JP2015071730A - Surface-modified particle - Google Patents
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- JP2015071730A JP2015071730A JP2013209185A JP2013209185A JP2015071730A JP 2015071730 A JP2015071730 A JP 2015071730A JP 2013209185 A JP2013209185 A JP 2013209185A JP 2013209185 A JP2013209185 A JP 2013209185A JP 2015071730 A JP2015071730 A JP 2015071730A
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- aluminum nitride
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- 239000002245 particle Substances 0.000 title claims abstract description 196
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 77
- 230000002378 acidificating effect Effects 0.000 claims abstract description 59
- 229910052582 BN Inorganic materials 0.000 claims abstract description 31
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 24
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 5
- 125000000743 hydrocarbylene group Chemical group 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- -1 phosphate ester Chemical class 0.000 claims description 64
- 229910019142 PO4 Inorganic materials 0.000 claims description 60
- 239000010452 phosphate Substances 0.000 claims description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 abstract description 104
- 239000011248 coating agent Substances 0.000 abstract description 40
- 238000000576 coating method Methods 0.000 abstract description 40
- 229920005989 resin Polymers 0.000 abstract description 34
- 239000011347 resin Substances 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 15
- 239000000945 filler Substances 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 72
- 239000000203 mixture Substances 0.000 description 72
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 48
- 239000011521 glass Substances 0.000 description 36
- 239000002002 slurry Substances 0.000 description 36
- 238000004381 surface treatment Methods 0.000 description 35
- 239000000126 substance Substances 0.000 description 32
- 239000003822 epoxy resin Substances 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 229930185605 Bisphenol Natural products 0.000 description 21
- 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 21
- 239000013500 performance material Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 19
- 238000002156 mixing Methods 0.000 description 19
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 229920001296 polysiloxane Polymers 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 12
- 238000007259 addition reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 11
- 229920002050 silicone resin Polymers 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 7
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- FGLHFQPDMSLJBI-UHFFFAOYSA-N 2-[2-(2-octadecoxyethoxy)ethoxy]ethyl dihydrogen phosphate Chemical compound [H]OP(=O)(O[H])OC([H])([H])C([H])([H])OC([H])([H])C([H])([H])OC([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] FGLHFQPDMSLJBI-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 241001340526 Chrysoclista linneella Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- NWBJYWHLCVSVIJ-UHFFFAOYSA-N N-benzyladenine Chemical compound N=1C=NC=2NC=NC=2C=1NCC1=CC=CC=C1 NWBJYWHLCVSVIJ-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000010947 wet-dispersion method Methods 0.000 description 1
Abstract
Description
本発明は、高熱伝導率の樹脂組成物を与えるフィラーとしての表面修飾粒子に関する。 The present invention relates to surface-modified particles as a filler that gives a resin composition having high thermal conductivity.
近年、半導体デバイスのパワー密度上昇に伴い、放熱材料にはより高度な放熱特性が求められている。デバイスの放熱を実現する材料としては、サーマルインターフェースマテリアルと呼ばれる一連の材料があり、その使用量は急速に拡大中である。サーマルインターフェースマテリアルとは、半導体素子の発生する熱をヒートシンクまたは筐体等に逃がす経路の熱抵抗を緩和するための材料であり、シート、ゲル、グリースなど多様な形態が用いられている。一般に、このサーマルインターフェースマテリアルは熱伝導性のフィラーを、エポキシ、シリコーンの様な樹脂に分散した複合材料で、フィラーとしてはシリカやアルミナが多く用いられている。しかし、シリカ、アルミナの熱伝導率は各々１Ｗ／ｍＫ、３０Ｗ／ｍＫ程度であり、アルミナを用いた複合材料でも、その熱伝導率も１〜３Ｗ／ｍＫ程度に留まっている。 In recent years, with the increase in power density of semiconductor devices, more advanced heat dissipation characteristics are required for heat dissipation materials. As a material for realizing heat dissipation of the device, there is a series of materials called thermal interface materials, and the amount of use is rapidly expanding. The thermal interface material is a material for relaxing the thermal resistance of the path through which heat generated by the semiconductor element is released to the heat sink or the housing, and various forms such as a sheet, gel, and grease are used. Generally, this thermal interface material is a composite material in which a thermally conductive filler is dispersed in a resin such as epoxy or silicone, and silica or alumina is often used as the filler. However, the thermal conductivities of silica and alumina are about 1 W / mK and 30 W / mK, respectively, and even in a composite material using alumina, the thermal conductivity remains at about 1 to 3 W / mK.
しかし、上述のように近年の半導体デバイスのパワー密度上昇により、サーマルインターフェースマテリアルには、より高い熱伝導率が求められるようになって来た。 However, as described above, due to the recent increase in power density of semiconductor devices, higher thermal conductivity has been required for thermal interface materials.
このため近年では、窒化ホウ素や酸化マグネシウム等の高熱伝導化合物をフィラーとするサーマルインターフェースマテリアルが市場シェアを拡大しつつある。ただし、これらの化合物は樹脂との親和性が低いため、樹脂への高充填が不可能であり、更に親和性の低さに起因してフィラー−樹脂界面での熱抵抗が高いため、未だ満足な熱伝導率を示す樹脂組成物を得ることが出来ていなかった。 For this reason, in recent years, the market share of thermal interface materials using high thermal conductive compounds such as boron nitride and magnesium oxide as fillers is increasing. However, since these compounds have low affinity with the resin, high filling into the resin is impossible, and furthermore, the thermal resistance at the filler-resin interface is high due to the low affinity, so it is still satisfactory. It was not possible to obtain a resin composition showing a good thermal conductivity.
一般に無機粉末を充填した樹脂の熱伝導率は、無機粉末の充填量と伴に上昇し、そのカーブは充填量が高いほど傾きが大きくなる事は周知の事実である。従って高熱伝導性の樹脂組成物を得るためには、高熱伝導の無機粉末を樹脂中に大量に分散せしめる必要があり、このためには無機粉末を充填しても樹脂組成物の流動性をなるべく低く抑える事が必須となる。従来この目的のために様々な工夫がなされて来た。粒子径の異なる球状粒子の組み合わせ（例えば特許文献１）、高沸点溶媒の添加（例えば特許文献２）、ポリアリーレンサルファイド樹脂への特定のリン酸エステル添加（例えば特許文献３）などである。しかし前二者をシリコーンなどの樹脂に適用した場合、樹脂−フィラー界面での熱抵抗の問題を解決できず、熱伝導率向上に不十分な効果しか得られなかった。また、上記特定のリン酸エステルとして例示されている物質はいずれもトリエステルであり、本発明者の検討によればこのような例示化合物は窒化ホウ素及び／または酸化マグネシウムとの親和性は必ずしも良好ではなかった。 It is a well-known fact that the thermal conductivity of a resin filled with an inorganic powder generally increases with the filling amount of the inorganic powder, and the slope of the curve increases as the filling amount increases. Therefore, in order to obtain a highly heat conductive resin composition, it is necessary to disperse a large amount of highly heat conductive inorganic powder in the resin. For this purpose, even if the inorganic powder is filled, the fluidity of the resin composition should be as much as possible. It is essential to keep it low. Various ideas have been made for this purpose. For example, a combination of spherical particles having different particle diameters (for example, Patent Document 1), addition of a high boiling point solvent (for example, Patent Document 2), and addition of a specific phosphate ester to a polyarylene sulfide resin (for example, Patent Document 3). However, when the former two were applied to a resin such as silicone, the problem of thermal resistance at the resin-filler interface could not be solved, and only an insufficient effect for improving the thermal conductivity could be obtained. In addition, all of the substances exemplified as the above specific phosphate ester are triesters, and according to the study of the present inventors, such an exemplified compound does not necessarily have good affinity with boron nitride and / or magnesium oxide. It wasn't.
また窒化アルミニウム、窒化ホウ素及び酸化マグネシウムには、その表面が水と反応して加水分解するという問題がある。この問題を解決するために、例えば有機珪素系、有機燐酸系、有機チタン系窒化アルミニウムによる窒化アルミニウムの処理（特許文献４）、
特定の酸性リン酸エステルによる酸化マグネシウムの処理（特許文献５）等があるが、これらの処理方法では耐水性に若干の改善は見られるものの、樹脂との親和性及び樹脂組成物の熱伝導率は不十分であった。本発明者の検討によれば、これらふたつの文献に記載されている表面処理剤は、水と反応して加水分解するという問題を解決するために用いられており、いずれも被覆量が多すぎるため、表面処理フィラーを樹脂と混合して複合材料とした場合、界面に多量に存在する表面処理剤が熱伝導を阻害して、フィラー本来の熱伝導率を発揮する事が出来ないことがわかった。
In addition, aluminum nitride, boron nitride, and magnesium oxide have a problem that their surfaces react with water and are hydrolyzed. In order to solve this problem, for example, treatment of aluminum nitride with organosilicon, organophosphate, or organotitanium aluminum nitride (Patent Document 4),
There is a treatment of magnesium oxide with a specific acidic phosphate ester (Patent Document 5), etc. Although these treatment methods show some improvement in water resistance, affinity with resin and thermal conductivity of resin composition Was insufficient. According to the study of the present inventor, the surface treatment agents described in these two documents are used to solve the problem of hydrolysis by reacting with water, both of which have too much coating amount. Therefore, when the surface treatment filler is mixed with the resin to form a composite material, it is understood that the surface treatment agent present in a large amount at the interface can inhibit the heat conduction and cannot exhibit the original heat conductivity of the filler. It was.
以上の様に、放熱用樹脂組成物のフィラーとして用いる窒化アルミニウム粒子、窒化ホウ素粒子または酸化マグネシウム粒子について、樹脂との親和性が高くフィラー−樹脂界面での熱抵抗を低減し、高い熱伝導性を実現するための表面処理方法が求められている。 As described above, aluminum nitride particles, boron nitride particles, or magnesium oxide particles used as a filler in a heat-dissipating resin composition have a high affinity with the resin, reduce the thermal resistance at the filler-resin interface, and have a high thermal conductivity. There is a demand for a surface treatment method for realizing the above.
本発明者は、高い熱伝導率を有する放熱用樹脂組成物を実現するため、窒化アルミニウム粒子、窒化ホウ素粒子または酸化マグネシウム粒子と樹脂との親和性を改善する手段について検討した。その結果、硬化性樹脂および熱可塑性樹脂に於いて、窒化アルミニウム粒子、窒化ホウ素粒子または酸化マグネシウム粒子を特定の酸性リン酸エステルにより表面修飾する事で、これら粒子と樹脂との親和性が改善され、樹脂組成物の熱伝導率が向上する事を見出し本発明に至った。 In order to realize a heat radiation resin composition having a high thermal conductivity, the present inventor has studied a means for improving the affinity between the aluminum nitride particles, boron nitride particles or magnesium oxide particles and the resin. As a result, in curable resins and thermoplastic resins, the surface affinity of aluminum nitride particles, boron nitride particles or magnesium oxide particles with a specific acidic phosphate ester improves the affinity between these particles and the resin. The present inventors have found that the thermal conductivity of the resin composition is improved and have reached the present invention.
即ち本発明は、窒化アルミニウム粒子、窒化ホウ素粒子、酸化マグネシウム粒子から選択される粒子の表面が、粒子に対して０．５〜５ｍｇ／ｍ２の下記一般式（１）で表される酸性リン酸エステルによって被覆されている表面修飾粒子である。 That is, in the present invention, the surface of particles selected from aluminum nitride particles, boron nitride particles, and magnesium oxide particles is 0.5 to 5 mg / m 2 with respect to the particles. Surface-modified particles coated with an acid ester.
（式（１）中、
Ｒ１：炭素数８〜２０の飽和または不飽和ヒドロカルビル基
Ｒ２：炭素数２または３の飽和ヒドロカルビレン基
ｍ：０〜６の整数
ｎ：１または２
であって、
Ｒ１が複数存在する場合には、複数のＲ１は同一でも異なっていてもよく、
Ｒ２が複数存在する場合には、複数のＲ２は同一でも異なっていてもよく、
ｎ＝２の場合、２個のＲ１Ｏ（Ｒ２Ｏ）ｍ基は同一でも異なっていてもよい。）
(In the formula (1),
R 1 : Saturated or unsaturated hydrocarbyl group having 8 to 20 carbon atoms R 2 : Saturated hydrocarbylene group having 2 or 3 carbon atoms m: Integer of 0 to 6 n: 1 or 2
Because
When a plurality of R 1 are present, the plurality of R 1 may be the same or different,
When a plurality of R 2 are present, the plurality of R 2 may be the same or different,
When n = 2, the two R 1 O (R 2 O) m groups may be the same or different. )
本発明の表面修飾粒子を樹脂と混合して樹脂組成物とすることで、良好な成型性と高い熱伝導率が達成される。この樹脂組成物は、ＭＥＤ、ＣＰＵ、パワー半導体などの放熱材料として広範な用途を有する。 By mixing the surface-modified particles of the present invention with a resin to obtain a resin composition, good moldability and high thermal conductivity are achieved. This resin composition has a wide range of uses as a heat-dissipating material such as MED, CPU, and power semiconductor.
本発明に使用される窒化アルミニウム粒子、窒化ホウ素粒子、酸化マグネシウム粒子としては、特に限定されず公知の窒化アルミニウム粒子、窒化ホウ素粒子、酸化マグネシウム粒子が用いられる。これら粒子の平均粒子径は制限されることはなく、１０ｎｍ〜１００μｍのものを使用することが出来る。但し樹脂組成物として高い耐水性が要求される場合にはサブミクロン領域以上、即ち平均粒子径が１００ｎｍ〜１００μｍであることが好ましい。更に、平均粒子径の異なるこれらの粒子を混合して用いる事も好ましい態様である。例えば平均粒子径１０〜１００μｍの粒子を粉末全体の３０〜８０重量%とし、１〜１０μｍの粒子を１０〜６０重量％、１００ｎｍ〜１μｍの粒子を３〜３０重量％程度で混合すると樹脂組成物の粘度を低く抑える事が出来、粒子の樹脂組成物への充填量を高くすることが可能となる。なお、「平均粒子径」とは、レーザー回折法によって測定される体積分布の中間値を与える球相当径（体積平均値Ｄ５０）を意味するものである。レーザー回折法による粒子の体積分布の測定は、日機装株式会社製マイクロトラックを用いて好ましく行うことができる。 The aluminum nitride particles, boron nitride particles, and magnesium oxide particles used in the present invention are not particularly limited, and known aluminum nitride particles, boron nitride particles, and magnesium oxide particles are used. The average particle diameter of these particles is not limited, and those having a particle size of 10 nm to 100 μm can be used. However, when high water resistance is required as the resin composition, it is preferable to have a submicron region or more, that is, an average particle diameter of 100 nm to 100 μm. Furthermore, it is also a preferred embodiment to use a mixture of these particles having different average particle sizes. For example, when the average particle diameter of 10 to 100 μm is 30 to 80% by weight of the whole powder, 1 to 10 μm particles are mixed at 10 to 60% by weight, and 100 nm to 1 μm particles are mixed at about 3 to 30% by weight. The viscosity of the resin composition can be kept low, and the filling amount of the particles into the resin composition can be increased. The “average particle diameter” means a sphere equivalent diameter (volume average value D50) that gives an intermediate value of volume distribution measured by a laser diffraction method. Measurement of the volume distribution of the particles by the laser diffraction method can be preferably performed using a microtrack manufactured by Nikkiso Co., Ltd.
本発明の樹脂組成物に使用される酸性リン酸エステルは下記構造（１）で表される構造を有する。 The acidic phosphate used in the resin composition of the present invention has a structure represented by the following structure (1).
（式（１）中、
Ｒ１：炭素数８〜２０の飽和または不飽和ヒドロカルビル基
Ｒ２：炭素数２または３の飽和ヒドロカルビレン基
ｍ：０〜６の整数
ｎ：１または２
であって、
Ｒ１が複数存在する場合には、複数のＲ１は同一でも異なっていてもよく、
Ｒ２が複数存在する場合には、複数のＲ２は同一でも異なっていてもよく、
ｎ＝２の場合、２個のＲ１Ｏ（Ｒ２Ｏ）ｍ基は同一でも異なっていてもよい。）
式中Ｒ１は、炭素数８〜２０、好ましくは８〜１８の飽和または不飽和ヒドロカルビル基であれば良く特に限定される事はない。Ｒ１の具体例としては、オクチル基、２−エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等が挙げられる。
(In the formula (1),
R 1 : Saturated or unsaturated hydrocarbyl group having 8 to 20 carbon atoms R 2 : Saturated hydrocarbylene group having 2 or 3 carbon atoms m: Integer of 0 to 6 n: 1 or 2
Because
When a plurality of R 1 are present, the plurality of R 1 may be the same or different,
When a plurality of R 2 are present, the plurality of R 2 may be the same or different,
When n = 2, the two R 1 O (R 2 O) m groups may be the same or different. )
In the formula, R 1 is not particularly limited as long as it is a saturated or unsaturated hydrocarbyl group having 8 to 20 carbon atoms, preferably 8 to 18 carbon atoms. Specific examples of R 1 include octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like.
式中Ｒ２は炭素数２または３の飽和ヒドロカルビレン基であるが、炭素数は２であることが好ましく、エチレン基であることがより好ましい。 In the formula, R 2 is a saturated hydrocarbylene group having 2 or 3 carbon atoms, preferably 2 carbon atoms, and more preferably an ethylene group.
式中ｍは０〜６の整数であるが、０〜４の整数である事が好ましい。 In the formula, m is an integer of 0 to 6, but is preferably an integer of 0 to 4.
式中ｎは、１または２であり、本発明の樹脂組成物に使用する一般式（１）で表される酸性リン酸エステルは、最低１個の酸性水酸基を必要とする。この理由は定かではないが、フィラーとなる窒化アルミニウムが固体塩基であり、その表面への吸着に酸性基が必要なためと推察している。 In the formula, n is 1 or 2, and the acidic phosphate ester represented by the general formula (1) used in the resin composition of the present invention requires at least one acidic hydroxyl group. The reason for this is not clear, but it is presumed that aluminum nitride serving as a filler is a solid base and an acidic group is required for adsorption onto the surface.
一般式（１）で表される酸性リン酸エステルはｎが１のものとｎが２のものとの混合物であっても構わない。また、一般式（１）で表される酸性リン酸エステルがｎ＝２の場合、同一分子内に異なる側鎖を有するものであっても構わない。更に上記一般式（１）で表される酸性リン酸エステルは、構造の異なる分子の混合物を用いても構わない。なお、一般式（１）で表される酸性リン酸エステルは、通常、ｎが１のものと２のものとの混合物で得られる。 The acidic phosphoric acid ester represented by the general formula (1) may be a mixture of those having n = 1 and n = 2. Moreover, when the acidic phosphate ester represented by General formula (1) is n = 2, you may have a different side chain in the same molecule. Furthermore, the acidic phosphate ester represented by the general formula (1) may be a mixture of molecules having different structures. In addition, the acidic phosphate ester represented by the general formula (1) is usually obtained as a mixture of those having n of 1 and 2.
酸性リン酸エステルであっても、一般式（１）で表される酸性リン酸エステルではないものは、窒化アルミニウムと熱硬化性樹脂または熱可塑性樹脂との親和性が十分でなく、粘度が上昇する、熱伝導率が低下する等の不利益を招く恐れがある。 Even if it is acidic phosphate ester, what is not acidic phosphate ester represented by General formula (1) does not have sufficient affinity with aluminum nitride, a thermosetting resin, or a thermoplastic resin, and a viscosity rises. There is a risk of causing disadvantages such as a decrease in thermal conductivity.
この様な酸性リン酸エステルの具体例を挙げれば、
Ｒ１がオクチル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がオクチル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がオクチル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がデシル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がオクチル基、ｍが０、ｎが１のもの、Ｒ１がオクチル基、ｍが０、ｎが２のもの、Ｒ１がデシル基、ｍが０、ｎが１のもの、Ｒ１がデシル基、ｍが０、ｎが２のもの、ｍが０、ｎが２、Ｒ１がオクチル基とデシル基のものとの混合物、
Ｒ１がウンデシル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが４、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが４、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がオクチルデシル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がオクチルデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がオクチルデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がオクチルデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がオクチルデシル基、ｍが４、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
などがある。
If the specific example of such acidic phosphate ester is given,
A mixture of R 1 is an octyl group, m is 0, n is 1 and 2;
A mixture of R 1 is an octyl group, m is 1, R 3 is an ethylene group, n is 1 and 2,
R 1 is an octyl group, m is 2, R 3 is an ethylene group, n is a mixture of 1 and 2,
A mixture of R 1 is a decyl group, m is 0, n is 1 and 2;
R 1 is a decyl group, m is 1, R 3 is an ethylene group, n is a mixture of 1 and 2,
R 1 is a decyl group, m is 2, R 3 is an ethylene group, n is a mixture of 1 and 2,
A mixture of R 1 is a decyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
R1 is an octyl group, m is 0, n is 1, R1 is an octyl group, m is 0, n is 2, R1 is a decyl group, m is 0, n is 1, R1 is a decyl group, a mixture of m = 0, n = 2, m = 0, n = 2, R1 octyl and decyl groups,
A mixture of R 1 is an undecyl group, m is 0, n is 1 and 2;
R 1 is an undecyl group, m is 1, R 3 is an ethylene group, n is a mixture of 1 and 2,
A mixture of R 1 is an undecyl group, m is 2, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 4, R 3 is an ethylene group, n is 1 and 2,
R 1 is a dodecyl group, m is 0, n is a mixture of 1 and 2,
A mixture of R 1 is a dodecyl group, m is 1, R 3 is an ethylene group, n is 1 and 2;
A mixture of R 1 is a dodecyl group, m is 2, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 4, R 3 is an ethylene group, n is 1 and 2,
R 1 is an octyldecyl group, m is 0, n is a mixture of 1 and 2,
R 1 is an octyldecyl group, m is 1, R 3 is an ethylene group, n is a mixture of 1 and 2,
R 1 is an octyldecyl group, m is 2, R 3 is an ethylene group, n is a mixture of 1 and 2,
A mixture of R 1 is an octyldecyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
R 1 is an octyldecyl group, m is 4, R 3 is an ethylene group, n is a mixture of 1 and 2,
and so on.
以上の化合物群の中でも好ましいものを例示すれば、
Ｒ１がデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが４、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが５、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが６、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが７、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが８、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが９、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がウンデシル基、ｍが１０、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが０、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが１、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが４、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが５、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが６、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが７、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが８、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが９、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
Ｒ１がドデシル基、ｍが１０、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物、
などを挙げることができる。
If a preferable thing is illustrated in the above compound groups,
R 1 is a decyl group, m is 1, R 3 is an ethylene group, n is a mixture of 1 and 2,
R 1 is a decyl group, m is 2, R 3 is an ethylene group, n is a mixture of 1 and 2,
A mixture of R 1 is a decyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 0, n is 1 and 2;
R 1 is an undecyl group, m is 1, R 3 is an ethylene group, n is a mixture of 1 and 2,
A mixture of R 1 is an undecyl group, m is 2, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 4, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 5, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 6, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 7, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 8, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 9, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is an undecyl group, m is 10, R 3 is an ethylene group, n is 1 and 2,
R 1 is a dodecyl group, m is 0, n is a mixture of 1 and 2,
A mixture of R 1 is a dodecyl group, m is 1, R 3 is an ethylene group, n is 1 and 2;
A mixture of R 1 is a dodecyl group, m is 2, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 3, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 4, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 5, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 6, R 3 is an ethylene group, n is 1 and 2;
A mixture of R 1 is a dodecyl group, m is 7, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 8, R 3 is an ethylene group, n is 1 and 2;
A mixture of R 1 is a dodecyl group, m is 9, R 3 is an ethylene group, n is 1 and 2,
A mixture of R 1 is a dodecyl group, m is 10, R 3 is an ethylene group, n is 1 and 2,
And so on.
上記酸性リン酸エステルの中で、一般的に入手可能なものの例を挙げれば、
Ｒ１がトリデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物（フォスファノールＲＳ−４１０：東邦化学社製）、
Ｒ１がトリデシル基、ｍが６、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物（フォスファノールＲＳ−６１０：東邦化学社製）、
Ｒ１がトリデシル基、ｍが０、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物（フォスファノールＧＦ−１８５：東邦化学社製）、
Ｒ１がオクチルデシル基、ｍが２、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物（フォスファノールＲＬ−２１０：東邦化学社製）、
Ｒ１がオクチルデシル基、ｍが３、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物（フォスファノールＲＬ−３１０：東邦化学社製）、
Ｒ１がオクチルデシル基、ｍが４、Ｒ３がエチレン基、ｎが１のものと２のものとの混合物（フォスファノールＲＢ−４１０：東邦化学社製）、
Ｒ１がドデシル基、ｍが０、ｎが１のものと２のものとの混合物で１の含有量が２より大きいもの（フォスファノールＭＬ−２００：東邦化学社製）、
Ｒ１がドデシル基、ｍが０、ｎが１のものと２のものとの混合物で１と２の含有量がほぼ等しいもの（フォスファノールＧＦ−１９９：東邦化学社製）
などがある。
Among the acidic phosphate esters, examples of those that are generally available are:
R 1 is a tridecyl group, m is 3, R 3 is an ethylene group, n is a mixture of 1 and 2 (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.),
R 1 is a tridecyl group, m is 6, R 3 is an ethylene group, n is a mixture of 1 and 2 (phosphanol RS-610: manufactured by Toho Chemical Co., Ltd.),
R 1 is a tridecyl group, m is 0, R 3 is an ethylene group, n is a mixture of 1 and 2 (phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.),
R 1 is an octyldecyl group, m is 2, R 3 is an ethylene group, n is a mixture of 1 and 2 (phosphanol RL-210: manufactured by Toho Chemical Co., Ltd.),
R 1 is an octyldecyl group, m is 3, R 3 is an ethylene group, n is a mixture of 1 and 2 (phosphanol RL-310: manufactured by Toho Chemical Co., Ltd.),
R 1 is an octyldecyl group, m is 4, R 3 is an ethylene group, n is a mixture of 1 and 2 (phosphanol RB-410: manufactured by Toho Chemical Co., Ltd.),
R 1 is a dodecyl group, m is 0, n is a mixture of 1 and 2, and the content of 1 is greater than 2 (Phosphanol ML-200: manufactured by Toho Chemical Co., Ltd.)
R 1 is a dodecyl group, m is 0, n is a mixture of 1 and 2, and the contents of 1 and 2 are almost equal (phosphanol GF-199: manufactured by Toho Chemical Co., Ltd.)
and so on.
本発明の酸性リン酸エステルのＨＬＢは５〜１０.５の範囲である事が好ましい。ＨＬＢがこの範囲を外れると樹脂との親和性が低下し、熱伝導率も低下する傾向にある。また、ＨＬＢが上記範囲より大きいと成型性が不良となる可能性がある一方、小さいものは工業的に入手が困難である。ここで言うＨＬＢとはＧｒｉｆｆｉｎにより提唱された界面活性剤の親水親油バランスのことであり（Griffin, W. C. Classification of Surface Active Agents by HLB. J. Soc. Cosmet. Chem. 1949, 1, 311-326.）、下記式で定義される。 The HLB of the acidic phosphate ester of the present invention is preferably in the range of 5 to 10.5. If the HLB is out of this range, the affinity with the resin is lowered and the thermal conductivity tends to be lowered. On the other hand, if the HLB is larger than the above range, the moldability may be poor, while the small one is difficult to obtain industrially. The HLB here is a hydrophilic / lipophilic balance of a surfactant proposed by Griffin (Griffin, WC Classification of Surface Active Agents by HLB. J. Soc. Cosmet. Chem. 1949, 1, 311-326). .), Defined by the following formula.
ＨＬＢ ＝ ２０ × Ｍｗ／Ｍ
ＨＬＢ：酸性リン酸エステルの親水新油バランス
Ｍｗ：酸性リン酸エステル中の親水部分の分子量
Ｍ： 酸性リン酸エステルの分子量
この数値は本来ノニオン界面活性剤に用いられるものであるが、本発明ではこの計算式を用いることで酸性リン酸エステルの有用性の尺度とすることが出来たため、この指標を採用することとした。本発明におけるＭｗはＭからＲ１の分子量を減じたものである。
HLB = 20 × Mw / M
HLB: hydrophilic new oil balance of acidic phosphate
Mw: Molecular weight of hydrophilic part in acidic phosphate
M: Molecular weight of acidic phosphate ester This value is originally used for nonionic surfactants, but in the present invention, this calculation formula can be used as a measure of the usefulness of acidic phosphate ester. This index was adopted. Mw in the present invention is M obtained by subtracting the molecular weight of R 1 from M.
一般式（１）の酸性リン酸エステルは通常ｎ＝１とｎ＝２のエステルがほぼ等モルの混合物であるため、上記Ｍとしてはｎ＝１とｎ＝２の分子量の平均値を用いた。このＭは、２００〜９００の範囲である事が好ましい。分子量が上記範囲より小さいと複合材料の成型性が不良となる可能性がある一方、上記範囲より大きいと複合材料の熱伝導率が不良となる可能性がある。 Since the acidic phosphoric acid ester of the general formula (1) is usually a mixture of substantially equimolar n = 1 and n = 2 esters, the average value of the molecular weights of n = 1 and n = 2 was used as M. . This M is preferably in the range of 200 to 900. When the molecular weight is smaller than the above range, the moldability of the composite material may be poor. On the other hand, when the molecular weight is larger than the above range, the thermal conductivity of the composite material may be poor.
窒化アルミニウム粒子、窒化ホウ素粒子、酸化マグネシウム粒子に対する上記酸性リン酸エステルの被覆量は粒子に対して０．５〜５ｍｇ／ｍ２であり、好ましくは０．８〜４ｍｇ／ｍ２である。被覆量が上記範囲より小さいと樹脂との親和性が不十分となり複合材料の成型性および熱伝導率が低下する可能性がある。また上記範囲より大きい場合には、酸性リン酸エステルの被膜が厚く界面での熱抵抗が大きくなり過ぎる事で、複合材料の熱伝導率が低下する可能性がある。 The coating amount of the acidic phosphate ester on the aluminum nitride particles, boron nitride particles, and magnesium oxide particles is 0.5 to 5 mg / m 2 , preferably 0.8 to 4 mg / m 2 . If the coating amount is smaller than the above range, the affinity with the resin is insufficient, and the moldability and thermal conductivity of the composite material may be lowered. On the other hand, if it is larger than the above range, the thermal conductivity of the composite material may be lowered because the acid phosphate ester film is thick and the thermal resistance at the interface becomes too large.
本発明の表面修飾粒子の製造方法は特に限定されず、公知の方法が採用され得る。例えば乾式法では無溶媒下での粒子と酸性リン酸エステルの分散・混合工程であり、湿式法では溶媒中での粒子と酸性リン酸エステルの分散・混合工程及びその後の脱溶媒乾燥工程である。但し、湿式法は乾式法に比べてより均一な被膜を形成することが可能で、より少ない量で酸性リン酸エステルの効果を発揮せしめる事が出来るため好適に採用される。湿式法に用いる装置の例としては、ディスパーザー、ホモジナイザー、超音波分散機、湿式ボールミル、湿式振動ボールミル、湿式ビーズミル、ナノマイザーまたは高圧分散機などの衝突分散機などを挙げることが出来る。また、この様な分散・混合工程では、窒化アルミニウム粉末をメジアン径／一次粒子径の比が５．０以下となるように分散することが好ましい。上記メジアン径／一次粒子径の比は好ましくは４．０であり、より好ましくは３．０である。この比が上記範囲より大きいと樹脂との親和性が低下し、複合材料の熱伝導率が低下する恐れがある。この理由は必ずしも明らかでないが、もし溶媒中に窒化アルミニウムが十分に分散しないと、乾燥工程にて凝集体の間にリン酸、金属リン酸塩または炭素数１２以下の有機リン酸が吸取られる事で、均一な被膜が形成されないためと考えられる。 The method for producing the surface-modified particles of the present invention is not particularly limited, and a known method can be adopted. For example, the dry method is a dispersion / mixing step of particles and acidic phosphate ester in the absence of a solvent, and the wet method is a dispersion / mixing step of particles and acidic phosphate ester in a solvent, followed by a desolvation drying step. . However, the wet method is preferably employed because it can form a more uniform film than the dry method and can exhibit the effect of acidic phosphate ester in a smaller amount. Examples of the apparatus used in the wet method include a disperser, a homogenizer, an ultrasonic disperser, a wet ball mill, a wet vibration ball mill, a wet bead mill, a nanomizer, and a collision disperser such as a high pressure disperser. In such a dispersion / mixing step, it is preferable to disperse the aluminum nitride powder so that the ratio of median diameter / primary particle diameter is 5.0 or less. The ratio of the median diameter / primary particle diameter is preferably 4.0, more preferably 3.0. When this ratio is larger than the above range, the affinity with the resin is lowered, and the thermal conductivity of the composite material may be lowered. The reason for this is not necessarily clear, but if the aluminum nitride is not sufficiently dispersed in the solvent, phosphoric acid, metal phosphate or organic phosphoric acid having 12 or less carbon atoms is absorbed between the aggregates in the drying step. This is probably because a uniform film is not formed.
湿式による分散・混合工程後の乾燥工程は、混合スラリーを８０℃〜３００℃の温度範囲に加熱する工程であれば特に限定されず、公知の方法を採用することが出来る。この様な乾燥に用いる装置の例を挙げれば、常圧オーブン、減圧オーブン、スプレードライヤー、媒体流動乾燥機、更には乾燥機構を備えた揺動ミキサー、プロシェアミキサーなどがある。 The drying step after the wet dispersion / mixing step is not particularly limited as long as the mixed slurry is heated to a temperature range of 80 ° C. to 300 ° C., and a known method can be adopted. Examples of such an apparatus used for drying include a normal pressure oven, a vacuum oven, a spray dryer, a medium fluidized dryer, a rocking mixer equipped with a drying mechanism, and a proshear mixer.
本発明の表面修飾粒子を樹脂と混合して熱伝導性樹脂組成物とすることが出来る。その様な目的に用いられる樹脂を例示すると、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、ポリメチルペンテン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、エチレン−酢酸ビニル共重合体、ポリビニルアルコール、ポリアセタール、フッ素樹脂（ポリフッ化ビニリデン、ポリテトラフルオロエチレン等）、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン２，６ナフタレート、ポリスチレン、ポリアクリロニトリル、スチレン−アクリロニトリル共重合体、ＡＢＳ樹脂、ポリフェニレンエーテル（ＰＰＥ）樹脂、変性ＰＰＥ樹脂、脂肪族ポリアミド類、芳香族ポリアミド類、ポリイミド、ポリアミドイミド、ポリメタクリル酸類（ポリメタクリル酸メチル等のポリメタクリル酸エステル）、ポリアクリル酸類、ポリカーボネート、ポリフェニレンスルフィド、ポリサルホン、ポリエーテルサルホン、ポリエーテルニトリル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリケトン、液晶ポリマー、アイオノマーなどの熱可塑性樹脂、更にエポキシ類、アクリル類、ウレタン類、シリコーン類、フェノール類、イミド類、熱硬化型変性ＰＰＥ類、および熱硬化型ＰＰＥ類などの熱硬化性樹脂を挙げることが出来る。 The surface-modified particles of the present invention can be mixed with a resin to obtain a heat conductive resin composition. Examples of resins used for such purposes include polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, Polyacetal, fluorine resin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6 naphthalate, polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin, polyphenylene ether (PPE) resin , Modified PPE resins, aliphatic polyamides, aromatic polyamides, polyimides, polyamideimides, polymethacrylic acids (polymethacrylic acid such as polymethylmethacrylate) Steal), polyacrylic acids, polycarbonate, polyphenylene sulfide, polysulfone, polyethersulfone, polyethernitrile, polyetherketone, polyetheretherketone, polyketone, liquid crystal polymer, ionomer, and other thermoplastic resins, epoxy, acrylics And thermosetting resins such as urethanes, silicones, phenols, imides, thermosetting modified PPEs, and thermosetting PPEs.
一般式（１）で表される酸性リン酸エステルを混合したこれらの樹脂と本発明の表面修飾粒子とを混合することもでき、この様な態様とすることで複合材料の成型性および熱伝導率をより一層向上するので好ましい。この場合、酸性リン酸エステルの樹脂に対する添加量は樹脂１００重量部に対して０．４〜５重量部であることが好ましく、０．６〜４重量部であることがより好ましい。 These resins mixed with the acidic phosphate ester represented by the general formula (1) can be mixed with the surface modified particles of the present invention. By adopting such an embodiment, the moldability and heat conduction of the composite material can be obtained. This is preferable because the rate is further improved. In this case, the amount of acid phosphate ester added to the resin is preferably 0.4 to 5 parts by weight, more preferably 0.6 to 4 parts by weight with respect to 100 parts by weight of the resin.
本発明の表面修飾粒子を用いた樹脂組成物の用途としては、家電製品、自動車、ノート型パーソナルコンピュータなどに搭載される半導体部品からの発熱を効率よく放熱するための放熱部材の材料があり、それらの例として、放熱グリース、放熱ゲル、放熱シート、フェイズチェンジシート、接着剤などがあり、またメタルベース基板、プリント基板、フレキシブル基板などに用いられる絶縁層など、更には半導体封止剤、アンダーフィル、筐体、放熱フィンなども挙げることが出来る。 As an application of the resin composition using the surface modified particles of the present invention, there is a material of a heat radiating member for efficiently radiating heat generated from a semiconductor component mounted on a home appliance, an automobile, a notebook personal computer, etc. Examples of these include heat-release grease, heat-release gel, heat-release sheet, phase change sheet, adhesive, etc., insulating layers used in metal-base boards, printed boards, flexible boards, etc. Examples include fills, housings, and heat radiating fins.
本発明の表面修飾粒子を用いた樹脂組成物の硬化体の熱伝導率は特に限定されないが、半導体部品等からの発熱を効率よく放熱するためにはなるべく高い方が望ましく、１．０Ｗ／ｍＫ以上であることが好ましい。 The thermal conductivity of the cured product of the resin composition using the surface-modified particles of the present invention is not particularly limited, but is preferably as high as possible in order to efficiently dissipate the heat generated from the semiconductor components and the like, and is 1.0 W / mK. The above is preferable.
以下、実施例および用途例によって本発明を具体的に説明するが、本発明はこれらの例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and an application example demonstrate this invention concretely, this invention is not limited to these examples.
本発明にて用いた試験方法を以下に示す。 The test method used in the present invention is shown below.
（１）樹脂組成物の粘度：
得られた樹脂組成物について、動的粘弾性測定装置（ＳＴＲＥＳＳ ＴＥＣＨ：セイコー電子工業社製）を用い、直径２０ｍｍのパラレルプレート、ギャップ幅１．００ｍｍ、測定温度２５℃、周波数０．１Ｈｚ、定常応力１０００Ｐａにて、測定開始から１２０秒後の粘度を求めた。
(1) Viscosity of resin composition:
About the obtained resin composition, using a dynamic viscoelasticity measuring apparatus (STRESS TECH: manufactured by Seiko Denshi Kogyo Co., Ltd.), a parallel plate having a diameter of 20 mm, a gap width of 1.00 mm, a measurement temperature of 25 ° C., a frequency of 0.1 Hz, and a steady state The viscosity after 120 seconds from the start of measurement was determined at a stress of 1000 Pa.
（２）樹脂組成物硬化体の熱伝導率：
得られた樹脂組成物をトルエンまたは２−メトキシエタノールにて適度な粘度に希釈後、バーコーター（ＰＩ−１２１０：テスター産業社製）を用いて離型ＰＥＴフィルム上に製膜し、１５０℃にて４時間保持後ＰＥＴフィルムを剥がした。熱硬化性イミド樹脂組成物では、その後試験片をテフロン（登録商標）板で挟み２５０℃にて２時間最終硬化を行った。樹脂組成物の樹脂がミラブル型シリコーンおよび熱可塑性樹脂であるポリフェニレンサルファイドの場合には、テフロン（登録商標）板に樹脂組成物を挟み樹脂製造者推奨の成型温度にて加圧成型した。尚、各々の樹脂について得られる硬化体の膜厚が約２００−３００μｍになる様、加圧条件を調節した。これら試料の熱伝導率を迅速熱伝導率計（ＱＴＭ−５００：京都電子工業社製）にて測定した。レファレンスには、厚さ２ｃｍ、長さ１５ｃｍ、幅６ｃｍの、石英ガラス、シリコーンゴムおよびジルコニアを用いた。
(2) Thermal conductivity of cured resin composition:
The obtained resin composition was diluted to an appropriate viscosity with toluene or 2-methoxyethanol, and then formed on a release PET film using a bar coater (PI-1210: manufactured by Tester Sangyo Co., Ltd.), and the temperature was increased to 150 ° C. After holding for 4 hours, the PET film was peeled off. In the thermosetting imide resin composition, the test piece was then sandwiched between Teflon (registered trademark) plates and finally cured at 250 ° C. for 2 hours. When the resin of the resin composition was millable silicone and polyphenylene sulfide which is a thermoplastic resin, the resin composition was sandwiched between Teflon (registered trademark) plates and pressure molded at a molding temperature recommended by the resin manufacturer. In addition, pressurization conditions were adjusted so that the film thickness of the cured body obtained about each resin might be set to about 200-300 micrometers. The thermal conductivity of these samples was measured with a rapid thermal conductivity meter (QTM-500: manufactured by Kyoto Electronics Industry Co., Ltd.). For the reference, quartz glass, silicone rubber and zirconia having a thickness of 2 cm, a length of 15 cm, and a width of 6 cm were used.
（実施例１）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 1)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.) 100 g, acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例２）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）１．０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 2)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.) 100 g, acidic phosphate ester (phosphanol GF-199: manufactured by Toho Chemical Co., Ltd.), and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例３）
窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：東洋アルミニウム社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 3)
Aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Toyo Aluminum Co., Ltd.) 100 g, acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: 150 g (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例４）
窒化アルミニウム粒子（グレードＪＤ、ＢＥＴ比表面積１．７ｍ２／ｇ：東洋アルミニウム社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１８５：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
Example 4
Aluminum nitride particles (grade JD, BET specific surface area 1.7 m 2 / g: manufactured by Toyo Aluminum Co., Ltd.), acidic phosphate ester (phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: 150 g (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）５ｇ、酸無水物（Ｂ−５７０：ＤＩＣ社製）５ｇ、促進剤としてＮ，Ｎ−ジメチルベンジルアミン（和光純薬社製）０．８ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 5 g of bisphenol F type epoxy resin (EXA-830CRP: manufactured by DIC), 5 g of acid anhydride (B-570: manufactured by DIC), 0.8 g of N, N-dimethylbenzylamine (manufactured by Wako Pure Chemical Industries) as an accelerator Were mixed to obtain a homogeneous solution. To this solution, 40 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例５）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：トクヤマ社製）５０ｇ、酸性リン酸エステル（フォスファノールＧＦ−１８５：東邦化学社製）０．２５ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 5)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Tokuyama Corporation) 50 g, acidic phosphate ester (Phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.) 0.25 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). Dispersion / mixing by ultrasonic waves was performed for 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 40 g of aluminum nitride particles having been subjected to the above surface treatment on 10 g of addition-type silicone (TSE325, containing a silicone resin containing a vinyl group, a hydrosilane compound and a platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) cured by addition reaction. In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例６）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：トクヤマ社製）５０ｇ、酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 6)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Tokuyama Corporation) 50 g, acidic phosphate ester (Phosphanol GF-199: manufactured by Toho Chemical Co., Ltd.) 0.50 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). Dispersion / mixing by ultrasonic waves was performed for 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 40 g of aluminum nitride particles having been subjected to the above surface treatment on 10 g of addition-type silicone (TSE325, containing a silicone resin containing a vinyl group, a hydrosilane compound and a platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) cured by addition reaction. In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例７）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）４０ｇ、窒化ホウ素粒子（ＰＴ−１４０、ＢＥＴ比表面積４．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）２０ｇ、酸性リン酸エステル（フォスファノールＲＢ−４１０：東邦化学社製）０．４５ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 7)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama) 40 g boron nitride particles (PT-140, BET specific surface area 4.9 m 2 / g: Momentive Performance Materials Japan) 20 g, 0.45 g of acid phosphate ester (Phosphanol RB-410: manufactured by Toho Chemical Co., Ltd.) and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) in a sealed glass bottle, shaken, and then an ultrasonic homogenizer ( The dispersion / mixing was carried out with ultrasonic waves for 10 minutes using SONIFIER250 (manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート（ＢＰＥ−１００、平均分子量４７８：新中村化学社製）５ｇ、トリエチレングリコールジメタクリレート（３Ｇ：新中村化学社製）５ｇ、およびベンゾイルパーオキサイド（日本油脂社製）０．１ｇを混合し均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物３０ｇを加えて混練した。 Dimethacrylate (BPE-100, average molecular weight 478: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, triethylene glycol dimethacrylate (3G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, and benzoyl peroxide (Nippon Yushi) 0.1 g) was mixed to make a uniform solution. To this solution, 30 g of a mixture of aluminum nitride particles and boron nitride particles subjected to the above surface treatment was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例８）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）４０ｇ、窒化ホウ素粒子（ＰＴ−１４０、ＢＥＴ比表面積４．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）２０ｇ、酸性リン酸エステル（フォスファノールＧＦ−１８５：東邦化学社製）０．６０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 8)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama) 40 g boron nitride particles (PT-140, BET specific surface area 4.9 m 2 / g: Momentive Performance Materials Japan) 20 g, acid phosphate ester (phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.) 0.60 g, and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer ( The dispersion / mixing was carried out with ultrasonic waves for 10 minutes using SONIFIER250 (manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート（ＢＰＥ−１００、平均分子量４７８：新中村化学社製）５ｇ、トリエチレングリコールジメタクリレート（３Ｇ：新中村化学社製）５ｇ、およびベンゾイルパーオキサイド（日本油脂社製）０．１ｇを混合し均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物３０ｇを加えて混練した。 Dimethacrylate (BPE-100, average molecular weight 478: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, triethylene glycol dimethacrylate (3G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, and benzoyl peroxide (Nippon Yushi) 0.1 g) was mixed to make a uniform solution. To this solution, 30 g of a mixture of aluminum nitride particles and boron nitride particles subjected to the above surface treatment was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例９）
窒化ホウ素粒子（ＰＴ−１４０、ＢＥＴ比表面積４．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＬ−３１０：東邦化学社製）１．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
Example 9
Boron nitride particles (PT-140, BET specific surface area 4.9 m 2 / g: manufactured by Momentive Performance Materials Japan) 100 g acid phosphate (phosphanol RL-310: manufactured by Toho Chemical Co., Ltd.) 00 g and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a sealed glass bottle and shaken, followed by ultrasonic dispersion / mixing for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化ホウ素粒子３０ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. 30 g of boron nitride particles subjected to the above surface treatment were added to this solution and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１０）
窒化ホウ素粒子（ＰＴ−１４０、ＢＥＴ比表面積４．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＬ−２１０：東邦化学社製）２．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 10)
Boron nitride particles (PT-140, BET specific surface area 4.9 m 2 / g: manufactured by Momentive Performance Materials Japan), acidic phosphate ester (phosphanol RL-210: manufactured by Toho Chemical Co., Ltd.) 00 g and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a sealed glass bottle and shaken, followed by ultrasonic dispersion / mixing for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化ホウ素粒子３５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 35 g of boron nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１１）
窒化ホウ素粒子（ＰＴ−１６０、ＢＥＴ比表面積８．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１８５：東邦化学社製）２．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 11)
1. Boron nitride particles (PT-160, BET specific surface area 8.9 m 2 / g: manufactured by Momentive Performance Materials Japan), acidic phosphate ester (phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.) 00 g and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a sealed glass bottle and shaken, followed by ultrasonic dispersion / mixing for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化ホウ素粒子３０ｇを加えて混練した。 Addition-type silicone cured by addition reaction (TSE325, containing silicone resin containing vinyl group, hydrosilane compound and platinum catalyst: manufactured by Momentive Performance Materials Japan) 30 g of boron nitride particles subjected to the above surface treatment In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１２）
酸化マグネシウム粒子（ＲＦ−１０Ｃ、ＢＥＴ比表面積１．７ｍ２／ｇ：宇部マテリアルズ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＢ−４１０：東邦化学社製）０．２５ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 12)
Magnesium oxide particles (RF-10C, BET specific surface area 1.7 m 2 / g: manufactured by Ube Materials Co., Ltd.) 100 g, acidic phosphate ester (Phosphanol RB-410: manufactured by Toho Chemical Co., Ltd.) 0.25 g, and ethanol ( 150 g of special grade (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した酸化マグネシウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of magnesium oxide particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１３）
酸化マグネシウム粒子（ＲＦ−１０Ｃ、ＢＥＴ比表面積１．７ｍ２／ｇ：宇部マテリアルズ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表１に示した。
(Example 13)
Magnesium oxide particles (RF-10C, BET specific surface area 1.7 m 2 / g: manufactured by Ube Materials Co., Ltd.) 100 g, acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 0.50 g, and ethanol ( 150 g of special grade (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 1 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した酸化マグネシウム粒子４０ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 40 g of magnesium oxide particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表４に示した。 Table 4 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１４）
窒化マグネシウム粒子（スターマグＰ、ＢＥＴ比表面積１０ｍ２／ｇ：神島化学工業社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１８５：東邦化学社製）２．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Example 14)
Magnesium nitride particles (Starmag P, BET specific surface area 10 m 2 / g: manufactured by Kamijima Chemical Co., Ltd.) 100 g, acidic phosphate ester (phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.) 2.00 g, and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した酸化マグネシウム粒子４０ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 40 g of magnesium oxide particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１５）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化ホウ素粒子（ＰＴ−１６０、ＢＥＴ比表面積８．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）５０ｇおよび酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）０．７５ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。
(Example 15)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama), boron nitride particles (PT-160, BET specific surface area 8.9 m 2 / g: Momentive Performance Materials Japan) 50 g and acid phosphate ester (phosphanol GF-199: manufactured by Toho Chemical Co., Ltd.) 0.75 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer ( The dispersion / mixing was carried out with ultrasonic waves for 10 minutes using SONIFIER250 (manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物４０ｇを加えて混練した。得られた表面修飾粒子の被覆量を表２に示した。 Addition-type silicone cured by addition reaction (TSE325, containing silicone resin containing vinyl group, hydrosilane compound and platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) 10 g of the above-mentioned surface treated aluminum nitride particles and nitriding 40 g of a mixture of boron particles was added and kneaded. Table 2 shows the coating amount of the obtained surface-modified particles.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１６）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化ホウ素粒子（ＰＴ−１６０、ＢＥＴ比表面積８．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）５０ｇおよび酸性リン酸エステル（フォスファノールＲＬ−２１０：東邦化学社製）２．７０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Example 16)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama), boron nitride particles (PT-160, BET specific surface area 8.9 m 2 / g: Momentive Performance Materials Japan) 50 g of acid phosphate ester (Phosphanol RL-210: manufactured by Toho Chemical Co., Ltd.) and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer ( The dispersion / mixing was carried out with ultrasonic waves for 10 minutes using SONIFIER250 (manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物４０ｇを加えて混練した。 Addition-type silicone cured by addition reaction (TSE325, containing silicone resin containing vinyl group, hydrosilane compound and platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) 10 g of the above-mentioned surface treated aluminum nitride particles and nitriding 40 g of a mixture of boron particles was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１７）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、酸化マグネシウム粒子（ＲＦ−１０Ｃ、ＢＥＴ比表面積１．７ｍ２／ｇ：宇部マテリアルズ社製）５０ｇ、および酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．４０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Example 17)
50 g of aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama), magnesium oxide particles (RF-10C, BET specific surface area 1.7 m 2 / g: manufactured by Ube Materials), and Acid phosphate ester (Phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 0.40 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, and then an ultrasonic homogenizer (SONIFIER 250: BRANSON) For 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート（ＢＰＥ−１００、平均分子量４７８：新中村化学社製）５ｇ、トリエチレングリコールジメタクリレート（３Ｇ：新中村化学社製）５ｇ、およびベンゾイルパーオキサイド（日本油脂社製）０．１ｇを混合し均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物３６ｇを加えて混練した。 Dimethacrylate (BPE-100, average molecular weight 478: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, triethylene glycol dimethacrylate (3G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, and benzoyl peroxide (Nippon Yushi) 0.1 g) was mixed to make a uniform solution. To this solution, 36 g of a mixture of aluminum nitride particles and boron nitride particles subjected to the above surface treatment was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１８）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、酸化マグネシウム粒子（ＲＦ−１０Ｃ、ＢＥＴ比表面積１．７ｍ２／ｇ：宇部マテリアルズ社製）５０ｇ、および酸性リン酸エステル（フォスファノールＧＦ−１８５：東邦化学社製）０．６０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Example 18)
50 g of aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama), magnesium oxide particles (RF-10C, BET specific surface area 1.7 m 2 / g: manufactured by Ube Materials), and 0.60 g of acidic phosphate ester (phosphanol GF-185: manufactured by Toho Chemical Co., Ltd.) and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a sealed glass bottle and shaken, and then an ultrasonic homogenizer (SONIFIER250: BRANSON) For 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＡのエチレンオキサイド付加物のジメタクリレート（ＢＰＥ−１００、平均分子量４７８：新中村化学社製）５ｇ、トリエチレングリコールジメタクリレート（３Ｇ：新中村化学社製）５ｇ、およびベンゾイルパーオキサイド（日本油脂社製）０．１ｇを混合し均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物３６ｇを加えて混練した。 Dimethacrylate (BPE-100, average molecular weight 478: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, triethylene glycol dimethacrylate (3G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g, and benzoyl peroxide (Nippon Yushi) 0.1 g) was mixed to make a uniform solution. To this solution, 36 g of a mixture of aluminum nitride particles and boron nitride particles subjected to the above surface treatment was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例１９）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Example 19)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.) 100 g, acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇ、２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇ、および酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．２ｇ、を混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子５０ｇを加えて混練した。 10 g of bisphenol F type epoxy resin (EXA-830CRP: manufactured by DIC), 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei), and acidic phosphate ester (phosphanol RS-410: Toho) Chemical Co., Ltd.) 0.2 g was mixed to make a uniform solution. To this solution, 50 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（実施例２０）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）１．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Example 20)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation) 100 g, acidic phosphate ester (phosphanol GF-199: manufactured by Toho Chemical Co., Ltd.) 1.00 g, and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇ、２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇ、および酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）０．１ｇ、を混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子５０ｇを加えて混練した。 10 g of bisphenol F type epoxy resin (EXA-830CRP: manufactured by DIC), 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei), and acidic phosphate ester (phosphanol GF-199: Toho) Chemical Co., Ltd.) 0.1 g was mixed to make a uniform solution. To this solution, 50 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１）
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）４５ｇを加えて混練した。
(Comparative Example 1)
10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation) was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例２）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．１０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Comparative Example 2)
100 g of aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama), 0.10 g of acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical), and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例３）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０、東邦化学社製）１．６０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Comparative Example 3)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama) 100 g, phosphoric acid ester (phosphanol RS-410, manufactured by Toho Chemical) 1.60 g, and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例４）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）３．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Comparative Example 4)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.) 100 g, acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 3.00 g, and ethanol (special grade: Japanese) 150 g (manufactured by Kojun Pharmaceutical Co., Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例５）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−７１０：一般式（１）においてＲ１がトリデシル基、Ｒ２がエチレン基、ｍが１０、ｎが１のものと２のものとの混合物、東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Comparative Example 5)
100 g of aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), acidic phosphate ester (phosphanol RS-710: in general formula (1), R 1 is a tridecyl group, R 2 is A mixture of ethylene group, m = 10, n = 1 and 2 (Toho Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken. Dispersion and mixing by ultrasonic waves were performed for 10 minutes with an ultrasonic homogenizer (SONIFIER250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例６）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、ノニオン界面活性剤（ペグノールＬ−４：東邦化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表２に示した。
(Comparative Example 6)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.) 100 g, nonionic surfactant (Pegnol L-4: manufactured by Toho Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: Wako Pure Chemical Industries, Ltd.) 150 g of the product was put into a glass bottle with a tight stopper and shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 2 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表５に示した。 Table 5 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例７）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（Ｐｈｏｓｌｅｘ Ａ−４：ブチルリン酸、ＳＣ有機化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 7)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.) 100 g, acidic phosphoric acid ester (Phoslex A-4: butyl phosphoric acid, manufactured by SC Organic Chemical Co., Ltd.) 0.50 g, and ethanol (special grade) : Wako Pure Chemical Industries, Ltd.) (150 g) was placed in a glass bottle with a tight stopper, shaken, and then subjected to ultrasonic dispersion / mixing for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例８）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）１００ｇ、酸性リン酸エステル（Ｗ−９０１０：酸性基を有するコポリマー、分子量１５００以上、ビックケミージャパン社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 8)
100 g of aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Co., Ltd.), acidic phosphate ester (W-9010: copolymer having an acidic group, molecular weight 1500 or more, manufactured by Big Chemie Japan Co.) 50 g and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a glass bottle with a tight stopper, shaken, and then subjected to ultrasonic dispersion / mixing for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４５ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例９）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：トクヤマ社製）５０ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）０．０７ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 9)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Tokuyama Corporation) 50 g, acidic phosphate ester (Phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 0.07 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). Dispersion / mixing by ultrasonic waves was performed for 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 40 g of aluminum nitride particles having been subjected to the above surface treatment on 10 g of addition-type silicone (TSE325, containing a silicone resin containing a vinyl group, a hydrosilane compound and a platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) cured by addition reaction. In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１０）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：トクヤマ社製）５０ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）１．２０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 10)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Tokuyama Corporation) 50 g, acidic phosphate ester (Phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 1.20 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, followed by an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). Dispersion / mixing by ultrasonic waves was performed for 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 40 g of aluminum nitride particles having been subjected to the above surface treatment on 10 g of addition-type silicone (TSE325, containing a silicone resin containing a vinyl group, a hydrosilane compound and a platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) cured by addition reaction. In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１１）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：トクヤマ社製）５０ｇ、酸性リン酸エステル（Ｐｈｏｓｌｅｘ Ａ−４：ブチルリン酸、ＳＣ有機化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 11)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Tokuyama Corporation) 50 g, acidic phosphate ester (Phoslex A-4: Butyl phosphoric acid, manufactured by SC Organic Chemical Co., Ltd.) 0.50 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken. The mixture was dispersed and mixed by ultrasonic for 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 40 g of aluminum nitride particles having been subjected to the above surface treatment on 10 g of addition-type silicone (TSE325, containing a silicone resin containing a vinyl group, a hydrosilane compound and a platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) cured by addition reaction. In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１２）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化アルミニウム粒子（グレードＵＭ、ＢＥＴ比表面積１．１ｍ２／ｇ：トクヤマ社製）５０ｇ、酸性リン酸エステル（Ｗ−９０１０：分子量１５００以上、ビックケミージャパン社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 12)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama Corporation), aluminum nitride particles (grade UM, BET specific surface area 1.1 m 2 / g: manufactured by Tokuyama Corporation) 50 g, acidic phosphate ester (W-9010: molecular weight 1500 or more, manufactured by Big Chemie Japan Co., Ltd.) 0.50 g and ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) 150 g were placed in a sealed glass bottle and shaken, and then an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON) The mixture was dispersed and mixed by ultrasonic for 10 minutes. The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 40 g of aluminum nitride particles having been subjected to the above surface treatment on 10 g of addition-type silicone (TSE325, containing a silicone resin containing a vinyl group, a hydrosilane compound and a platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) cured by addition reaction. In addition, kneading.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１３）
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に窒化ホウ素粒子（ＰＴ−１４０、ＢＥＴ比表面積４．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）３０ｇを加えて混練した。
(Comparative Example 13)
10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 30 g of boron nitride particles (PT-140, BET specific surface area of 4.9 m 2 / g: manufactured by Momentive Performance Materials Japan) was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１４）
窒化ホウ素粒子（ＰＴ−１４０、ＢＥＴ比表面積４．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）０．２０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 14)
Boron nitride particles (PT-140, BET specific surface area 4.9 m 2 / g: manufactured by Momentive Performance Materials Japan) 100 g phosphoric acid ester (phosphanol GF-199: manufactured by Toho Chemical Co.) 20 g and 150 g of ethanol (special grade: manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a sealed glass bottle and shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化ホウ素粒子３０ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. 30 g of boron nitride particles subjected to the above surface treatment were added to this solution and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１５）
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に酸化マグネシウム粒子（ＲＦ−１０Ｃ、ＢＥＴ比表面積１．７ｍ２／ｇ：宇部マテリアルズ社製）４５ｇを加えて混練した。
(Comparative Example 15)
10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 45 g of magnesium oxide particles (RF-10C, BET specific surface area 1.7 m 2 / g: manufactured by Ube Materials) was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１６）
酸化マグネシウム粒子（ＲＦ−１０Ｃ、ＢＥＴ比表面積１．７ｍ２／ｇ：宇部マテリアルズ社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＳ−４１０：東邦化学社製）１．００ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 16)
Magnesium oxide particles (RF-10C, BET specific surface area 1.7 m 2 / g: manufactured by Ube Materials Co., Ltd.) 100 g, acidic phosphate ester (phosphanol RS-410: manufactured by Toho Chemical Co., Ltd.) 1.00 g, and ethanol ( 150 g of special grade (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した酸化マグネシウム粒子４０ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 40 g of magnesium oxide particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１７）
アルミナ粒子（ＡＫＰ−２０、ＢＥＴ比表面積５．１ｍ２／ｇ：住友化学社製）１００ｇ、酸性リン酸エステル（フォスファノールＧＦ−１９９：東邦化学社製）０．７５ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 17)
100 g of alumina particles (AKP-20, BET specific surface area 5.1 m 2 / g: manufactured by Sumitomo Chemical Co., Ltd.), 0.75 g of acid phosphate ester (phosphanol GF-199: manufactured by Toho Chemical Co., Ltd.), and ethanol (special grade: 150 g (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
ビスフェノールＦ型エポキシ樹脂（ＥＸＡ−８３０ＣＲＰ：ＤＩＣ社製）１０ｇと２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ：四国化成社製）０．２ｇを混合して均一溶液とした。この溶液に上記表面処理を施した窒化アルミニウム粒子４０ｇを加えて混練した。 10 g of bisphenol F-type epoxy resin (EXA-830CRP: manufactured by DIC) and 0.2 g of 2-ethyl-4-methylimidazole (2E4MZ: manufactured by Shikoku Kasei) were mixed to obtain a uniform solution. To this solution, 40 g of aluminum nitride particles subjected to the above surface treatment were added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１８）
アルミナ粒子（ＡＫＰ−２０、ＢＥＴ比表面積５．１ｍ２／ｇ：住友化学社製）１００ｇ、酸性リン酸エステル（フォスファノールＲＬ−２１０：東邦化学社製）０．７５ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 18)
100 g of alumina particles (AKP-20, BET specific surface area 5.1 m 2 / g: manufactured by Sumitomo Chemical Co., Ltd.), 0.75 g of acidic phosphate ester (Phosphanol RL-210: manufactured by Toho Chemical Co., Ltd.), and ethanol (special grade: 150 g (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a glass bottle with a tight stopper, shaken, and then dispersed and mixed with ultrasonic waves for 10 minutes using an ultrasonic homogenizer (SONIFIER 250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施したアルミナ粒子４０ｇを加えて混練した。 Addition-type silicone cured by addition reaction (TSE325, containing silicone resin containing vinyl group, hydrosilane compound and platinum catalyst: manufactured by Momentive Performance Materials Japan) 40 g of alumina particles subjected to the above surface treatment were added. And kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。 Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
（比較例１９）
窒化アルミニウム粒子（グレードＨ、ＢＥＴ比表面積２．６ｍ２／ｇ：トクヤマ社製）５０ｇ、窒化ホウ素粒子（ＰＴ−１６０、ＢＥＴ比表面積８．９ｍ２／ｇ：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）５０ｇ、酸性リン酸エステル（Ｐｈｏｓｌｅｘ Ａ−４：ブチルリン酸、ＳＣ有機化学社製）０．５０ｇ、およびエタノール（特級：和光純薬社製）１５０ｇを密栓付きガラス瓶に入れ振盪後、超音波ホモジナイザー（ＳＯＮＩＦＩＥＲ２５０：ＢＲＡＮＳＯＮ社製）にて１０分間超音波による分散・混合を行った。得られたスラリーを琺瑯パッドに移し、送風乾燥器中１２０℃にて１５時間乾燥した。得られた表面修飾粒子の被覆量を表３に示した。
(Comparative Example 19)
Aluminum nitride particles (grade H, BET specific surface area 2.6 m 2 / g: manufactured by Tokuyama), boron nitride particles (PT-160, BET specific surface area 8.9 m 2 / g: Momentive Performance Materials Japan) 50 g, acidic phosphoric acid ester (Phoslex A-4: butylphosphoric acid, SC Organic Chemical Co., Ltd.) 0.50 g, and ethanol (special grade: Wako Pure Chemical Industries, Ltd.) 150 g are placed in a sealed glass bottle and shaken. The mixture was dispersed and mixed with ultrasonic waves for 10 minutes using a homogenizer (SONIFIER250: manufactured by BRANSON). The obtained slurry was transferred to a paddle pad and dried at 120 ° C. for 15 hours in an air dryer. Table 3 shows the coating amount of the obtained surface-modified particles.
付加反応により硬化する付加型シリコーン（ＴＳＥ３２５、ビニル基を含むシリコーン樹脂、ヒドロシラン化合物および白金触媒を含有：モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製）１０ｇに上記表面処理を施した窒化アルミニウム粒子と窒化ホウ素粒子の混合物４０ｇを加えて混練した。 Addition-type silicone cured by addition reaction (TSE325, containing silicone resin containing vinyl group, hydrosilane compound and platinum catalyst: manufactured by Momentive Performance Materials Japan Co., Ltd.) 10 g of the above-mentioned surface treated aluminum nitride particles and nitriding 40 g of a mixture of boron particles was added and kneaded.
得られた樹脂組成物の粘度と該樹脂組成物から得られた硬化体の熱伝導率を測定した結果を表６に示した。
Table 6 shows the results of measuring the viscosity of the obtained resin composition and the thermal conductivity of the cured product obtained from the resin composition.
Claims (3)
（式（１）中、
Ｒ１：炭素数８〜２０の飽和または不飽和ヒドロカルビル基
Ｒ２：炭素数２または３の飽和ヒドロカルビレン基
ｍ：０〜６の整数
ｎ：１または２
であって、
Ｒ１が複数存在する場合には、複数のＲ１は同一でも異なっていてもよく、
Ｒ２が複数存在する場合には、複数のＲ２は同一でも異なっていてもよく、
ｎ＝２の場合、２個のＲ１Ｏ（Ｒ２Ｏ）ｍ基は同一でも異なっていてもよい。） The surface of particles selected from aluminum nitride particles, boron nitride particles, and magnesium oxide particles is coated with an acidic phosphate ester represented by the following general formula (1) of 0.5 to 5 mg / m 2 with respect to the particles. Surface modified particles.
(In the formula (1),
R 1 : Saturated or unsaturated hydrocarbyl group having 8 to 20 carbon atoms R 2 : Saturated hydrocarbylene group having 2 or 3 carbon atoms m: Integer of 0 to 6 n: 1 or 2
Because
When a plurality of R 1 are present, the plurality of R 1 may be the same or different,
When a plurality of R 2 are present, the plurality of R 2 may be the same or different,
When n = 2, the two R 1 O (R 2 O) m groups may be the same or different. )
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|---|---|---|---|---|
| WO2019124147A1 (en) | 2017-12-21 | 2019-06-27 | 昭和電工株式会社 | Glass-coated aluminum nitride particles, method for producing same, and heat dissipating resin composition containing same |
| JP2019206459A (en) * | 2018-05-30 | 2019-12-05 | 大日精化工業株式会社 | Thermally conductive oxide and method for producing the same |
| WO2019235234A1 (en) | 2018-06-06 | 2019-12-12 | 昭和電工株式会社 | Method for producing glass-coated aluminum nitride particles, and method for producing heat-dissipating resin composition containing said glass-coated aluminum nitride particles |
| WO2020040309A1 (en) | 2018-08-24 | 2020-02-27 | 昭和電工株式会社 | Method for producing silicon-containing oxide-coated aluminum nitride particles, and silicon-containing oxide-coated aluminum nitride particles |
| WO2021006310A1 (en) | 2019-07-11 | 2021-01-14 | 昭和電工株式会社 | Method for producing silica-coated boron nitride particles and silica-coated boron nitride particles |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881640A (en) * | 1993-10-21 | 1996-03-26 | Ajinomoto Co Inc | Filler surface modifier |
| JP2001115057A (en) * | 1999-08-06 | 2001-04-24 | Kyowa Chem Ind Co Ltd | Magnesium oxide particle having high acid resistance and high hydration resistance and resin composition |
| JP2007070608A (en) * | 2005-08-11 | 2007-03-22 | Techno Polymer Co Ltd | Magnesium oxide filler for compounding in resin and heat-conductive resin composition containing the same |
| JP2008074683A (en) * | 2006-09-25 | 2008-04-03 | Tateho Chem Ind Co Ltd | Coated magnesium oxide powder, its production method, and resin composition comprising the same |
| JP2009173726A (en) * | 2008-01-23 | 2009-08-06 | Panasonic Corp | Prepreg, method for producing it, and printed wiring board using the same |
| WO2013147086A1 (en) * | 2012-03-30 | 2013-10-03 | 株式会社トクヤマ | Curable resin composition, method for producing same, highly thermally conductive resin composition, and highly thermally conductive multilayer substrate |
-
2013
- 2013-10-04 JP JP2013209185A patent/JP6169466B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881640A (en) * | 1993-10-21 | 1996-03-26 | Ajinomoto Co Inc | Filler surface modifier |
| JP2001115057A (en) * | 1999-08-06 | 2001-04-24 | Kyowa Chem Ind Co Ltd | Magnesium oxide particle having high acid resistance and high hydration resistance and resin composition |
| JP2007070608A (en) * | 2005-08-11 | 2007-03-22 | Techno Polymer Co Ltd | Magnesium oxide filler for compounding in resin and heat-conductive resin composition containing the same |
| JP2008074683A (en) * | 2006-09-25 | 2008-04-03 | Tateho Chem Ind Co Ltd | Coated magnesium oxide powder, its production method, and resin composition comprising the same |
| JP2009173726A (en) * | 2008-01-23 | 2009-08-06 | Panasonic Corp | Prepreg, method for producing it, and printed wiring board using the same |
| WO2013147086A1 (en) * | 2012-03-30 | 2013-10-03 | 株式会社トクヤマ | Curable resin composition, method for producing same, highly thermally conductive resin composition, and highly thermally conductive multilayer substrate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019124147A1 (en) | 2017-12-21 | 2019-06-27 | 昭和電工株式会社 | Glass-coated aluminum nitride particles, method for producing same, and heat dissipating resin composition containing same |
| US11254572B2 (en) | 2017-12-21 | 2022-02-22 | Showa Denko K.K. | Glass-coated aluminum nitride particles, method for producing same, and heat dissipating resin composition containing same |
| JP2019206459A (en) * | 2018-05-30 | 2019-12-05 | 大日精化工業株式会社 | Thermally conductive oxide and method for producing the same |
| WO2019235234A1 (en) | 2018-06-06 | 2019-12-12 | 昭和電工株式会社 | Method for producing glass-coated aluminum nitride particles, and method for producing heat-dissipating resin composition containing said glass-coated aluminum nitride particles |
| WO2020040309A1 (en) | 2018-08-24 | 2020-02-27 | 昭和電工株式会社 | Method for producing silicon-containing oxide-coated aluminum nitride particles, and silicon-containing oxide-coated aluminum nitride particles |
| US11396602B2 (en) | 2018-08-24 | 2022-07-26 | Showa Denko K.K. | Silicon-containing oxide-coated aluminum nitride particle and method of manufacturing the same |
| EP4253483A2 (en) | 2018-08-24 | 2023-10-04 | Resonac Corporation | Silicon-containing oxide-coated aluminum nitride particles |
| WO2021006310A1 (en) | 2019-07-11 | 2021-01-14 | 昭和電工株式会社 | Method for producing silica-coated boron nitride particles and silica-coated boron nitride particles |
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| JP2021178916A (en) * | 2020-05-13 | 2021-11-18 | 三菱製紙株式会社 | Heat conductive sheet |
| JP7386755B2 (en) | 2020-05-13 | 2023-11-27 | 三菱製紙株式会社 | thermal conductive sheet |
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