JP2021167422A - Epoxy resin composition, epoxy resin cured product, and electronic component device - Google Patents
Epoxy resin composition, epoxy resin cured product, and electronic component device Download PDFInfo
- Publication number
- JP2021167422A JP2021167422A JP2021109917A JP2021109917A JP2021167422A JP 2021167422 A JP2021167422 A JP 2021167422A JP 2021109917 A JP2021109917 A JP 2021109917A JP 2021109917 A JP2021109917 A JP 2021109917A JP 2021167422 A JP2021167422 A JP 2021167422A
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- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- mass
- content
- inorganic filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 204
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 204
- 239000000203 mixture Substances 0.000 title claims abstract description 129
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 239000011256 inorganic filler Substances 0.000 claims abstract description 38
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 238000009835 boiling Methods 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 description 27
- 239000002245 particle Substances 0.000 description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- 150000001450 anions Chemical class 0.000 description 15
- 239000005011 phenolic resin Substances 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 12
- -1 phenol compound Chemical class 0.000 description 12
- 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 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- 239000006082 mold release agent Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 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
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000004203 carnauba wax Substances 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 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 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000002249 anxiolytic agent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- QDOIZVITZUBGOQ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluoro-n,n-bis(1,1,2,2,3,3,4,4,4-nonafluorobutyl)butan-1-amine;1,1,2,2,3,3,4,4,4-nonafluoro-n-(1,1,2,2,3,3,4,4,4-nonafluorobutyl)-n-(trifluoromethyl)butan-1-amine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QDOIZVITZUBGOQ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004206 montan acid ester Substances 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 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
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000058 polyacrylate Polymers 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
Abstract
Description
本発明は、エポキシ樹脂組成物、エポキシ樹脂硬化物及び電子部品装置に関する。 The present invention relates to epoxy resin compositions, epoxy resin cured products, and electronic component devices.
従来から、成形品、積層板、接着剤、各種電子電気部品、塗料、インキ等の材料として、エポキシ樹脂等の硬化性樹脂が広く使用されている。特に、トランジスタ、ＩＣ（Integrated Circuit）等の電子部品素子の封止技術に関する分野では、封止材料としてエポキシ樹脂組成物が広く使用されている。この理由としては、エポキシ樹脂は、成形性、電気特性、耐湿性、耐熱性、機械特性、インサート品との接着性等の諸特性においてバランスがとれているためである。 Conventionally, curable resins such as epoxy resins have been widely used as materials for molded products, laminated boards, adhesives, various electronic and electrical parts, paints, inks, and the like. In particular, in the field of sealing technology for electronic component elements such as transistors and ICs (Integrated Circuits), epoxy resin compositions are widely used as sealing materials. The reason for this is that the epoxy resin is well-balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness to insert products.
一方、近年、電子部品の分野では高速化及び高密度化が進んでおり、それに伴って、電子部品の発熱量が顕著に増大している。また、高温下で作動する電子部品に対する需要も増加している。そのため、電子部品に使用されるプラスチック、特にエポキシ樹脂の硬化物に対しては、熱伝導性の向上が求められている。 On the other hand, in recent years, the speed and density of electronic components have been increasing, and the amount of heat generated by electronic components has increased remarkably. There is also an increasing demand for electronic components that operate at high temperatures. Therefore, it is required to improve the thermal conductivity of plastics used for electronic parts, particularly cured products of epoxy resins.
エポキシ樹脂の硬化物の熱伝導性を向上させるための手法として、結晶性のエポキシ樹脂を用いる方法、高熱伝導性フィラーのエポキシ樹脂組成物中の充填量を増やす方法等が報告されている（例えば、特許文献１〜４参照）。 As a method for improving the thermal conductivity of the cured product of the epoxy resin, a method using a crystalline epoxy resin, a method of increasing the filling amount of the highly thermally conductive filler in the epoxy resin composition, and the like have been reported (for example). , Patent Documents 1 to 4).
しかしながら、上記特許文献に記載された方法では、エポキシ樹脂の軟化点の上昇又はフィラー充填量の増大を伴うため、エポキシ樹脂組成物の流動性が低下して成形性を損なう可能性がある。従って、硬化後の熱伝導性を高く維持しつつ、かつ流動性に優れるエポキシ樹脂組成物の開発が求められている。
本発明の課題は、流動性に優れるエポキシ樹脂組成物、前記エポキシ樹脂組成物の硬化物であるエポキシ樹脂硬化物、並びに前記エポキシ樹脂硬化物によって封止された素子を備える電子部品装置を提供することである。
However, in the method described in the above patent document, since the softening point of the epoxy resin is increased or the filler filling amount is increased, the fluidity of the epoxy resin composition may be lowered and the moldability may be impaired. Therefore, it is required to develop an epoxy resin composition having excellent fluidity while maintaining high thermal conductivity after curing.
An object of the present invention is to provide an electronic component device including an epoxy resin composition having excellent fluidity, an epoxy resin cured product which is a cured product of the epoxy resin composition, and an element sealed by the epoxy resin cured product. That is.
本発明は、以下の実施形態を含む。
＜１＞ エポキシ樹脂と、硬化剤と、無機充填材と、沸点が５０℃〜１００℃である有機溶剤と、を含有するエポキシ樹脂組成物。
＜２＞ 前記有機溶剤の含有率が、０．１質量％〜１０質量％である＜１＞に記載のエポキシ樹脂組成物。
＜３＞ 前記無機充填材の含有率が、５５質量％〜９５質量％である＜１＞又は＜２＞に記載のエポキシ樹脂組成物。
＜４＞ 更にカップリング剤を含有する＜１＞〜＜３＞のいずれか１つに記載のエポキシ樹脂組成物。
＜５＞ 前記カップリング剤の含有率が、０．０５質量％〜５．０質量％である＜４＞に記載のエポキシ樹脂組成物。
＜６＞ タブレット状であり、かつ沸点が５０℃〜１００℃である有機溶剤の含有率が、０．３質量％〜３．０質量％であるエポキシ樹脂組成物。
The present invention includes the following embodiments.
<1> An epoxy resin composition containing an epoxy resin, a curing agent, an inorganic filler, and an organic solvent having a boiling point of 50 ° C. to 100 ° C.
<2> The epoxy resin composition according to <1>, wherein the content of the organic solvent is 0.1% by mass to 10% by mass.
<3> The epoxy resin composition according to <1> or <2>, wherein the content of the inorganic filler is 55% by mass to 95% by mass.
<4> The epoxy resin composition according to any one of <1> to <3>, which further contains a coupling agent.
<5> The epoxy resin composition according to <4>, wherein the content of the coupling agent is 0.05% by mass to 5.0% by mass.
<6> An epoxy resin composition having a tablet-like shape and a boiling point of 50 ° C. to 100 ° C. and a content of an organic solvent of 0.3% by mass to 3.0% by mass.
＜７＞ ＜１＞〜＜６＞のいずれか１つに記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。 <7> An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of <1> to <6>.
＜８＞ 素子と、前記素子を封止している＜７＞に記載のエポキシ樹脂硬化物と、を有する電子部品装置。 <8> An electronic component device comprising the element and the epoxy resin cured product according to <7>, which seals the element.
本発明によれば、流動性に優れるエポキシ樹脂組成物、前記エポキシ樹脂組成物の硬化物であるエポキシ樹脂硬化物、並びに前記エポキシ樹脂硬化物によって封止された素子を備える電子部品装置を提供することができる。 According to the present invention, there is provided an electronic component device including an epoxy resin composition having excellent fluidity, an epoxy resin cured product which is a cured product of the epoxy resin composition, and an element sealed by the epoxy resin cured product. be able to.
本明細書において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本明細書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、本明細書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。
本明細書において組成物中の各成分の含有量及び含有率は、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、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量及び含有率を意味する。
本明細書において組成物中の各成分の粒子径は、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、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。
In the present specification, 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. Is done.
The numerical range indicated by using "~" in the present specification indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present specification, 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. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present specification, the content and the content rate of each component in the composition are the same when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. It means the total content and content of substances.
In the present specification, the particle size of each component in the composition is a mixture of the plurality of particles existing in the composition unless otherwise specified, when a plurality of particles corresponding to each component are present in the composition. Means a value for.
＜エポキシ樹脂組成物＞
本発明の一実施形態におけるエポキシ樹脂組成物は、エポキシ樹脂と、硬化剤と、無機充填材と、沸点が５０℃〜１００℃である有機溶剤と、を含有する。これにより、本実施形態のエポキシ樹脂組成物は、流動性に優れる。
<Epoxy resin composition>
The epoxy resin composition in one embodiment of the present invention contains an epoxy resin, a curing agent, an inorganic filler, and an organic solvent having a boiling point of 50 ° C. to 100 ° C. As a result, the epoxy resin composition of the present embodiment has excellent fluidity.
［エポキシ樹脂］
本実施形態のエポキシ樹脂組成物は、エポキシ樹脂を含有し、好ましくは、１分子中に２個以上のエポキシ基を有するエポキシ樹脂を含有する。１分子中に２個以上のエポキシ基を有するエポキシ樹脂としては、ビフェニレン型エポキシ樹脂、スチルベン型エポキシ樹脂、硫黄原子含有エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、サリチルアルデヒド型エポキシ樹脂、ナフトール類とフェノール類との共重合型エポキシ樹脂、アラルキル型エポキシ樹脂、ジフェニルメタン型エポキシ樹脂及びトリフェニルメタン型エポキシ樹脂からなる群より選択される少なくとも１種（以下、特定エポキシ樹脂ともいう）が挙げられる。中でも、ビフェニレン型エポキシ樹脂及びジフェニルメタン型エポキシ樹脂が好ましい。エポキシ樹脂は、１種単独で用いても２種以上を組み合わせて用いてもよい。
[Epoxy resin]
The epoxy resin composition of the present embodiment contains an epoxy resin, and preferably contains an epoxy resin having two or more epoxy groups in one molecule. Examples of the epoxy resin having two or more epoxy groups in one molecule include biphenylene type epoxy resin, stillben type epoxy resin, sulfur atom-containing epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, and salicylaldehyde type epoxy resin. , At least one selected from the group consisting of a copolymerized epoxy resin of naphthols and phenols, an aralkyl type epoxy resin, a diphenylmethane type epoxy resin and a triphenylmethane type epoxy resin (hereinafter, also referred to as a specific epoxy resin). Can be mentioned. Of these, biphenylene type epoxy resin and diphenylmethane type epoxy resin are preferable. The epoxy resin may be used alone or in combination of two or more.
エポキシ樹脂組成物がエポキシ樹脂として特定エポキシ樹脂を含む場合、特定エポキシ樹脂以外のその他のエポキシ樹脂をエポキシ樹脂として更に含んでもよい。その他のエポキシ樹脂としては、当該分野で通常用いられるエポキシ樹脂を挙げることができる。具体的には、例えば、柔軟性又は接着性を向上させるために官能基又は骨格を変性したエポキシ−シリカハイブリッド樹脂、及び柔軟強靭性液状エポキシ樹脂を挙げることができる。その他のエポキシ樹脂は、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。 When the epoxy resin composition contains the specific epoxy resin as the epoxy resin, other epoxy resins other than the specific epoxy resin may be further contained as the epoxy resin. Examples of other epoxy resins include epoxy resins usually used in the art. Specific examples thereof include an epoxy-silica hybrid resin in which a functional group or a skeleton is modified in order to improve flexibility or adhesiveness, and a flexible tough liquid epoxy resin. As for other epoxy resins, one type may be used alone or two or more types may be used in combination.
エポキシ樹脂組成物がエポキシ樹脂として特定エポキシ樹脂を含む場合、エポキシ樹脂全量中の特定エポキシ樹脂の総含有率は、特定エポキシ樹脂の性能を充分に発揮する観点から、６０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。 When the epoxy resin composition contains the specific epoxy resin as the epoxy resin, the total content of the specific epoxy resin in the total amount of the epoxy resin is 60% by mass or more from the viewpoint of fully exhibiting the performance of the specific epoxy resin. It is more preferably 75% by mass or more, and even more preferably 90% by mass or more.
エポキシ樹脂組成物に含まれるエポキシ樹脂のエポキシ当量は、９０ｇ／ｅｑ〜５００ｇ／ｅｑであることが好ましく、１４０ｇ／ｅｑ〜４５０ｇ／ｅｑであることがより好ましく、１９０ｇ／ｅｑ〜４００ｇ／ｅｑであることが更に好ましい。 The epoxy equivalent of the epoxy resin contained in the epoxy resin composition is preferably 90 g / eq to 500 g / eq, more preferably 140 g / eq to 450 g / eq, and 190 g / eq to 400 g / eq. Is even more preferable.
エポキシ樹脂のエポキシ当量は、ＪＩＳ Ｋ ７２３６：２００９に準じた方法で測定される値とする。 The epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.
エポキシ樹脂の融点又は軟化点は、５０℃〜２５０℃であることが好ましく、６５℃〜２００℃であることがより好ましく、８０℃〜１７０℃であることが更に好ましい。 The melting point or softening point of the epoxy resin is preferably 50 ° C. to 250 ° C., more preferably 65 ° C. to 200 ° C., and even more preferably 80 ° C. to 170 ° C.
エポキシ樹脂の融点又は軟化点は、ＪＩＳ Ｋ ７２３４：１９８６及びＪＩＳ Ｋ ７２３３：１９８６に記載の単一円筒回転粘度計法により測定される値とする。 The melting point or softening point of the epoxy resin shall be a value measured by the single cylinder rotational viscometer method described in JIS K 7234: 1986 and JIS K 7233: 1986.
［硬化剤］
本実施形態のエポキシ樹脂組成物は、硬化剤を含有する。硬化剤は、エポキシ樹脂と反応しうるものであれば特に制限されない。耐熱性向上の観点から、硬化剤は、１分子中に２個以上のフェノール性水酸基を有する化合物（以下、フェノール硬化剤ともいう）が好ましい。フェノール硬化剤は、低分子のフェノール化合物であっても、低分子のフェノール化合物を高分子化したフェノール樹脂であってもよい。熱伝導性の観点からは、フェノール硬化剤はフェノール樹脂であることが好ましい。
[Curing agent]
The epoxy resin composition of the present embodiment contains a curing agent. The curing agent is not particularly limited as long as it can react with the epoxy resin. From the viewpoint of improving heat resistance, the curing agent is preferably a compound having two or more phenolic hydroxyl groups in one molecule (hereinafter, also referred to as a phenol curing agent). The phenol curing agent may be a low-molecular-weight phenol compound or a phenol resin obtained by polymerizing a low-molecular-weight phenol compound. From the viewpoint of thermal conductivity, the phenol curing agent is preferably a phenol resin.
フェノール樹脂としては、ビフェニレン型フェノール樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ベンズアルデヒド型フェノール樹脂とアラルキル型フェノール樹脂との共重合樹脂及びトリフェニルメタン型フェノール樹脂からなる群より選択される少なくとも１種（以下、特定フェノール硬化剤ともいう）が挙げられる。中でも、トリフェニルメタン型フェノール樹脂が好ましい。硬化剤は、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。 The phenol resin is selected from the group consisting of biphenylene-type phenol resin, aralkyl-type phenol resin, dicyclopentadiene-type phenol resin, copolymer resin of benzaldehyde-type phenol resin and aralkyl-type phenol resin, and triphenylmethane-type phenol resin. At least one type (hereinafter, also referred to as a specific phenol curing agent) can be mentioned. Of these, a triphenylmethane type phenol resin is preferable. As the curing agent, one type may be used alone or two or more types may be used in combination.
エポキシ樹脂組成物が硬化剤として特定フェノール硬化剤を含む場合、特定フェノール硬化剤以外のその他の硬化剤を更に含んでもよい。その他の硬化剤としては、当該分野で通常用いられる、特定フェノール硬化剤以外のフェノール樹脂を挙げることができる。その他の硬化剤は、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。 When the epoxy resin composition contains a specific phenol curing agent as a curing agent, other curing agents other than the specific phenol curing agent may be further contained. Examples of other curing agents include phenol resins other than the specific phenol curing agents commonly used in the art. Other curing agents may be used alone or in combination of two or more.
エポキシ樹脂組成物が硬化剤として特定フェノール硬化剤を含む場合、特定フェノール硬化剤の性能を充分に発揮する観点から、硬化剤全量中の特定フェノール硬化剤の含有率は、６０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。 When the epoxy resin composition contains a specific phenol curing agent as a curing agent, the content of the specific phenol curing agent in the total amount of the curing agent is 60% by mass or more from the viewpoint of fully exhibiting the performance of the specific phenol curing agent. It is preferably 75% by mass or more, more preferably 90% by mass or more.
エポキシ樹脂組成物に含まれる硬化剤の水酸基当量は、７０ｇ／ｅｑ〜５００ｇ／ｅｑであることが好ましく、１００ｇ／ｅｑ〜４５０ｇ／ｅｑであることがより好ましく、１５０ｇ／ｅｑ〜４００ｇ／ｅｑであることが更に好ましい。 The hydroxyl group equivalent of the curing agent contained in the epoxy resin composition is preferably 70 g / eq to 500 g / eq, more preferably 100 g / eq to 450 g / eq, and more preferably 150 g / eq to 400 g / eq. Is even more preferable.
硬化剤の水酸基当量は、ＪＩＳ Ｋ ００７０：１９９２に準じた方法により測定される値とする。 The hydroxyl group equivalent of the curing agent shall be a value measured by a method according to JIS K 0070: 1992.
エポキシ樹脂組成物に含まれる硬化剤の融点又は軟化点は、５０℃〜２５０℃であることが好ましく、６５℃〜２００℃であることがより好ましく、８０℃〜１７０℃であることが更に好ましい。 The melting point or softening point of the curing agent contained in the epoxy resin composition is preferably 50 ° C. to 250 ° C., more preferably 65 ° C. to 200 ° C., and even more preferably 80 ° C. to 170 ° C. ..
硬化剤の融点又は軟化点は、ＪＩＳ Ｋ ７２３４：１９８６及びＪＩＳ Ｋ ７２３３：１９８６に記載の単一円筒回転粘度計法により測定される値とする。 The melting point or softening point of the curing agent shall be a value measured by the single cylinder rotational viscometer method described in JIS K 7234: 1986 and JIS K 7233: 1986.
エポキシ樹脂組成物における、エポキシ樹脂と硬化剤との含有比率は、エポキシ樹脂のエポキシ基の当量数に対する硬化剤の水酸基の当量数の比率（水酸基の当量数／エポキシ基の当量数）が０．５〜２．０の範囲となるように設定されることが好ましく、０．７〜１．５となるように設定されることがより好ましく、０．８〜１．３となるように設定されることが更に好ましい。前記比率が０．５以上であると、エポキシ樹脂の硬化が充分となり、硬化物の耐熱性、耐湿性、及び電気特性に優れる傾向にある。また、前記比率が２．０以下であると、硬化樹脂中に残存するフェノール性水酸基の量が抑えられ、電気特性及び耐湿性に優れる傾向にある。 In the epoxy resin composition, the content ratio of the epoxy resin and the curing agent is such that the ratio of the number of hydroxyl groups of the curing agent to the number of equivalents of the epoxy groups of the epoxy resin (the number of hydroxyl groups / the number of epoxy groups) is 0. It is preferably set to be in the range of 5 to 2.0, more preferably set to 0.7 to 1.5, and set to be 0.8 to 1.3. Is more preferable. When the ratio is 0.5 or more, the epoxy resin is sufficiently cured, and the cured product tends to be excellent in heat resistance, moisture resistance, and electrical characteristics. Further, when the ratio is 2.0 or less, the amount of phenolic hydroxyl groups remaining in the cured resin is suppressed, and the electrical characteristics and moisture resistance tend to be excellent.
エポキシ樹脂組成物における、エポキシ樹脂と硬化剤との組み合わせの例としては、以下のものが挙げられる。
（１）エポキシ樹脂が特定エポキシ樹脂から選択される少なくとも１種を含み、硬化剤が特定フェノール硬化剤から選択される少なくとも１種を含む組み合わせ
（２）エポキシ樹脂がビフェニレン型エポキシ樹脂を含み、硬化剤が特定フェノール硬化剤から選択される少なくとも１種を含む組み合わせ
（３）エポキシ樹脂がジフェニルメタン型エポキシ樹脂を含み、硬化剤がトリフェニルメタン型フェノール樹脂を含む組み合わせ
Examples of the combination of the epoxy resin and the curing agent in the epoxy resin composition include the following.
(1) A combination in which the epoxy resin contains at least one selected from the specific epoxy resin and the curing agent contains at least one selected from the specific phenol curing agent (2) The epoxy resin contains a biphenylene type epoxy resin and is cured. A combination in which the agent contains at least one selected from specific phenol curing agents (3) A combination in which the epoxy resin contains a diphenylmethane type epoxy resin and the curing agent contains a triphenylmethane type phenol resin.
［無機充填材］
本実施形態のエポキシ樹脂組成物は、無機充填材を含有する。エポキシ樹脂組成物が無機充填材を含有することで、エポキシ樹脂組成物の硬化物の熱膨張係数（線膨張係数）、熱伝導率、弾性率等の向上を図ることができる。
[Inorganic filler]
The epoxy resin composition of the present embodiment contains an inorganic filler. When the epoxy resin composition contains an inorganic filler, it is possible to improve the thermal expansion coefficient (linear expansion coefficient), thermal conductivity, elastic modulus, etc. of the cured product of the epoxy resin composition.
無機充填材は特に制限されず、封止用エポキシ樹脂組成物に一般に用いられているものを適宜選択して使用することができる。無機充填材としては、溶融シリカ、結晶シリカ、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、酸化マグネシウム、ケイ酸カルシウム、窒化ケイ素、窒化アルミニウム、窒化ホウ素、炭化ケイ素、工業用ダイヤモンド、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカ等の無機物の粒子、これらの粒子を球形化したビーズなどが挙げられる。その他、難燃効果のある無機充填材も使用できる。難燃効果のあ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との複合水酸化物等の複合金属水酸化物、ホウ酸亜鉛などの粒子が挙げられる。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。 The inorganic filler is not particularly limited, and those generally used for the sealing epoxy resin composition can be appropriately selected and used. Inorganic fillers include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, magnesium oxide, calcium silicate, silicon nitride, aluminum nitride, boron nitride, silicon carbide, industrial diamond, beryllium, zirconia, Examples include inorganic particles such as zircon, fosterite, steatite, spinel, mulite, titania, talc, clay, and mica, and spherical beads of these particles. In addition, an inorganic filler having a flame-retardant effect can also 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 particles such as zinc borate. As the inorganic filler, one type may be used alone or two or more types may be used in combination.
無機充填材の中でも、エポキシ樹脂組成物の硬化物の線膨張係数を低減する観点からは溶融シリカ等のシリカ粒子が好ましく、エポキシ樹脂組成物の硬化物の熱伝導性を向上する観点からはアルミナ粒子が好ましい。 Among the inorganic fillers, silica particles such as molten silica are preferable from the viewpoint of reducing the linear expansion coefficient of the cured product of the epoxy resin composition, and alumina is preferable from the viewpoint of improving the thermal conductivity of the cured product of the epoxy resin composition. Particles are preferred.
エポキシ樹脂組成物中の無機充填材の含有率は、特に制限されない。無機充填材の含有率は、例えば、エポキシ樹脂組成物の全質量に対して５５質量％〜９５質量％であることが好ましく、６０質量％〜９０質量％であることがより好ましい。無機充填材の含有率が５５質量％以上であると、エポキシ樹脂組成物の硬化物の線膨張係数、熱伝導率、弾性率等に優れる傾向にある。無機充填材の含有率が９５質量％以下であると、エポキシ樹脂組成物の粘度の上昇が抑えられて流動性に優れ、パッケージの成形が容易になる傾向にある。 The content of the inorganic filler in the epoxy resin composition is not particularly limited. The content of the inorganic filler is, for example, preferably 55% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, based on the total mass of the epoxy resin composition. When the content of the inorganic filler is 55% by mass or more, the cured product of the epoxy resin composition tends to have excellent linear expansion coefficient, thermal conductivity, elastic modulus and the like. When the content of the inorganic filler is 95% by mass or less, the increase in viscosity of the epoxy resin composition is suppressed, the fluidity is excellent, and the molding of the package tends to be easy.
無機充填材の平均粒子径は、特に制限されない。無機充填材の平均粒子径は、例えば、０．１μｍ〜８０μｍであることが好ましく、０．３μｍ〜５０μｍであることがより好ましい。無機充填材の平均粒子径が０．１μｍ以上であると、エポキシ樹脂組成物の粘度の上昇を抑えやすい傾向にある。無機充填材の平均粒子径が８０μｍ以下であると、エポキシ樹脂組成物と無機充填材との混合性が向上し、硬化によって得られるパッケージの状態がより均質化して特性のばらつきが抑えられる傾向にあり、更に狭い領域への充填性が向上する傾向にある。なお、無機充填材の粒子径の分布は、０．１μｍ〜８０μｍの範囲内に最大値を有することが好ましい。 The average particle size of the inorganic filler is not particularly limited. The average particle size of the inorganic filler is, for example, preferably 0.1 μm to 80 μm, and more preferably 0.3 μm to 50 μm. When the average particle size of the inorganic filler is 0.1 μm or more, it tends to be easy to suppress an increase in the viscosity of the epoxy resin composition. When the average particle size of the inorganic filler is 80 μm or less, the mixing property of the epoxy resin composition and the inorganic filler is improved, and the state of the package obtained by curing tends to be more homogenized and the variation in characteristics is suppressed. There is a tendency to improve the filling property in a narrower area. The distribution of the particle size of the inorganic filler preferably has a maximum value in the range of 0.1 μm to 80 μm.
本明細書において無機充填材の平均粒子径は、乾式の粒度分布計を使用して、又は、水若しくは有機溶媒中に無機充填材を分散したスラリーの状態で湿式の粒度分布測定装置を使用して測定できる。特に１μｍ以下の粒子を含む場合は、湿式の粒度分布計を使用して測定することが好ましい。具体的には、無機充填材の濃度を約０．０１質量％に調整した水スラリーをバス式超音波洗浄機で５分間処理し、レーザー回折式粒度測定装置（ＬＡ−９６０、株式会社堀場製作所）を用いて検出された全粒子の平均値より求めることができる。 In the present specification, the average particle size of the inorganic filler is determined by using a dry particle size distribution meter or by using a wet particle size distribution measuring device in the state of a slurry in which the inorganic filler is dispersed in water or an organic solvent. Can be measured. In particular, when particles of 1 μm or less are contained, it is preferable to measure using a wet particle size distribution meter. Specifically, a water slurry in which the concentration of the inorganic filler is adjusted to about 0.01% by mass is treated with a bath-type ultrasonic cleaner for 5 minutes, and a laser diffraction type particle size measuring device (LA-960, HORIBA, Ltd.) ) Can be obtained from the average value of all particles detected using.
エポキシ樹脂組成物の流動性の観点から、無機充填材の粒子形状は角形より球形が好ましく、無機充填材の粒度分布は広範囲に分布したものが好ましい。例えば、無機充填材を５５体積％以上含有する場合、その７０質量％以上を球状粒子とし、この球状粒子の粒径は０．１μｍ〜８０μｍという広範囲に分布したものが好ましい。このような無機充填材は、大きさが異なる粒子が混在することで最密充填構造を形成しやすいため、無機充填材の含有率を増加させてもエポキシ樹脂組成物の粘度上昇が抑えられ、流動性に優れるエポキシ樹脂組成物が得られる傾向にある。 From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical rather than square, and the particle size distribution of the inorganic filler is preferably widely distributed. For example, when the inorganic filler is contained in an amount of 55% by volume or more, it is preferable that 70% by mass or more of the inorganic filler is spherical particles and the particle size of the spherical particles is widely distributed from 0.1 μm to 80 μm. Since such an inorganic filler tends to form a close-packed structure by mixing particles of different sizes, an increase in the viscosity of the epoxy resin composition can be suppressed even if the content of the inorganic filler is increased. There is a tendency to obtain an epoxy resin composition having excellent fluidity.
［有機溶剤］
本実施形態のエポキシ樹脂組成物は、沸点が５０℃〜１００℃である有機溶剤（以下、特定有機溶剤ともいう）を含有する。エポキシ樹脂組成物が特定有機溶剤を含有することで、組成物の粘度が低下するため、混練性及び流動性が向上する。
[Organic solvent]
The epoxy resin composition of the present embodiment contains an organic solvent having a boiling point of 50 ° C. to 100 ° C. (hereinafter, also referred to as a specific organic solvent). When the epoxy resin composition contains a specific organic solvent, the viscosity of the composition is lowered, so that the kneadability and fluidity are improved.
特定有機溶剤は特に制限されず、例えば、沸点が５０℃〜１００℃であり、好ましくはエポキシ樹脂組成物中の成分と非反応性のものを適宜選択して使用することができる。特定有機溶剤としては、アルコール系溶剤、エーテル系溶剤、ケトン系溶剤、エステル系溶剤等が挙げられる。中でもアルコール系溶剤が好ましく、メタノール（沸点６４．７℃）、エタノール（沸点７８．３７℃）、プロパノール（沸点９７℃）及びイソプロパノール（沸点８２．６℃）がより好ましい。特定有機溶剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。なお、特定有機溶剤としては、エポキシ樹脂組成物を調製する際に添加されるものであってもよく、エポキシ樹脂組成物を調製する際の混練過程の反応で発生するものであってもよい。なお、本明細書において特定有機溶剤の沸点は、常圧にて測定される特定有機溶剤の沸点を指す。 The specific organic solvent is not particularly limited, and for example, a solvent having a boiling point of 50 ° C. to 100 ° C. and which is not reactive with the components in the epoxy resin composition can be appropriately selected and used. Examples of the specific organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents and the like. Of these, alcohol solvents are preferable, and methanol (boiling point 64.7 ° C.), ethanol (boiling point 78.37 ° C.), propanol (boiling point 97 ° C.) and isopropanol (boiling point 82.6 ° C.) are more preferable. As the specific organic solvent, one type may be used alone or two or more types may be used in combination. The specific organic solvent may be one added when preparing the epoxy resin composition, or may be one generated by the reaction in the kneading process when preparing the epoxy resin composition. In the present specification, the boiling point of the specific organic solvent refers to the boiling point of the specific organic solvent measured at normal pressure.
エポキシ樹脂組成物中の特定有機溶剤の含有率は、特に制限されない。特定有機溶剤の含有率は、例えば、エポキシ樹脂組成物の全質量に対して０．１質量％〜１０質量％であることが好ましく、熱伝導性をより向上させる観点から、０．３質量％〜４．０質量％であることがより好ましく、０．３質量％〜３．０質量％であることが更に好ましく、０．３質量％〜２．５質量％であることが特に好ましい。特定有機溶剤の含有率が０．３質量％以上であると、流動性の向上効果がより高まる傾向にある。特定有機溶剤の含有率が３．０質量％以下であると、エポキシ樹脂組成物中のエポキシ樹脂を硬化するときにボイドの発生がより抑制され、絶縁信頼性の低下がより抑制される傾向にある。 The content of the specific organic solvent in the epoxy resin composition is not particularly limited. The content of the specific organic solvent is, for example, preferably 0.1% by mass to 10% by mass with respect to the total mass of the epoxy resin composition, and is 0.3% by mass from the viewpoint of further improving thermal conductivity. It is more preferably ~ 4.0% by mass, further preferably 0.3% by mass to 3.0% by mass, and particularly preferably 0.3% by mass to 2.5% by mass. When the content of the specific organic solvent is 0.3% by mass or more, the effect of improving the fluidity tends to be further enhanced. When the content of the specific organic solvent is 3.0% by mass or less, the generation of voids is more suppressed when the epoxy resin in the epoxy resin composition is cured, and the decrease in insulation reliability tends to be further suppressed. be.
特定有機溶剤中のアルコール系溶剤の含有率は、特に限定されない。アルコール系溶剤の含有率は例えば、特定有機溶剤の全質量に対して５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましく、９５質量％以上であることが特に好ましい。また、エポキシ樹脂組成物は、アルコール系溶剤以外の特定有機溶剤を実質的に含有していなくてもよい。 The content of the alcohol solvent in the specific organic solvent is not particularly limited. The content of the alcohol solvent is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on the total mass of the specific organic solvent. It is particularly preferably 95% by mass or more. Further, the epoxy resin composition may not substantially contain a specific organic solvent other than the alcohol solvent.
［硬化促進剤］
本実施形態のエポキシ樹脂組成物は、必要に応じて硬化促進剤を含有してもよい。硬化促進剤としては、封止用エポキシ樹脂組成物に一般に用いられているものを適宜選択して使用することができる。硬化促進剤としては、例えば、トリフェニルホスフィン等の有機リン化合物、イミダゾール化合物、第３級アミン、及び第４級アンモニウム塩が挙げられる。中でも、トリフェニルホスフィン等の有機リン化合物が好ましい。硬化促進剤は、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。
[Curing accelerator]
The epoxy resin composition of the present embodiment may contain a curing accelerator, if necessary. As the curing accelerator, those generally used for the sealing epoxy resin composition can be appropriately selected and used. Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine, imidazole compounds, tertiary amines, and quaternary ammonium salts. Of these, organic phosphorus compounds such as triphenylphosphine are preferable. The curing accelerator may be used alone or in combination of two or more.
エポキシ樹脂組成物が硬化促進剤を含有する場合、硬化促進剤の含有率は特に制限されず、例えば、エポキシ樹脂及び硬化剤の総量に対して１．０質量％〜１０質量％であることが好ましく、１．５質量％〜７質量％であることがより好ましく、２．０質量％〜６質量％であることが更に好ましい。 When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator is not particularly limited, and may be, for example, 1.0% by mass to 10% by mass with respect to the total amount of the epoxy resin and the curing agent. It is more preferably 1.5% by mass to 7% by mass, and even more preferably 2.0% by mass to 6% by mass.
［添加剤］
本実施形態のエポキシ樹脂組成物は、必要に応じて陰イオン交換体、離型剤、難燃剤、カップリング剤、応力緩和剤、着色剤等の添加剤を含有してもよい。
[Additive]
The epoxy resin composition of the present embodiment may contain additives such as an anion exchanger, a mold release agent, a flame retardant, a coupling agent, a stress relaxation agent, and a colorant, if necessary.
（陰イオン交換体）
エポキシ樹脂組成物は、必要に応じて陰イオン交換体を含有してもよい。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、陰イオン交換体を含有することが好ましい。
(Anion exchanger)
The epoxy resin composition may contain an anion exchanger, if necessary. In particular, when the epoxy resin composition is used as a molding material for sealing, an anion exchanger may be contained from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed. preferable.
陰イオン交換体は特に制限されず、従来から当該技術分野において一般的に使用されるものから選択できる。例えば、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選ばれる元素の含水酸化物が挙げられる。 The anion exchanger is not particularly limited and can be selected from those commonly used in the art. Examples include hydrotalcite compounds and hydroxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth.
陰イオン交換体は特に制限されず、従来から当該技術分野において一般に使用されるものから選択できる。陰イオン交換体としては、例えば、下記式（Ｉ）で示される組成の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、ビスマス及びアンチモンからなる群より選ばれる元素の含水酸化物が挙げられる。陰イオン交換体は、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。
Ｍｇ１−ｘＡｌｘ（ＯＨ）２（ＣＯ３）ｘ／２・ｍＨ２Ｏ （Ｉ）
（０＜Ｘ≦０．５、ｍは正の数）
The anion exchanger is not particularly limited and can be selected from those commonly used in the art. Examples of the anion exchanger include hydrotalcite compounds having a composition represented by the following formula (I), and hydrous oxides of elements selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony. .. As the anion exchanger, one type may be used alone or two or more types may be used in combination.
Mg 1-x Al x (OH) 2 (CO 3 ) x / 2 · mH 2 O (I)
(0 <X ≤ 0.5, m is a positive number)
ハイドロタルサイト化合物は、ハロゲンイオンなどの陰イオンを構造中のＣＯ3と置換することで捕捉し、結晶構造の中に取り込まれたハロゲンイオンは約３５０℃以上で結晶構造が破壊するまで脱離しない性質を持つ化合物である。この様な性質を有するハイドロタルサイトとしては、天然物として産出されるＭｇ6Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ、合成品としてＭｇ４．３Ａｌ２（ＯＨ）１２．６ＣＯ３・ｍＨ２Ｏ等が挙げられる。 Hydrotalcite compounds capture anions such as halogen ions by substituting CO 3 in the structure, and the halogen ions incorporated into the crystal structure are desorbed at about 350 ° C or higher until the crystal structure is destroyed. It is a compound with no properties. The hydrotalcite having such properties, Mg 6 Al 2 which is produced as a natural product (OH) 16 CO 3 · 4H 2 O, Mg 4.3 Al 2 (OH) 12.6 CO 3 as synthetic products・ MH 2 O and the like can be mentioned.
エポキシ樹脂組成物が硬化剤としてフェノール硬化剤を含有する場合、フェノール硬化剤の影響でエポキシ樹脂組成物は酸性を示す（例えば、純水を使用した硬化物の抽出液がｐＨ３〜５となる）。この場合、例えば、両性金属であるアルミニウムは、エポキシ樹脂組成物によって腐食されやすい環境となるが、酸を吸着する作用も持つハイドロタルサイト化合物をエポキシ樹脂組成物が含有することで、アルミニウムの腐食が抑制される傾向にある。 When the epoxy resin composition contains a phenol curing agent as a curing agent, the epoxy resin composition is acidic due to the influence of the phenol curing agent (for example, the extract of the cured product using pure water has a pH of 3 to 5). .. In this case, for example, aluminum, which is an amphoteric metal, is easily corroded by the epoxy resin composition, but the epoxy resin composition contains a hydrotalcite compound that also has an acid-adsorbing effect, so that aluminum is corroded. Tends to be suppressed.
また、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマス及びアンチモン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も、ハロゲンイオン等の陰イオンを水酸化物イオンと置換することで捕捉でき、更にこれらのイオン交換体は酸性側で優れたイオン交換能を示す。従って、これらのイオン交換体をエポキシ樹脂組成物が含有することで、ハイドロタルサイト化合物を含有する場合と同様に、アルミニウムの腐食が抑制される傾向にある。含水酸化物としては、ＭｇＯ・ｎＨ２Ｏ、Ａｌ２Ｏ３・ｎＨ２Ｏ、ＺｒＯ２・Ｈ２Ｏ、Ｂｉ２Ｏ３・Ｈ２Ｏ、Ｓｂ２Ｏ５・ｎＨ２Ｏ等が挙げられる。 Further, the hydrous oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony can also be captured by substituting anions such as halogen ions with hydroxide ions, and further. These ion exchangers show excellent ion exchange ability on the acidic side. Therefore, when these ion exchangers are contained in the epoxy resin composition, the corrosion of aluminum tends to be suppressed as in the case where the hydrotalcite compound is contained. Examples of the hydrous oxide include MgO · nH 2 O, Al 2 O 3 · nH 2 O, ZrO 2 · H 2 O, Bi 2 O 3 · H 2 O, Sb 2 O 5 · nH 2 O and the like.
エポキシ樹脂組成物が陰イオン交換体を含有する場合、陰イオン交換体の含有率は、ハロゲンイオン等の陰イオンを捕捉できる充分な量であれば特に制限はない。エポキシ樹脂組成物が陰イオン交換体を含有する場合、陰イオン交換体の含有率は、例えば、０．１質量％〜３０質量％であることが好ましく、１．０質量％〜５質量％であることがより好ましい。 When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is in a sufficient amount to capture anions such as halogen ions. When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is preferably, for example, 0.1% by mass to 30% by mass, and 1.0% by mass to 5% by mass. More preferably.
（離型剤）
エポキシ樹脂組成物は、成形工程において金型に対する良好な離型性を発揮させる観点から、必要に応じて離型剤を含有してもよい。離型剤の種類は特に制限されず、当該技術分野において公知の離型剤が挙げられる。具体的に、離型剤としては、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。中でも、カルナバワックス及びポリオレフィン系ワックスが好ましい。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。
(Release agent)
The epoxy resin composition may contain a mold release agent, if necessary, from the viewpoint of exhibiting good mold releasability with respect to the mold in the molding process. The type of mold release agent is not particularly limited, and examples thereof include mold release agents known in the art. Specific examples of the mold release agent 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. Can be mentioned. Of these, carnauba wax and polyolefin wax are preferable. The release agent may be used alone or in combination of two or more.
ポリオレフィン系ワックスとしては、市販品を用いてもよく、例えば、ヘキスト社製のＨ４、ＰＥ、ＰＥＤシリーズ等の数平均分子量が５００〜１００００程度の低分子量ポリエチレンなどが挙げられる。 As the polyolefin wax, a commercially available product may be used, and examples thereof include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as H4, PE, and PED series manufactured by Hoechst AG.
エポキシ樹脂組成物がポリオレフィン系ワックスを含有する場合、ポリオレフィン系ワックスの含有率は、エポキシ樹脂に対して０．０１質量％〜１０質量％であることが好ましく、０．１０質量％〜５質量％であることがより好ましい。ポリオレフィン系ワックスの含有率が０．０１質量％以上であると充分な離型性が得られる傾向にあり、１０質量％以下であると充分な接着性が得られる傾向にある。
また、エポキシ樹脂組成物がポリオレフィン系ワックス以外のその他の離型剤を含有する場合、又はエポキシ樹脂組成物がポリオレフィン系ワックス及びその他の離型剤を含有する場合、その他の離型剤の含有率は、エポキシ樹脂に対して０．１質量％〜１０質量％であることが好ましく、０．５質量％〜３質量％であることがより好ましい。
When the epoxy resin composition contains a polyolefin-based wax, the content of the polyolefin-based wax is preferably 0.01% by mass to 10% by mass, preferably 0.10% by mass to 5% by mass, based on the epoxy resin. Is more preferable. When the content of the polyolefin wax is 0.01% by mass or more, sufficient releasability tends to be obtained, and when it is 10% by mass or less, sufficient adhesiveness tends to be obtained.
When the epoxy resin composition contains a mold release agent other than the polyolefin wax, or when the epoxy resin composition contains a polyolefin wax and another mold release agent, the content of the other mold release agent Is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 3% by mass, based on the epoxy resin.
（難燃剤）
エポキシ樹脂組成物は、難燃性を付与する観点から、必要に応じて難燃剤を含有してもよい。難燃剤は特に制限されず、例えば、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む公知の有機化合物及び無機化合物、金属水酸化物並びにアセナフチレンが挙げられる。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。
(Flame retardants)
The epoxy resin composition may contain a flame retardant, if necessary, from the viewpoint of imparting flame retardancy. The flame retardant is not particularly limited, and examples thereof include known organic and inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides, and acenaphthylene. The flame retardant may be used alone or in combination of two or more.
エポキシ樹脂組成物が難燃剤を含有する場合、難燃剤の含有率は、難燃効果が得られる量であれば特に制限はない。エポキシ樹脂組成物が難燃剤を含有する場合、難燃剤の含有率は、エポキシ樹脂に対して、１質量％〜３０質量％であることが好ましく、２質量％〜１５質量％であることがより好ましい。 When the epoxy resin composition contains a flame retardant, the content of the flame retardant is not particularly limited as long as the flame retardant effect can be obtained. When the epoxy resin composition contains a flame retardant, the content of the flame retardant is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 15% by mass, based on the epoxy resin. preferable.
（カップリング剤）
エポキシ樹脂組成物は、必要に応じて、樹脂成分と無機充填材との接着性を高める観点から、カップリング剤を含有してもよい。カップリング剤の種類は、特に制限されない。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、メタクリルシラン、アクリルシラン、ビニルシラン等の各種シラン化合物、チタン化合物、アルミニウムキレート化合物、アルミニウム及びジルコニウム含有化合物などが挙げられる。カップリング剤は、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。
(Coupling agent)
If necessary, the epoxy resin composition may contain a coupling agent from the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler. The type of coupling agent is not particularly limited. Examples of the coupling agent include various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, methacrylsilane, acrylicsilane and vinylsilane, titanium compounds, aluminum chelate compounds, aluminum and zirconium-containing compounds. As the coupling agent, one type may be used alone or two or more types may be used in combination.
エポキシ樹脂組成物がカップリング剤を含有する場合、カップリング剤の含有率は、無機充填材に対して０．０５質量％〜５．０質量％であることが好ましく、０．１０質量％〜２．５質量％であることがより好ましい。カップリング剤の含有率が０．０５質量％以上であるとフレームとの接着性が向上する傾向にあり、５質量％以下であるとパッケージの成形性に優れる傾向にある。 When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.05% by mass to 5.0% by mass, preferably 0.10% by mass to 5.0% by mass with respect to the inorganic filler. More preferably, it is 2.5% by mass. When the content of the coupling agent is 0.05% by mass or more, the adhesiveness with the frame tends to be improved, and when it is 5% by mass or less, the moldability of the package tends to be excellent.
（応力緩和剤）
エポキシ樹脂組成物は、パッケージの反り変形量及びパッケージクラックを低減させる観点から、必要に応じて、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有してもよい。使用可能な応力緩和剤としては、当該技術分野で一般に用いられる公知の可とう剤（応力緩和剤）を適宜選択して使用することができる。
(Stress relaxation agent)
The epoxy resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles, if necessary, from the viewpoint of reducing the amount of warping deformation of the package and the package cracks. As the stress relaxation agent that can be used, a known flexible agent (stress relaxation agent) generally used in the art can be appropriately selected and used.
応力緩和剤として具体的には、シリコーン、ポリスチレン、ポリオレフィン、ポリウレタン、ポリエステル、ポリエーテル、ポリアミド、ポリブタジエン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。中でも、シリコーンを含有する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。応力緩和剤は、１種を単独で用いても２種以上組み合わせて用いてもよい。 Specific examples of the stress relieving agent include thermoplastic elastomers such as silicone, polystyrene, polyolefin, polyurethane, polyester, polyether, polyamide, and polybutadiene; NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, and urethane rubber. , Rubber particles such as silicone powder; rubber having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer Particles; etc. Of these, a silicone-based stress relaxant containing silicone is preferable. Examples of the silicone-based stress relaxant include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether. As the stress relaxation agent, one type may be used alone or two or more types may be used in combination.
（着色剤）
エポキシ樹脂組成物は、カーボンブラック、繊維状カーボン、有機染料、有機着色剤、酸化チタン、鉛丹、ベンガラ等の着色剤を含有してもよい。エポキシ樹脂組成物が着色剤を含有する場合、着色剤の含有率は、無機充填材に対して０．０５質量％〜５．０質量％であることが好ましく、０．１０質量％〜２．５質量％であることがより好ましい。
(Colorant)
The epoxy resin composition may contain a colorant such as carbon black, fibrous carbon, an organic dye, an organic colorant, titanium oxide, lead tan, and red iron oxide. When the epoxy resin composition contains a colorant, the content of the colorant is preferably 0.05% by mass to 5.0% by mass, and 0.10% by mass to 2.% by mass with respect to the inorganic filler. More preferably, it is 5% by mass.
［エポキシ樹脂組成物の調製方法］
エポキシ樹脂組成物の調製には、各種成分を分散混合できるのであれば、いずれの手法を用いてもよい。一般的な手法として、所定の配合量の成分をミキサー等によって充分混合した後、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、エポキシ樹脂組成物は、例えば、上述した成分の所定量を混合して攪拌し、予め７０℃〜１４０℃に加熱してあるニーダー、ロール、エクストルーダー等で混練した後、冷却し、粉砕する等の方法によって得ることができる。エポキシ樹脂組成物は、パッケージの成形条件に合うような寸法及び質量でタブレット化してもよい。エポキシ樹脂組成物をタブレット化することで、取り扱いが容易になる。また、タブレット状のエポキシ樹脂組成物は、特定有機溶剤の含有率が、エポキシ樹脂組成物の全質量に対して０．１質量％〜１０質量％であることが好ましく、熱伝導性をより向上させる観点から、０．３質量％〜４．０質量％であることがより好ましく、０．３質量％〜３．０質量％であることが更に好ましく、０．３質量％〜２．５質量％であることが特に好ましい。
[Preparation method of epoxy resin composition]
Any method may be used for preparing the epoxy resin composition as long as various components can be dispersed and mixed. As a general method, 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, the epoxy resin composition is, for example, mixed with a predetermined amount of the above-mentioned components, stirred, kneaded with a kneader, a roll, an extruder or the like which has been preheated to 70 ° C. to 140 ° C., and then kneaded. It can be obtained by a method such as cooling and pulverizing. The epoxy resin composition may be tableted in dimensions and mass that meet the molding conditions of the package. Tableting the epoxy resin composition facilitates handling. Further, the tablet-shaped epoxy resin composition preferably has a specific organic solvent content of 0.1% by mass to 10% by mass with respect to the total mass of the epoxy resin composition, further improving thermal conductivity. From the viewpoint of making it, it is more preferably 0.3% by mass to 4.0% by mass, further preferably 0.3% by mass to 3.0% by mass, and 0.3% by mass to 2.5% by mass. % Is particularly preferable.
＜エポキシ樹脂硬化物＞
本実施形態のエポキシ樹脂硬化物は、上述したエポキシ樹脂組成物の硬化物である。本実施形態のエポキシ樹脂硬化物は、上述したエポキシ樹脂組成物を硬化して得られることから、熱伝導性に優れている傾向にある。
<Epoxy resin cured product>
The epoxy resin cured product of the present embodiment is a cured product of the epoxy resin composition described above. Since the cured epoxy resin of the present embodiment is obtained by curing the above-mentioned epoxy resin composition, it tends to have excellent thermal conductivity.
＜電子部品装置＞
本実施形態の電子部品装置は、素子と、前記素子を封止している上述したエポキシ樹脂組成物の硬化物と、を有する。電子部品装置としては、例えば、支持部材に、能動素子、受動素子等の素子が搭載され、この素子が上述したエポキシ樹脂組成物を用いて封止されたものが挙げられる。支持部材としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス板、シリコンウエハ等が挙げられる。能動素子としては、半導体チップ、トランジスタ、ダイオード、サイリスタ等が挙げられる。受動素子としては、コンデンサ、抵抗体、コイル等が挙げられる。
<Electronic component equipment>
The electronic component device of the present embodiment includes an element and a cured product of the above-mentioned epoxy resin composition that seals the element. Examples of the electronic component device include those in which an element such as an active element or a passive element is mounted on a support member, and this element is sealed by using the above-mentioned epoxy resin composition. Examples of the support member include a lead frame, a pre-wired tape carrier, a wiring plate, a glass plate, a silicon wafer, and the like. Examples of the active element include semiconductor chips, transistors, diodes, thyristors and the like. Examples of the passive element include a capacitor, a resistor, a coil and the like.
より具体的には、例えば、リードフレーム上に半導体素子を固定し、ボンディングパッド等の素子の端子部とリード部とをワイヤボンディング又はバンプで接続した後、上述した実施形態のエポキシ樹脂組成物を用いてトランスファー成形等によって封止した、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 Pacakage）等の一般的な樹脂封止型ＩＣ；テープキャリアにバンプで接続した半導体チップを、上述した実施形態のエポキシ樹脂組成物で封止したＴＣＰ（Tape Carrier Package）；配線板又はガラス上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子及び／又はコンデンサ、抵抗体、コイル等の受動素子を、上述した実施形態のエポキシ樹脂組成物で封止したＣＯＢ（Chip On Board）モジュール、ハイブリッドＩＣ、マルチチップモジュール；裏面に配線板接続用の端子を形成した有機基板の表面に素子を搭載し、バンプ又はワイヤボンディングにより素子と有機基板に形成された配線を接続した後、上述した実施形態のエポキシ樹脂組成物で素子を封止したＢＧＡ（Ball Grid Array）、ＣＳＰ（Chip Size Package）；などが挙げられる。また、プリント回路板にも上述した実施形態のエポキシ樹脂組成物は有効に使用できる。 More specifically, for example, after fixing the semiconductor element on the lead frame and connecting the terminal portion and the lead portion of the element such as a bonding pad by wire bonding or bumps, the epoxy resin composition of the above-described embodiment is applied. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead Package), TOP (Thin Small Outline Package), TQFP (Thin Quad Flat Pacakage) and other general resin-sealed ICs; TCP in which a semiconductor chip connected to a tape carrier with a bump is sealed with the epoxy resin composition of the above-described embodiment. (Tape Carrier Package); Active elements such as semiconductor chips, transistors, diodes, thyristors, etc. connected by wire bonding, flip chip bonding, solder, etc. to wiring formed on a wiring plate or glass, and / or capacitors, resistors, coils. A COB (Chip On Board) module, a hybrid IC, or a multi-chip module in which passive elements such as the above are sealed with the epoxy resin composition of the above-described embodiment; BGA (Ball Grid Array), CSP (Chip Size), in which the element is mounted and the element is connected to the wiring formed on the organic substrate by bump or wire bonding, and then the element is sealed with the epoxy resin composition of the above-described embodiment. Package); etc. Further, the epoxy resin composition of the above-described embodiment can be effectively used for the printed circuit board.
本実施形態の電子部品装置において、素子をエポキシ樹脂硬化物で封止する方法は、特に制限されず、当技術分野において公知の方法を適用することが可能である。例えば、低圧トランスファー成形法が一般的であるが、インジェクション成形法、圧縮成形法等を用いてもよい。 In the electronic component device of the present embodiment, the method of sealing the element with the cured epoxy resin is not particularly limited, and a method known in the art can be applied. For example, a low-pressure transfer molding method is generally used, but an injection molding method, a compression molding method, or the like may be used.
以下、本実施形態を実施例により具体的に説明するが、本実施形態はこれらの実施例に限定されるものではない。 Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited to these Examples.
［実施例１〜７及び比較例１］
以下に示す各種成分をそれぞれ表１に示す比率（質量部基準）で配合し、混練温度８０℃及び混練時間１５分の条件下でロール混練を行うことによって、それぞれ実施例１〜７及び比較例１のエポキシ樹脂組成物を調製した。
[Examples 1 to 7 and Comparative Example 1]
Examples 1 to 7 and Comparative Examples are obtained by blending the various components shown below at the ratios shown in Table 1 (based on parts by mass) and performing roll kneading under the conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, respectively. The epoxy resin composition of 1 was prepared.
エポキシ樹脂組成物の調製に用いた各成分は以下の通りである。
・エポキシ樹脂：エポキシ当量１９２ｇ／ｅｑ、融点７９℃のジフェニルメタン型エポキシ樹脂（新日鉄住金化学株式会社製、商品名：ＹＳＬＶ−８０ＸＹ）
・硬化剤（フェノール樹脂）：水酸基当量１０２ｇ／ｅｑ、軟化点７０℃のトリフェニルメタン型フェノール樹脂（エアーウォータ株式会社製、商品名：ＨＥ９１０−０９）
・硬化促進剤：トリフェニルホスフィン
・離型剤：カルナバワックス（株式会社セラリカＮＯＤＡ製）
・カップリング剤：エポキシシラン（γ−グリシドキシプロピルトリメトキシシラン）
・着色剤：カーボンブラック（三菱化学株式会社製、商品名ＭＡ−１００）
・無機充填材：平均粒径１０μｍのアルミナフィラー（ＤＥＮＫＡ株式会社製、商品名：ＤＯＷシリーズ混合）
The components used in the preparation of the epoxy resin composition are as follows.
-Epoxy resin: Diphenylmethane type epoxy resin having an epoxy equivalent of 192 g / eq and a melting point of 79 ° C. (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name: YSLV-80XY)
-Curing agent (phenol resin): Triphenylmethane-type phenol resin having a hydroxyl group equivalent of 102 g / eq and a softening point of 70 ° C. (manufactured by Airwater Co., Ltd., trade name: HE910-09)
・ Curing accelerator: Triphenylphosphine ・ Release agent: Carnauba wax (manufactured by Ceralica NODA Co., Ltd.)
-Coupling agent: Epoxysilane (γ-glycidoxypropyltrimethoxysilane)
-Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, trade name MA-100)
-Inorganic filler: Alumina filler with an average particle size of 10 μm (manufactured by DENKA Co., Ltd., trade name: DOWN series mixed)
［エポキシ樹脂組成物の熱伝導率評価］
実施例１〜７及び比較例１によって得られたエポキシ樹脂組成物の熱伝導率を以下に示す試験法によって評価した。評価結果を表２に示す。なお、熱伝導率測定用のエポキシ樹脂組成物の成形は、真空ハンドプレス成形機を用い、金型温度１８０℃、成形圧力６．９ＭＰａ、及び硬化時間１０分の条件下で行った。また、後硬化は１７５℃で６時間行った。
[Epoxy resin composition thermal conductivity evaluation]
The thermal conductivity of the epoxy resin compositions obtained in Examples 1 to 7 and Comparative Example 1 was evaluated by the test method shown below. The evaluation results are shown in Table 2. The epoxy resin composition for measuring the thermal conductivity was molded using a vacuum hand press molding machine under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 10 minutes. Post-curing was performed at 175 ° C. for 6 hours.
次に、上記方法で成形した硬化物（１ｃｍ×１ｃｍ）の厚さ方向の熱拡散率を、レーザーフラッシュ法にて測定した。より具体的には、キセノンフラッシュアナライザー（装置：ＬＦＡ４４７ ｎａｎｏｆｌａｓｈ、ＮＥＴＺＳＣＨ社製）を用いて熱拡散率を測定した。パルス光照射は、パルス幅０．１ｍｓ、及び印加電圧２４７Ｖの条件で行った。測定は雰囲気温度２５℃±１℃で行った。次いで、以下の式（１）を用いて比熱及び密度を熱拡散率に乗算することによって，熱伝導率の値を得た。なお、硬化物の比熱は、ＪＩＳ Ｋ ７１２３：２０１２に準じた方法により、ＤＳＣの測定データより算出し、密度を電子比重計（アルファーミラージュ株式会社、ＳＤ−２００Ｌ）によって測定した。
λ＝α・Ｃｐ・ρ 式（１）
式（Ｉ）中、λは熱伝導率（Ｗ／（ｍ・Ｋ））、αは熱拡散率（ｍ２／ｓ）、Ｃｐは比熱（Ｊ／（ｋｇ・Ｋ））、ρは密度（ｄ：ｋｇ／ｍ３）をそれぞれ示す。
Next, the thermal diffusivity in the thickness direction of the cured product (1 cm × 1 cm) molded by the above method was measured by a laser flash method. More specifically, the thermal diffusivity was measured using a xenon flash analyzer (apparatus: LFA447 nanoflash, manufactured by NETZSCH). The pulsed light irradiation was performed under the conditions of a pulse width of 0.1 ms and an applied voltage of 247 V. The measurement was performed at an atmospheric temperature of 25 ° C. ± 1 ° C. Then, the value of thermal conductivity was obtained by multiplying the specific heat and density by the thermal diffusivity using the following equation (1). The specific heat of the cured product was calculated from the measurement data of DSC by a method according to JIS K 7123: 2012, and the density was measured by an electronic hydrometer (Alpha Mirage Co., Ltd., SD-200L).
λ = α ・ Cp ・ ρ equation (1)
In formula (I), λ is the thermal conductivity (W / (m · K)), α is the thermal diffusivity (m 2 / s), Cp is the specific heat (J / (kg · K)), and ρ is the density ( d: kg / m 3 ) is shown respectively.
比較例１の熱伝導率を規準とし、熱伝導率が向上したものをＡ、ほぼ同等であったものをＢとした。 Based on the thermal conductivity of Comparative Example 1, the one with improved thermal conductivity was designated as A, and the one with substantially the same thermal conductivity was designated as B.
［エポキシ樹脂組成物の流動性評価］
実施例１〜７及び比較例１によって得られたエポキシ樹脂組成物の流動性を以下に示す試験法によって評価した。評価結果を表２に示す。なお、エポキシ樹脂組成物の成形は、トランスファー成形機を用い、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件下で行った。また、後硬化は１７５℃で６時間行った。
[Epoxy resin composition fluidity evaluation]
The fluidity of the epoxy resin compositions obtained in Examples 1 to 7 and Comparative Example 1 was evaluated by the test method shown below. The evaluation results are shown in Table 2. The epoxy resin composition was molded using a transfer molding machine under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Post-curing was performed at 175 ° C. for 6 hours.
スパイラルフロー試験は、ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型を用いて、上記条件でエポキシ樹脂組成物を成形して流動距離（ｃｍ）を測定することにより実施した。比較例１の流動距離を規準とし、流動性が向上したものをＡ、流動性がやや向上したものをＢとした。 The spiral flow test was carried out by molding an epoxy resin composition under the above conditions using a spiral flow measuring die according to EMMI-1-66 and measuring the flow distance (cm). Based on the flow distance of Comparative Example 1, the one with improved fluidity was designated as A, and the one with slightly improved fluidity was designated as B.
［エポキシ樹脂組成物の信頼性評価］
実施例１〜７及び比較例１によって得られたエポキシ樹脂組成物の信頼性（絶縁信頼性）を以下に示す部分放電試験によって評価した。
まず、上述のトランスファー成形機を用いた成形によりエポキシ樹脂組成物から得られたエポキシ樹脂硬化物の両面に銅箔を設けた。両面銅箔付きのエポキシ樹脂硬化物（サンプルサイズ５０ｍｍ×５０ｍｍ、樹脂厚み０．２ｍｍ、銅箔厚み０．１ｍｍ）の一方に直径２０ｍｍ円形のパターンをエッチングにより形成した。次いで、エポキシ樹脂組成物を１２０℃のホットプレート上で１時間乾燥し、電極形成サンプルとし以下の部分放電試験に用いた。なお、電極形成サンプルにおけるパターンが形成された面を表側とした。
[Reliability evaluation of epoxy resin composition]
The reliability (insulation reliability) of the epoxy resin compositions obtained in Examples 1 to 7 and Comparative Example 1 was evaluated by the partial discharge test shown below.
First, copper foils were provided on both sides of the epoxy resin cured product obtained from the epoxy resin composition by molding using the above-mentioned transfer molding machine. A circular pattern having a diameter of 20 mm was formed by etching on one of the cured epoxy resin products with double-sided copper foil (sample size 50 mm × 50 mm, resin thickness 0.2 mm, copper foil thickness 0.1 mm). Next, the epoxy resin composition was dried on a hot plate at 120 ° C. for 1 hour to prepare an electrode-forming sample, which was used in the following partial discharge test. The surface on which the pattern was formed in the electrode forming sample was set as the front side.
次に、絶縁油（スリーエム社製 フロリナート ＦＣ−４０）をステンレス容器に満たし、上記電極測定サンプルを浸漬した後、サンプル表側電極にアルミ製の重りを置いてサンプルを固定した。部分放電試験装置（総研電気株式会社 ＤＡＣ−６０３２Ｃ）の測定ボックスにステンレス容器ごと設置し、表側電極を高圧側、ステンレス容器をアース端子に接続した。周波数を６０Ｈｚ、昇降圧速度を０．１ｋＶステップ／秒に設定し、放電電荷量を測定した。２ｐＣ以上の放電電荷が検出された電圧を部分放電開始電圧と定義し、電圧が、比較例１を基準として同等以上であったものをＡ、低下したものをＢとした。なお、電圧が低下している場合、信頼性（絶縁信頼性）が低下していることを意味する。 Next, a stainless steel container was filled with insulating oil (Fluorinert FC-40 manufactured by 3M), the electrode measurement sample was immersed, and then an aluminum weight was placed on the front electrode of the sample to fix the sample. The stainless steel container was installed in the measurement box of the partial discharge test device (Soken Electric Co., Ltd. DAC-6032C), the front electrode was connected to the high voltage side, and the stainless steel container was connected to the ground terminal. The frequency was set to 60 Hz, the buck-boost speed was set to 0.1 kV step / sec, and the amount of discharge charge was measured. The voltage at which a discharge charge of 2 pC or more was detected was defined as the partial discharge start voltage, and the voltage whose voltage was equal to or higher than that of Comparative Example 1 was defined as A, and the voltage decreased was defined as B. When the voltage is lowered, it means that the reliability (insulation reliability) is lowered.
表２に示されるように、エポキシ樹脂組成物が有機溶剤を含有する実施例１〜７は、スパイラルフローで評価した流動性が有機溶剤を含有しない比較例１と比較して良好であり、特に実施例１〜５は、熱伝導率（硬化後の熱伝導性）及びスパイラルフローで評価した流動性が比較例１と比較して良好であった。また、実施例１〜６は、部分放電試験で評価した信頼性が比較例１と同等以上であった。
また、特に実施例１〜５では、低粘度化によりエポキシ樹脂の分散性が向上し硬化性（反応率）が向上し、かつエポキシ樹脂の分子運動が促進され配向性が向上することが、熱伝導率の向上に寄与していると推測される。
As shown in Table 2, Examples 1 to 7 in which the epoxy resin composition contains an organic solvent have better fluidity evaluated by spiral flow than Comparative Example 1 in which the epoxy resin composition does not contain an organic solvent, and in particular. In Examples 1 to 5, the thermal conductivity (thermal conductivity after curing) and the fluidity evaluated by the spiral flow were better than those of Comparative Example 1. Further, in Examples 1 to 6, the reliability evaluated in the partial discharge test was equal to or higher than that of Comparative Example 1.
Further, particularly in Examples 1 to 5, it is heat that the dispersibility of the epoxy resin is improved by lowering the viscosity, the curability (reaction rate) is improved, and the molecular motion of the epoxy resin is promoted to improve the orientation. It is presumed that it contributes to the improvement of conductivity.
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、本明細書中に参照により取り込まれる。 All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
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