WO2021157623A1 - トランスファ成形用エポキシ樹脂組成物及びその製造方法、コンプレッション成形用エポキシ樹脂組成物、並びに電子部品装置 - Google Patents
トランスファ成形用エポキシ樹脂組成物及びその製造方法、コンプレッション成形用エポキシ樹脂組成物、並びに電子部品装置 Download PDFInfo
- Publication number
- WO2021157623A1 WO2021157623A1 PCT/JP2021/003980 JP2021003980W WO2021157623A1 WO 2021157623 A1 WO2021157623 A1 WO 2021157623A1 JP 2021003980 W JP2021003980 W JP 2021003980W WO 2021157623 A1 WO2021157623 A1 WO 2021157623A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- mass
- inorganic filler
- general formula
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 584
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 584
- 239000000203 mixture Substances 0.000 title claims abstract description 290
- 238000001721 transfer moulding Methods 0.000 title claims abstract description 44
- 238000000748 compression moulding Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000011256 inorganic filler Substances 0.000 claims abstract description 203
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 203
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 84
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 125000000962 organic group Chemical group 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims description 158
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 74
- 238000000034 method Methods 0.000 claims description 52
- 239000004305 biphenyl Substances 0.000 claims description 37
- 235000010290 biphenyl Nutrition 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 14
- 239000006082 mold release agent Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 100
- 238000001723 curing Methods 0.000 description 89
- 239000005011 phenolic resin Substances 0.000 description 86
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 61
- 239000000047 product Substances 0.000 description 61
- 239000000377 silicon dioxide Substances 0.000 description 49
- -1 aliphatic aldehyde compound Chemical class 0.000 description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 36
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 35
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 150000002989 phenols Chemical class 0.000 description 30
- 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 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 28
- 229920003986 novolac Polymers 0.000 description 25
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 24
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 23
- 238000011049 filling Methods 0.000 description 22
- 238000000465 moulding Methods 0.000 description 21
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 19
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- 125000003710 aryl alkyl group Chemical group 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 239000003063 flame retardant Substances 0.000 description 13
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 239000007822 coupling agent Substances 0.000 description 12
- 238000004898 kneading Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 229920001568 phenolic resin Polymers 0.000 description 11
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 10
- 239000003086 colorant Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 10
- 239000007983 Tris buffer Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000004780 naphthols Chemical class 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 239000012778 molding material Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 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
- 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 4
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 4
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000790 scattering method Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 150000003739 xylenols Chemical class 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ZEGDFCCYTFPECB-UHFFFAOYSA-N 2,3-dimethoxy-1,4-benzoquinone Natural products C1=CC=C2C(=O)C(OC)=C(OC)C(=O)C2=C1 ZEGDFCCYTFPECB-UHFFFAOYSA-N 0.000 description 2
- AIACLXROWHONEE-UHFFFAOYSA-N 2,3-dimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=C(C)C(=O)C=CC1=O AIACLXROWHONEE-UHFFFAOYSA-N 0.000 description 2
- QXHLMWWPSWWKOK-UHFFFAOYSA-N 2,3-dimethylnaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(C)C(C)=CC2=C1 QXHLMWWPSWWKOK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GGIBUEPJJRWWNM-UHFFFAOYSA-N 2-[[2-[2-(oxiran-2-ylmethoxy)phenyl]phenoxy]methyl]oxirane Chemical class C1OC1COC1=CC=CC=C1C1=CC=CC=C1OCC1CO1 GGIBUEPJJRWWNM-UHFFFAOYSA-N 0.000 description 2
- RLQZIECDMISZHS-UHFFFAOYSA-N 2-phenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1 RLQZIECDMISZHS-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- NHOGGUYTANYCGQ-UHFFFAOYSA-N C=COc1ccccc1 Chemical compound C=COc1ccccc1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(C)(C)Nc(c(*)c1**c2c3*)c(*)c(C4*C4)c1-c2c(*)c(**)c3I Chemical compound CCC(C)(C)Nc(c(*)c1**c2c3*)c(*)c(C4*C4)c1-c2c(*)c(**)c3I 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000010919 Copernicia prunifera Nutrition 0.000 description 2
- 244000180278 Copernicia prunifera Species 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000002249 anxiolytic agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- CRGRWBQSZSQVIE-UHFFFAOYSA-N diazomethylbenzene Chemical compound [N-]=[N+]=CC1=CC=CC=C1 CRGRWBQSZSQVIE-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000010330 laser marking Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-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
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- QJIMTLTYXBDJFC-UHFFFAOYSA-N (4-methylphenyl)-diphenylphosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJIMTLTYXBDJFC-UHFFFAOYSA-N 0.000 description 1
- FQJZPYXGPYJJIH-UHFFFAOYSA-N 1-bromonaphthalen-2-ol Chemical compound C1=CC=CC2=C(Br)C(O)=CC=C21 FQJZPYXGPYJJIH-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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- XIQOOGFLYJKEQV-UHFFFAOYSA-N 3-bromo-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=C(Br)C(C(C)(C)C)=C1O XIQOOGFLYJKEQV-UHFFFAOYSA-N 0.000 description 1
- MNOJRWOWILAHAV-UHFFFAOYSA-N 3-bromophenol Chemical compound OC1=CC=CC(Br)=C1 MNOJRWOWILAHAV-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 1
- ZLVFYUORUHNMBO-UHFFFAOYSA-N 4-bromo-2,6-dimethylphenol Chemical compound CC1=CC(Br)=CC(C)=C1O ZLVFYUORUHNMBO-UHFFFAOYSA-N 0.000 description 1
- IWJGMJHAIUBWKT-UHFFFAOYSA-N 4-bromo-2-methylphenol Chemical compound CC1=CC(Br)=CC=C1O IWJGMJHAIUBWKT-UHFFFAOYSA-N 0.000 description 1
- WMUWDPLTTLJNPE-UHFFFAOYSA-N 4-bromo-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Br WMUWDPLTTLJNPE-UHFFFAOYSA-N 0.000 description 1
- GPOQODYGMUTOQL-UHFFFAOYSA-N 4-bromo-3-methylphenol Chemical compound CC1=CC(O)=CC=C1Br GPOQODYGMUTOQL-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- LVSPDZAGCBEQAV-UHFFFAOYSA-N 4-chloronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=CC=C(Cl)C2=C1 LVSPDZAGCBEQAV-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N C=[O]c1ccccc1 Chemical compound C=[O]c1ccccc1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- UIPMHTFTTCDTSB-SNAWJCMRSA-N CC(/C=C/C)(NC)I Chemical compound CC(/C=C/C)(NC)I UIPMHTFTTCDTSB-SNAWJCMRSA-N 0.000 description 1
- ZMVHRWPZFKGQRN-UHFFFAOYSA-N CCC(C)(CC)NC Chemical compound CCC(C)(CC)NC ZMVHRWPZFKGQRN-UHFFFAOYSA-N 0.000 description 1
- BVFPUANFWJXGGJ-UHFFFAOYSA-N C[O](c1ccccc1)=C Chemical compound C[O](c1ccccc1)=C BVFPUANFWJXGGJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 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 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- 125000006840 diphenylmethane group Chemical group 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004206 montan acid ester Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005496 phosphonium group Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 description 1
- PSEQWFPWQRZBOO-UHFFFAOYSA-M tetrahexylazanium;benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC PSEQWFPWQRZBOO-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present disclosure relates to an epoxy resin composition for transfer molding and a method for producing the same, an epoxy resin composition for compression molding, and an electronic component device.
- epoxy resin compositions have been widely used in the field of encapsulating electronic components such as transistors and ICs (Integrated Circuits).
- the reason for this is that the epoxy resin has a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesiveness to insert products, and the like.
- a transfer molding method, an injection molding method, a compression molding method and the like are known, and among them, the transfer molding method is the most commonly used. ..
- the density of mounting has increased, and surface mount type packages have been adopted for electronic component devices from the conventional pin insertion type.
- the conventional pin insertion type package does not directly expose the package to high temperature because the pins are inserted into the wiring board and then soldered from the back surface of the wiring board.
- the surface mount type package since the entire semiconductor device is processed by a solder bath, a reflow device, or the like, it is directly exposed to the soldering temperature.
- transfer molding is the most common method for sealing electronic components using an epoxy resin composition.
- transfer molding since the molten epoxy resin composition is made to flow in the mold by pressurization, wire flow may occur due to the flow.
- Compression molding compression molding
- compression molding an epoxy resin composition is placed in a cavity of a mold, melted, and the mold is closed and pressurized to seal the element. According to the compression molding, the flow of the epoxy resin composition is less likely to occur as compared with the transfer molding, so that the occurrence of wire flow can be suppressed.
- Patent Document 3 describes an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, a fatty acid having a melting point of 70 ° C. or less, and a boiling point of 200.
- a particulate epoxy resin composition containing a silane coupling agent at ° C. or higher and having a particle size distribution of 85% by mass or more in the range of 100 ⁇ m to 3 mm has been proposed. It is described that by using such an epoxy resin composition, it can be sufficiently melted in compression molding and the filling property can be improved.
- Japanese Unexamined Patent Publication No. 06-224328 Japanese Unexamined Patent Publication No. 2007-1593969 Japanese Unexamined Patent Publication No. 2011-153173
- the epoxy resin composition for transfer molding may contain an inorganic filler in a high proportion in order to achieve various properties such as low hygroscopicity and high thermal conductivity of the cured product.
- the inorganic filler when the inorganic filler is contained in a high proportion, the viscosity of the composition may increase and the kneading load may increase, or the fluidity may decrease, causing wire flow, unfilling, and the like.
- the epoxy resin composition in order to suppress the generation of burrs and improve the filling property in a narrow portion, may contain an inorganic filler having a small particle size (ultrafine silica or the like). In this case, the increase in viscosity and the decrease in fluidity are more remarkable.
- the epoxy resin composition for sealing is desired to have good continuous moldability from the viewpoint of mass production.
- an epoxy resin composition having good continuous moldability while suppressing an increase in viscosity has not been obtained so far.
- an epoxy resin composition for transfer molding having suppressed increase in viscosity and excellent continuous moldability, a method for producing the same, and curing of the epoxy resin composition. It is an object of the present invention to provide an electronic component device equipped with an object.
- the proportion and particle size distribution of the inorganic filler may be adjusted in order to achieve various properties such as low hygroscopicity and high thermal conductivity of the cured product. Further, from the viewpoint of obtaining desired physical characteristics such as maintaining low viscosity while maintaining high filling by adjusting the ratio and particle size distribution of the inorganic filler, it is desired that the epoxy resin composition has a high degree of freedom in design. .. Therefore, it is desirable to obtain an epoxy resin composition that is easily melted and suitable for device encapsulation by compression molding by a method other than the method described in Patent Document 3. In view of the above circumstances, it is an object of the fourth embodiment of the present disclosure to provide an epoxy resin composition which is easily melted and an electronic component device including a cured product of the epoxy resin composition.
- the means for solving the above problems include the following aspects.
- An epoxy resin composition for transfer molding which comprises mixing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a curing agent containing a compound represented by the following general formula (B). How to make things.
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- ⁇ 3> The production method according to ⁇ 2>, wherein the content of the biphenyl type epoxy resin in the transfer molding epoxy resin composition is 30% by mass to 100% by mass with respect to the total mass of the epoxy resin. ..
- ⁇ 4> The production method according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the inorganic filler is 60% by volume or more with respect to the total volume of the transfer molding epoxy resin composition.
- ⁇ 5> The content of the compound represented by the general formula (B) in the epoxy resin composition for transfer molding with respect to the total mass of the curing agent is 30% by mass to 100% by mass, ⁇ 1> to ⁇
- Epoxy resin and Inorganic filler and A curing agent containing a compound represented by the following general formula (B), and Contains
- the inorganic filler is a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, and the content of the inorganic filler having an average particle diameter of 50 nm or less is the epoxy resin 100. 5 parts by mass or more with respect to the mass part, Epoxy resin composition for transfer molding.
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- the inorganic filler contains an inorganic filler having a particle diameter of 50 nm or less, and the content of the inorganic filler having a particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.
- Epoxy resin composition for transfer molding is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- ⁇ 9> The epoxy resin composition for transfer molding according to ⁇ 8>, wherein the content of the biphenyl type epoxy resin is 30% by mass to 100% by mass with respect to the total mass of the epoxy resin.
- the means for solving the above problems include the following aspects. ⁇ 13> Epoxy resin and Inorganic filler and A curing agent containing a compound represented by the following general formula (B), and Epoxy resin composition for compression molding containing.
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- ⁇ 15> The epoxy resin for compression molding according to ⁇ 13> or ⁇ 14>, wherein the content of the compound represented by the general formula (B) with respect to the total mass of the curing agent is 30% by mass to 100% by mass.
- the content of the mold release agent is more than 0% by mass and 2.0% by mass or less with respect to the total mass of the compression molding epoxy resin composition.
- the epoxy resin composition for transfer molding which suppresses an increase in viscosity and is excellent in continuous moldability, a method for producing the same, and a cured product of the epoxy resin composition are provided.
- Electronic component equipment is provided.
- an electronic component device including an epoxy resin composition that is easily melted and a cured product of the epoxy resin composition is provided.
- the term "process” includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
- the numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
- each component may contain a plurality of applicable substances.
- the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
- a plurality of types of particles corresponding to each component may be contained.
- the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
- the method for producing an epoxy resin composition for transfer molding according to the first embodiment is a curing method containing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a compound represented by the following general formula (B). Includes mixing with the agent.
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- the epoxy resin composition produced by the method for producing an epoxy resin composition for transfer molding according to the first embodiment is produced by mixing an inorganic filler having an average particle diameter of 50 nm or less.
- an inorganic filler having an average particle diameter of 50 nm or less.
- the viscosity of the composition tends to increase remarkably, but when a compound represented by the general formula (B) is used in combination, the viscosity is satisfactorily increased. It was found that an epoxy resin composition capable of suppressing the rise and having excellent continuous moldability can be obtained.
- the epoxy resin composition produced by the method for producing the epoxy resin composition for transfer molding of the present embodiment is also referred to as "the epoxy resin composition according to the first embodiment".
- an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a curing agent containing a compound represented by the general formula (B) are mixed.
- the other steps are not particularly limited.
- a method for preparing the epoxy resin composition according to the first embodiment for example, after sufficiently mixing the components in a predetermined blending amount with a mixer or the like, melt-kneading with a mixing roll, an extruder or the like, cooling and pulverization are performed. The method can be mentioned.
- a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. can be mentioned.
- Epoxy resin composition according to the first embodiment is produced by the method for producing an epoxy resin composition for transfer molding according to the first embodiment, and is represented by an epoxy resin, an inorganic filler, and a general formula (B). It contains a curing agent containing the compound to be used.
- the epoxy resin composition according to the first embodiment may further contain a curing accelerator, other additives, and the like.
- the epoxy resin composition according to the second embodiment contains an epoxy resin, an inorganic filler, and a curing agent containing the compound represented by the above-mentioned general formula (B), and the inorganic filler is averaged. It is a mixture of an inorganic filler having a particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, and the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 with respect to 100 parts by mass of the epoxy resin. It is more than a part by mass.
- the epoxy resin composition according to the second embodiment contains an inorganic filler having an average particle diameter of 50 nm or less in an amount of 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin, but a remarkable increase in viscosity is suppressed. It was also found that the continuous moldability was excellent.
- the epoxy resin composition according to the third embodiment contains an epoxy resin, an inorganic filler, and a curing agent containing the compound represented by the above-mentioned general formula (B), and the inorganic filler contains particles.
- the content of the inorganic filler having a particle diameter of 50 nm or less, which contains an inorganic filler having a diameter of 50 nm or less, is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.
- the epoxy resin composition according to the third embodiment contains 5 parts by mass or more of an inorganic filler having a particle diameter of 50 nm or less with respect to 100 parts by mass of the epoxy resin, but a remarkable increase in viscosity is suppressed and the viscosity is suppressed. It was found to be excellent in continuous moldability.
- epoxy resin composition the epoxy resin, the inorganic filler, the curing agent, and other optional components contained in the epoxy resin composition according to the first to third embodiments will be described in detail.
- the epoxy resin compositions according to the first to third embodiments are used. Inclusively, it may be simply referred to as "epoxy resin composition”.
- the epoxy resin composition according to the first to third embodiments contains an epoxy resin.
- the type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
- at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene.
- a novolak type epoxy resin (phenol novolak type epoxy resin) which is an epoxidized novolak resin obtained by condensing or cocondensing a sex compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. , Orthocresol novolac type epoxy resin, etc.); Epoxy of triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst.
- Triphenylmethane type epoxy resin a copolymerized epoxy resin obtained by co-condensing the above phenol compound, naphthol compound, and aldehyde compound under an acidic catalyst and epoxidizing a novolak resin; bisphenol.
- Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben type epoxy resin which is a diglycidyl ether of a stillben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin that is a diglycidyl ether such as S; epoxy resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; polyvalent carboxylic acid such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid.
- Glysidyl ester type epoxy resin which is a glycidyl ester of a compound
- Glysidylamine type epoxy resin which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group
- Dicyclopentadiene type epoxy resin which is an epoxidized co-condensation resin of Rate, 2- (3,4-epoxy) cyclohexyl-5,5-spi B (3,4-Epoxy)
- Alicyclic epoxy resin such as cyclohexane-m-dioxane
- paraxylylene-modified epoxy resin which is a glycidyl ether of paraxylylene-modified phenol resin
- metaxylylene-modified epoxy resin which is glycidyl ether of metaxylylene-modified phenol resin
- epoxy resins from the viewpoint of the balance between reflow resistance and fluidity, biphenyl type epoxy resin, stillben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy
- An epoxy resin selected from the group consisting of a resin, a triphenylmethane type epoxy resin, a copolymerized epoxy resin, and an aralkyl type epoxy resin (these are referred to as "specific epoxy resins”) is preferable.
- the specific epoxy resin may be used alone or in combination of two or more.
- the total content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, from the viewpoint of exhibiting the performance of the specific epoxy resin. preferable.
- epoxy resins a biphenyl type epoxy resin, a stillben type epoxy resin, a diphenylmethane type epoxy resin, and a sulfur atom-containing epoxy resin are more preferable from the viewpoint of fluidity, and a dicyclopentadiene type from the viewpoint of heat resistance.
- Epoxy resins, triphenylmethane-type epoxy resins, and aralkyl-type epoxy resins are preferred.
- the epoxy resin preferably contains at least one selected from the group consisting of a diphenylmethane type epoxy resin, a biphenyl type epoxy resin, and a triphenylmethane type epoxy resin. It is more preferable to use two or more of them in combination.
- the content of the diphenylmethane type epoxy resin may be 40% by mass or more, 50% by mass or more, or 60% by mass, based on the total mass of the epoxy resin. It may be mass% or more.
- the content of the diphenylmethane type epoxy resin may be 90% by mass or less, 80% by mass or less, or 70% by mass or less with respect to the total mass of the epoxy resin.
- the content of the biphenyl type epoxy resin may be 10% by mass or more, 20% by mass or more, or 30% by mass, based on the total mass of the epoxy resin. It may be mass% or more.
- the content of the biphenyl type epoxy resin may be 70% by mass or less, 60% by mass or less, or 50% by mass or less with respect to the total mass of the epoxy resin.
- the content of the biphenyl type epoxy resin is preferably 30% by mass to 100% by mass, more preferably 30% by mass to 90% by mass, and 30% by mass, based on the total mass of the epoxy resin. It is more preferably to 80% by mass.
- the content of the triphenylmethane type epoxy resin may be 30% by mass or more, or 40% by mass or more, based on the total mass of the epoxy resin. It may be 50% by mass or more.
- the content of the triphenylmethane type epoxy resin may be 70% by mass or less, 60% by mass or less, or 50% by mass or less with respect to the total mass of the epoxy resin. good.
- the epoxy resin preferably contains a combination of a diphenylmethane type epoxy resin and a biphenyl type epoxy resin.
- the ratio of the diphenylmethane type epoxy resin to the biphenyl type epoxy resin is preferably 40:60 to 90:10 on a mass basis, and 50: It is more preferably 50 to 80:20, and even more preferably 60:40 to 70:30.
- the epoxy resin preferably contains a combination of a biphenyl type epoxy resin and a triphenylmethane type epoxy resin.
- the epoxy resin contains a combination of a biphenyl type epoxy resin and a triphenylmethane type epoxy resin
- the ratio of the biphenyl type epoxy resin to the triphenylmethane type epoxy resin may be 20:80 to 80:20 on a mass basis. It is preferably 30:70 to 70:30, more preferably 40:60 to 60:40.
- the biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton.
- an epoxy resin represented by the following general formula (II) is preferable.
- R 8 is a hydrogen atom YX-4000H (Mitsubishi Chemical Co., Ltd., trade name)
- all R 8 are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl
- YL-6121H Mitsubishi Chemical Co., Ltd., trade name
- YL-6121H Mitsubishi Chemical Co., Ltd., trade name
- R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, all of which may be the same or different.
- n is an average value and indicates a number from 0 to 10.
- the stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton.
- an epoxy resin represented by the following general formula (III) is preferable.
- the epoxy resins represented by the following general formula (III) '3,3 when the position', 5,5 'position methyl group 4 and 4 positions of oxygen atoms of R 9 is substituted
- the other cases where R 9 is a hydrogen atom and all of R 10 are hydrogen atoms, and three of the 3, 3', 5, and 5'positions of R 9 are methyl groups.
- ESLV-210 (Sumitomo Chemical Co., Ltd., trade name), which is a mixture with the case where one is a t-butyl group, the other R 9 is a hydrogen atom, and all of R 10 are hydrogen atoms, etc. It is available as a commercial product.
- R 9 and R 10 represent hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- n is an average value and indicates a number from 0 to 10.
- the diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton.
- an epoxy resin represented by the following general formula (IV) is preferable.
- all of R 11 are hydrogen atoms, and the positions of R 12 in which oxygen atoms are substituted are set to the 4 and 4'positions of 3,3.
- YSLV-80XY Nittetsu Chemical & Materials Co., Ltd., trade name
- the', 5, and 5'positions are methyl groups and the other R 12 is a hydrogen atom is available as a commercially available product.
- R 11 and R 12 represent hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- n is an average value and indicates a number from 0 to 10.
- the sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom.
- an epoxy resin represented by the following general formula (V) can be mentioned.
- a position is t- butyl group '3,3 when the position' 4 and 4 a position where the oxygen atoms are replaced among R 13, 6,6 'position is a methyl group, is available other than the R 13 is a hydrogen atom YSLV-120TE (Nippon steel Chemical & Materials Co., Ltd., trade name) and the like as a commercially available product.
- R 13 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- n is an average value and indicates a number from 0 to 10.
- the novolak type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak type phenol resin.
- an epoxy resin obtained by epoxidizing a novolak-type phenol resin such as a phenol novolac resin, a cresol novolak resin, or a naphthol novolak resin by a method such as glycidyl etherification is preferable, and is represented by the following general formula (VI).
- Epoxy resin is more preferred.
- R 14 are hydrogen atoms
- R 15 is a methyl group
- i 1, ESCN-190 and ESCN-195 (Sumitomo Chemical Co., Ltd.) , Trade name)
- all of R 14 are hydrogen atoms
- i 0 N-770, N-775 (DIC Co., Ltd., trade name)
- all of R 14 are hydrogen atoms
- i 0 YDAN-1000-10C (Nittetsu Chemical & Materials Co., Ltd., product)
- i 0 YDAN-1000-10C (Nittetsu Chemical & Materials Co., Ltd., product)
- i 0 YDAN-1000-10C (Nittetsu Chemical & Materials Co., Ltd., product)
- R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- R 15 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- i independently represents an integer of 0 to 3.
- n is an average value and indicates a number from 0 to 10.
- the dicyclopentadiene type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxyizing a compound having a dicyclopentadiene skeleton as a raw material.
- an epoxy resin represented by the following general formula (VII) is preferable.
- R 16 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- i independently represents an integer of 0 to 3.
- n is an average value and indicates a number from 0 to 10.
- the triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton.
- an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin such as a novolak-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable, and is represented by the following general formula (VIII).
- the epoxy resin to be used is more preferable.
- epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and EPPN-502H (Nippon Kayaku Co., Ltd., trade name) in which i is 0 and k is 0. Etc. are available as commercial products.
- R 17 and R 18 represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- i indicates an integer of 0 to 3 independently
- k indicates an integer of 0 to 4 independently.
- n is an average value and indicates a number from 0 to 10.
- the copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton. Not done.
- an epoxy resin obtained by glycidyl etherification of a novolak-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and an epoxy resin represented by the following general formula (IX) is more preferable.
- R 19 to R 21 represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- i is an integer of 0 to 3 independently
- j is an integer of 0 to 2 independently
- k is an integer of 0 to 4 independently.
- l and m are average values, respectively, and are numbers from 1 to 10, and (l + m) indicates a number from 2 to 10.
- the end of the epoxy resin represented by the formula (IX) is the following formula (IX-1) or (IX-2).
- R 19 ⁇ R 21, i, j and k are the same as R 19 ⁇ R 21, i, of j and k defined in Formula (IX) .. n is 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).
- the epoxy resin represented by the above general formula (IX) includes a random copolymer randomly containing l structural units and m structural units, an alternating copolymer containing alternately, and a copolymer containing regularly.
- Block copolymers contained in a block shape and the like Any one of these may be used alone, or two or more thereof may be used in combination.
- the copolymerized epoxy resin is a methoxynaphthalene / cresol formaldehyde cocondensation type epoxy resin containing two types of structural units in the following general formula (IX-3) in a random, alternating or block order.
- Epicron HP-5000 (DIC Corporation, trade name) represented by (IX-3) is also preferable.
- n and m are average values, which are numbers from 1 to 10
- (n + m) are numbers from 2 to 10
- n and m are preferably average values, respectively. Yes, it is a number from 1 to 9, and (n + m) indicates a number from 2 to 10.
- the aralkyl type epoxy resin is composed of at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or derivatives thereof.
- the epoxy resin is not particularly limited as long as it is an epoxy resin made from a synthetic phenol resin.
- An epoxy resin obtained by converting the resin into glycidyl ether is preferable, and an epoxy resin represented by the following general formulas (X) and (XI) is more preferable.
- epoxy resins represented by the following general formula (X) i is 0 and R 38 is a hydrogen atom NC-3000S (Nippon Kayaku Co., Ltd., trade name), i is 0, and R 38.
- ESN-175 Niittetsu Chemical & Materials Co., Ltd., trade name
- R 38 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- R 37 and R 39 to R 41 represent monovalent organic groups having 1 to 18 carbon atoms, and all of them may be the same or different.
- i is an integer of 0 to 3 independently
- j is an integer of 0 to 2 independently
- k is an integer of 0 to 4 independently
- l is an integer of 0 to 6 independently.
- n is an average value, which is independently a number from 0 to 10.
- R 8 to R 21 and R 37 to R 41 in the general formulas (II) to (XI) “all may be the same or different” means, for example, 8 to 8 in the formula (II). all of the 88 pieces of R 8 are means that may be the same or different. It means that all of the other R 9 to R 21 and R 37 to R 41 may be the same or different for each number included in the equation. Further, R 8 to R 21 and R 37 to R 41 may be the same or different from each other. For example, all of R 9 and R 10 may be the same or different. Further, the monovalent organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.
- N in the above general formulas (II) to (XI) is an average value, and it is preferable that each is independently in the range of 0 to 10.
- n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the epoxy resin composition during melt molding decreases, filling defects, deformation of the bonding wire (gold wire connecting the element and the lead), etc. Tends to be suppressed. It is more preferable that n is set in the range of 0 to 4.
- the epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and is 150 g / eq to 500 g / eq. Is more preferable.
- the epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.
- the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the epoxy resin composition, the temperature is more preferably 50 ° C. to 130 ° C.
- the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC)
- the softening point of the epoxy resin is a value measured by a method (ring ball method) according to JIS K 7234: 1986.
- the content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. More preferably.
- the epoxy resin composition according to the first to third embodiments contains an inorganic filler.
- the material of the inorganic filler is not particularly limited. Specifically, silica (molten silica, crystalline silica, etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite. , Spinel, Murite, Titania, Tark, Clay, Mica and other inorganic materials.
- An inorganic filler having a flame-retardant effect may be used.
- Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Of these, silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.
- the inorganic filler may be used alone or in combination of two or more. Examples of the state of the inorganic filler include unpowdered beads, spherical beads of powder, fibers, and the like.
- the shape of the inorganic filler is not particularly limited. From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.
- the epoxy resin composition according to the first embodiment is produced by mixing an inorganic filler having an average particle diameter of 50 nm or less.
- an epoxy resin composition is produced by mixing an inorganic filler having an average particle diameter of 50 nm or less, the filling property of the epoxy resin composition into a narrow portion is enhanced, and the generation of burrs during molding tends to be suppressed.
- an inorganic filler having an average particle size of more than 50 nm is mixed in addition to the inorganic filler having an average particle size of 50 nm or less.
- the inorganic filler having an average particle diameter of 50 nm or less and the inorganic filler having an average particle diameter of more than 50 nm may be one kind or two or more kinds, respectively.
- the inorganic filler is a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, and having an average particle diameter of 50 nm or less.
- the content of the inorganic filler is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.
- the inorganic filler contains an inorganic filler having a particle diameter of 50 nm or less, and the content of the inorganic filler having a particle diameter of 50 nm or less is 5 with respect to 100 parts by mass of the epoxy resin. It is more than a part by mass.
- the average particle size of the inorganic filler having an average particle size of 50 nm or less is preferably 5 nm to 50 nm, more preferably 10 nm to 50 nm, and even more preferably 15 nm to 50 nm.
- the maximum particle size of the inorganic filler having an average particle size of 50 nm or less is not particularly limited, and may be 2 ⁇ m or less, 1 ⁇ m or less, 500 nm or less, or 50 nm or less. good.
- the maximum particle size of the inorganic filler means the particle size (D90%) when the accumulation from the small diameter side is 90% in the volume-based particle size distribution obtained by the laser diffraction / scattering method particle size distribution measuring device. ..
- the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin. It is preferably 10 parts by mass or more, more preferably 11 parts by mass or more, particularly preferably 13 parts by mass or more, and extremely preferably 15 parts by mass or more. Further, the content of the inorganic filler having an average particle diameter of 50 nm or less may be 30 parts by mass or less and 25% by mass or less with respect to 100 parts by mass of the epoxy resin from the viewpoint of suppressing an increase in viscosity. It may be 20 parts by mass or less.
- the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 with respect to 100 parts by mass of the epoxy resin from the viewpoint of preferably obtaining effects such as improvement of filling property in a narrow portion and suppression of burrs during molding. It is preferably from 10 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 30 parts by mass, further preferably 11 parts by mass to 25 parts by mass, and 13 parts by mass to 20 parts by mass. Is particularly preferable.
- the average particle size of the inorganic filler having an average particle size larger than 50 nm is preferably more than 50 nm and 80 ⁇ m or less, more preferably 0.1 ⁇ m to 70 ⁇ m, and 0.2 ⁇ m to 50 ⁇ m. Is even more preferable.
- the inorganic filler includes an inorganic filler having an average particle diameter of more than 50 nm and 2.0 ⁇ m or less, and an inorganic filler having an average particle diameter of more than 2.0 ⁇ m and 80 ⁇ m or less, in addition to the inorganic filler having an average particle diameter of 50 nm or less.
- the filler and the filler are mixed.
- the inorganic filler includes an inorganic filler having an average particle diameter of 0.1 ⁇ m to 1 ⁇ m, an inorganic filler having an average particle diameter of 2 ⁇ m to 50 ⁇ m, and an inorganic filler having an average particle diameter of 50 nm or less. Are mixed.
- the inorganic filler includes an inorganic filler having an average particle diameter of 0.2 ⁇ m to 1 ⁇ m, an inorganic filler having an average particle diameter of 5 ⁇ m to 30 ⁇ m, and an inorganic filler having an average particle diameter of 50 nm or less. Are mixed.
- the content of the inorganic filler having a particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin. It is preferably 10 parts by mass or more, more preferably 11 parts by mass or more, particularly preferably 13 parts by mass or more, and extremely preferably 15 parts by mass or more.
- the content of the inorganic filler having a particle diameter of 50 nm or less may be 30 parts by mass or less, and 25% by mass or less, based on 100 parts by mass of the epoxy resin, from the viewpoint of suppressing an increase in viscosity. It may be 20 parts by mass or less.
- the content of the inorganic filler having a particle diameter of 50 nm or less is 5% by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of preferably obtaining effects such as improvement of filling property in a narrow portion and suppression of burrs during molding. It may be 10 parts to 30 parts by mass, 10 parts by mass to 30 parts by mass, 11 parts by mass to 25 parts by mass, 13 parts by mass to 20 parts by mass, and so on. It may be 15 parts by mass to 20 parts by mass.
- the content of the inorganic filler having a particle size of 50 nm or less is the particle with respect to the total amount of the inorganic filler in the volume-based particle size distribution measured by a dynamic light scattering particle size analyzer (for example, Nanotrack manufactured by Microtrac Bell Co., Ltd.). It can be obtained by converting the proportion of particles having a diameter of 50 nm or less into a mass reference.
- a dynamic light scattering particle size analyzer for example, Nanotrack manufactured by Microtrac Bell Co., Ltd.
- the inorganic filler when a cured product having high thermal conductivity is obtained, preferably contains alumina, and more preferably contains alumina as a main component (that is, 50% by volume or more of the inorganic filler). Specifically, for example, it is preferable that silica having an average particle size of 50 nm or less and alumina having an average particle size of larger than 50 nm are mixed.
- the inorganic filler preferably contains silica from the viewpoints of reflow resistance, suppression of viscosity increase, improvement of fluidity, etc., and contains silica as a main component (that is, 50% by volume or more of the inorganic filler). ) It is more preferable to include it. Specifically, for example, it is preferable that silica having an average particle size of 50 nm or less and silica having an average particle size larger than 50 nm are mixed.
- the average particle size of the entire inorganic filler contained in the epoxy resin composition is not particularly limited.
- the average particle size is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m, and even more preferably 1 ⁇ m to 50 ⁇ m.
- the average particle size is 0.2 ⁇ m or more, the increase in viscosity of the epoxy resin composition tends to be suppressed.
- the average particle size is 80 ⁇ m or less, the filling property into a narrow gap tends to be improved. From the viewpoint of the fluidity of the epoxy resin composition, it is preferable that the particle size of the inorganic filler is widely distributed.
- the maximum particle size (also called cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling properties into narrow gaps, the maximum particle size of the inorganic filler is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and further preferably 55 ⁇ m or less.
- the content of the inorganic filler is not particularly limited.
- the content of the inorganic filler is preferably 50% by volume or more, more preferably 60% by volume or more, further preferably 70% by volume or more, and more preferably 75% by volume, based on the total volume of the epoxy resin composition. It is particularly preferably 50% by volume or more, and extremely preferably 80% by volume or more.
- the content of the inorganic filler is preferably 95% by volume or less, more preferably 90% by volume or less, and further preferably 87% by volume or less with respect to the total volume of the epoxy resin composition. ..
- the content of the inorganic filler is preferably 50% by volume to 95% by volume, more preferably 60% by volume to 95% by volume, and 70 by volume, based on the total volume of the epoxy resin composition. It is more preferably from% to 95% by volume, particularly preferably from 75% to 90% by volume, and extremely preferably from 80% to 87% by volume.
- the average particle size of the inorganic filler in the present disclosure is the volume average particle size.
- the average particle size of the inorganic filler in the present disclosure can be measured as a volume average particle size (D50) by a laser diffraction / scattering method particle size distribution measuring device.
- the average particle size of the epoxy resin composition or the cured product thereof can be specifically measured by the following method. A crucible containing the epoxy resin composition or a cured product thereof is placed in a muffle furnace and heated to 800 ° C. Leave the sample for about 4 hours until it is completely incinerated. The sample is naturally cooled until it returns to room temperature, and the ash (inorganic filler) is extracted.
- the volume average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured by the laser diffraction / scattering method particle size distribution measuring device.
- "using two or more kinds of inorganic fillers together” means, for example, when two or more kinds of inorganic fillers having the same component but different average particle diameters are used, the inorganic fillers having the same average particle size but different components have different components. There are cases where two or more kinds of inorganic fillers are used, and cases where two or more kinds of inorganic fillers having different average particle diameters and types are used.
- the epoxy resin composition according to the first to third embodiments contains a curing agent containing a compound represented by the following general formula (B) (hereinafter, also referred to as a specific curing agent).
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- R 1 to R 5 are independently monovalent organic groups having 1 to 6 carbon atoms, and preferably monovalent organic groups having 1 to 3 carbon atoms.
- the monovalent organic group having 1 to 6 carbon atoms represented by R 1 to R 5 includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group and a t-butyl. Group etc. can be mentioned.
- X1 to X3 are each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
- X4 and X5 are each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
- N1 and n2 are the average values of the number of repetitions of the structural unit in parentheses, respectively.
- the hydroxyl group equivalent of the specific curing agent is preferably 130 g / eq to 200 g / eq, and more preferably 150 g / eq to 180 g / eq.
- the hydroxyl group equivalent of a particular curing agent is measured by the method described below.
- the specific curing agent is a solid, its softening point or melting point is not particularly limited, and from the viewpoint of moldability and reflow resistance, it is preferably 40 ° C. to 180 ° C. during the production of the epoxy resin composition. From the viewpoint of handleability in the above, the temperature is more preferably 50 ° C to 130 ° C. From the viewpoint of improving the fluidity and reducing the high temperature elastic modulus of the cured product of the epoxy resin composition and improving the reflow resistance, the softening point or melting point of the specific curing agent is 50 ° C to 100 ° C. , More preferably 50 ° C to 75 ° C, and even more preferably 50 ° C to 70 ° C.
- any one type may be used alone, or two or more types may be used in combination.
- other curing agents may be used in combination in addition to the specific curing agent.
- the content of the specific curing agent with respect to the total mass of the curing agent is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and 70% by mass to 100% by mass. It is more preferable to have.
- curing agents examples include those having a phenolic hydroxyl group in the molecule (phenol curing agent) other than the compound represented by the general formula (B).
- Examples of the phenol curing agent other than the compound represented by the general formula (B) include a phenol resin having two or more phenolic hydroxyl groups in one molecule and a polyhydric phenol compound.
- polyvalent phenol compounds such as resorsin, catecor, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, m-cresol, p-cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, At least one phenolic compound selected from the group consisting of phenol compounds such as phenylphenol and aminophenol and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene, and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like.
- Novolac-type phenolic resin obtained by condensing or co-condensing the aldehyde compound of the above;
- Aralyl-type phenolic resins such as naphthol aralkyl resins (excluding compounds represented by the general formula (B)); paraxylylene and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; Dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin synthesized from cyclopentadiene by copolymerization; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl-type phenol resin; Examples thereof include a triphenylmethane-type phenol resin obtained by condensing or co-condensing an aromatic aldehyde compound such as benzaldehyde or salicyl alde
- the aralkyl type phenol resin (excluding the compound represented by the general formula (B)) and the dicyclopentadiene type phenol resin from the viewpoint of reflow resistance.
- At least one selected from the group consisting of a triphenylmethane type phenol resin, a copolymerized phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a novolak type phenol resin (these are referred to as "specific phenol curing agents"). ) Is preferable.
- the specific phenol curing agent may be used alone or in combination of two or more.
- Examples of the aralkyl-type phenol resin excluding the compound represented by the general formula (B) include phenol aralkyl resins, naphthol aralkyl resins and the like synthesized from phenolic compounds, dimethoxyparaxylene, bis (methoxymethyl) biphenyl and the like. Can be mentioned.
- the aralkyl type phenol resin may be further copolymerized with another phenol resin.
- Examples of the copolymerized aralkyl type phenol resin include a copolymerized phenol resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, a copolymerized phenol resin of a salicyl aldehyde type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. Examples thereof include a copolymerized phenol resin with an aralkyl type phenol resin.
- the aralkyl-type phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of a phenol compound and a naphthol compound, and dimethoxyparaxylene, bis (methoxymethyl) biphenyl or a derivative thereof. ..
- phenolic resins represented by the following general formulas (XII) to (XIV) are preferable.
- R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- R 22 , R 24 , R 25 and R 28 represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- R 26 and R 27 represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
- i is an integer of 0 to 3 independently
- j is an integer of 0 to 2 independently
- k is an integer of 0 to 4 independently
- p is an integer of 0 to 4 independently.
- n is an average value, which is independently a number from 0 to 10.
- phenolic resins represented by the above general formula (XIII), XL-225, XLC (Mitsui Kagaku Co., Ltd., trade name), MEH-7800 (Meiwa Kasei Co., Ltd.,) in which i is 0 and k is 0. Product name) etc. are available as commercial products.
- phenolic resins represented by the above general formula (XIV) SN-170 (Nittetsu Chemical & Materials Co., Ltd., trade name) and j in which j is 0, k is 0, and p is 0 are SN-395 (Nittetsu Chemical & Materials Co., Ltd., trade name) and the like, which are 0, k is 1, R 27 is a hydroxyl group, and p is 0, are available as commercial products.
- the dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material.
- a phenol resin represented by the following general formula (XV) is preferable.
- the phenolic resins represented by the following general formula (XV) DPP (Nippon Petrochemicals Co., Ltd., trade name) in which i is 0 is available as a commercially available product.
- R 29 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- i independently represents an integer of 0 to 3.
- n is an average value and indicates a number from 0 to 10.
- the triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a triphenylmethane skeleton as a raw material.
- a phenol resin represented by the following general formula (XVI) is preferable.
- phenolic resins represented by the following general formula (XVI), MEH-7500 (Meiwa Kasei Co., Ltd., trade name) in which i is 0 and k is 0 is available as a commercially available product.
- R 30 and R 31 represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- i is an integer of 0 to 3 independently
- k is an integer of 0 to 4 independently.
- n is an average value, which is a number from 0 to 10.
- the copolymer-type phenol resin of the benzaldehyde-type phenol resin and the aralkyl-type phenol resin is not particularly limited as long as it is a copolymer-type phenol resin of the phenol resin obtained from a compound having a benzaldehyde skeleton as a raw material and the aralkyl-type phenol resin.
- a phenol resin represented by the following general formula (XVII) is preferable.
- phenolic resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., trade name) in which i is 0, k is 0, and q is 0 is commercially available. It is available as a product.
- R 32 to R 34 represent monovalent organic groups having 1 to 18 carbon atoms, all of which may be the same or different.
- i is an integer of 0 to 3 independently
- k is an integer of 0 to 4 independently
- q is an integer of 0 to 5 independently.
- l and m are average values, respectively, and are independently numbers from 0 to 11. However, the total of l and m is a number from 1 to 11.
- the novolak-type phenol resin is particularly limited as long as it is a phenol resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds and an aldehyde compound under an acidic catalyst. Not done.
- a phenol resin represented by the following general formula (XVIII) is preferable.
- phenol resins represented by the following general formula (XVIII) i is 0, R 35 are all hydrogen atoms TAMANOL 758, 759 (Arakawa Chemical Industries, Ltd., trade name), H-4 (Meiwa Co., Ltd., product name) etc. are available as commercial products.
- R 35 represents a monovalent organic group hydrogen atom or a C 1-18, all respectively may be the same or different.
- R 36 represents a monovalent organic group having 1 to 18 carbon atoms, all of which may be the same or different.
- i independently represents an integer of 0 to 3.
- n is an average value and indicates a number from 0 to 10.
- each of them may be the same or different" described for R 22 to R 36 in the above general formulas (XII) to (XVIII) is, for example, even if all of R 22s in the formula (XII) are the same or mutually. It means that they can be different. It means that all of the other R 23 to R 36 may be the same or different from each other for each number included in the equation. Further, R 22 to R 36 may be the same or different from each other. For example, all of R 22 and R 23 may be the same or different, and all of R 30 and R 31 may be the same or different.
- N in the above general formulas (XII) to (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the epoxy resin composition during melt molding also becomes low, and poor filling, deformation of the bonding wire (gold wire connecting the element and the lead), etc. occur. It becomes difficult to do.
- the average n in one molecule is preferably set in the range of 0 to 4.
- the functional group equivalent of a curing agent other than the compound represented by the general formula (B) is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.
- the functional group equivalent of the curing agent (for a curing agent having a phenolic hydroxyl group in the molecule, the hydroxyl group equivalent) may be, for example, a value measured by a method according to JIS K 0070: 1992.
- the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the epoxy resin composition, the temperature is more preferably 50 ° C. to 130 ° C.
- the softening point or melting point of the curing agent shall be 50 ° C. to 100 ° C. from the viewpoint of improving the fluidity and reducing the high temperature elastic modulus of the cured product of the epoxy resin composition to improve the reflow resistance. , More preferably 50 ° C to 75 ° C, and even more preferably 50 ° C to 65 ° C.
- the melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.
- the equivalent ratio of the epoxy resin to the curing agent is not particularly limited. From the viewpoint of suppressing each unreacted component to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the range from 0.8 to 1.2.
- the epoxy resin composition according to the first to third embodiments may contain a curing accelerator.
- the type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin, desired properties of the epoxy resin composition, and the like.
- curing accelerator examples include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
- Cyclic amidin compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidin compound; phenol novolac salts of the cyclic amidin compound or derivatives thereof; Maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other qui
- Cyclic amidinium compounds such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt; pyridine, triethylamine, tri Tertiary amine compounds such as ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of the tertiary amine compound; tetra-n-butylammonium acetate, tetra-n-phosphate Ammonium salt compounds such as butylammonium, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; primary phosphine such as ethylphosphin
- 1,4-benzoquinone 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4 -Has intramolecular polarization by adding a quinone compound such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, or a compound having a ⁇ bond such as diazophenylmethane.
- a quinone compound such as benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, or a compound having a ⁇ bond such as diazophenylmethane.
- the curing accelerator preferably contains a phosphorus-based curing accelerator, and more preferably contains a phosphonium compound.
- the curing accelerator may be used alone or in combination of two or more.
- the content thereof is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (that is, the total of the resin and the curing agent). It is more preferably 1 part by mass to 15 parts by mass.
- the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time.
- the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.
- the epoxy resin compositions according to the first to third embodiments include coupling agents, ion exchangers, mold release agents, flame retardants, colorants, stress relaxation agents, etc., which are exemplified below.
- Various additives may be included.
- the epoxy resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
- a coupling agent may be included in order to enhance the adhesiveness between the resin component and the inorganic filler.
- the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. ..
- the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass to 2 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably 5.5 parts by mass.
- the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved.
- the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
- the epoxy resin composition may contain an ion exchanger.
- an ion exchanger when the epoxy resin composition is used as a molding material for sealing, it is preferable to include an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed.
- the ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.
- the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions.
- it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the resin component.
- the epoxy resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding.
- the release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene.
- the release agent may be used alone or in combination of two or more.
- the amount thereof is preferably 0.01 part by mass to 15 parts by mass, more preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component.
- the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained.
- it is 15 parts by mass or less, better adhesiveness tends to be obtained.
- the epoxy resin composition may contain a flame retardant.
- the flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like.
- the flame retardant may be used alone or in combination of two or more.
- the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect.
- it is preferably 1 part by mass to 300 parts by mass, and more preferably 2 parts by mass to 150 parts by mass with respect to 100 parts by mass of the resin component.
- the epoxy resin composition may further contain a colorant.
- a colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide.
- the content of the colorant can be appropriately selected according to the purpose and the like.
- the colorant one type may be used alone or two or more types may be used in combination.
- the epoxy resin composition may contain a stress relaxation agent such as silicone oil and silicone rubber particles.
- a stress relaxation agent such as silicone oil and silicone rubber particles.
- the stress relaxation agent include commonly used known stress relaxation agents (flexible agents).
- thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic.
- Rubber particles such as rubber, urethane rubber, silicone powder, core-shell such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer
- examples include rubber particles having a structure.
- the stress relaxation agent one type may be used alone or two or more types may be used in combination. Of these, a silicone-based stress relaxant is preferable.
- the silicone-based stress relaxant include those having an epoxy group, those having an amino group, and those obtained by modifying these with polyether.
- the method for preparing the epoxy resin composition is not particularly limited.
- a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.
- the epoxy resin composition according to the first embodiment contains an epoxy resin, an inorganic filler having an average particle size of 50 nm or less, and a curing agent containing a compound represented by the following general formula (B). Others, including mixing, can be adjusted according to the above preparation method.
- the epoxy resin compositions according to the first to third embodiments are excellent in continuous moldability because the increase in viscosity is suppressed. Even if the epoxy resin composition according to the first to third embodiments contains an inorganic filler in a high proportion, it is excellent in fluidity during transfer molding, so that the occurrence of wire flow, unfilling, etc. can be suppressed. It is advantageous in that it can be done. Further, in general, when an inorganic filler such as alumina is contained in a high proportion, the continuous moldability tends to decrease, but the epoxy resin compositions according to the first to third embodiments are advantageous because they are excellent in continuous moldability. be.
- the epoxy resin composition is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure).
- the shape is not particularly limited, and examples thereof include powder, granules, and tablets.
- the epoxy resin composition is in the form of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.
- the epoxy resin compositions according to the first to third embodiments tend to have excellent kneadability. Therefore, even if the content of the inorganic filler is increased, the epoxy resin composition tends to be satisfactorily prepared.
- the flow distance may be 100 inches (2540 mm) or less. Specifically, the measurement is performed by the method described in the examples.
- the hardness at heat when the epoxy resin composition is a cured product is not particularly limited.
- the thermal hardness measured using a Shore D hardness tester is preferably 60 or more, preferably 65 or more. Is more preferable, 70 or more is further preferable, and 75 or more is particularly preferable.
- the melt viscosity of the epoxy resin composition at 175 ° C. is not particularly limited, and is preferably 350 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or less, further preferably 250 Pa ⁇ s or less, and 200 Pa ⁇ s or less. -It is particularly preferable that it is s or less.
- the melt viscosity is measured by a flow tester (for example, an enhanced flow tester) as follows. A predetermined amount of the epoxy resin composition is weighed with an electronic balance, and a tablet is prepared using a locker. After confirming that the temperature of the test mold is at the specified temperature, the sample is put into the pot. Immediately set the plunger and start the measurement. Specifically, the measurement can be performed by the method described in the examples.
- the thermal conductivity when the epoxy resin composition is a cured product is not particularly limited.
- the thermal conductivity of the cured product may be 0.5 W / (m ⁇ K) or more at room temperature (25 ° C.).
- the thermal conductivity of the cured product can be measured by a xenon flash (Xe-flash) method (for example, manufactured by NETZSCH, trade name: LFA467 type Hyper Flash apparatus).
- the epoxy resin compositions according to the first to third embodiments are used for transfer molding.
- the epoxy resin composition according to the first to third embodiments is preferably used as a molding material for sealing an element by transfer molding.
- the electronic component device includes an element and a cured product of the epoxy resin composition according to any one of the first to third embodiments that seals the element.
- Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors). , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with an epoxy resin composition.
- the element is fixed on the lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding, bumps, etc., and then sealed by transfer molding using an epoxy resin composition.
- DIP Dual Inline Package
- PLCC Plastic Leaded Chip Carrier
- QFP Quad Flat Package
- SOP Small Outline Package
- SOJ SmallOutlinePack
- TCP Teape Carrier Package having a structure in which an element connected to a tape carrier with a bump is sealed with an epoxy resin composition; on a support member.
- the epoxy resin composition can also be preferably used in the printed wiring board.
- the method for manufacturing an electronic component device according to the first to third embodiments includes sealing the device with the epoxy resin composition according to any one of the first to third embodiments described above. Examples of the sealing method include the methods described above.
- Epoxy resin composition for compression molding includes an epoxy resin, an inorganic filler, and the following general. It contains a curing agent containing a compound represented by the formula (B).
- R 1 to R 5 independently represent monovalent organic groups having 1 to 6 carbon atoms.
- X1 to X3 independently represent an integer of 0 to 4, respectively.
- X4 and X5 each independently represent an integer of 0 to 3.
- n1 represents a number from 1 to 10 and represents n2 represents a number from 1 to 10.
- the epoxy resin composition was easily melted. The reason for this is not necessarily clear, but it is presumed that the epoxy resin composition is easily melted because it contains a curing agent containing a compound represented by the general formula (B). Therefore, it is considered that the epoxy resin composition according to the fourth embodiment is suitable for compression molding.
- the ease of melting of the epoxy resin composition is also referred to as "dissolvability".
- the epoxy resin composition according to the fourth embodiment may further contain a curing accelerator, other additives, and the like.
- a curing accelerator other additives, and the like.
- the epoxy resin composition according to the fourth embodiment contains an epoxy resin.
- the type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
- at least one phenol selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene.
- a novolak type epoxy resin (phenol novolak type epoxy resin) which is an epoxidized novolak resin obtained by condensing or cocondensing a sex compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. , Orthocresol novolac type epoxy resin, etc.); Epoxy of triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst.
- Triphenylmethane type epoxy resin a copolymerized epoxy resin obtained by co-condensing the above phenol compound, naphthol compound, and aldehyde compound under an acidic catalyst and epoxidizing a novolak resin; bisphenol.
- Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben type epoxy resin which is a diglycidyl ether of a stillben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin that is a diglycidyl ether such as S; epoxy resin that is an alcoholic glycidyl ether such as butanediol, polyethylene glycol, polypropylene glycol; polyvalent carboxylic acid such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid.
- Glysidyl ester type epoxy resin which is a glycidyl ester of a compound
- Glysidylamine type epoxy resin which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, or isocyanuric acid with a glycidyl group
- Dicyclopentadiene type epoxy resin which is an epoxidized co-condensation resin of Rate, 2- (3,4-epoxy) cyclohexyl-5,5-spi B (3,4-Epoxy)
- Alicyclic epoxy resin such as cyclohexane-m-dioxane
- paraxylylene-modified epoxy resin which is a glycidyl ether of paraxylylene-modified phenol resin
- metaxylylene-modified epoxy resin which is glycidyl ether of metaxylylene-modified phenol resin
- epoxy resins from the viewpoint of the balance between reflow resistance and viscosity, biphenyl type epoxy resin, stillben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin , Epoxy resins selected from the group consisting of triphenylmethane type epoxy resins, copolymerized epoxy resins and aralkyl type epoxy resins (these are referred to as "specific epoxy resins") are preferable.
- the details and preferred embodiments of the specific epoxy resin are as described in the section of the epoxy resin contained in the epoxy resin composition according to the first to third embodiments.
- the specific epoxy resin may be used alone or in combination of two or more.
- the total content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, from the viewpoint of exhibiting the performance of the specific epoxy resin. preferable.
- biphenyl type epoxy resin, stillben type epoxy resin, diphenylmethane type epoxy resin, and sulfur atom-containing epoxy resin are more preferable from the viewpoint of viscosity, and dicyclopentadiene type epoxy from the viewpoint of heat resistance.
- Resins, triphenylmethane-type epoxy resins, and aralkyl-type epoxy resins are preferred.
- the epoxy resin composition may contain at least one selected from the group consisting of diphenylmethane type epoxy resin and biphenyl type epoxy resin.
- the epoxy resin composition contains a diphenylmethane type epoxy resin
- the content of the diphenylmethane type epoxy resin may be 40% by mass to 100% by mass, or 50% by mass to 100% by mass, based on the total mass of the epoxy resin. It may be 60% by mass to 100% by mass.
- the epoxy resin composition contains a biphenyl type epoxy resin
- the content of the biphenyl type epoxy resin may be 20% by mass to 100% by mass, or 25% by mass to 100% by mass, based on the total mass of the epoxy resin. It may be.
- the diphenylmethane type epoxy resin and the biphenyl type epoxy resin may be used in combination.
- the total content of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin with respect to the total mass of the epoxy resin is preferably 70% by mass or more, preferably 80% by mass or more, and 90% by mass or more. Is preferable.
- the content ratio of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin is 90:10 to 10: 10 on a mass basis. It may be 90, or 80:20 to 50:50.
- the epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and is 150 g / eq to 500 g / eq. Is more preferable.
- the epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.
- the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the epoxy resin composition, the temperature is more preferably 50 ° C. to 130 ° C.
- the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC)
- the softening point of the epoxy resin is a value measured by a method (ring ball method) according to JIS K 7234: 1986.
- the content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, viscosity, heat resistance, moldability, and the like. Is more preferable.
- the epoxy resin composition according to the fourth embodiment contains an inorganic filler.
- the material of the inorganic filler is not particularly limited. Specifically, silica (molten silica, crystalline silica, etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite. , Spinel, Murite, Titania, Tark, Clay, Mica and other inorganic materials.
- An inorganic filler having a flame-retardant effect may be used.
- Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate. Of these, molten silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.
- the inorganic filler may be used alone or in combination of two or more. Examples of the state of the inorganic filler include unpowdered beads, spherical beads of powder, fibers, and the like.
- the average particle size of the inorganic filler contained in the epoxy resin composition is not particularly limited.
- the average particle size of the inorganic filler is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m, and even more preferably 1 ⁇ m to 50 ⁇ m.
- the average particle size of the inorganic filler is 0.2 ⁇ m or more, the increase in viscosity of the epoxy resin composition tends to be suppressed.
- the average particle size of the inorganic filler is 80 ⁇ m or less, the filling property into a narrow gap tends to be improved.
- the average particle size of the inorganic filler in the present disclosure is the volume average particle size.
- the maximum particle size (also called cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling properties into narrow gaps, the maximum particle size of the inorganic filler is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and further preferably 55 ⁇ m or less.
- the shape of the inorganic filler is not particularly limited. From the viewpoint of kneadability of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.
- the content of the inorganic filler is not particularly limited.
- the content of the inorganic filler is preferably 50% by volume or more, more preferably 60% by volume or more, further preferably 70% by volume or more, and more preferably 75% by volume, based on the total volume of the epoxy resin composition. It is particularly preferably 50% by volume or more, and extremely preferably 80% by volume or more.
- the content of the inorganic filler is preferably 95% by volume or less, more preferably 90% by volume or less, and further preferably 87% by volume or less with respect to the total volume of the epoxy resin composition. ..
- the content of the inorganic filler is preferably 50% by volume to 95% by volume, more preferably 60% by volume to 95% by volume, and 70 by volume, based on the total volume of the epoxy resin composition. It is more preferably from% to 95% by volume, particularly preferably from 75% to 90% by volume, and extremely preferably from 80% to 87% by volume.
- the content of the inorganic filler is, for example, 82% by volume or more, more preferably 84% by volume or more, still more preferably 85% by volume or more, and particularly preferably 86% by volume or more of the epoxy resin composition. Even if it is extremely preferably 87% by volume or more, it tends to be able to be kneaded well.
- an inorganic filler having high thermal conductivity such as alumina and setting the content of the inorganic filler to the above ratio, a cured product having high thermal conductivity can be obtained.
- the content of the inorganic filler is, for example, 90% by mass or more, more preferably 92% by mass or more of the epoxy resin composition, it tends to be able to be kneaded well.
- the inorganic filler preferably contains alumina, and more preferably contains alumina as a main component (that is, 50% by volume or more with respect to the total volume of the inorganic filler).
- the average particle size of alumina is not particularly limited.
- the average particle size of alumina is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m, and even more preferably 1 ⁇ m to 50 ⁇ m.
- the average particle size is 0.2 ⁇ m or more, the increase in viscosity of the epoxy resin composition tends to be suppressed.
- the average particle size is 80 ⁇ m or less, the filling property into a narrow gap tends to be improved.
- the maximum particle size of alumina is not particularly limited. From the viewpoint of filling properties into narrow gaps, the maximum particle size of alumina is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and further preferably 55 ⁇ m or less.
- the average particle size is 0.1 ⁇ m to 2.0 ⁇ m, preferably 0.2 ⁇ m to 1.5 ⁇ m, more preferably 0.3 ⁇ m to 1.0 ⁇ m, and the average particle size exceeds 2.0 ⁇ m.
- Alumina of 75 ⁇ m or less, preferably 5.0 ⁇ m to 55 ⁇ m, more preferably 8.0 ⁇ m to 20 ⁇ m may be used in combination. By using two or more types of alumina having different average particle sizes in combination, the filling property and fluidity tend to be suitable.
- the shape of alumina is not particularly limited. From the viewpoint of kneadability of the epoxy resin composition, the particle shape of alumina is preferably spherical.
- the content of alumina with respect to the total mass of the inorganic filler is preferably 75% by mass or more, more preferably 80% by mass or more, from the viewpoint of high thermal conductivity. , 85% by mass or more, particularly preferably 90% by mass or more, and extremely preferably 95% by mass or more. Further, from the viewpoint of low viscosity and workability of kneading, the content of alumina with respect to the total mass of the inorganic filler is preferably 99.9% by mass or less, and 99.8% by mass or less. Is more preferable, and 99.7% by mass or less is further preferable.
- the inorganic filler When the inorganic filler contains alumina, the inorganic filler preferably contains silica in addition to alumina. When the inorganic filler contains silica in addition to alumina, the kneading property tends to be improved as compared with the case where the inorganic filler contains only alumina.
- fine silica for example, silica having an average particle size of 0.1 ⁇ m to 2.0 ⁇ m, preferably 0.2 ⁇ m to 1.5 ⁇ m, and more preferably 0.3 ⁇ m to 1.0 ⁇ m
- alumina fine silica (for example, silica having an average particle size of 0.1 ⁇ m to 2.0 ⁇ m, preferably 0.2 ⁇ m to 1.5 ⁇ m, and more preferably 0.3 ⁇ m to 1.0 ⁇ m) is used in addition to alumina. It may be included.
- the inorganic filler may contain particularly fine silica (for example, silica having an average particle diameter of 1 nm to 500 nm, more preferably 5 nm to 300 nm, still more preferably 10 nm to 200 nm) in addition to alumina. Since the inorganic filler contains fine silica, the generation of burrs when it is made into a cured product tends to be suppressed.
- silica content is preferably 0.1% by mass or more, preferably 0.2% by mass, based on the total mass of the inorganic filler from the viewpoint of kneadability and the like.
- the silica content is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass or less with respect to the total amount of the inorganic filler. Is even more preferable.
- the inorganic filler preferably contains silica, and even if silica is contained as a main component (that is, 50% by volume or more with respect to the total volume of the inorganic filler). good.
- the average particle size of silica is not particularly limited.
- the average particle size of silica is preferably 0.2 ⁇ m to 80 ⁇ m, more preferably 0.5 ⁇ m to 70 ⁇ m, and even more preferably 1 ⁇ m to 50 ⁇ m.
- the average particle size is 0.2 ⁇ m or more, the increase in viscosity of the epoxy resin composition tends to be suppressed.
- the average particle size is 80 ⁇ m or less, the filling property into a narrow gap tends to be improved.
- the inorganic filler may contain fine-grained silica (for example, silica having an average particle size of 0.1 ⁇ m to 2.0 ⁇ m, preferably 0.2 ⁇ m to 1.5 ⁇ m, and more preferably 0.3 ⁇ m to 1.0 ⁇ m). good.
- fine-grained silica for example, silica having an average particle size of 0.1 ⁇ m to 2.0 ⁇ m, preferably 0.2 ⁇ m to 1.5 ⁇ m, and more preferably 0.3 ⁇ m to 1.0 ⁇ m). good.
- the inorganic filler may contain particularly fine silica (for example, silica having an average particle diameter of 1 nm to 500 nm, more preferably 5 nm to 300 nm, and further preferably 10 nm to 200 nm). Since the inorganic filler contains fine silica, the generation of burrs when it is made into a cured product tends to be suppressed.
- silica having an average particle diameter of 1 nm to 500 nm, more preferably 5 nm to 300 nm, and further preferably 10 nm to 200 nm. Since the inorganic filler contains fine silica, the generation of burrs when it is made into a cured product tends to be suppressed.
- the inorganic filler may contain large particle size silica.
- the large particle size silica include large particle size silica having an average particle size of more than 2.0 ⁇ m and 75 ⁇ m or less, preferably 5.0 ⁇ m to 55 ⁇ m, and more preferably 8.0 ⁇ m to 20 ⁇ m.
- the maximum particle size of silica is not particularly limited. From the viewpoint of filling properties into narrow gaps, the maximum particle size of silica is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and further preferably 55 ⁇ m or less.
- the shape of silica is not particularly limited. From the viewpoint of kneadability of the epoxy resin composition, the particle shape of silica is preferably spherical.
- the content of silica is not particularly limited, and may be 70% by mass to 100% by mass, or 80% by mass to 100% by mass, based on the total mass of the inorganic filler. It may be 90% by mass to 100% by mass.
- the silica content when silica is used in combination with alumina is as described above.
- the epoxy resin composition according to the fourth embodiment contains a curing agent containing a compound (specific curing agent) represented by the general formula (B), and may contain another curing agent.
- the details of the curing agent are as described in the section of the curing agent contained in the epoxy resin composition according to the first to third embodiments.
- the epoxy resin composition according to the fourth embodiment may contain a curing accelerator.
- the details of the curing accelerator are as described in the section of the curing accelerator which may be contained in the epoxy resin composition according to the first to third embodiments.
- the epoxy resin composition according to the fourth embodiment may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent.
- additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, a colorant, and a stress relaxation agent.
- the details of the additive are as described in the section of the additive that may be contained in the epoxy resin composition according to the first to third embodiments.
- the epoxy resin composition preferably contains a mold release agent, and the content of the mold release agent is preferably more than 0% by mass and 2.0% by mass or less with respect to the total mass of the epoxy resin composition. It is more preferably more than 0% by mass and 1.5% by mass or less, and further preferably more than 0% by mass and 1.2% by mass or less.
- the release agent at the above-mentioned content rate, it tends to be possible to suppress a significant decrease in appearance, adhesive strength, and laser marking property as compared with the case where the release agent is contained in a larger amount than the above-mentioned content rate.
- the epoxy resin composition according to one aspect of the fourth embodiment even if the content of the mold release agent is in the above range, good mold release property tends to be maintained.
- the method for preparing the epoxy resin composition according to the fourth embodiment is not particularly limited, and specific examples are as described in the item of the epoxy resin composition according to the first to third embodiments.
- the epoxy resin composition according to the fourth embodiment is preferably solid at normal temperature and pressure (for example, 25 ° C. and atmospheric pressure).
- the shape is not particularly limited, and examples thereof include powder, granules, and tablets.
- the epoxy resin composition is in the form of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.
- the epoxy resin composition according to one aspect of the fourth embodiment tends to have excellent kneadability. Therefore, even when the content of the inorganic filler is increased or the inorganic filler having a small particle size is used, the epoxy resin composition tends to be satisfactorily prepared.
- the epoxy resin composition according to the fourth embodiment is used for compression molding.
- the epoxy resin composition is preferably used as a molding material for sealing an element by compression molding.
- the epoxy resin composition according to the fourth embodiment has excellent solubility. Therefore, the epoxy resin composition according to the fourth embodiment is suitable for sealing the device by compression molding. Further, in general, when the solubility of an epoxy resin composition is improved, the curability tends to decrease, but according to the epoxy resin composition according to the fourth embodiment, excellent curability also tends to be maintained. It is in.
- the hardness at heat when the epoxy resin composition is a cured product is not particularly limited.
- the thermal hardness measured using a Shore D hardness tester is preferably 60 or more, preferably 65 or more. Is more preferable, 70 or more is further preferable, and 75 or more is particularly preferable.
- the disc flow when 5 g of the epoxy resin composition is compression-molded under the conditions of 180 ° C., a load of 78 N, and a curing time of 90 seconds using a flat plate mold for measuring disk flow is preferably 75.0 mm or more. , 78.0 mm or more, more preferably 80.0 mm or more. Further, the disk flow may be 110 mm or less.
- the melt viscosity of the epoxy resin composition at 175 ° C. is not particularly limited, and is preferably 250 Pa ⁇ s or less, more preferably 240 Pa ⁇ s or less, and further preferably 230 Pa ⁇ s or less.
- the melt viscosity is measured by a flow tester (for example, an enhanced flow tester) as follows. A predetermined amount of the epoxy resin composition is weighed with an electronic balance, and a tablet is prepared using a locker. After confirming that the temperature of the test mold is at the specified temperature, the sample is put into the pot. Immediately set the plunger and start the measurement.
- the thermal conductivity when the epoxy resin composition is a cured product is not particularly limited.
- the thermal conductivity of the cured product may be 0.5 W / (m ⁇ K) or more at room temperature (25 ° C.).
- the thermal conductivity of the cured product can be measured by a xenon flash (Xe-flash) method (for example, manufactured by NETZSCH, trade name: LFA467 type Hyper Flash apparatus).
- the epoxy resin composition according to one aspect of the fourth embodiment tends to have excellent releasability when made into a cured product. Therefore, for example, even if the amount of the mold release agent is reduced in order to improve the appearance, adhesive strength, and laser marking property of the cured product, it tends to be possible to maintain good mold release property.
- the electronic component device includes an element and a cured product of the epoxy resin composition according to the fourth embodiment described above that seals the element.
- Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors). , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with an epoxy resin composition.
- a structure in which an element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding, bumps, etc., and then sealed with an epoxy resin composition DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline Page)
- DIP Dual Inline Package
- PLCC Physical Leaded Chip Carrier
- QFP Quad Flat Package
- SOP Small Outline Package
- SOJ Small Outline Page
- a general resin-sealed IC such as a Thin Quad Flat Package
- TCP Teape Carrier Package having a structure in which an element connected to a tape carrier with a bump is sealed with an epoxy resin composition; a wiring formed on a support member.
- COB Chip On Board
- hybrid IC hybrid IC
- multi-chip module etc. having a structure in which elements connected by wire bonding, flip chip bonding, solder, etc. are sealed with an epoxy resin composition; for connecting a wiring board on the back surface.
- BGA BGA
- BGA BGA
- Ball Grid Array CSP (Chip Size Package), MCP (Multi Chip Package), and the like.
- the epoxy resin composition can also be preferably used in the printed wiring board.
- the method for manufacturing an electronic component device according to a fourth embodiment includes sealing the element by compression molding of the epoxy resin composition according to the fourth embodiment described above.
- Examples of the first to third embodiments >> [Preparation of epoxy resin composition]
- the epoxy resin compositions of Examples and Comparative Examples were prepared by mixing the following materials with the compositions shown in Table 1 and performing roll kneading under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes.
- "-" in Table 1 means that the component is not blended.
- Epoxy resin -Epoxy resin 1: Diphenylmethane type epoxy resin (bisphenol type epoxy resin) (trade name: YSLV-80XY, Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent 190 g / eq) -Epoxy resin 2: Biphenyl type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Co., Ltd., epoxy equivalent 190 g / eq) -Epoxy resin 3: Triphenylmethane type epoxy resin (trade name: 1032H60, Mitsubishi Chemical Co., Ltd., epoxy equivalent 170 g / eq)
- (Hardener) -Curing agent 1 In the general formula (B), x1 to x5 are all 0, n1 is 1 to 10, and n2 is 1 to 10 (trade name: MEHC7841-4S, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 164 g).
- -Curing agent 2 Aralkyl type phenol resin other than the general formula (B); in the general formula (XII), a compound in which i is 0 and R 23 is all hydrogen atoms (trade name: MEHC7851-SS, Meiwa Kasei Co., Ltd.) Company, hydroxyl group equivalent 201 g / eq-205 g / eq, softening point 64 ° C-69 ° C) -Curing agent 3: Triphenylmethane type phenol resin (trade name: MEH7500, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 95 to 105 g / eq, softening point 105 ° C to 115 ° C)
- epoxy resin composition evaluation The properties of the epoxy resin compositions prepared in Examples and Comparative Examples were evaluated by the following property tests. Unless otherwise specified, the epoxy resin composition was molded by a transfer molding machine under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. If necessary, post-curing was performed at 175 ° C. for 5 hours.
- the epoxy resin composition is molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D type hardness tester (HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.) is used. Measured using.
- a Shore D type hardness tester HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.
- the epoxy resin compositions of Examples have a low viscosity and are excellent in continuous moldability. Further, as can be seen from the evaluation of burrs, burrs can be suitably suppressed in the examples using ultrafine silica. Further, even when ultrafine silica is used, the epoxy resin composition of the example maintains excellent fluidity.
- Example according to the fourth embodiment >> [Preparation of epoxy resin composition]
- the epoxy resin compositions of Examples and Comparative Examples were prepared by mixing the following materials with the compositions shown in Table 4 and performing roll kneading under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes.
- "-" in Table 4 means that the component is not blended.
- Epoxy resin 1 Diphenylmethane type epoxy resin (bisphenol type epoxy resin) (trade name: YSLV-80XY, Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent 190 g / eq)
- Epoxy resin 2 Biphenyl type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Co., Ltd., epoxy equivalent 190 g / eq)
- (Hardener) -Curing agent 1 Novolac type phenol resin (trade name: H-4, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 103 g / eq to 107 g / eq, softening point 67 ° C to 75 ° C)
- -Curing agent 2 Aralkyl type phenol resin (trade name: MEHC7800-4S, hydroxyl group equivalent 167 g / eq to 179 g / eq, softening point 61 ° C.
- -Curing agent 3 In the general formula (B), x1 to x5 are all 0, n1 is 1 to 10, and n2 is 1 to 10 (trade name: MEHC7841-4S, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 164 g). / Eq to 168 g / eq, softening point 58 ° C to 65 ° C) -Curing agent 4: Aralkyl type phenol resin (trade name: MEHC7851-SS, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 201 g / eq to 205 g / eq, softening point 64 ° C to 69 ° C)
- Inorganic filler -Inorganic filler 1: Fine particle alumina (average particle size 0.4 ⁇ m, maximum particle size 2.0 ⁇ m) -Inorganic filler 2: Large particle alumina (average particle size 10 ⁇ m, maximum particle size 75 ⁇ m) -Inorganic filler 3: Ultrafine silica (average particle size 0.1 ⁇ m, maximum particle size 2.0 ⁇ m)
- epoxy resin composition evaluation The properties of the epoxy resin compositions prepared in Examples and Comparative Examples were evaluated by the following property tests.
- the time when the upper mold fell (that is, the time when the upper mold reached the upper surface of the powder) was set to 0 seconds, and the falling distance of the upper mold after the epoxy resin composition powder began to melt was measured by a laser displacement meter.
- the height of the upper surface of the epoxy resin composition at 0 seconds was A
- the height after 1 second was B
- the calculation was performed as B / A ⁇ 100 (%), and the solubility of the powder was investigated.
- Kneadability (kneaded product temperature)
- the set temperature of the heating range of the kneader was set to 90 ° C.
- the temperatures of the kneaded products were measured at four locations in the kneader, and the degree of temperature rise was used as an index of kneading property.
- the temperature of the kneaded product tends to rise above the set temperature due to the solubility of the epoxy resin composition, heat generation by shearing, friction of the inorganic filler, and the like. It was judged that the closer the average value of the temperatures of the kneaded products at the four locations was to the set temperature, the better the kneading property.
- the epoxy resin composition of the example has excellent solubility. Further, in the epoxy resin composition of the example, good results were obtained in the evaluation of kneadability, continuous moldability, and thermal conductivity of the cured product.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
Abstract
Description
また、トランスファ成形法においてバリの発生を抑制したり狭部への充填性を向上するために、エポキシ樹脂組成物に粒子径の小さい無機充填材(超微細シリカ等)を含有させる場合があるが、この場合には粘度の上昇及び流動性の低下がより顕著である。
また、封止用エポキシ樹脂組成物は、量産の観点から、良好な連続成形性を有することが望まれる。しかしながら、粘度の上昇を抑えつつ、かつ良好な連続成形性を有するエポキシ樹脂組成物は、これまでに得られていなかった。
上記事情に鑑み、本開示の第1~第3の実施形態は、粘度の上昇が抑えられており連続成形性に優れるトランスファ成形用エポキシ樹脂組成物及びその製造方法、並びにエポキシ樹脂組成物の硬化物を備える電子部品装置を提供することを目的とする。
上記事情に鑑み、本開示の第4の実施形態は、溶融しやすいエポキシ樹脂組成物、及び当該エポキシ樹脂組成物の硬化物を備える電子部品装置を提供することを課題とする。
<1> エポキシ樹脂と、平均粒子径が50nm以下の無機充填材と、以下の一般式(B)で表される化合物を含む硬化剤と、を混合することを含む、トランスファ成形用エポキシ樹脂組成物の製造方法。
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
<2> 前記エポキシ樹脂が、ビフェニル型エポキシ樹脂を含む、<1>に記載の製造方法。
<3> 前記トランスファ成形用エポキシ樹脂組成物中の前記ビフェニル型エポキシ樹脂の含有率が、前記エポキシ樹脂の全質量に対して30質量%~100質量%である、<2>に記載の製造方法。
<4> 前記無機充填材の含有率が前記トランスファ成形用エポキシ樹脂組成物の全体積に対して60体積%以上である、<1>~<3>のいずれか1項に記載の製造方法。
<5> 前記トランスファ成形用エポキシ樹脂組成物中の前記硬化剤の全質量に対する前記一般式(B)で表される化合物の含有率が30質量%~100質量%である、<1>~<4>のいずれか1項に記載の製造方法。
<6> エポキシ樹脂と、
無機充填材と、
以下の一般式(B)で表される化合物を含む硬化剤と、
を含有し、
前記無機充填材は平均粒子径50nm以下の無機充填材と平均粒子径が50nmより大きい無機充填材との混合物であり、前記平均粒子径50nm以下の無機充填材の含有量は、前記エポキシ樹脂100質量部に対して5質量部以上である、
トランスファ成形用エポキシ樹脂組成物。
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
<7> エポキシ樹脂と、
無機充填材と、
以下の一般式(B)で表される化合物を含む硬化剤と、
を含有し、
前記無機充填材は粒子径50nm以下の無機充填材を含み、前記粒子径50nm以下の無機充填材の含有量は、前記エポキシ樹脂100質量部に対して5質量部以上である、
トランスファ成形用エポキシ樹脂組成物。
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
<8> 前記エポキシ樹脂が、ビフェニル型エポキシ樹脂を含む、<6>又は<7>に記載のトランスファ成形用エポキシ樹脂組成物。
<9> 前記ビフェニル型エポキシ樹脂の含有率が、前記エポキシ樹脂の全質量に対して30質量%~100質量%である、<8>に記載のトランスファ成形用エポキシ樹脂組成物。
<10> 前記無機充填材の含有率が、前記エポキシ樹脂組成物の全体積に対して60体積%以上である、<6>~<9>のいずれか1項に記載のトランスファ成形用エポキシ樹脂組成物。
<11> 前記硬化剤の全質量に対する前記一般式(B)で表される化合物の含有率が30質量%~100質量%である、<6>~<10>のいずれか1項に記載のトランスファ成形用エポキシ樹脂組成物。
<12> 素子と、
前記素子を封止する、<1>~<5>のいずれか1項に記載の製造方法により得られたエポキシ樹脂組成物の硬化物、又は<6>~<11>のいずれか1項に記載のエポキシ樹脂組成物の硬化物と、
を備える電子部品装置。
<13> エポキシ樹脂と、
無機充填材と、
以下の一般式(B)で表される化合物を含む硬化剤と、
を含有する、コンプレッション成形用エポキシ樹脂組成物。
一般式(B)中、
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
<14> 前記無機充填材の含有率が前記コンプレッション成形用エポキシ樹脂組成物の全体積に対して60体積%以上である、<13>に記載のコンプレッション成形用エポキシ樹脂組成物。
<15> 前記硬化剤の全質量に対する前記一般式(B)で表される化合物の含有率が30質量%~100質量%である、<13>又は<14>に記載のコンプレッション成形用エポキシ樹脂組成物。
<16> さらに離型剤を含有し、前記離型剤の含有率が前記コンプレッション成形用エポキシ樹脂組成物の全質量に対して0質量%を超え2.0質量%以下である、<13>~<15>のいずれか1項に記載のコンプレッション成形用エポキシ樹脂組成物。
<17> 素子と、
前記素子を封止する<13>~<16>のいずれか1項に記載のコンプレッション成形用エポキシ樹脂組成物の硬化物と、
を備える電子部品装置。
本開示において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含まれていてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
まず、第1~第3の実施形態について詳述する。
第1の実施形態に係るトランスファ成形用エポキシ樹脂組成物の製造方法は、エポキシ樹脂と、平均粒子径が50nm以下の無機充填材と、以下の一般式(B)で表される化合物を含む硬化剤と、を混合することを含む。
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
以下、本実施形態のトランスファ成形用エポキシ樹脂組成物の製造方法により製造されるエポキシ樹脂組成物を「第1の実施形態に係るエポキシ樹脂組成物」とも称する。
第1の実施形態に係るエポキシ樹脂組成物は、第1の実施形態に係るトランスファ成形用エポキシ樹脂組成物の製造方法により製造され、エポキシ樹脂と、無機充填材と、一般式(B)で表される化合物を含む硬化剤と、を含有する。第1の実施形態に係るエポキシ樹脂組成物は、さらに硬化促進剤、その他の添加剤等を含有してもよい。
第2の実施形態に係るエポキシ樹脂組成物は、エポキシ樹脂と、無機充填材と、上述の一般式(B)で表される化合物を含む硬化剤と、を含有し、前記無機充填材は平均粒子径50nm以下の無機充填材と平均粒子径が50nmより大きい無機充填材との混合物であり、前記平均粒子径50nm以下の無機充填材の含有量は、前記エポキシ樹脂100質量部に対して5質量部以上である。
第3の実施形態に係るエポキシ樹脂組成物は、エポキシ樹脂と、無機充填材と、上述の一般式(B)で表される化合物を含む硬化剤と、を含有し、前記無機充填材は粒子径50nm以下の無機充填材を含み、前記粒子径50nm以下の無機充填材の含有量は、前記エポキシ樹脂100質量部に対して5質量部以上である。
第1~第3の実施形態に係るエポキシ樹脂組成物はエポキシ樹脂を含む。エポキシ樹脂は1分子中に2個以上のエポキシ基を有するものであればその種類は特に制限されない。
具体的には、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等のフェノール化合物及び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化合物からなる群より選ばれる少なくとも1種のフェノール性化合物と、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等の脂肪族アルデヒド化合物と、を酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したものであるノボラック型エポキシ樹脂(フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等);上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド化合物と、を酸性触媒下で縮合又は共縮合させて得られるトリフェニルメタン型フェノール樹脂をエポキシ化したものであるトリフェニルメタン型エポキシ樹脂;上記フェノール化合物及びナフトール化合物と、アルデヒド化合物と、を酸性触媒下で共縮合させて得られるノボラック樹脂をエポキシ化したものである共重合型エポキシ樹脂;ビスフェノールA、ビスフェノールF等のジグリシジルエーテルであるジフェニルメタン型エポキシ樹脂;アルキル置換又は非置換のビフェノールのジグリシジルエーテルであるビフェニル型エポキシ樹脂;スチルベン系フェノール化合物のジグリシジルエーテルであるスチルベン型エポキシ樹脂;ビスフェノールS等のジグリシジルエーテルである硫黄原子含有型エポキシ樹脂;ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテルであるエポキシ樹脂;フタル酸、イソフタル酸、テトラヒドロフタル酸等の多価カルボン酸化合物のグリシジルエステルであるグリシジルエステル型エポキシ樹脂;アニリン、ジアミノジフェニルメタン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したものであ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化合物との共縮合樹脂をエポキシ化したものであるジシクロペンタジエン型エポキシ樹脂;分子内のオレフィン結合をエポキシ化したものであるビニルシクロヘキセンジエポキシド、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、2-(3,4-エポキシ)シクロヘキシル-5,5-スピロ(3,4-エポキシ)シクロヘキサン-m-ジオキサン等の脂環型エポキシ樹脂;パラキシリレン変性フェノール樹脂のグリシジルエーテルであるパラキシリレン変性エポキシ樹脂;メタキシリレン変性フェノール樹脂のグリシジルエーテルであるメタキシリレン変性エポキシ樹脂;テルペン変性フェノール樹脂のグリシジルエーテルであるテルペン変性エポキシ樹脂;ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるジシクロペンタジエン変性エポキシ樹脂;シクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるシクロペンタジエン変性エポキシ樹脂;多環芳香環変性フェノール樹脂のグリシジルエーテルである多環芳香環変性エポキシ樹脂;ナフタレン環含有フェノール樹脂のグリシジルエーテルであるナフタレン型エポキシ樹脂;ハロゲン化フェノールノボラック型エポキシ樹脂;ハイドロキノン型エポキシ樹脂;トリメチロールプロパン型エポキシ樹脂;オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂;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をエポキシ化したものであるアラルキル型エポキシ樹脂;などが挙げられる。さらにはシリコーン樹脂のエポキシ化物、アクリル樹脂のエポキシ化物等もエポキシ樹脂として挙げられる。これらのエポキシ樹脂は、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。
また、一般式(III)~(XI)における炭素数1~18の1価の有機基はアルキル基又はアリール基であることが好ましい。
第1~第3の実施形態に係るエポキシ樹脂組成物は、無機充填材を含有する。無機充填材の材質は、特に制限されない。具体的には、シリカ(溶融シリカ、結晶シリカ等)、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカなどの無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有する無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。中でも、線膨張係数低減の観点からはシリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。無機充填材は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。無機充填材の状態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。
第1の実施形態に係るエポキシ樹脂組成物において、平均粒子径が50nm以下の無機充填材に加えて、平均粒子径が50nmより大きい無機充填材が混合されていることが好ましい。平均粒子径が50nm以下の無機充填材、及び平均粒子径が50nmより大きい無機充填材は、それぞれ1種であっても2種以上であってもよい。
本開示において無機充填材の最大粒子径は、レーザー回折散乱法粒度分布測定装置により得られる体積基準の粒度分布において小径側からの累積が90%となるときの粒子径(D90%)を意味する。
より好ましい一態様において、無機充填材は、平均粒子径50nm以下の無機充填材に加えて、平均粒子径0.1μm~1μmの無機充填材と、平均粒子径2μm~50μmの無機充填材と、が混合されてなる。
さらに好ましい一態様において、無機充填材は、平均粒子径50nm以下の無機充填材に加えて、平均粒子径0.2μm~1μmの無機充填材と、平均粒子径5μm~30μmの無機充填材と、が混合されてなる。
また、無機充填材の含有率はエポキシ樹脂組成物の全体積に対して95体積%以下であることが好ましく、90体積%以下であることがより好ましく、87体積%以下であることがさらに好ましい。無機充填材の含有率がエポキシ樹脂組成物全体の95体積%以下であると、エポキシ樹脂組成物の粘度の上昇が抑制され、流動性がより向上して成形性がより良好になる傾向にある。
以上の観点から、無機充填材の含有率はエポキシ樹脂組成物の全体積に対して50体積%~95体積%であることが好ましく、60体積%~95体積%であることがより好ましく、70体積%~95体積%であることがさらに好ましく、75体積%~90体積%であることが特に好ましく、80体積%~87体積%であることが極めて好ましい。
本開示における無機充填材の平均粒子径は、レーザー回折散乱法粒度分布測定装置により、体積平均粒子径(D50)として測定することができる。
また、エポキシ樹脂組成物又はその硬化物中の無機充填材の平均粒子径は、具体的には以下の方法によって測定することができる。エポキシ樹脂組成物又はその硬化物を入れたるつぼを、マッフル炉に入れ、800℃に加熱する。試料が完全に灰化するまで約4時間放置する。常温に戻るまで試料を自然冷却し、灰分(無機充填材)を抽出する。超音波分散機等で無機充填材を十分に分散して分散液を調製する。この分散液を用いて、レーザー回折散乱法粒度分布測定装置により測定される体積基準の粒度分布から、無機充填材の体積平均粒子径を測定することができる。
第1~第3の実施形態に係るエポキシ樹脂組成物は、以下の一般式(B)で表される化合物(以下、特定の硬化剤ともいう)を含む硬化剤を含有する。
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
硬化剤としては、特定の硬化剤以外にさらに他の硬化剤を併用してもよい。硬化剤の全質量に対する特定の硬化剤の含有率は、30質量%~100質量%であることが好ましく、50質量%~100質量%であることがより好ましく、70質量%~100質量%であることがさらに好ましい。
第1~第3の実施形態に係るエポキシ樹脂組成物は、硬化促進剤を含んでもよい。硬化促進剤の種類は特に制限されず、エポキシ樹脂の種類、エポキシ樹脂組成物の所望の特性等に応じて選択できる。
第1~第3の実施形態に係るエポキシ樹脂組成物は、上述の成分に加えて、以下に例示するカップリング剤、イオン交換体、離型剤、難燃剤、着色剤、応力緩和剤等の各種添加剤を含んでもよい。エポキシ樹脂組成物は、以下に例示する添加剤以外にも必要に応じて当技術分野で周知の各種添加剤を含んでもよい。
エポキシ樹脂組成物が無機充填材を含む場合は、樹脂成分と無機充填材との接着性を高めるために、カップリング剤を含んでもよい。カップリング剤としては、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、ビニルシラン等のシラン系化合物、チタン系化合物、アルミニウムキレート化合物、アルミニウム/ジルコニウム系化合物などの公知のカップリング剤が挙げられる。
エポキシ樹脂組成物は、イオン交換体を含んでもよい。特に、エポキシ樹脂組成物を封止用成形材料として用いる場合には、封止される素子を備える電子部品装置の耐湿性及び高温放置特性を向上させる観点から、イオン交換体を含むことが好ましい。イオン交換体は特に制限されず、従来公知のものを用いることができる。具体的には、ハイドロタルサイト化合物、並びにマグネシウム、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少なくとも1種の元素の含水酸化物等が挙げられる。イオン交換体は、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。中でも、下記一般式(A)で表されるハイドロタルサイトが好ましい。
(0<X≦0.5、mは正の数)
エポキシ樹脂組成物は、成形時における金型との良好な離型性を得る観点から、離型剤を含んでもよい。離型剤は特に制限されず、従来公知のものを用いることができる。具体的には、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックスなどが挙げられる。離型剤は、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。
エポキシ樹脂組成物は、難燃剤を含んでもよい。難燃剤は特に制限されず、従来公知のものを用いることができる。具体的には、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む有機又は無機の化合物、金属水酸化物等が挙げられる。難燃剤は、1種を単独で用いても2種以上を組み合わせて用いてもよい。
エポキシ樹脂組成物は、着色剤をさらに含んでもよい。着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を挙げることができる。着色剤の含有量は目的等に応じて適宜選択できる。着色剤は、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。
エポキシ樹脂組成物は、シリコーンオイル、シリコーンゴム粒子等の応力緩和剤を含んでもよい。応力緩和剤を含むことにより、パッケージの反り変形及びパッケージクラックの発生をより低減させることができる。応力緩和剤としては、一般に使用されている公知の応力緩和剤(可とう剤)が挙げられる。具体的には、シリコーン系、スチレン系、オレフィン系、ウレタン系、ポリエステル系、ポリエーテル系、ポリアミド系、ポリブタジエン系等の熱可塑性エラストマー、NR(天然ゴム)、NBR(アクリロニトリル-ブタジエンゴム)、アクリルゴム、ウレタンゴム、シリコーンパウダー等のゴム粒子、メタクリル酸メチル-スチレン-ブタジエン共重合体(MBS)、メタクリル酸メチル-シリコーン共重合体、メタクリル酸メチル-アクリル酸ブチル共重合体等のコア-シェル構造を有するゴム粒子などが挙げられる。応力緩和剤は、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。中でも、シリコーン系応力緩和剤が好ましい。シリコーン系応力緩和剤としては、エポキシ基を有するもの、アミノ基を有するもの、これらをポリエーテル変性したもの等が挙げられる。
エポキシ樹脂組成物の調製方法は、特に制限されない。一般的な手法としては、所定の配合量の成分をミキサー等によって十分混合した後、ミキシングロール、押出機等によって溶融混練し、冷却し、粉砕する方法を挙げることができる。より具体的には、例えば、上述した成分の所定量を均一に撹拌及び混合し、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、冷却し、粉砕する方法を挙げることができる。なお、第1の実施形態に係るエポキシ樹脂組成物は、エポキシ樹脂と、平均粒子径が50nm以下の無機充填材と、以下の一般式(B)で表される化合物を含む硬化剤と、を混合することを含み、その他は上記調製方法に準じて調整することができる。
第1~第3の実施形態に係るエポキシ樹脂組成物は粘度の上昇が抑えられており連続成形性に優れることが見出されている。第1~第3の実施形態に係るエポキシ樹脂組成物は、無機充填材を高割合で含有させても、トランスファ成形の際に流動性に優れるためワイヤ流れ、未充填等の発生を抑えることができる点で有利である。また、一般的にアルミナ等の無機充填材を高割合で含有させると連続成形性が低下しやすいところ、第1~第3の実施形態に係るエポキシ樹脂組成物は連続成形性に優れるため有利である。
第1~第3の実施形態に係るエポキシ樹脂組成物はトランスファ成形用に用いられる。第1~第3の実施形態に係るエポキシ樹脂組成物はトランスファ成形による素子の封止用成形材料として用いられることが好ましい。
第1~第3の実施形態に係る電子部品装置は、素子と、前記素子を封止する、第1~第3のいずれかの実施形態に係るエポキシ樹脂組成物の硬化物と、を備える。
電子部品装置としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ、有機基板等の支持部材に、素子(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など)を搭載して得られた素子部をエポキシ樹脂組成物で封止したものが挙げられる。
より具体的には、リードフレーム上に素子を固定し、ボンディングパッド等の素子の端子部とリード部とをワイヤボンディング、バンプ等で接続した後、エポキシ樹脂組成物を用いてトランスファ成形によって封止した構造を有するDIP(Dual Inline Package)、PLCC(Plastic Leaded Chip Carrier)、QFP(Quad Flat Package)、SOP(Small Outline Package)、SOJ(Small Outline J-lead package)、TSOP(Thin Small Outline Package)、TQFP(Thin Quad Flat Package)等の一般的な樹脂封止型IC;テープキャリアにバンプで接続した素子をエポキシ樹脂組成物で封止した構造を有するTCP(Tape Carrier Package);支持部材上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した素子を、エポキシ樹脂組成物で封止した構造を有するCOB(Chip On Board)モジュール、ハイブリッドIC、マルチチップモジュール等;裏面に配線板接続用の端子を形成した支持部材の表面に素子を搭載し、バンプ又はワイヤボンディングにより素子と支持部材に形成された配線とを接続した後、エポキシ樹脂組成物で素子を封止した構造を有するBGA(Ball Grid Array)、CSP(Chip Size Package)、MCP(Multi Chip Package)などが挙げられる。また、プリント配線板においてもエポキシ樹脂組成物を好適に使用することができる。
第1~第3の実施形態に係る電子部品装置の製造方法は、上述の第1~第3のいずれかの実施形態に係るエポキシ樹脂組成物により素子を封止することを含む。封止方法としては前述した方法が挙げられる。
続いて、第4の実施形態について詳述する。
第4の実施形態に係るコンプレッション成形用エポキシ樹脂組成物(以下、第4の実施形態の説明において、単に「エポキシ樹脂組成物」ともいう)は、エポキシ樹脂と、無機充填材と、以下の一般式(B)で表される化合物を含む硬化剤と、を含有する。
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。
第4の実施形態に係るエポキシ樹脂組成物はエポキシ樹脂を含む。エポキシ樹脂は1分子中に2個以上のエポキシ基を有するものであればその種類は特に制限されない。
具体的には、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等のフェノール化合物及び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化合物からなる群より選ばれる少なくとも1種のフェノール性化合物と、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等の脂肪族アルデヒド化合物と、を酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したものであるノボラック型エポキシ樹脂(フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等);上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド化合物と、を酸性触媒下で縮合又は共縮合させて得られるトリフェニルメタン型フェノール樹脂をエポキシ化したものであるトリフェニルメタン型エポキシ樹脂;上記フェノール化合物及びナフトール化合物と、アルデヒド化合物と、を酸性触媒下で共縮合させて得られるノボラック樹脂をエポキシ化したものである共重合型エポキシ樹脂;ビスフェノールA、ビスフェノールF等のジグリシジルエーテルであるジフェニルメタン型エポキシ樹脂;アルキル置換又は非置換のビフェノールのジグリシジルエーテルであるビフェニル型エポキシ樹脂;スチルベン系フェノール化合物のジグリシジルエーテルであるスチルベン型エポキシ樹脂;ビスフェノールS等のジグリシジルエーテルである硫黄原子含有型エポキシ樹脂;ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテルであるエポキシ樹脂;フタル酸、イソフタル酸、テトラヒドロフタル酸等の多価カルボン酸化合物のグリシジルエステルであるグリシジルエステル型エポキシ樹脂;アニリン、ジアミノジフェニルメタン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したものであ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化合物との共縮合樹脂をエポキシ化したものであるジシクロペンタジエン型エポキシ樹脂;分子内のオレフィン結合をエポキシ化したものであるビニルシクロヘキセンジエポキシド、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、2-(3,4-エポキシ)シクロヘキシル-5,5-スピロ(3,4-エポキシ)シクロヘキサン-m-ジオキサン等の脂環型エポキシ樹脂;パラキシリレン変性フェノール樹脂のグリシジルエーテルであるパラキシリレン変性エポキシ樹脂;メタキシリレン変性フェノール樹脂のグリシジルエーテルであるメタキシリレン変性エポキシ樹脂;テルペン変性フェノール樹脂のグリシジルエーテルであるテルペン変性エポキシ樹脂;ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるジシクロペンタジエン変性エポキシ樹脂;シクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるシクロペンタジエン変性エポキシ樹脂;多環芳香環変性フェノール樹脂のグリシジルエーテルである多環芳香環変性エポキシ樹脂;ナフタレン環含有フェノール樹脂のグリシジルエーテルであるナフタレン型エポキシ樹脂;ハロゲン化フェノールノボラック型エポキシ樹脂;ハイドロキノン型エポキシ樹脂;トリメチロールプロパン型エポキシ樹脂;オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂;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をエポキシ化したものであるアラルキル型エポキシ樹脂;などが挙げられる。さらにはシリコーン樹脂のエポキシ化物、アクリル樹脂のエポキシ化物等もエポキシ樹脂として挙げられる。これらのエポキシ樹脂は、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。
特定エポキシ樹脂の詳細及び好ましい態様は、第1~第3の実施形態に係るエポキシ樹脂組成物に含まれるエポキシ樹脂の項目において説明した通りである。
特定エポキシ樹脂は、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。
エポキシ樹脂組成物がジフェニルメタン型エポキシ樹脂を含有する場合、ジフェニルメタン型エポキシ樹脂の含有率はエポキシ樹脂の全質量に対して40質量%~100質量%であってもよく、50質量%~100質量%であってもよく、60質量%~100質量%であってもよい。
エポキシ樹脂組成物がビフェニル型エポキシ樹脂を含有する場合、ビフェニル型エポキシ樹脂の含有率はエポキシ樹脂の全質量に対して20質量%~100質量%であってもよく、25質量%~100質量%であってもよい。
ジフェニルメタン型エポキシ樹脂とビフェニル型エポキシ樹脂とを組み合わせて用いる場合、ジフェニルメタン型エポキシ樹脂とビフェニル型エポキシ樹脂の含有量比(ジフェニルメタン型エポキシ樹脂:ビフェニル型エポキシ樹脂)は質量基準で90:10~10:90であってもよく、80:20~50:50であってもよい。
第4の実施形態に係るエポキシ樹脂組成物は、無機充填材を含有する。無機充填材の材質は、特に制限されない。具体的には、シリカ(溶融シリカ、結晶シリカ等)、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカなどの無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有する無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。中でも、線膨張係数低減の観点からは溶融シリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。無機充填材は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。無機充填材の状態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。
本開示における無機充填材の平均粒子径は、体積平均粒子径とする。
また、無機充填材の含有率はエポキシ樹脂組成物の全体積に対して95体積%以下であることが好ましく、90体積%以下であることがより好ましく、87体積%以下であることがさらに好ましい。無機充填材の含有率がエポキシ樹脂組成物全体の95体積%以下であると、エポキシ樹脂組成物の粘度の上昇が抑制される傾向にある。
以上の観点から、無機充填材の含有率はエポキシ樹脂組成物の全体積に対して50体積%~95体積%であることが好ましく、60体積%~95体積%であることがより好ましく、70体積%~95体積%であることがさらに好ましく、75体積%~90体積%であることが特に好ましく、80体積%~87体積%であることが極めて好ましい。
高熱伝導性の硬化物を得る場合には、無機充填材はアルミナを含むことが好ましく、アルミナを主成分として(すなわち無機充填材の全体積に対して50体積%以上)含むことがより好ましい。無機充填材がアルミナを含む場合のアルミナの平均粒子径は特に制限されない。例えば、アルミナの平均粒子径は0.2μm~80μmであることが好ましく、0.5μm~70μmであることがより好ましく、1μm~50μmであることがさらに好ましい。平均粒子径が0.2μm以上であると、エポキシ樹脂組成物の粘度の上昇が抑制される傾向がある。平均粒子径が80μm以下であると、狭い隙間への充填性が向上する傾向にある。
無機充填材としてアルミナとシリカを併用する場合、混練性等の観点からは、シリカの含有率は無機充填材の全質量に対して0.1質量%以上であることが好ましく、0.2質量%以上であることがより好ましく、0.3質量%以上であることがさらに好ましい。また、高熱伝導化の観点からはシリカの含有率は無機充填材の全量に対して10質量%以下であることが好ましく、5質量%以下であることがより好ましく、2質量%以下であることがさらに好ましい。
耐リフロー性、粘度の上昇抑制等の観点からは、無機充填材はシリカを含むことが好ましく、シリカを主成分として(すなわち無機充填材の全体積に対して50体積%以上)含んでいてもよい。無機充填材がシリカを含む場合のシリカの平均粒子径は特に制限されない。例えば、シリカの平均粒子径は0.2μm~80μmであることが好ましく、0.5μm~70μmであることがより好ましく、1μm~50μmであることがさらに好ましい。平均粒子径が0.2μm以上であると、エポキシ樹脂組成物の粘度の上昇が抑制される傾向がある。平均粒子径が80μm以下であると、狭い隙間への充填性が向上する傾向にある。
第4の実施形態に係るエポキシ樹脂組成物は、一般式(B)で表される化合物(特定の硬化剤)を含む硬化剤を含有し、他の硬化剤を含有してもよい。硬化剤の詳細は、第1~第3の実施形態に係るエポキシ樹脂組成物に含まれる硬化剤の項目で説明した通りである。
第4の実施形態に係るエポキシ樹脂組成物は、硬化促進剤を含んでもよい。硬化促進剤の詳細は、第1~第3の実施形態に係るエポキシ樹脂組成物に含まれていてもよい硬化促進剤の項目で説明した通りである。
第4の実施形態に係るエポキシ樹脂組成物は、カップリング剤、イオン交換体、離型剤、難燃剤、着色剤、応力緩和剤等の各種添加剤を含んでもよい。添加剤の詳細は、第1~第3の実施形態に係るエポキシ樹脂組成物に含まれていてもよい添加剤の項目で説明した通りである。
第4の実施形態に係るエポキシ樹脂組成物の調製方法は、特に制限されず、具体例は、第1~第3の実施形態に係るエポキシ樹脂組成物の項目で説明した通りである。
第4の実施形態に係るエポキシ樹脂組成物はコンプレッション成形用に用いられる。エポキシ樹脂組成物はコンプレッション成形による素子の封止用成形材料として用いられることが好ましい。
第4の実施形態に係るエポキシ樹脂組成物は溶け性に優れることが見出されている。したがって、第4の実施形態に係るエポキシ樹脂組成物は、コンプレッション成形による素子の封止に適している。また、一般的にエポキシ樹脂組成物において溶け性の向上を図ると硬化性が低下する傾向にあるが、第4の実施形態に係るエポキシ樹脂組成物によれば優れた硬化性も維持される傾向にある。
第4の実施形態に係る電子部品装置は、素子と、前記素子を封止する上述の第4の実施形態に係るエポキシ樹脂組成物の硬化物と、を備える。
電子部品装置としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ、有機基板等の支持部材に、素子(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など)を搭載して得られた素子部をエポキシ樹脂組成物で封止したものが挙げられる。
より具体的には、リードフレーム上に素子を固定し、ボンディングパッド等の素子の端子部とリード部とをワイヤボンディング、バンプ等で接続した後、エポキシ樹脂組成物を用いて封止した構造を有するDIP(Dual Inline Package)、PLCC(Plastic Leaded Chip Carrier)、QFP(Quad Flat Package)、SOP(Small Outline Package)、SOJ(Small Outline J-lead package)、TSOP(Thin Small Outline Package)、TQFP(Thin Quad Flat Package)等の一般的な樹脂封止型IC;テープキャリアにバンプで接続した素子をエポキシ樹脂組成物で封止した構造を有するTCP(Tape Carrier Package);支持部材上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した素子を、エポキシ樹脂組成物で封止した構造を有するCOB(Chip On Board)モジュール、ハイブリッドIC、マルチチップモジュール等;裏面に配線板接続用の端子を形成した支持部材の表面に素子を搭載し、バンプ又はワイヤボンディングにより素子と支持部材に形成された配線とを接続した後、エポキシ樹脂組成物で素子を封止した構造を有するBGA(Ball Grid Array)、CSP(Chip Size Package)、MCP(Multi Chip Package)などが挙げられる。また、プリント配線板においてもエポキシ樹脂組成物を好適に使用することができる。
第4の実施形態に係る電子部品装置の製造方法は、上述の第4の実施形態に係るエポキシ樹脂組成物のコンプレッション成形により素子を封止することを含む。
〔エポキシ樹脂組成物の調製〕
下記の材料を表1に記載の組成で混合し、混練温度80℃、混練時間15分の条件でロール混練を行うことによって、実施例及び比較例のエポキシ樹脂組成物をそれぞれ調製した。なお、表1中の「-」は、その成分が未配合であることを意味する。
・エポキシ樹脂1:ジフェニルメタン型エポキシ樹脂(ビスフェノール型エポキシ樹脂)(商品名:YSLV-80XY、日鉄ケミカル&マテリアル株式会社、エポキシ当量190g/eq)
・エポキシ樹脂2:ビフェニル型エポキシ樹脂(商品名:YX-4000、三菱ケミカル株式会社、エポキシ当量190g/eq)
・エポキシ樹脂3:トリフェニルメタン型エポキシ樹脂(商品名:1032H60、三菱ケミカル株式会社、エポキシ当量170g/eq)
・硬化剤1: 一般式(B)において、x1~x5はいずれも0、n1は1~10、n2は1~10である化合物(商品名:MEHC7841-4S、明和化成株式会社、水酸基当量164g/eq~168g/eq、軟化点58℃~65℃)
・硬化剤2:一般式(B)以外のアラルキル型フェノール樹脂;一般式(XII)において、iが0であり、R23が全て水素原子である化合物(商品名:MEHC7851-SS、明和化成株式会社、水酸基当量201g/eq~205g/eq、軟化点64℃~69℃)
・硬化剤3:トリフェニルメタン型フェノール樹脂(商品名:MEH7500、明和化成株式会社、水酸基当量95~105g/eq、軟化点105℃~115℃)
・無機充填材1:微粒子アルミナ(平均粒子径0.4μm、最大粒子径2.0μm程度)
・無機充填材2:大粒子アルミナ(平均粒子径10μm、最大粒子径75μm)
・無機充填材3:超微細シリカ(平均粒子径25nm、最大粒子径50nm)
・無機充填材4:微粒子シリカ(平均粒子径0.6μm、最大粒子径5.0μm)
・無機充填材5:大粒子シリカ(平均粒子径10μm、最大粒子径75μm)
・硬化促進剤:リン系硬化促進剤
・カップリング剤:N-フェニル-3-アミノプロピルトリメトキシシラン(商品名:KBM-573、信越化学工業株式会社)
・離型剤:カルナバワックス
・着色剤:カーボンブラック
・イオン交換体:ハイドロタルサイト類化合物(商品名:DHT-4A、協和化学工業株式会社)
実施例及び比較例で調製したエポキシ樹脂組成物の特性を、次の特性試験により評価した。なお、エポキシ樹脂組成物の成形は、明記しない限りトランスファ成形機により、金型温度175℃、成形圧力6.9MPa、硬化時間90秒の条件で成形した。また、必要に応じて後硬化を175℃で5時間の条件で行った。
EMMI-1-66に準じたスパイラルフロー測定用金型を用いて、エポキシ樹脂組成物を上記条件で成形し、流動距離(inch)を求めた。
エポキシ樹脂組成物15gをプレス熱板上の180℃の金型上に乗せ、硬化時間90秒で成形した。成形後、金型に作製された50μm、30μm、20μm、10μm、5μm及び2μmのスリットで一番長くエポキシ樹脂組成物が流れた部分の長さを、ノギスを用いて測定し、この測定値をバリの長さとした。
エポキシ樹脂組成物を上記条件で直径50mm×厚み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。
縦50mm×横35mm×厚さ0.4mmのクロムめっきステンレス板を挿入し、この上に直径20mmの円板を成形する金型を用いて、エポキシ樹脂組成物を上記条件で成形し、成形後直ちに該ステンレス板を引き抜いて最大引き抜き力を記録した。これを同一のステンレス板に対して連続で10回繰り返し、2回目から10回目までの引き抜き力の平均値を求めて評価した。
フローテスタを用いて、175℃に加熱したエポキシ樹脂組成物の溶融粘度を測定した。エポキシ樹脂組成物を電子天秤で計量し、打錠機を用いてタブレットを作製した。試験金型の温度が175℃になっていることを確認し、試料をポット内に投入した。直ちにプランジャをセットし、測定をスタートさせた。
〔エポキシ樹脂組成物の調製〕
下記の材料を表4に記載の組成で混合し、混練温度80℃、混練時間15分の条件でロール混練を行うことによって、実施例及び比較例のエポキシ樹脂組成物をそれぞれ調製した。なお、表4中の「-」は、その成分が未配合であることを意味する。
エポキシ樹脂1:ジフェニルメタン型エポキシ樹脂(ビスフェノール型エポキシ樹脂)(商品名:YSLV-80XY、日鉄ケミカル&マテリアル株式会社、エポキシ当量190g/eq)
エポキシ樹脂2:ビフェニル型エポキシ樹脂(商品名:YX-4000、三菱ケミカル株式会社、エポキシ当量190g/eq)
・硬化剤1:ノボラック型フェノール樹脂(商品名:H-4、明和化成株式会社、水酸基当量103g/eq~107g/eq、軟化点67℃~75℃)
・硬化剤2:アラルキル型フェノール樹脂(商品名:MEHC7800-4S、水酸基当量167g/eq~179g/eq、軟化点61℃~65℃)
・硬化剤3: 一般式(B)において、x1~x5はいずれも0、n1は1~10、n2は1~10である化合物(商品名:MEHC7841-4S、明和化成株式会社、水酸基当量164g/eq~168g/eq、軟化点58℃~65℃)
・硬化剤4:アラルキル型フェノール樹脂(商品名:MEHC7851-SS、明和化成株式会社、水酸基当量201g/eq~205g/eq、軟化点64℃~69℃)
・無機充填材1:微粒子アルミナ(平均粒子径0.4μm、最大粒子径2.0μm程度)
・無機充填材2:大粒子アルミナ(平均粒子径10μm、最大粒子径75μm)
・無機充填材3:超微細シリカ(平均粒子径0.1μm、最大粒子径2.0μm程度)
・硬化促進剤:リン系硬化促進剤
・カップリング剤:N-フェニル-3-アミノプロピルトリメトキシシラン(商品名:KBM-573、信越化学工業株式会社)
・離型剤:カルナバワックス
・着色剤:カーボンブラック
・イオン交換体:ハイドロタルサイト類化合物(商品名:DHT-4A、協和化学工業株式会社)
実施例及び比較例で調製したエポキシ樹脂組成物の特性を、次の特性試験により評価した。
約1.5gのエポキシ樹脂組成物パウダー(3.5mmメッシュパス、1.0mmメッシュオン)を用意した。175℃に熱した熱板(下型)上に、面内円形に、エポキシ樹脂組成物パウダーを高さが約3mmになるように設置した。設置したエポキシ樹脂組成物の上に、同じく175℃に熱した200gの上型を水平方向に自由落下させた。上型は下型と垂直支柱により支えられているため、面内に一定の加重がかかるようにセットしている。上型の落下の時点(すなわち、上型がパウダー上面に到達した時点)を測定0秒とし、エポキシ樹脂組成物パウダーが溶け始めてからの上型の落下距離をレーザー変位計により測定した。エポキシ樹脂組成物の上面の0秒時点の高さをA、1秒後の高さをBとし、B/A×100(%)で計算し、パウダーの溶け性を調査した。
エポキシ樹脂組成物を用いて、圧縮成形機により、金型温度175℃~180℃、成形圧力7MPa、硬化時間150秒の条件で半導体素子を封止して熱伝導率評価用の試験片を作製した。次いで、試験片の熱伝導率をキセノンフラッシュ(Xe-flash)法により測定した。
縦50mm×横35mm×厚さ0.4mmのクロムめっきステンレス板を挿入し、この上に直径20mmの円板を成形する金型を用いて、封止用エポキシ樹脂成形材料を上記条件で成形し、成形後直ちに該ステンレス板を引き抜いて最大引き抜き力を記録した。これを同一のステンレス板に対して連続で10回繰り返し、2回目から10回目までの引き抜き力の平均値を求めて連続成形性を評価した。
混練機の加温域の設定温度を90℃とし、混練機中の4か所における混練物の温度を測定し、温度上昇の度合いを混練性の指標とした。混練物の温度は、エポキシ樹脂組成物の溶け性、せん断発熱、無機充填材の摩擦等により、設定温度よりも上昇する傾向にある。4か所における混練物の温度の平均値が設定温度に近いほど、混練性に優れると判断した。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に援用されて取り込まれる。
Claims (17)
- 前記エポキシ樹脂が、ビフェニル型エポキシ樹脂を含む、請求項1に記載の製造方法。
- 前記トランスファ成形用エポキシ樹脂組成物中の前記ビフェニル型エポキシ樹脂の含有率が、前記エポキシ樹脂の全質量に対して30質量%~100質量%である、請求項2に記載の製造方法。
- 前記無機充填材の含有率が前記トランスファ成形用エポキシ樹脂組成物の全体積に対して60体積%以上である、請求項1~請求項3のいずれか1項に記載の製造方法。
- 前記トランスファ成形用エポキシ樹脂組成物中の前記硬化剤の全質量に対する前記一般式(B)で表される化合物の含有率が30質量%~100質量%である、請求項1~請求項4のいずれか1項に記載の製造方法。
- エポキシ樹脂と、
無機充填材と、
以下の一般式(B)で表される化合物を含む硬化剤と、
を含有し、
前記無機充填材は平均粒子径50nm以下の無機充填材と平均粒子径が50nmより大きい無機充填材との混合物であり、前記平均粒子径50nm以下の無機充填材の含有量は、前記エポキシ樹脂100質量部に対して5質量部以上である、
トランスファ成形用エポキシ樹脂組成物。
一般式(B)中、
R1~R5は、それぞれ独立に、炭素数1~6の1価の有機基を表し、
X1~X3は、それぞれ独立に、0~4の整数を表し、
X4及びX5は、それぞれ独立に、0~3の整数を表し、
n1は1~10の数を表し、
n2は1~10の数を表す。 - 前記エポキシ樹脂が、ビフェニル型エポキシ樹脂を含む、請求項6又は請求項7に記載のトランスファ成形用エポキシ樹脂組成物。
- 前記ビフェニル型エポキシ樹脂の含有率が、前記エポキシ樹脂の全質量に対して30質量%~100質量%である、請求項8に記載のトランスファ成形用エポキシ樹脂組成物。
- 前記無機充填材の含有率が、前記エポキシ樹脂組成物の全体積に対して60体積%以上である、請求項6~請求項9のいずれか1項に記載のトランスファ成形用エポキシ樹脂組成物。
- 前記硬化剤の全質量に対する前記一般式(B)で表される化合物の含有率が30質量%~100質量%である、請求項6~請求項10のいずれか1項に記載のトランスファ成形用エポキシ樹脂組成物。
- 素子と、
前記素子を封止する、請求項1~請求項5のいずれか1項に記載の製造方法により得られたエポキシ樹脂組成物の硬化物、又は請求項6~請求項11のいずれか1項に記載のエポキシ樹脂組成物の硬化物と、
を備える電子部品装置。 - 前記無機充填材の含有率が前記コンプレッション成形用エポキシ樹脂組成物の全体積に対して60体積%以上である、請求項13に記載のコンプレッション成形用エポキシ樹脂組成物。
- 前記硬化剤の全質量に対する前記一般式(B)で表される化合物の含有率が30質量%~100質量%である、請求項13又は請求項14に記載のコンプレッション成形用エポキシ樹脂組成物。
- さらに離型剤を含有し、前記離型剤の含有率が前記コンプレッション成形用エポキシ樹脂組成物の全質量に対して0質量%を超え2.0質量%以下である、請求項13~請求項15のいずれか1項に記載のコンプレッション成形用エポキシ樹脂組成物。
- 素子と、
前記素子を封止する請求項13~請求項16のいずれか1項に記載のコンプレッション成形用エポキシ樹脂組成物の硬化物と、
を備える電子部品装置。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021575838A JPWO2021157623A1 (ja) | 2020-02-06 | 2021-02-03 | |
CN202180007355.1A CN114945618A (zh) | 2020-02-06 | 2021-02-03 | 转注成形用环氧树脂组合物及其制造方法、压缩成形用环氧树脂组合物和电子零件装置 |
KR1020227021998A KR20220139855A (ko) | 2020-02-06 | 2021-02-03 | 트랜스퍼 성형용 에폭시 수지 조성물 및 그 제조 방법, 컴프레션 성형용 에폭시 수지 조성물, 그리고 전자 부품 장치 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-019082 | 2020-02-06 | ||
JP2020019082 | 2020-02-06 | ||
JP2020-019083 | 2020-02-06 | ||
JP2020019083 | 2020-02-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021157623A1 true WO2021157623A1 (ja) | 2021-08-12 |
Family
ID=77200504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/003980 WO2021157623A1 (ja) | 2020-02-06 | 2021-02-03 | トランスファ成形用エポキシ樹脂組成物及びその製造方法、コンプレッション成形用エポキシ樹脂組成物、並びに電子部品装置 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPWO2021157623A1 (ja) |
KR (1) | KR20220139855A (ja) |
CN (1) | CN114945618A (ja) |
TW (1) | TW202231704A (ja) |
WO (1) | WO2021157623A1 (ja) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006143784A (ja) * | 2004-11-16 | 2006-06-08 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
WO2006095914A1 (ja) * | 2005-03-10 | 2006-09-14 | Sumitomo Bakelite Co., Ltd. | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2008208222A (ja) * | 2007-02-26 | 2008-09-11 | Sumitomo Bakelite Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2011012125A (ja) * | 2009-06-30 | 2011-01-20 | Mitsui Chemicals Inc | 封止用エポキシ樹脂成形材料、および半導体装置用中空パッケージ、並びに半導体部品装置 |
JP2018016669A (ja) * | 2016-07-25 | 2018-02-01 | スリーエム イノベイティブ プロパティズ カンパニー | 成形体、電気機器部品及び電気機器部品の製造方法 |
WO2020129249A1 (ja) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | 封止用樹脂組成物及び電子部品装置 |
WO2020129248A1 (ja) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | 封止用樹脂組成物及び電子部品装置 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06224328A (ja) | 1993-01-26 | 1994-08-12 | Nippon Steel Corp | 半導体封止用樹脂組成物 |
JP2007153969A (ja) | 2005-12-02 | 2007-06-21 | Showa Denko Kk | 高熱伝導性樹脂組成物および配線用基板 |
JP5189606B2 (ja) | 2010-01-26 | 2013-04-24 | パナソニック株式会社 | 半導体封止用エポキシ樹脂組成物、及び半導体装置 |
-
2021
- 2021-02-03 CN CN202180007355.1A patent/CN114945618A/zh active Pending
- 2021-02-03 WO PCT/JP2021/003980 patent/WO2021157623A1/ja active Application Filing
- 2021-02-03 KR KR1020227021998A patent/KR20220139855A/ko unknown
- 2021-02-03 JP JP2021575838A patent/JPWO2021157623A1/ja active Pending
- 2021-02-04 TW TW110104265A patent/TW202231704A/zh unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006143784A (ja) * | 2004-11-16 | 2006-06-08 | Sumitomo Bakelite Co Ltd | エポキシ樹脂組成物及び半導体装置 |
WO2006095914A1 (ja) * | 2005-03-10 | 2006-09-14 | Sumitomo Bakelite Co., Ltd. | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2008208222A (ja) * | 2007-02-26 | 2008-09-11 | Sumitomo Bakelite Co Ltd | 半導体封止用エポキシ樹脂組成物及び半導体装置 |
JP2011012125A (ja) * | 2009-06-30 | 2011-01-20 | Mitsui Chemicals Inc | 封止用エポキシ樹脂成形材料、および半導体装置用中空パッケージ、並びに半導体部品装置 |
JP2018016669A (ja) * | 2016-07-25 | 2018-02-01 | スリーエム イノベイティブ プロパティズ カンパニー | 成形体、電気機器部品及び電気機器部品の製造方法 |
WO2020129249A1 (ja) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | 封止用樹脂組成物及び電子部品装置 |
WO2020129248A1 (ja) * | 2018-12-21 | 2020-06-25 | 日立化成株式会社 | 封止用樹脂組成物及び電子部品装置 |
Also Published As
Publication number | Publication date |
---|---|
KR20220139855A (ko) | 2022-10-17 |
CN114945618A (zh) | 2022-08-26 |
JPWO2021157623A1 (ja) | 2021-08-12 |
TW202231704A (zh) | 2022-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7302598B2 (ja) | 硬化性樹脂組成物及び電子部品装置 | |
JP2023068032A (ja) | 硬化性樹脂組成物用添加剤、硬化性樹脂組成物及び電子部品装置 | |
JP2022101587A (ja) | エポキシ樹脂組成物、硬化性樹脂組成物、及び電子部品装置 | |
WO2021075207A1 (ja) | エポキシ樹脂組成物、電子部品装置、及び電子部品装置の製造方法 | |
JP7484081B2 (ja) | 硬化性樹脂組成物及び電子部品装置 | |
JP7322368B2 (ja) | 硬化性樹脂組成物及び電子部品装置 | |
JP7269579B2 (ja) | エポキシ樹脂組成物及び電子部品装置 | |
JPWO2019176859A1 (ja) | エポキシ樹脂組成物、及び電子部品装置 | |
CN111094450A (zh) | 环氧树脂组合物和电子部件装置 | |
JP2018104603A (ja) | 硬化性樹脂組成物及び電子部品装置 | |
WO2021157623A1 (ja) | トランスファ成形用エポキシ樹脂組成物及びその製造方法、コンプレッション成形用エポキシ樹脂組成物、並びに電子部品装置 | |
JP6708242B2 (ja) | モールドアンダーフィル用樹脂組成物及び電子部品装置 | |
WO2021220726A1 (ja) | 封止用エポキシ樹脂組成物、電子部品装置及びその製造方法 | |
WO2022075453A1 (ja) | 硬化性樹脂組成物及び電子部品装置 | |
WO2023120738A1 (ja) | 封止材組成物及び電子部品装置 | |
WO2023032971A1 (ja) | 圧縮成形用エポキシ樹脂組成物及び電子部品装置 | |
WO2022149602A1 (ja) | 熱硬化性樹脂組成物及び電子部品装置 | |
JP2022107374A (ja) | 熱硬化性樹脂組成物の製造方法、熱硬化性樹脂組成物、及び電子部品装置 | |
JP2022007673A (ja) | 封止用樹脂組成物の製造方法、封止用樹脂組成物、電子部品装置の製造方法、及び電子部品装置 | |
JP2023034255A (ja) | 樹脂硬化物及び電子部品装置 | |
CN113195585A (zh) | 硬化性树脂组合物及电子零件装置 | |
JP2021195480A (ja) | 封止用樹脂組成物及び電子部品装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21750173 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021575838 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 08/11/2022). |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21750173 Country of ref document: EP Kind code of ref document: A1 |