキシ樹脂１００質量部に対して、２０質量部〜３００質量部であることが好ましく、４０質量部〜２００質量部であることがより好ましい。
From the viewpoint of curability and heat resistance, the content of the polyfunctional cyanate resin in the thermosetting resin molding material is preferably 2% by mass to 10% by mass, and more preferably 3% by mass to 8% by mass. preferable.
Moreover, it is preferable that content of polyfunctional cyanate resin in a thermosetting resin molding material is 20 mass parts-300 mass parts with respect to 100 mass parts of epoxy resins from a viewpoint of sclerosis | hardenability and heat resistance, and 40 It is more preferable that it is mass parts-200 mass parts.
熱硬化性樹脂成形材料における多官能エポキシ樹脂と多官能シアネート樹脂との当量比、すなわちエポキシ基数に対するシアネート基数の含有比（シアネート樹脂中のシアネート基数／エポキシ樹脂中のエポキシ基数）は特に制限はない。エポキシ基数に対するシアネート基数の含有比は、０．４０以上３．００以下の範囲に設定されることが好ましく、作業性及び成形性に優れる観点から、０．７０以上２．００以下の範囲に設定されることがより好ましい。前記含有比が０．４０以上であると、硬化物のガラス転移温度（Ｔｇ）がより向上する傾向があり、３．００以下であると、硬化性がより向上し、硬化物中に未反応のシアネート基が残存することが抑制される傾向がある。またガラス転移温度（Ｔｇ）がより向上する傾向がある。 There is no particular limitation on the equivalent ratio of the polyfunctional epoxy resin and the polyfunctional cyanate resin in the thermosetting resin molding material, that is, the content ratio of the number of cyanate groups to the number of epoxy groups (the number of cyanate groups in the cyanate resin / the number of epoxy groups in the epoxy resin). . The content ratio of the number of cyanate groups to the number of epoxy groups is preferably set in the range of 0.40 or more and 3.00 or less, and is set in the range of 0.70 or more and 2.00 or less from the viewpoint of excellent workability and moldability. More preferably. When the content ratio is 0.40 or more, the glass transition temperature (Tg) of the cured product tends to be further improved, and when it is 3.00 or less, the curability is further improved and unreacted in the cured product. The remaining cyanate group tends to be suppressed. Moreover, there exists a tendency for a glass transition temperature (Tg) to improve more.
（Ｃ）ベンゾフェノン誘導体
熱硬化性樹脂成形材料は、フェノール性水酸基を有するベンゾフェノン誘導体（以下、「ヒドロキシベンゾフェノン誘導体」ともいう）の少なくとも１種を含有する。前記ベンゾフェノン誘導体は、カルボニル基に２つの芳香族基が結合し、芳香族基の少なくとも一方がフェノール性水酸基を有していればよく、ジフェニルケトン誘導体に限定されるものではない。またカルボニル基に結合する２つの芳香族基は、メチレン基、酸素原子等の連結基又は単結合により、互いに連結して環状ケトンを構成していてもよい。前記芳香族基は芳香族炭化水素基であることが好ましく、ベンゼン、ナフタレン等に由来する芳香族炭化水素基であることがより好ましい。またベンゾフェノン誘導体におけるフェノール性水酸基の数は１個以上であればよく、１〜６であることが好ましく、１〜４であることがより好ましい。
(C) Benzophenone Derivative The thermosetting resin molding material contains at least one benzophenone derivative having a phenolic hydroxyl group (hereinafter also referred to as “hydroxybenzophenone derivative”). The benzophenone derivative is not limited to a diphenyl ketone derivative as long as two aromatic groups are bonded to a carbonyl group and at least one of the aromatic groups has a phenolic hydroxyl group. Two aromatic groups bonded to the carbonyl group may be linked to each other by a linking group such as a methylene group or an oxygen atom or a single bond to form a cyclic ketone. The aromatic group is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group derived from benzene, naphthalene or the like. Moreover, the number of the phenolic hydroxyl groups in a benzophenone derivative should just be one or more, it is preferable that it is 1-6, and it is more preferable that it is 1-4.
ヒドロキシベンゾフェノン誘導体は、ベンゾフェノン、ナフチルフェニルケトン、ジナフチルケトン、キサントン、フルオレノン及びアントラキノンからなる群より選ばれる少なくとも１種のベンゾフェノン誘導体の芳香環上に１個以上の水酸基が直接結合している化合物であることが好ましい。また、ヒドロキシベンゾフェノン誘導体は、１個以上の水酸基に加えて更に置換基を有していてもよい。ヒドロキシベンゾフェノン誘導体における置換基としては、炭素数１〜１２のアルコキシ基、炭素数１〜１２のアルケニルオキシ基、炭素数１〜１２のアルキル基等を挙げることができる。フェノール性水酸基を有するベンゾフェノン誘導体は、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。ヒドロキシベンゾフェノン誘導体の水酸基当量は特に制限されず、硬化性と耐熱性の観点から、５０ｇ／ｅｑ〜４００ｇ／ｅｑであることが好ましく、７０ｇ／ｅｑ〜３００ｇ／ｅｑであることがより好ましい。ここで水酸基当量とはヒドロキシベンゾフェノン誘導体に含まれる水酸基１モルあたりの質量（ｇ）である。 A hydroxybenzophenone derivative is a compound in which one or more hydroxyl groups are directly bonded to the aromatic ring of at least one benzophenone derivative selected from the group consisting of benzophenone, naphthyl phenyl ketone, dinaphthyl ketone, xanthone, fluorenone and anthraquinone. Preferably there is. The hydroxybenzophenone derivative may further have a substituent in addition to one or more hydroxyl groups. Examples of the substituent in the hydroxybenzophenone derivative include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms. A benzophenone derivative having a phenolic hydroxyl group may be used alone or in combination of two or more. The hydroxyl equivalent of the hydroxybenzophenone derivative is not particularly limited, and is preferably 50 g / eq to 400 g / eq, more preferably 70 g / eq to 300 g / eq from the viewpoint of curability and heat resistance. Here, the hydroxyl equivalent is the mass (g) per mole of hydroxyl group contained in the hydroxybenzophenone derivative.
ヒドロキシベンゾフェノン誘導体として具体的には、ｏ−ヒドロキシベンゾフェノン、ｍ−ヒドロキシベンゾフェノン、ｐ−ヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクチルオキシベンゾフェノン、２−ヒドロキシ−４−アリルオキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、５−ｔｅｒｔ−ブチル−２，４−ジヒドロキシベンゾフェノン、４，４’−ジヒドロキシベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２，３，４−トリヒドロキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２，３，４，４’−テトラヒドロキシベンゾフェノン、２，３，３’，４，４’，５−ヘキサヒドロキシベンゾフェノン、これらの位置異性体、これらの置換体等が挙げられる。 Specific examples of the hydroxybenzophenone derivative include o-hydroxybenzophenone, m-hydroxybenzophenone, p-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2-hydroxy-4. -Allyloxybenzophenone, 2,4-dihydroxybenzophenone, 5-tert-butyl-2,4-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'- Dihydroxy-4,4′-dimethoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophene Emissions, 2,3,3 ', 4,4', 5-hexahydroxybenzophenone, these regioisomers, substituted versions thereof, and the like.
ヒドロキシベンゾフェノン誘導体は、硬化性及び硬化物の耐熱性向上の観点では、ｐ−ヒドロキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン、５−ｔｅｒｔ−ブチル−２，４−ジヒドロキシベンゾフェノン、４，４’−ジヒドロキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２，３，４，４’−テトラヒドロキシベンゾフェノン及び２，３，３’，４，４’，５−ヘキサヒドロキシベンゾフェノンからなる群より選ばれる少なくとも１種が好ましく、さらに流動性の観点では、ｐ−ヒドロキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン及び４，４’−ジヒドロキシベンゾフェノンからなる群より選ばれる少なくとも１種がより好ましい。 Hydroxybenzophenone derivatives are p-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 5-tert-butyl-2,4-dihydroxybenzophenone, and 4,4′-dihydroxybenzophenone in terms of curability and improved heat resistance of the cured product. 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone and 2,3,3 ′, 4,4 ′, 5-hexahydroxybenzophenone In view of fluidity, at least one selected from the group consisting of p-hydroxybenzophenone, 2,4-dihydroxybenzophenone and 4,4′-dihydroxybenzophenone is more preferable.
熱硬化性樹脂成形材料におけるヒドロキシベンゾフェノン誘導体の含有率は、硬化性及び耐熱性の観点から、０．３質量％〜３質量％であることが好ましく、０．５質量％〜２質量％であることがより好ましい。
また、熱硬化性樹脂成形材料におけるヒドロキシベンゾフェノン誘導体の含有率は、硬化性及び耐熱性の観点から、エポキシ樹脂１００質量部に対して、３質量部〜５０質量部であることが好ましく、５質量部〜２５質量部であることがより好ましい。
From the viewpoint of curability and heat resistance, the content of the hydroxybenzophenone derivative in the thermosetting resin molding material is preferably 0.3% by mass to 3% by mass, and 0.5% by mass to 2% by mass. It is more preferable.
Moreover, it is preferable that the content rate of the hydroxybenzophenone derivative in a thermosetting resin molding material is 3 mass parts-50 mass parts with respect to 100 mass parts of epoxy resins from a viewpoint of sclerosis | hardenability and heat resistance. It is more preferable that it is 25 parts by mass.
熱硬化性樹脂成形材料において、多官能エポキシ樹脂と、ヒドロキシベンゾフェノン誘導体との当量比、すなわちエポキシ基数に対するフェノール性水酸基数の比（ヒドロキシベンゾフェノン誘導体中のフェノール性水酸基数／エポキシ樹脂中のエポキシ基数）は、０．１０以上０．６０以下の範囲に設定されることが好ましく、作業性及び成形性により優れる熱硬化性樹脂成形材料を得る観点から、０．１０以上０．５０以下の範囲に設定されることがより好ましい。前記当量比が０．１０以上であると充分な硬化性が得られる傾向がある。また当量比が０．６０以下であると硬化物のガラス転移温度（Ｔｇ）がより向上する傾向がある。 In thermosetting resin molding materials, the equivalent ratio of polyfunctional epoxy resin and hydroxybenzophenone derivative, that is, the ratio of the number of phenolic hydroxyl groups to the number of epoxy groups (number of phenolic hydroxyl groups in hydroxybenzophenone derivative / number of epoxy groups in epoxy resin) Is preferably set in the range of 0.10 to 0.60, and from the viewpoint of obtaining a thermosetting resin molding material having better workability and moldability, it is set in the range of 0.10 to 0.50. More preferably. When the equivalent ratio is 0.10 or more, sufficient curability tends to be obtained. Moreover, there exists a tendency for the glass transition temperature (Tg) of hardened | cured material to improve more that an equivalent ratio is 0.60 or less.
また熱硬化性樹脂成形材料において、多官能エポキシ樹脂と、多官能シアネート樹脂及びフェノール性水酸基を有するベンゾフェノン誘導体の総量との当量比、すなわちエポキシ基数に対するシアネート基及びフェノール性水酸基の総数の比（(多官能シアネート樹脂中のシアネート基数＋フェノール性水酸基を有するベンゾフェノン誘導体中のフェノール性水酸基数)／エポキシ樹脂中のエポキシ基数）は、０．７０以上３．５０以下の範囲に設定されることが好ましく、作業性及び成形性により優れる熱硬化性樹脂成形材料を得る観点から、０．８０以上２．５０以下の範囲に設定されることがより好ましい。前記当量比が０．７０以上であると充分な硬化性が得られる傾向がある。また当量比が３．５０以下であると硬化物のガラス転移温度（Ｔｇ）がより向上する傾向がある。 In the thermosetting resin molding material, the equivalent ratio of the polyfunctional epoxy resin to the total amount of the polyfunctional cyanate resin and the benzophenone derivative having a phenolic hydroxyl group, that is, the ratio of the total number of cyanate groups and phenolic hydroxyl groups to the number of epoxy groups (( The number of cyanate groups in the polyfunctional cyanate resin + the number of phenolic hydroxyl groups in the benzophenone derivative having a phenolic hydroxyl group) / the number of epoxy groups in the epoxy resin) is preferably set in the range of 0.70 to 3.50. From the viewpoint of obtaining a thermosetting resin molding material that is more excellent in workability and moldability, it is more preferably set in the range of 0.80 to 2.50. When the equivalent ratio is 0.70 or more, sufficient curability tends to be obtained. If the equivalent ratio is 3.50 or less, the glass transition temperature (Tg) of the cured product tends to be further improved.
（Ｄ）シラン化合物
熱硬化性樹脂成形材料は、シラン化合物の少なくとも１種を更に含有してもよい。ここでシラン化合物とは、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、（メタ）アクリロイルオキシシラン、イソシアネートシラン、アリールシラン等の各種シラン系化合物である。これらを例示すると、ビニルトリクロロシラン、ビニルトリメトキシシラン、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、ビニルトリアセトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン等のビニルシラン；γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルジメチルメトキシシラン、γ−メタクリロキシプロピルジメチルエトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン等の（メタ）アクリロイルオキシシラン；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トリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルジメチルメトキシシラン、γ−グリシドキシプロピルジメチルエトキシシラン等のエポキシシラン；γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド等のメルカプトシラン；γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−［ビス（β−ヒドロキシエチル）］アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、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、２−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−（３−トリエトキシシリルプロピル）フェニルイミン、３−（３−（トリエトキシシリル）プロピルアミノ）−Ｎ，Ｎ−ジメチルプロピオンアミド、Ｎ−トリエトキシシリルプロピル−β−アラニンメチルエステル等のアミノシラン；イソシアネートプロピルトリメトキシシラン、イソシアネートプロピルトリエトキシシラン等のイソシアネートシラン；メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、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等のアルキルシラン；フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジフェニルシランジオール、トリフェニルメトキシシラン、トリフェニルエトキシシラン、トリフェニルシラノール、ビス（トリメトキシシリル）ベンゼン等のアリールシラン；３−（トリエトキシシリルプロピル）ジヒドロ−３，５−フランジオン等のシラン系化合物、１Ｈ−イミダゾール、２−アルキルイミダゾール、２，４−ジアルキルイミダゾール、４−ビニルイミダゾール等のイミダゾール化合物と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トリエトキシシラン等のγ−グリシドキシプロピルアルコキシシランの反応物であるイミダゾール系シラン化合物などが挙げられる。これらのシラン化合物は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。
(D) Silane compound The thermosetting resin molding material may further contain at least one silane compound. Here, the silane compound refers to various silane compounds such as epoxy silane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, (meth) acryloyloxysilane, isocyanate silane, and arylsilane. Examples of these include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl. Vinylsilanes such as trimethoxysilane; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldimethyl (Meth) acryloyloxy such as methoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane Silane: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycine Epoxy silanes such as sidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, bis ( Mercaptosilanes such as triethoxysilylpropyl) tetrasulfide; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, 2-triethoxysilyl-N -(1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3 Aminosilanes such as-(triethoxysilyl) propylamino) -N, N-dimethylpropionamide, N-triethoxysilylpropyl-β-alanine methyl ester; isocyanate silanes such as isocyanatepropyltrimethoxysilane and isocyanatepropyltriethoxysilane; Me Alkyl silanes such as rutrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane; phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldi Arylsilanes such as ethoxysilane, diphenylsilanediol, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, bis (trimethoxysilyl) benzene; 3- (triethoxysilylpropyl) dihydro-3,5-furandion, etc. Silane compounds such as 1H-imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole, and γ-glycol De trimethoxysilane, etc. imidazole silane compound is the reaction product of γ- -glycidoxypropylalkoxysilane such γ- glycidoxypropyl triethoxy silane. These silane compounds may be used alone or in combination of two or more.
熱硬化性樹脂成形材料がシラン化合物を含む場合、シラン化合物の総含有率は、成形性及び流動性の観点から熱硬化性樹脂成形材料中に、０．０６質量％以上２質量％以下が好ましく、０．１質量％以上０．７５質量％以下がより好ましく、０．２質量％以上０．７質量％以下がさらに好ましい。シラン化合物の総含有率が０．０６質量％以上であると流動性がより向上する傾向にある。シラン化合物の総含有率が２質量％以下であるとボイド等の成形不良の発生がより抑制される傾向がある。 When the thermosetting resin molding material contains a silane compound, the total content of the silane compound is preferably 0.06% by mass or more and 2% by mass or less in the thermosetting resin molding material from the viewpoint of moldability and fluidity. 0.1 mass% or more and 0.75 mass% or less are more preferable, and 0.2 mass% or more and 0.7 mass% or less are more preferable. When the total content of the silane compound is 0.06% by mass or more, the fluidity tends to be further improved. There exists a tendency for generation | occurrence | production of shaping | molding defects, such as a void, to be suppressed more that the total content rate of a silane compound is 2 mass% or less.
（Ｅ）硬化促進剤
熱硬化性樹脂成形材料は、硬化促進剤の少なくとも１種を更に含有してもよい。硬化促進剤としては、熱硬化性樹脂成形材料で一般に使用されているもので特に限定はない。硬化促進剤としては、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、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；これらのシクロアミジ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化合物；ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の三級アミン化合物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化合物及びこれらの誘導体；トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４−メチルフェニル）ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物；これらの有機ホスフィン化合物に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物；テトラフェニルホスホニウムテトラフェニルボレート、テトラフェニルホスホニウムエチルトリフェニルボレート、テトラブチルホスホニウムテトラブチ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及びこれらの誘導体；などが挙げられる。これらの硬化促進剤は１種を単独で用いても２種以上組み合わせて用いてもよい。
(E) Curing accelerator The thermosetting resin molding material may further contain at least one curing accelerator. As a hardening accelerator, it is generally used with the thermosetting resin molding material, and there is no limitation in particular. Examples of the curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5,6-dibutylamino-1,8-diazabicyclo. [5.4.0] cycloamidine compounds such as undecene-7; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone Quinone compounds such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane Compound having intramolecular polarization formed by adding a compound having π bond such as phenol resin; benzyldimethylamine, triethanol Tertiary amine compounds such as amine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Imidazole compounds and derivatives thereof; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; maleic anhydride and quinone Phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as a compound, diazophenylmethane, phenol resin, etc .; tetraphenylphosphonium tetraphenylborate Tetraphenylphosphonium / tetraphenylborate such as tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate; tetraphenylboron such as 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate Salts and derivatives thereof; and the like. These curing accelerators may be used alone or in combination of two or more.
有機ホスフィン化合物（第三ホスフィン）とキノン化合物との付加物に用いられる有機ホスフィンとしては特に制限はない。有機ホスフィン化合物としては、ジブチルフェニルホスフィン、ブチルジフェニルホスフィン、エチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４−メチルフェニル）ホスフィン、トリス（４−エチルフェニル）ホスフィン、トリス（４−プロピルフェニル）ホスフィン、トリス（４−ブチルフェニル）ホスフィン、トリス（イソプロピルフェニル）ホスフィン、トリス（ｔｅｒｔ−ブチルフェニル）ホスフィン、トリス（２，４−ジメチルフェニル）ホスフィン、トリス（２，６−ジメチルフェニル）ホスフィン、トリス（２，４，６−トリメチルフェニル）ホスフィン、トリス（２，６−ジメチル−４−エトキシフェニル）ホスフィン、トリス（４−メトキシフェニル）ホスフィン、トリス（４−エトキシフェニル）ホスフィン等のアリール基を有する有機ホスフィンが挙げられる。中でも有機ホスフィン化合物は、成形性の点からはトリフェニルホスフィンが好ましい。
また、有機ホスフィン化合物（第三ホスフィン）とキノン化合物との付加物に用いられるキノン化合物としては特に制限はない。キノン化合物としては、ｏ−ベンゾキノン、ｐ−ベンゾキノン、ジフェノキノン、１，４−ナフトキノン、アントラキノン等が挙げられる。中でもキノン化合物は、耐湿性又は保存安定性の観点からはｐ−ベンゾキノンが好ましい。
There is no restriction | limiting in particular as an organic phosphine used for the adduct of an organic phosphine compound (tertiary phosphine) and a quinone compound. Examples of organic phosphine compounds include dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2, 4,6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phos Organic phosphines having an aryl group such as a fin like. Among them, the organic phosphine compound is preferably triphenylphosphine from the viewpoint of moldability.
Moreover, there is no restriction | limiting in particular as a quinone compound used for the adduct of an organic phosphine compound (tertiary phosphine) and a quinone compound. Examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. Among them, the quinone compound is preferably p-benzoquinone from the viewpoint of moisture resistance or storage stability.
熱硬化性樹脂成形材料が硬化促進剤を含む場合、硬化促進剤の含有量は、硬化促進効果が達成される量であれば特に限定されるものではない。硬化促進剤の含有量は、多官能エポキシ樹脂、多官能シアネート樹脂、及びヒドロキシベンゾフェノン誘導体の合計量１００質量部に対して０．１質量部以上１０質量部以下が好ましく、０．３質量部以上６質量部以下がより好ましい。硬化促進剤の含有量が０．１質量部以上であるとより短時間で硬化させることが容易になる傾向がある。硬化促進剤の含有量が１０質量部以下であると、硬化速度が早くなりすぎず、より良好な成形品が得られる傾向がある。 When the thermosetting resin molding material includes a curing accelerator, the content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. The content of the curing accelerator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.3 parts by mass or more with respect to 100 parts by mass of the total amount of the polyfunctional epoxy resin, polyfunctional cyanate resin, and hydroxybenzophenone derivative. 6 parts by mass or less is more preferable. When the content of the curing accelerator is 0.1 parts by mass or more, it tends to be easier to cure in a shorter time. When the content of the curing accelerator is 10 parts by mass or less, the curing rate does not become too fast, and a better molded product tends to be obtained.
（Ｆ）無機充てん剤
熱硬化性樹脂成形材料は、無機充てん剤の少なくとも１種を更に含有してもよい。無機充てん剤を更に含むことで、吸湿性の低減、線膨張係数の低減、熱伝導性向上及び強度向上がより効果的に達成される。無機充てん剤としては、熱硬化性樹脂成形材料に一般に使用されているものであれば特に制限されるものではない。無機充てん剤としては、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア等の粉体、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。これらの無機充てん剤は、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。なかでも、線膨張係数低減の観点からは溶融シリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。また無機充てん剤の形状は、成形時の流動性及び金型摩耗性の点から球形が好ましい。特にコストと性能のバランスの観点から、無機充てん剤は球状溶融シリカが好ましい。
(F) Inorganic filler The thermosetting resin molding material may further contain at least one inorganic filler. By further including an inorganic filler, a reduction in hygroscopicity, a reduction in linear expansion coefficient, an improvement in thermal conductivity, and an improvement in strength are achieved more effectively. The inorganic filler is not particularly limited as long as it is generally used for thermosetting resin molding materials. Inorganic fillers include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples thereof include powders such as spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. These inorganic fillers may be used alone or in combination of two or more. Of 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. The shape of the inorganic filler is preferably spherical from the viewpoint of fluidity during molding and mold wear. In particular, from the viewpoint of a balance between cost and performance, the inorganic filler is preferably spherical fused silica.
熱硬化性樹脂成形材料が無機充てん剤を含む場合、無機充てん剤の含有率は、難燃性、成形性、吸湿性、線膨張係数低減及び強度向上の観点から、熱硬化性樹脂成形材料中７０質量％以上９５質量％以下が好ましい。無機充てん剤の含有率が７０質量％以上であると、充分に難燃性が向上する傾向がある。無機充てん剤の含有率が９５質量％以下であると、より良好な流動性が得られる傾向がある。 When the thermosetting resin molding material contains an inorganic filler, the content of the inorganic filler is in the thermosetting resin molding material from the viewpoints of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient and strength improvement. 70 mass% or more and 95 mass% or less are preferable. There exists a tendency for a flame retardance to fully improve that the content rate of an inorganic filler is 70 mass% or more. When the content of the inorganic filler is 95% by mass or less, better fluidity tends to be obtained.
（Ｇ）その他の添加剤
熱硬化性樹脂成形材料は、必要に応じて、陰イオン交換体、離型剤、難燃剤、着色剤等のその他の添加剤を更に含有してもよい。
(G) Other additives The thermosetting resin molding material may further contain other additives such as an anion exchanger, a release agent, a flame retardant, and a colorant, if necessary.
熱硬化性樹脂成形材料は、陰イオン交換体を必要に応じて更に含有することができる。陰イオン交換体を含むことで、ＩＣの耐湿性及び高温放置特性をより向上させることができる。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。陰イオン交換体としては、ハイドロタルサイト類、マグネシウム、アルミニウム、チタン、ジルコニウム及びビスマスからなる群より選ばれる金属元素の含水酸化物等が挙げられる。これらの陰イオン交換体は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。 The thermosetting resin molding material can further contain an anion exchanger as required. By including the anion exchanger, it is possible to further improve the moisture resistance and high temperature storage characteristics of the IC. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples of the anion exchanger include hydrotalcites, hydrated oxides of metal elements selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. These anion exchangers may be used alone or in combination of two or more.
熱硬化性樹脂成形材料が陰イオン交換体を含む場合、陰イオン交換体の含有量は、ハロゲンイオン等の陰イオンを捕捉できる充分量であれば特に限定されるものではない。陰イオン交換体の含有量は、多官能エポキシ樹脂１００質量部に対して、０．１質量部以上３０質量部以下が好ましく、１質量部以上５質量部以下がより好ましい。 When the thermosetting resin molding material contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is a sufficient amount that can capture anions such as halogen ions. The content of the anion exchanger is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polyfunctional epoxy resin.
熱硬化性樹脂成形材料は、必要に応じて離型剤の少なくとも１種を更に含有してもよい。離型剤としては、酸化型又は非酸化型のポリオレフィンであるクラリアントジャパン株式会社製商品名ＰＥ及び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等が挙げられる。また、これ以外のその他の離型剤としては、カルナバワックス、モンタン酸エステル、モンタン酸、ステアリン酸等が挙げられる。これらの離型剤は１種を単独で用いても２種以上組み合わせて用いてもよい。 The thermosetting resin molding material may further contain at least one release agent as required. Examples of the release agent include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as trade name PE and PED series manufactured by Clariant Japan Co., Ltd., which is an oxidized or non-oxidized polyolefin. Other examples of the mold release agent include carnauba wax, montanic acid ester, montanic acid, stearic acid, and the like. These release agents may be used alone or in combination of two or more.
熱硬化性樹脂成形材料が離型剤として酸化型又は非酸化型のポリオレフィンを含む場合、その含有量は、多官能エポキシ樹脂１００質量部に対して０．０１質量部以上１０質量部以下用いることが好ましく、０．１質量部以上５質量部以下用いることがより好ましい。含有量が０．０１質量部以上であると充分な離型性が得られる傾向がある。含有量が１０質量部以下であると接着性がより向上する傾向がある。
熱硬化性樹脂成形材料が離型剤として酸化型又は非酸化型のポリオレフィンに加えてその他の離型剤を含有する場合、離型剤の総含有量は、多官能エポキシ樹脂１００質量部に対して０．１質量部以上１０質量部以下が好ましく、０．５質量部以上３質量部以下がより好ましい。
When the thermosetting resin molding material contains an oxidized or non-oxidized polyolefin as a release agent, the content thereof is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyfunctional epoxy resin. It is more preferable to use 0.1 parts by mass or more and 5 parts by mass or less. If the content is 0.01 parts by mass or more, sufficient releasability tends to be obtained. There exists a tendency for adhesiveness to improve more that content is 10 mass parts or less.
When the thermosetting resin molding material contains other release agents in addition to the oxidized or non-oxidized polyolefin as the release agent, the total content of the release agent is based on 100 parts by mass of the polyfunctional epoxy resin. 0.1 to 10 parts by mass is preferable, and 0.5 to 3 parts by mass is more preferable.
熱硬化性樹脂成形材料は、従来公知の難燃剤の少なくとも１種を必要に応じて更に含有してもよい。難燃剤としては、ブロム化エポキシ樹脂、三酸化アンチモン、赤リン、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛等の無機物及び／又はフェノール樹脂等の熱硬化性樹脂などで被覆された赤リン、リン酸エステル等のリン化合物、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、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛、錫酸亜鉛、硼酸亜鉛、酸化鉄、酸化モリブデン、モリブデン酸亜鉛、ジシクロペンタジエニル鉄等の金属元素を含む化合物などが挙げられる。これらの難燃剤は１種を単独で用いても２種以上を組合せて用いてもよい。 The thermosetting resin molding material may further contain at least one conventionally known flame retardant as required. Flame retardants include brominated epoxy resins, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide, etc. and / or red phosphorus and phosphorus coated with thermosetting resins such as phenolic resins. Phosphorus compounds such as acid esters, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, Examples thereof include compounds containing metal elements such as magnesium hydroxide, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, and dicyclopentadienyl iron. These flame retardants may be used alone or in combination of two or more.
熱硬化性樹脂成形材料が難燃剤を含む場合、その含有量は特に制限されない。難燃剤の含有量は、多官能エポキシ樹脂１００質量部に対して１質量部以上３０質量部以下が好ましく、２質量部以上１５質量部以下がより好ましい。 When the thermosetting resin molding material contains a flame retardant, its content is not particularly limited. 1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of polyfunctional epoxy resins, and, as for content of a flame retardant, 2 mass parts or more and 15 mass parts or less are more preferable.
熱硬化性樹脂成形材料は、カーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の着色剤を更に含有してもよい。さらにその他の添加剤として、シリコーンオイルや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。 The thermosetting resin molding material may further contain a colorant such as carbon black, an organic dye, an organic pigment, titanium oxide, red lead, or bengara. Furthermore, as other additives, stress relaxation agents such as silicone oil and silicone rubber powder can be blended as required.
熱硬化性樹脂成形材料は、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。一般的な手法として、所定の配合量の成分をミキサー等を用いて充分混合し、ミキシングロール、押出機等を用いて溶融混練した後、冷却、粉砕する方法を挙げることができる。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した後、冷却し、粉砕するなどの方法で得ることができる。また熱硬化性樹脂成形材料は、成形条件に合うような寸法及び質量でタブレット化すると使いやすい。 The thermosetting resin molding material can be prepared by any method as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed using a mixer or the like, melt-kneaded using a mixing roll, an extruder or the like, and then cooled and pulverized. A predetermined amount of the above-mentioned components can be uniformly stirred and mixed, and then kneaded with a kneader, roll, extruder or the like that has been heated to 70 ° C. to 140 ° C., and then cooled and pulverized. . The thermosetting resin molding material is easy to use if it is tableted with dimensions and mass that meet the molding conditions.
＜電子部品装置＞
本発明の電子部品装置は、素子と、前記素子を封止する前記熱硬化性樹脂成形材料の硬化物とを備える。熱硬化性樹脂成形材料により封止した素子を備えた電子部品装置としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ等の支持部材に、半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子、コンデンサ、抵抗体、コイル等の受動素子等の素子を搭載し、必要な部分を本発明の熱硬化性樹脂成形材料で封止した電子部品装置などが挙げられる。特に本発明の熱硬化性樹脂成形材料は、耐熱性、電気絶縁性等の観点から、過酷な動作環境に曝されるパワー半導体用途に好適に使用することができる。
本発明の熱硬化性樹脂成形材料を用いて素子を封止する方法としては、低圧トランスファ成形法が最も一般的であるが、インジェクション成形法、圧縮成形法等を用いてもよい。
<Electronic component device>
The electronic component device of the present invention includes an element and a cured product of the thermosetting resin molding material that seals the element. Electronic component devices having elements sealed with thermosetting resin molding materials include lead frames, wired tape carriers, wiring boards, glass, silicon wafers, and other support members such as semiconductor chips, transistors, diodes, thyristors. Examples thereof include an electronic component device in which elements such as active elements such as capacitors, passive elements such as capacitors, resistors, and coils are mounted, and necessary portions are sealed with the thermosetting resin molding material of the present invention. In particular, the thermosetting resin molding material of the present invention can be suitably used for power semiconductor applications exposed to harsh operating environments from the viewpoints of heat resistance, electrical insulation and the like.
As a method for sealing an element using the thermosetting resin molding material 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.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
＜実施例１〜２４、比較例１〜２６＞
以下に示す各材料を、それぞれ下記表１〜７に示す質量部で配合し、混練温度８０℃、混練時間１０分の条件でロール混練を行い、実施例１〜２４（表１〜３）及び比較例１〜２６（表４〜７）の熱硬化性樹脂成形材料を作製した。なお表中の「−」は配合していないことを表す。
<Examples 1-24, Comparative Examples 1-26>
Each material shown below is mix | blended by the mass part shown in following Table 1-7, respectively, knead | mixing temperature 80 degreeC, kneading | mixing time 10 minutes, roll kneading | mixing, Examples 1-24 (Tables 1-3) and The thermosetting resin molding material of Comparative Examples 1-26 (Tables 4-7) was produced. In addition, "-" in a table | surface represents not mix | blending.
（Ａ）多官能エポキシ樹脂
・エポキシ樹脂１：エポキシ当量１７０、軟化点６７℃のヒドロキシベンズアルデヒド型エポキシ樹脂（日本化薬株式会社製商品名ＥＰＰＮ−５０２Ｈ）
・エポキシ樹脂２：エポキシ当量２００、軟化点６０℃のオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ化学工業株式会社製商品名Ｎ−６６０）
・エポキシ樹脂３：エポキシ当量２５８、軟化点６０℃のジシクロペンタジエン型エポキシ樹脂（ＤＩＣ株式会社製商品名ＨＰ−７２００）
・エポキシ樹脂４：エポキシ当量２５０、軟化点５８℃のナフタレン変性ノボラック型エポキシ樹脂（ＤＩＣ株式会社製商品名ＨＰ−５０００）
・エポキシ樹脂５：エポキシ当量２８６、軟化点１０４℃のジシクロペンタジエン型エポキシ樹脂（ＤＩＣ株式会社製商品名ＨＰ−７２００ＨＨＨ）
・エポキシ樹脂６：エポキシ当量２０９、軟化点９６℃のオルソクレゾールノボラック型エポキシ樹脂（新日鐵化学株式会社製商品名ＹＤＣＮ−７０４Ａ）
(A) Polyfunctional epoxy resin / epoxy resin 1: Hydroxybenzaldehyde type epoxy resin having an epoxy equivalent of 170 and a softening point of 67 ° C. (trade name EPPN-502H manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 2: Orthocresol novolak type epoxy resin having an epoxy equivalent of 200 and a softening point of 60 ° C. (trade name N-660, manufactured by DIC Chemical Industries, Ltd.)
Epoxy resin 3: epoxy equivalent 258, dicyclopentadiene type epoxy resin having a softening point of 60 ° C. (trade name HP-7200 manufactured by DIC Corporation)
Epoxy resin 4: Naphthalene-modified novolak epoxy resin having an epoxy equivalent of 250 and a softening point of 58 ° C. (trade name HP-5000, manufactured by DIC Corporation)
Epoxy resin 5: dicyclopentadiene type epoxy resin having an epoxy equivalent of 286 and a softening point of 104 ° C. (trade name HP-7200HHH manufactured by DIC Corporation)
Epoxy resin 6: Orthocresol novolak type epoxy resin having an epoxy equivalent of 209 and a softening point of 96 ° C. (trade name YDCN-704A manufactured by Nippon Steel Chemical Co., Ltd.)
（Ｂ）多官能シアネート樹脂
・シアネート樹脂１：シアネート当量１３９、融点８０℃の２，２−ビス（４−シアナトフェニル）プロパン（ロンザ製商品名Ｐｒｉｍａｓｅｔ ＢＡＤＣｙ）
・シアネート樹脂２：シアネート当量２４０、軟化点９５℃の２，２−ビス（４−シアナトフェニル）プロパンのオリゴマー（ロンザ製商品名Ｐｒｉｍａｓｅｔ ＢＡ−２００）
・シアネート樹脂３：シアネート当量１３１、軟化点８０℃のフェノールノボラック型シアネート樹脂（ロンザ製商品名Ｐｒｉｍａｓｅｔ ＰＴ−６０）
(B) Polyfunctional cyanate resin / cyanate resin 1: 2,2-bis (4-cyanatophenyl) propane having a cyanate equivalent weight of 139 and a melting point of 80 ° C. (trade name Primaset BADCy manufactured by Lonza)
Cyanate resin 2: oligomer of 2,2-bis (4-cyanatophenyl) propane having a cyanate equivalent of 240 and a softening point of 95 ° C. (Lonza product name Primaset BA-200)
Cyanate resin 3: Phenol novolac type cyanate resin having a cyanate equivalent of 131 and a softening point of 80 ° C. (Lonza product name Primaset PT-60)
比較例でシアネート樹脂の替わりに使用した材料は、以下のフェノール樹脂である。
・フェノール樹脂１：水酸基当量１０３、軟化点８８℃のヒドロキシベンズアルデヒド型フェノール樹脂（明和化成株式会社製商品名ＭＥＨ−７５００）
・フェノール樹脂２：水酸基当量１７５、軟化点７０℃のフェノール・アラルキル樹脂（明和化成株式会社製商品名ＭＥＨ−７８００）
The material used instead of cyanate resin in the comparative example is the following phenol resin.
・ Phenolic resin 1: Hydroxyl aldehyde type phenolic resin having hydroxyl group equivalent of 103 and softening point of 88 ° C.
Phenol resin 2: phenol aralkyl resin having a hydroxyl group equivalent of 175 and a softening point of 70 ° C. (trade name MEH-7800, manufactured by Meiwa Kasei Co., Ltd.)
（Ｃ）フェノール性水酸基を有するベンゾフェノン誘導体（ヒドロキシベンゾフェノン誘導体）
・ヒドロキシベンゾフェノン誘導体１：４，４’−ジヒドロキシベンゾフェノン
・ヒドロキシベンゾフェノン誘導体２：２，４−ジヒドロキシベンゾフェノン
・ヒドロキシベンゾフェノン誘導体３：ｐ−ヒドロキシベンゾフェノン
(C) Benzophenone derivative having a phenolic hydroxyl group (hydroxybenzophenone derivative)
Hydroxybenzophenone derivative 1: 4,4′-dihydroxybenzophenone Hydroxybenzophenone derivative 2: 2,4-dihydroxybenzophenone Hydroxybenzophenone derivative 3: p-hydroxybenzophenone
また、比較例でヒドロキシベンゾフェノン誘導体の替わりに使用した材料は、以下のフェノール化合物及び金属錯体である。
・フェノール化合物１：フェノール
・フェノール化合物２：カテコール
・フェノール化合物３：レソルシノール
・フェノール化合物４：ヒドロキノン
・金属錯体１：ナフテン酸コバルト
Moreover, the material used instead of the hydroxybenzophenone derivative in the comparative example is the following phenol compound and metal complex.
-Phenol compound 1: Phenol-Phenol compound 2: Catechol-Phenol compound 3: Resorcinol-Phenol compound 4: Hydroquinone-Metal complex 1: Cobalt naphthenate
（Ｄ）シラン化合物
・シラン化合物１：γ−グリシドキシプロピルトリメトキシシラン
（Ｅ）硬化促進剤
・硬化促進剤１：トリフェニルホスフィンとｐ−ベンゾキノンとのベタイン型付加物
（Ｆ）無機充てん剤
・無機充てん剤１：平均粒径１７．５μｍ、比表面積３．８ｍ２／ｇの球状溶融シリカ
その他の添加成分
・離型剤：モンタン酸エステル（クラリアントジャパン株式会社製商品名ＨＷ−Ｅ）
・着色剤：カーボンブラック（三菱化学株式会社製商品名ＭＡ−６００）
(D) Silane compound / silane compound 1: γ-glycidoxypropyltrimethoxysilane (E) curing accelerator / curing accelerator 1: betaine-type adduct of triphenylphosphine and p-benzoquinone (F) inorganic filler Inorganic filler 1: Spherical fused silica having an average particle size of 17.5 μm and a specific surface area of 3.8 m 2 / g Other additive components: Mold release agent: Montanic acid ester (trade name HW-E manufactured by Clariant Japan Co., Ltd.)
Colorant: Carbon black (trade name MA-600 manufactured by Mitsubishi Chemical Corporation)
＜評価＞
上記で得られた実施例及び比較例の熱硬化性樹脂成形材料を、次の（１）〜（５）の各種特性試験により評価した。評価結果を下記表８〜１３に示す。なお、熱硬化性樹脂成形材料の成形は、明記しない限りトランスファ成形機により、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で行った。また、後硬化は１８０℃で６時間行った。
<Evaluation>
The thermosetting resin molding materials of Examples and Comparative Examples obtained above were evaluated by the following various characteristic tests (1) to (5). The evaluation results are shown in Tables 8 to 13 below. The thermosetting resin molding material 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 unless otherwise specified. Further, post-curing was performed at 180 ° C. for 6 hours.
（１）熱時硬度（硬化性）
熱硬化性樹脂成形材料を上記条件で直径５０ｍｍ×厚さ３ｍｍの円板に成形し、成形後直ちにショアＤ型硬度計（株式会社上島製作所製ＨＤ−１１２０（タイプＤ））を用いて測定した。
(1) Heat hardness (curability)
The thermosetting resin molding material 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 hardness meter (HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.). .
（２）ガラス転移温度（Ｔｇ）測定（動的粘弾性）
熱硬化性樹脂組成物を上記条件で長さ８０ｍｍ×幅１０ｍｍ×厚さ３ｍｍの大きさに成形し、後硬化した。次いで、ダイヤモンドカッターで幅５ｍｍ、長さ５５ｍｍに切断し、粘弾性測定装置ＲＳＡ３（ＴＡインスツルメンツ社製）を用い、３点曲げモードで昇温速度５℃／ｍｉｎ、周波数６．２８ｒａｄ／ｓの条件で測定した。この動的粘弾性測定で得られる損失正接（ｔａｎδ）の極大値（ピークトップ）を示したときの温度をガラス転移温度（Ｔｇ）とした。
(2) Glass transition temperature (Tg) measurement (dynamic viscoelasticity)
The thermosetting resin composition was molded into a size of length 80 mm × width 10 mm × thickness 3 mm under the above conditions and post-cured. Next, it is cut into a width of 5 mm and a length of 55 mm with a diamond cutter, and using a viscoelasticity measuring device RSA3 (manufactured by TA Instruments), a temperature rising rate of 5 ° C./min and a frequency of 6.28 rad / s in a three-point bending mode. Measured with The temperature at which the maximum value (peak top) of loss tangent (tan δ) obtained by this dynamic viscoelasticity measurement was shown was the glass transition temperature (Tg).
（３）体積抵抗率
熱硬化性樹脂組成物を上記条件で直径１００ｍｍ×厚さ２ｍｍの円板に成形し、後硬化して試験片とした。次いでＪＩＳ Ｋ ６９１１規格に基づき、この試験片に絶縁抵抗測定器の電極を取り付け、５００Ｖの電圧を印加して１分間の電流値を測定し、以下の式によって体積抵抗率を算出した。測定は、１５０℃及び１８０℃で実施した。
Ｒｖ＝５００／Ｉｖ
ρｖ＝（πｄ２／４ｔ）×Ｒｖ
ここで、Ｉｖ：測定された電流値（Ａ）、ρｖ：体積抵抗率（Ω・ｃｍ）、ｄ：主電極の内円の外径（ｃｍ）、ｔ：試験片の厚さ（ｃｍ）、Ｒｖ：体積抵抗（Ω）、π：円周率（３．１４）をそれぞれ示す。
(3) Volume resistivity The thermosetting resin composition was molded into a disc having a diameter of 100 mm and a thickness of 2 mm under the above conditions, and post-cured to obtain a test piece. Next, based on JIS K 6911 standard, an electrode of an insulation resistance measuring instrument was attached to this test piece, a voltage of 500 V was applied to measure a current value for 1 minute, and a volume resistivity was calculated by the following formula. The measurement was performed at 150 ° C. and 180 ° C.
Rv = 500 / Iv
ρv = (πd 2 / 4t) × Rv
Here, Iv: measured current value (A), ρv: volume resistivity (Ω · cm), d: outer diameter of inner circle of main electrode (cm), t: thickness of test piece (cm), Rv: Volume resistance (Ω), π: Circumferential ratio (3.14), respectively.
（４）難燃性評価
ＵＬ−９４規格に基づき、熱硬化性樹脂組成物を上記条件で長さ１２７ｍｍ×幅１２．５ｍｍ×厚さ６．３５ｍｍの大きさに成形し、後硬化して試験片とした。次いで、この試験片をクランプに垂直に吊るし、高さ１９ｍｍの炎に１０秒間かざした後、炎を遠ざけ試験片の残炎時間を測定し、消火と共に再び１０秒間炎にかざした後の残炎時間を測定した。これを１サンプルにつき５本行なった。火がクランプにまで達した場合は、表中に「クランプ」と記載した。１回の残炎時間の最大値(最大残炎時間)が１０秒以下かつ５本全部の残炎時間の合計(総残炎時間)が５０秒以下のときＶ−０とし、最大残炎時間が３０秒以下かつ総残炎時間が２５０秒以下のときＶ−１とし、それ以外を規格外と判定した。
(4) Flame retardancy evaluation Based on the UL-94 standard, a thermosetting resin composition was molded into a size of 127 mm long × 12.5 mm wide × 6.35 mm thick under the above conditions, and then post-cured and tested. It was a piece. Next, the test piece was hung perpendicularly to the clamp, held over a flame with a height of 19 mm for 10 seconds, the flame was moved away, the afterflame time of the test piece was measured, and after flame was put on the flame again for 10 seconds together with extinction. Time was measured. This was performed 5 times per sample. When the fire reached the clamp, it was written as “Clamp” in the table. The maximum afterflame time is V-0 when the maximum afterflame time (maximum afterflame time) is 10 seconds or less and the sum of all afterflame times (total afterflame time) is 50 seconds or less. Was set to V-1 when 30 seconds or less and the total afterflame time was 250 seconds or less, and the others were determined to be out of specification.
（５）２００℃及び２５０℃における金属との接着力測定
熱硬化性樹脂成形材料を上記条件で、銅板上、銀メッキした銅板上又はニッケルメッキした銅板上にそれぞれ底面４ｍｍφ、上面３ｍｍφ、高さ４ｍｍのサイズに成形し、後硬化して試験片とした。ボンドテスター（デイジ社製シリーズ４０００）によって、各種銅板の温度を２００℃又は２５０℃に保ちながら、せん断速度５０μｍ／ｓでせん断接着力を測定した。
(5) Measurement of adhesive strength with metal at 200 ° C. and 250 ° C. Thermosetting resin molding material on the copper plate, on the silver-plated copper plate or on the nickel-plated copper plate, respectively, with a bottom surface of 4 mmφ and a top surface of 3 mmφ, height The test piece was molded into a size of 4 mm and post-cured. The shear adhesive strength was measured at a shear rate of 50 μm / s using a bond tester (Daily series 4000) while keeping the temperature of the various copper plates at 200 ° C. or 250 ° C.
上記評価結果から、いずれの実施例も、ガラス転移温度、難燃性、せん断接着力、体積抵抗率が比較例よりも優れていた。
なお、表１１の比較例５〜８及び表１３の比較例１７〜２４の「−」は、硬化性が悪く、試験片が成形できなかったためにデータ取得できなかったことを示している。これらは、例えば、ヒドロキシベンゾフェノン誘導体を含有していないために硬化性が悪く、成形物を得ることができなかったと考えられる。
From the above evaluation results, all of the examples were superior in glass transition temperature, flame retardancy, shear adhesive strength, and volume resistivity to the comparative examples.
In addition, "-" of Comparative Examples 5 to 8 in Table 11 and Comparative Examples 17 to 24 in Table 13 indicates that the data could not be acquired because the curability was poor and the test piece could not be molded. For example, it is considered that since these did not contain a hydroxybenzophenone derivative, the curability was poor and a molded product could not be obtained.
また、ヒドロキシベンゾフェノン誘導体の替わりに金属錯体１（ナフテン酸コバルト）を使用した比較例２５と２６については、所定の評価が実施できなかったため、表には記載していない。比較例２５はロール混練後に取り出した混錬物の性状が飴状になり、粉砕不可であった。これを１８０℃で２分以上加熱したが硬化は進まず、所定の成形物を得るどころか、熱時硬度を測定することも不可能であった。一方、比較例２６はロール混錬時に混錬物の硬化が急速に進行した。取り出した混錬物を１８０℃で加熱したが、溶融せず、ほぼ完全硬化に近い状態であったため、これも所定の成形物を得ることができなかった。
金属錯体の含有量は、エポキシ樹脂１００部に対して、比較例２５で０．５部、比較例２６で０．７部であるが、わずか０．２部の違いで上記のように硬化挙動が著しく変化した。このため、仮に金属錯体を用いて成形可能な封止材が得られても、その硬化性及び他の特性の再現性を確保するのは困難と考えられる。
Further, Comparative Examples 25 and 26 using metal complex 1 (cobalt naphthenate) instead of the hydroxybenzophenone derivative were not described in the table because predetermined evaluation could not be performed. In Comparative Example 25, the kneaded product taken out after the roll kneading was in the form of a bowl and was not pulverized. Although this was heated at 180 ° C. for 2 minutes or more, curing did not proceed, and it was impossible to measure the hot hardness, rather than obtaining a predetermined molded product. On the other hand, in Comparative Example 26, the kneaded material hardened rapidly during the kneading of the roll. The kneaded product taken out was heated at 180 ° C., but it did not melt and was almost completely cured, so that a predetermined molded product could not be obtained.
The content of the metal complex is 0.5 parts in Comparative Example 25 and 0.7 parts in Comparative Example 26 with respect to 100 parts of the epoxy resin, but the curing behavior is as described above with a difference of only 0.2 parts. Changed significantly. For this reason, even if a moldable sealing material is obtained using a metal complex, it is considered difficult to ensure the curability and reproducibility of other characteristics.
Claims (10)
１分子中にシアネート基（−ＯＣＮ）を２個以上有するシアネート樹脂と、
フェノール性水酸基を有するベンゾフェノン誘導体と、
を含有し、
前記エポキシ樹脂に含まれるエポキシ基数に対する前記シアネート樹脂に含まれるシアネート基及び前記ベンゾフェノン誘導体に含まれるフェノール性水酸基数の総数の比が、０．７０以上３．５０以下である、熱硬化性樹脂成形材料。 An epoxy resin having two or more epoxy groups in one molecule;
A cyanate resin having two or more cyanate groups (—OCN) in one molecule;
A benzophenone derivative having a phenolic hydroxyl group;
Containing
Thermosetting resin molding wherein the ratio of the total number of cyanate groups contained in the cyanate resin and the number of phenolic hydroxyl groups contained in the benzophenone derivative to the number of epoxy groups contained in the epoxy resin is 0.70 or more and 3.50 or less. material.
１分子中にシアネート基（−ＯＣＮ）を２個以上有するシアネート樹脂と、
フェノール性水酸基を有するベンゾフェノン誘導体と、
を含有させることを含み、
前記エポキシ樹脂に含まれるエポキシ基数に対する前記シアネート樹脂に含まれるシアネート基及び前記ベンゾフェノン誘導体に含まれるフェノール性水酸基数の総数の比が、０．７０以上３．５０以下である、熱硬化性樹脂成形材料の製造方法。 An epoxy resin having two or more epoxy groups in one molecule;
A cyanate resin having two or more cyanate groups (—OCN) in one molecule;
A benzophenone derivative having a phenolic hydroxyl group;
Including,
Thermosetting resin molding wherein the ratio of the total number of cyanate groups contained in the cyanate resin and the number of phenolic hydroxyl groups contained in the benzophenone derivative to the number of epoxy groups contained in the epoxy resin is 0.70 or more and 3.50 or less. Material manufacturing method.
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