JP4197141B2 - Spherical alumina powder and use thereof - Google Patents
Spherical alumina powder and use thereof Download PDFInfo
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- JP4197141B2 JP4197141B2 JP2003298141A JP2003298141A JP4197141B2 JP 4197141 B2 JP4197141 B2 JP 4197141B2 JP 2003298141 A JP2003298141 A JP 2003298141A JP 2003298141 A JP2003298141 A JP 2003298141A JP 4197141 B2 JP4197141 B2 JP 4197141B2
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- Prior art keywords
- spherical alumina
- alumina powder
- spherical
- epoxy resin
- powder
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- 239000000843 powder Substances 0.000 title claims description 76
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 64
- 239000003822 epoxy resin Substances 0.000 claims description 41
- 229920000647 polyepoxide Polymers 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000005350 fused silica glass Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 229910018540 Si C Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 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 8
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 novolak-type resin Chemical class 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007921 spray Substances 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
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- 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 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-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
- 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 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 230000002742 anti-folding effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Description
本発明は、球状アルミナ粉末及びその用途に関する。詳しくは、アクリル系シランカップリング剤による表面処理の施された球状アルミナ粉末と、これを含む混合粉末と、それが充填されたエポキシ樹脂組成物に関する。 The present invention relates to a spherical alumina powder and its use. Specifically, the present invention relates to a spherical alumina powder which has been surface-treated with an acrylic silane coupling agent, a mixed powder containing the same, and an epoxy resin composition filled with the powder.
エポキシ樹脂の用途が半導体封止剤である場合、その絶縁性を確保する必要から、球状溶融シリカ、球状アルミナなどの無機質酸化粉末が充填材として用いられている。球状アルミナは、球状溶融シリカよりも熱伝導率が高いという利点がある。 When the epoxy resin is used as a semiconductor encapsulant, inorganic oxide powders such as spherical fused silica and spherical alumina are used as fillers because it is necessary to ensure insulation. Spherical alumina has the advantage of higher thermal conductivity than spherical fused silica.
球状アルミナは、アルミナ、水酸化アルミニウム等の原料粉末を高温火炎中に投入し溶融球状化することによって製造されるが、同じく高温火炎処理で製造される球状溶融シリカと異なり、表面ＯＨ基が減少するので、粉末同士の凝集が少ない。 Spherical alumina is manufactured by putting raw material powder such as alumina and aluminum hydroxide into a high temperature flame and spheroidizing it. Unlike spherical fused silica, which is also manufactured by high temperature flame treatment, surface OH groups are reduced. Therefore, there is little aggregation of powder.
半導体封止剤の重要特性の一つに耐湿信頼性があることに鑑み、球状アルミナ粉末原料を、アルコキシ基を有するシランカップリング剤で表面処理することが提案されている（特許文献１）。これによって、耐湿信頼性は向上したが、強度、弾性率が球状溶融シリカのレベルまでには改善されないことが課題であった。
本発明の目的は、半導体封止剤として好都合なエポキシ樹脂組成物の強度、弾性率、耐湿信頼性を一挙に改善させるべく、高充填可能な球状アルミナ粉末とそれが充填されたエポキシ樹脂組成物を提供することである。本発明の目的は、球状アルミナ粉末原料、好適には２つ以上の極大ピークを有する球状アルミナ粉末原料を、アクリル系シランカップリング剤で表面処理をすること、更にはこの球状アルミナ粉末と、アクリル系シランカップリング剤による表面処理が施された溶融球状シリカ微粉末とを併用することによって達成することができる。 An object of the present invention is to provide a spherical alumina powder that can be highly filled and an epoxy resin composition filled therewith in order to improve the strength, elastic modulus, and moisture resistance reliability of an epoxy resin composition that is convenient as a semiconductor encapsulant. Is to provide. An object of the present invention is to surface-treat a spherical alumina powder raw material, preferably a spherical alumina powder raw material having two or more maximum peaks, with an acrylic silane coupling agent, and further, the spherical alumina powder and an acrylic This can be achieved by using in combination with fused spherical silica fine powder that has been surface-treated with a silane coupling agent.
すなわち、本発明は、平均粒径が１００μｍ以下、平均球形度が０．８０以上、表面ＯＨ基数が１０個／ｎｍ２ 以下の球状アルミナ粉末原料が、アクリル系シランカップリング剤による表面処理が施されてなることを特徴とする球状アルミナ粉末である。この場合において、アクリル系シランカップリング剤が、化学式（１）で表されるものであり、しかも球状アルミナ粉末原料の粒度分布が、極大ピークを２つ以上有し、その極大ピークの１つが３μｍ以下であることが好ましい。 That is, in the present invention, a spherical alumina powder raw material having an average particle size of 100 μm or less, an average sphericity of 0.80 or more, and a surface OH group number of 10 / nm 2 or less is subjected to a surface treatment with an acrylic silane coupling agent. It is a spherical alumina powder characterized by being made. In this case, the acrylic silane coupling agent is represented by the chemical formula (1), and the particle size distribution of the spherical alumina powder raw material has two or more maximum peaks, and one of the maximum peaks is 3 μm. The following is preferable.
（ＣnＨ３ｎＯ）３−Ｓｉ−ＣmＨ２m−０−ＣＯＣＨ＝ＣＨ２ ・・・化学式（１）
但し、式中、Ｒはメチル基又はエチル基、ｎは１以上の整数。ｍは０又は１以上の整数。
(C n H 3n O) 3 -Si-C m H 2m -0-COCH = CH 2 ··· formula (1)
In the formula, R is a methyl group or an ethyl group, and n is an integer of 1 or more. m is 0 or an integer of 1 or more.
また、本発明は、球状アルミナ粉末の２０質量％以下（０を含まない）が、アクリル系シランカップリング剤による表面処理が施された球状溶融シリカ微粉末で混合置換されてなることを特徴とする球状アルミナ混合粉末である。この場合において、アクリル系シランカップリング剤による表面処理が施される球状溶融シリカ粉末原料の平均粒径は５μｍ以下であることが好ましい。更に、本発明は、上記球状アルミナ粉末又は球状アルミナ混合粉末を含有してなることを特徴とするエポキシ樹脂組成物である。 Further, the present invention is characterized in that 20% by mass or less (not including 0) of the spherical alumina powder is mixed and replaced with a spherical fused silica fine powder subjected to a surface treatment with an acrylic silane coupling agent. It is a spherical alumina mixed powder. In this case, it is preferable that the average particle diameter of the spherical fused silica powder raw material subjected to the surface treatment with the acrylic silane coupling agent is 5 μm or less. Furthermore, the present invention is an epoxy resin composition comprising the spherical alumina powder or the spherical alumina mixed powder.
本発明によれば、エポキシ樹脂への高充填が可能な球状アルミナ粉末又は球状アルミナ混合粉末が提供されるので、これの充填されたエポキシ樹脂組成物の強度、弾性率、耐湿信頼性は、溶融球状シリカ粉末の充填されたそれに匹敵したものとなり、しかも高熱伝導性となる。 According to the present invention, a spherical alumina powder or a spherical alumina mixed powder that can be highly filled into an epoxy resin is provided. Therefore, the strength, elastic modulus, and moisture resistance reliability of the filled epoxy resin composition are melted. It is comparable to that filled with spherical silica powder and has high thermal conductivity.
本発明で用いる球状アルミナ粉末原料は、平均粒径が１００μｍ以下、平均球形度が０．８０以上、表面ＯＨ基数が１０個／ｎｍ２以下である。平均粒径が１００μｍをこえるとエポキシ樹脂組成物の粘度が急激に高くなる。また、平均球形度が０．８０未満であるか、又は表面ＯＨ基数が１０個／ｎｍ２ をこえると、本発明による表面処理を施しても、エポキシ樹脂組成物の強度、弾性率を十分に改善することができない。 The spherical alumina powder raw material used in the present invention has an average particle size of 100 μm or less, an average sphericity of 0.80 or more, and a surface OH group number of 10 / nm 2 or less. When the average particle size exceeds 100 μm, the viscosity of the epoxy resin composition increases rapidly. In addition, when the average sphericity is less than 0.80 or the number of surface OH groups exceeds 10 / nm 2 , the strength and elastic modulus of the epoxy resin composition are sufficiently obtained even when the surface treatment according to the present invention is performed. It cannot be improved.
平均球形度は、走査型電子顕微鏡（日本電子社製「ＪＸＡ−８６００Ｍ型」）と画像解析装置（日本アビオニクス社製）を用いて測定することができる。すなわち、粉末のＳＥＭ写真から粒子の投影面積（Ａ）と周囲長（ＰＭ）を測定する。周囲長（ＰＭ）に対応する真円の面積を（Ｂ）とすると、その粒子の真円度はＡ／Ｂとして表される。そこで、試料粒子の周囲長（ＰＭ）と同一の周囲長を持つ真円を想定すると、ＰＭ＝２πｒ、Ｂ＝πｒ２であるから、Ｂ＝π×（ＰＭ／２π）２となり、この粒子の真円度は、真円度＝Ａ／Ｂ＝Ａ×４π／（ＰＭ）２として算出することができる。そこで、本発明においては、任意１００個の粒子について測定し、その平均値でもって平均球形度とする。 The average sphericity can be measured using a scanning electron microscope (“JXA-8600M type” manufactured by JEOL Ltd.) and an image analysis device (manufactured by Nippon Avionics Co., Ltd.). That is, the projected area (A) and the perimeter (PM) of the particles are measured from the SEM photograph of the powder. When the area of a perfect circle corresponding to the perimeter (PM) is (B), the roundness of the particle is expressed as A / B. Therefore, assuming a perfect circle having the same circumference as that of the sample particle (PM), PM = 2πr and B = πr 2 , so that B = π × (PM / 2π) 2 . The roundness can be calculated as roundness = A / B = A × 4π / (PM) 2 . Therefore, in the present invention, 100 arbitrary particles are measured, and the average value is used as the average sphericity.
本発明において、表面ＯＨ基数とは、シランカップリング剤と反応するか、又は反応する可能性のあるＯＨ基である。これは、温度５５０〜９００℃で発生した水分量Ｘ（ｐｐｍ）をカールフィッシャー法により測定し、粉末の比表面積をＹｍ２／ｇから、式、表面ＯＨ基数Ｚ（個／ｎｍ２ ）＝０．０６６８×Ｘ／Ｙ、によって算出することができる。 In the present invention, the number of surface OH groups is an OH group that reacts with or possibly reacts with a silane coupling agent. This is because the moisture content X (ppm) generated at a temperature of 550 to 900 ° C. is measured by the Karl Fischer method, and the specific surface area of the powder is calculated from Ym 2 / g, the formula: surface OH group number Z (pieces / nm 2 ) = 0. .0668 × X / Y.
本発明で用いる球状アルミナ粉末原料は、既存の溶射技術（例えば「製綱窯炉に対する溶射補集技術について」製鉄研究１９８２第３１０号）を基本とし、水素、天然ガス、アセチレンガス、プロパンガス、ブタン等の燃料ガスと、酸素ガス、空気等の助燃ガスとで形成された高温火炎中に原料粉末を投入し、溶融球状化させることによって製造することができる。その原料として、アルミナ粉末、水酸化アルミニウム粉末、硫酸アルミニウム粉末等が使用されるが、球状化前後での粒径の変化が少ないアルミナ粉末が好ましい。また、金属アルミニウム粉末を高温火炎中で燃焼させる方法であってもよく、これによって平均粒径１０μｍ以下の微細な球状アルミナ粉末が得られやすくなる。 The spherical alumina powder raw material used in the present invention is based on the existing thermal spraying technology (for example, “Technology for Thermal Spray Collection for Steelmaking Furnace Furnace”, Steel Research 1982 310), hydrogen, natural gas, acetylene gas, propane gas, It can be manufactured by putting raw material powder into a high-temperature flame formed of a fuel gas such as butane and an auxiliary combustion gas such as oxygen gas or air, and melt spheroidizing. As the raw material, alumina powder, aluminum hydroxide powder, aluminum sulfate powder or the like is used, and alumina powder with little change in particle size before and after spheroidization is preferable. Moreover, the method of burning a metal aluminum powder in a high temperature flame may be sufficient, and it becomes easy to obtain the fine spherical alumina powder with an average particle diameter of 10 micrometers or less by this.
上記球状アルミナ粉末原料の製造方法にあっては、球状アルミナ粉末原料の平均粒径は球状化前の原料の粒度調整等によって、平均球形度、表面ＯＨ基数は球状化時の燃料ガス量の調整、原料粉末の供給量等によって調整することができる。 In the method for producing the spherical alumina powder raw material, the average particle diameter of the spherical alumina powder raw material is adjusted by adjusting the particle size of the raw material before spheroidization, the average sphericity, and the surface OH group number is adjusted by the amount of fuel gas during spheroidization. It can be adjusted by the supply amount of the raw material powder.
本発明の球状アルミナ粉末は、上記球状アルミナ粉末原料を、好ましくは上記化学式（１）で示されるアクリル系シランカップリング剤によって表面処理されたものである。ＯＨ基数が調整された球状アルミナ粉末原料を、アクリル系シランカップリング剤で表面処理を行うと、エポキシ樹脂に良く分散し、高充填することが可能となり、エポキシ樹脂組成物の強度、弾性率が大幅に向上する。このような効果は、アルコキシ基を有するシランカップリング剤やアミノ基を有するシランカップリング剤では発現しない。特に好ましいアクリル系シランカップリング剤は、化学式（２）に示される３−アクリロキシプロピルトリメトキシシランである。 The spherical alumina powder of the present invention is obtained by surface-treating the above spherical alumina powder raw material, preferably with an acrylic silane coupling agent represented by the above chemical formula (1). When the surface treatment is performed with an acrylic silane coupling agent on a spherical alumina powder raw material with an adjusted number of OH groups, the epoxy resin composition can be well dispersed and highly filled, and the strength and elastic modulus of the epoxy resin composition can be reduced. Greatly improved. Such an effect is not exhibited by a silane coupling agent having an alkoxy group or a silane coupling agent having an amino group. A particularly preferred acrylic silane coupling agent is 3-acryloxypropyltrimethoxysilane represented by chemical formula (2).
（ＣＨ３Ｏ）３−Ｓｉ−Ｃ3Ｈ6−０−ＣＯＣＨ＝ＣＨ２ ・・・化学式（２） (CH 3 O) 3 -Si- C 3 H 6 -0-COCH = CH 2 ··· formula (2)
アクリル系シランカップリング剤の使用量は、球状アルミナ粉末原料１００質量部に対して０．２〜５質量部であることが好ましい。０．２質量部よりも少ないとその効果は小さく、５質量部％よりも多くしても、使用量に見合った効果は発現しない。 It is preferable that the usage-amount of an acryl-type silane coupling agent is 0.2-5 mass parts with respect to 100 mass parts of spherical alumina powder raw materials. If the amount is less than 0.2 parts by mass, the effect is small, and even if the amount is more than 5 parts by mass, an effect commensurate with the amount used is not exhibited.
表面処理方法としては、流体ノズルを用いた噴霧方式、せん断力のある攪拌方式、ボールミル、ミキサー等の乾式法、水系又は有機溶剤系等の湿式法を採用することができる。攪拌方式は、球状アルミナ粉末原料又は球状アルミナ粉末の破壊が起こらない程度にして行うことが肝要である。乾式法における系内温度又は処理後の乾燥温度は、表面処理剤の種類に応じ熱分解しない領域で適宜決定されるが、概ね８０〜１５０℃である。 As the surface treatment method, a spray method using a fluid nozzle, a stirring method having shearing force, a dry method such as a ball mill or a mixer, or a wet method such as an aqueous or organic solvent method can be employed. It is important that the stirring method be performed to such an extent that the spherical alumina powder raw material or the spherical alumina powder does not break. The system temperature in the dry method or the drying temperature after the treatment is appropriately determined in a region where thermal decomposition does not occur depending on the type of the surface treatment agent, but is generally 80 to 150 ° C.
本発明の球状アルミナ粉末は、その球状アルミナ粉末原料の粒度を調整することによって、エポキシ樹脂と混合した際に一段と低粘度化することができる。すなわち、極大ピークを２つ以上有し、その極大ピークの１つは３μｍ以下にすることである。このような低粘度化の作用効果は、本発明の球状アルミナ粉末の２０質量％（０を含まず）を、アクリル系シランカップリング剤で表面処理された球状溶融シリカ微粉末で混合置換することによって助長される。球状溶融シリカ微粉末の平均粒径は、アクリル系シランカップリング剤による表面処理の施される球状溶融シリカ粉末の平均粒径として、５μｍ以下であることが好ましい。 The spherical alumina powder of the present invention can be further reduced in viscosity when mixed with the epoxy resin by adjusting the particle size of the spherical alumina powder raw material. That is, it has two or more maximum peaks, and one of the maximum peaks is 3 μm or less. Such an effect of lowering viscosity is obtained by mixing and replacing 20% by mass (excluding 0) of the spherical alumina powder of the present invention with a spherical fused silica fine powder surface-treated with an acrylic silane coupling agent. Conduced by The average particle size of the spherical fused silica fine powder is preferably 5 μm or less as the average particle size of the spherical fused silica powder subjected to the surface treatment with the acrylic silane coupling agent.
本発明の球状アルミナ粉末又は球状アルミナ混合粉末は、種々の樹脂組成物を製造する充填材として用いることができるが、特にエポキシ樹脂組成物の製造に適合する。本発明のエポキシ樹脂組成物は、半導体封止剤としての用途がある。 The spherical alumina powder or spherical alumina mixed powder of the present invention can be used as a filler for producing various resin compositions, and is particularly suitable for the production of epoxy resin compositions. The epoxy resin composition of this invention has a use as a semiconductor sealing agent.
本発明で用いられるエポキシ樹脂は、一分子中にエポキシ基を二個以上有するものであり、それを例示すれば、ビスフェノールＡ型エポキシ樹脂、フェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、臭素化エポキシ樹脂等であり、これらの一種又は二種以上が使用される。とくに、低吸湿等の特性を付与したいときは、ビフェニル系エポキシ樹脂が好ましい。エポキシ樹脂組成物の用途がアンダーフィル材のように液状エポキシ樹脂組成物である場合には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂などの常温で液状のエポキシ樹脂が用いられる。 The epoxy resin used in the present invention has two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, phenol A type epoxy resin, phenol novolac type epoxy resin, biphenyl type are exemplified. An epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene ring-containing epoxy resin, a brominated epoxy resin, and the like, and one or more of these are used. In particular, when it is desired to impart characteristics such as low moisture absorption, a biphenyl type epoxy resin is preferable. When the application of the epoxy resin composition is a liquid epoxy resin composition such as an underfill material, the room temperature of a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, or an alicyclic epoxy resin A liquid epoxy resin is used.
エポキシ樹脂の硬化剤については、エポキシ樹脂と反応して硬化させるものであれば特に限定されず、例えば、フェノール、クレゾール、キシレノール、レゾルシノール、クロロフェノール、ｔ−ブチルフェノール、ノニルフェノール、イソプロピルフェノール、オクチルフェノール等の群から選ばれた１種又は２種以上の混合物をホルムアルデヒド、パラホルムアルデヒド又はパラキシレンとともに酸化触媒下で反応させて得られるノボラック型樹脂、ポリパラヒドロキシスチレン樹脂、ビスフェノールＡやビスフェノールＳ等のビスフェノール化合物、ピロガロールやフロログルシノール等の３官能フェノール類、無水マレイン酸、無水フタル酸や無水ピロメリット酸等の酸無水物、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族アミン等を挙げることができる。 The epoxy resin curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin. For example, phenol, cresol, xylenol, resorcinol, chlorophenol, t-butylphenol, nonylphenol, isopropylphenol, octylphenol, etc. Bisphenol compounds such as novolak-type resin, polyparahydroxystyrene resin, bisphenol A and bisphenol S obtained by reacting a mixture of one or more selected from the group with formaldehyde, paraformaldehyde or paraxylene under an oxidation catalyst , Trifunctional phenols such as pyrogallol and phloroglucinol, acid anhydrides such as maleic anhydride, phthalic anhydride and pyromellitic anhydride, metaphenylenediamine, diaminodiphenylmethane Aromatic amines such as diaminodiphenyl sulfone, and the like.
本発明のエポキシ樹脂組成物には、エポキシ樹脂と硬化剤との反応を促進させるために硬化促進剤を配合することができる。その硬化促進剤としては、１，８−ジアザビシクロ（５，４，０）ウンデセン−７，トリフェニルホスフィン、ベンジルジメチルアミン、２−メチルイミダゾール等がある。 In the epoxy resin composition of the present invention, a curing accelerator can be blended in order to accelerate the reaction between the epoxy resin and the curing agent. Examples of the curing accelerator include 1,8-diazabicyclo (5,4,0) undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like.
更には、本発明のエポキシ樹脂組成物には、次の成分を必要に応じて配合することができる。すなわち、低応力化剤として、シリコーンゴム、ポリサルファイドゴム、アクリル系ゴム、ブタジエン系ゴム、スチレン系ブロックコポリマーや飽和型エラストマー等のゴム状物質、各種熱可塑性樹脂、シリコーン樹脂等の樹脂状物質、更にはエポキシ樹脂、フェノール樹脂の一部又は全部をアミノシリコーン、エポキシシリコーン、アルコキシシリコーンなどで変性した樹脂など、シランカップリング剤として、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシシラン、アミノプロピルトリエトキシシラン、ウレイドプロピルトリエトキシシラン、Ｎ−フェニルアミノプロピルトリメトキシシラン等のアミノシラン、フェニルトリメトキシシラン、メチルトリメトキシシラン、オクタデシルトリメトキシシラン等の疎水性シラン化合物やメルカプトシランなど、難燃助剤として、Ｓｂ２Ｏ３、Ｓｂ２Ｏ４、Ｓｂ２Ｏ５など、難燃剤として、ハロゲン化エポキシ樹脂やリン化合物など、着色剤として、カーボンブラック、酸化鉄、染料、顔料などである。 Furthermore, the following component can be mix | blended with the epoxy resin composition of this invention as needed. That is, as a low stress agent, silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, rubbery substances such as styrene block copolymers and saturated elastomers, various thermoplastic resins, resinous substances such as silicone resins, Is an epoxy resin, a resin obtained by modifying a part or all of a phenol resin with aminosilicone, epoxysilicone, alkoxysilicone, or the like. As a silane coupling agent, γ-glycidoxypropyltrimethoxysilane, β- (3,4- Epoxy cyclohexyl) Epoxy silanes such as ethyltrimethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, aminosilanes such as N-phenylaminopropyltrimethoxysilane, phenyltrimethoxysilane, methyltri Hydrophobic silane compounds such as methoxysilane and octadecyltrimethoxysilane, mercaptosilane and the like, flame retardant aids such as Sb 2 O 3 , Sb 2 O 4 and Sb 2 O 5 , flame retardants such as halogenated epoxy resins and phosphorus Examples of colorants such as compounds include carbon black, iron oxide, dyes, and pigments.
本発明のエポキシ樹脂組成物は、上記各材料の所定量を撹拌、溶解、混合、分散させることにより製造することができる。これらの混合物の混合、撹拌、分散等の装置は特に限定されないが、撹拌、加熱装置を備えたライカイ機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。またこれらの装置を適宜組み合わせて使用してもよい。 The epoxy resin composition of the present invention can be produced by stirring, dissolving, mixing, and dispersing predetermined amounts of each of the above materials. A device for mixing, stirring, and dispersing these mixtures is not particularly limited, and a lykai machine equipped with a stirring and heating device, a three-roll, a ball mill, a planetary mixer, and the like can be used. Moreover, you may use combining these apparatuses suitably.
実施例１〜５ 比較例１〜６
ＬＰＧと酸素ガスによって形成された高温火炎中に、アルミナ粉末を供給し、球状化処理を行った。ＬＰＧ量の調整によって、平均粒径と平均球形度と表面ＯＨ基数の異なる球状アルミナ粉末原料Ａ〜Ｋを製造し、それをシランカップリング剤Ａ〜Ｄにより表面処理を行った。表面処理は、ボール径２０ｍｍ、ボール充填率５０体積％の１０リットル容器内に、球状アルミナ粉末原料１ｋｇとシランカップリング剤の表１に示される添加量（外割％）とを投入し、常温、常圧の条件下、１回／秒の速度で１時間運転後、１２０℃にて１時間乾燥させて行った。シランカップリング剤は、一般式、Ｘ３−Ｓｉ−ＣｎＨ２ｎ−Ｏ−Ｙ（但し、官能基Ｘ、Ｙと、ｎ数は表２に記載。）、である。
Examples 1-5 Comparative Examples 1-6
Alumina powder was supplied into a high-temperature flame formed by LPG and oxygen gas, and spheroidizing treatment was performed. By adjusting the amount of LPG, spherical alumina powder raw materials AK having different average particle diameter, average sphericity, and surface OH group number were produced, and surface treatment was performed with silane coupling agents AD. In the surface treatment, 1 kg of spherical alumina powder raw material and the addition amount (outer percent%) shown in Table 1 of the silane coupling agent are put into a 10 liter container having a ball diameter of 20 mm and a ball filling rate of 50% by volume. Under normal pressure conditions, the operation was carried out at a rate of once per second for 1 hour and then dried at 120 ° C. for 1 hour. The silane coupling agent has a general formula, X 3 —Si—C n H 2n —O—Y (provided that functional groups X and Y and n number are described in Table 2).
得られた球状アルミナ粉末を用いてエポキシ樹脂組成物を製造し、（１）粘度、（２）強度、（３）弾性率、（４）耐湿信頼性を以下に従い測定した。比較例６は、球状アルミナ粉末のかわりに溶融球状シリカ粉末Ｌ（比較例６）を用いた。これらの結果を表５に示す。 An epoxy resin composition was produced using the obtained spherical alumina powder, and (1) viscosity, (2) strength, (3) elastic modulus, and (4) moisture resistance reliability were measured as follows. In Comparative Example 6, fused spherical silica powder L (Comparative Example 6) was used instead of the spherical alumina powder. These results are shown in Table 5.
（１）粘度
表３の割合で調合された樹脂分４５質量部と、球状アルミナ粉末Ａ〜Ｋ又は溶融球状シリカ粉末Ｌの５５質量部とを混合し、Ｅ型粘度計型（東京計器社製「ＥＨＤ粘度計」）により、温度４０℃、５ｒｐｍの回転数による粘度を測定した。
(1) Viscosity 45 parts by mass of the resin component prepared at the ratio shown in Table 3 and 55 parts by mass of spherical alumina powders A to K or fused spherical silica powder L are mixed to obtain an E type viscometer type (manufactured by Tokyo Keiki Co., Ltd.). Using an “EHD viscometer”), the viscosity at a temperature of 40 ° C. and a rotation speed of 5 rpm was measured.
（２）強度、弾性率
表４の割合で調合された樹脂分４０質量部と、球状アルミナ粉末Ａ〜Ｋ又は溶融球状シリカ粉末Ｌの６０質量部とを混合し、ＪＩＳ Ｋ ６９１１に準じて、１７５℃、６．９ＭＰａ、成形時間２分の条件で１０×４×１００ｍｍの抗折棒を成形し、室温強度、弾性率を測定した。
(2) Strength, elastic modulus 40 parts by mass of the resin component prepared in the ratio of Table 4 and 60 parts by mass of the spherical alumina powders A to K or the fused spherical silica powder L are mixed, according to JIS K 6911, A 10 × 4 × 100 mm anti-folding rod was molded under the conditions of 175 ° C., 6.9 MPa, and molding time of 2 minutes, and the room temperature strength and elastic modulus were measured.
（３）耐湿信頼性
アルミニウム配線を有する１６ピンモニターＩＣをトランスファー成形し、硬化後２６０℃のハンダ浴に１０秒間浸漬した後、１２０℃、２気圧の水蒸気中で２０Ｖ印加してアルミニウム配線のオープン不良率（断線率）とリーク不良率（アルミニウム線間の洩れ電流値が１０ｎＡ以上になった率）との和が５０％以上になるまでの時間を求めた。試料個数は２０個である。
(3) Moisture resistance reliability 16-pin monitor IC with aluminum wiring is transfer molded, and after curing, immersed in a 260 ° C solder bath for 10 seconds, then 20V is applied in water vapor at 120 ° C and 2 atm to open the aluminum wiring. The time until the sum of the defect rate (disconnection rate) and the leak defect rate (the rate at which the leakage current value between the aluminum wires was 10 nA or more) reached 50% or more was determined. The number of samples is 20.
表１〜５から明らかなように、本発明の球状アルミナ粉末を用いたエポキシ樹脂組成物は、粘度、強度、弾性率、耐湿信頼性の全てにおいて、比較例よりも優れていた。 As is clear from Tables 1 to 5, the epoxy resin composition using the spherical alumina powder of the present invention was superior to the comparative example in all of viscosity, strength, elastic modulus, and moisture resistance reliability.
実施例６〜９
実施例６、７では、球状アルミナ粉末原料Ｂに球状溶融シリカ粉末Ｌを混合した。実施例８では、球状アルミナ粉末原料Ｂ、Ｈを用い、極大ピークを２つ有し、その１つが３μｍ以下である球状アルミナ粉末原料を調整した。実施例９では、実施例８において、更に球状溶融シリカ粉末Ｌの混合された球状アルミナ混合粉末原料を調整した。これらの原料を実施例１の球状アルミナ粉末原料のかわりに用いたこと以外は、実施例１と同様にして試験した。それらの結果を表７に示す。
Examples 6-9
In Examples 6 and 7, the spherical fused silica powder L was mixed with the spherical alumina powder raw material B. In Example 8, spherical alumina powder raw materials B and H were used, and a spherical alumina powder raw material having two maximum peaks, one of which was 3 μm or less was prepared. In Example 9, the spherical alumina mixed powder raw material in which the spherical fused silica powder L was further mixed in Example 8 was prepared. The test was conducted in the same manner as in Example 1 except that these raw materials were used in place of the spherical alumina powder raw material of Example 1. The results are shown in Table 7.
表６、７から、極大ピークを２つ以上有し、その１つが３μｍ以下である球状アルミナ粉末原料を用いることによって更に粘度が低減し、また本発明の球状アルミナ粉末とアクリル系シランカップリング剤で表面処理された球状溶融シリカ粉末とを併用することによって、一段と粘度が低減したことが分かる。 From Tables 6 and 7, the viscosity is further reduced by using a spherical alumina powder raw material having two or more maximum peaks, one of which is 3 μm or less, and the spherical alumina powder and acrylic silane coupling agent of the present invention. It can be seen that the viscosity was further reduced by using in combination with the spherical fused silica powder surface-treated with.
本発明によれば、エポキシ樹脂への高充填が可能な球状アルミナ粉末又は球状アルミナ混合粉末が提供されるので、これの充填されたエポキシ樹脂組成物の強度、弾性率、耐湿信頼性は、溶融球状シリカ粉末の充填されたそれに匹敵したものとなり、しかも高熱伝導性となる。本発明のエポキシ樹脂組成物は半導体封止剤として使用される。 According to the present invention, a spherical alumina powder or a spherical alumina mixed powder that can be highly filled into an epoxy resin is provided. Therefore, the strength, elastic modulus, and moisture resistance reliability of the filled epoxy resin composition are melted. It is comparable to that filled with spherical silica powder and has high thermal conductivity. The epoxy resin composition of the present invention is used as a semiconductor sealing agent.
Claims (4)
（ＣnＨ３ｎＯ）３−Ｓｉ−ＣmＨ２m−０−ＣＯＣＨ＝ＣＨ２ ・・・化学式（１）
但し、式中、Ｒはメチル基又はエチル基、ｎは１以上の整数。
ｍは０又は１以上の整数。 The acrylic silane coupling agent is represented by the chemical formula (1), and the particle size distribution of the spherical alumina powder raw material has two or more maximum peaks, and one of the maximum peaks is 3 μm or less. The spherical alumina powder according to claim 1.
(C n H 3n O) 3 -Si-C m H 2m -0-COCH = CH 2 ··· formula (1)
In the formula, R is a methyl group or an ethyl group, and n is an integer of 1 or more.
m is 0 or an integer of 1 or more.
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