JP4667882B2 - High thermal conductivity compound - Google Patents
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- JP4667882B2 JP4667882B2 JP2005017455A JP2005017455A JP4667882B2 JP 4667882 B2 JP4667882 B2 JP 4667882B2 JP 2005017455 A JP2005017455 A JP 2005017455A JP 2005017455 A JP2005017455 A JP 2005017455A JP 4667882 B2 JP4667882 B2 JP 4667882B2
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- 150000001875 compounds Chemical class 0.000 title claims description 72
- 239000011256 inorganic filler Substances 0.000 claims description 47
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 28
- -1 alkenyl succinimide Chemical compound 0.000 claims description 27
- 239000002199 base oil Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000003607 modifier Substances 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000005690 diesters Chemical class 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001638 boron Chemical class 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
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- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229960002317 succinimide Drugs 0.000 claims description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
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- 238000004898 kneading Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 239000002923 metal particle Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- RGAHHPQKNPTZEY-UHFFFAOYSA-N 2-ethyl-4-methylhexane-1,1-diol Chemical compound CCC(C)CC(CC)C(O)O RGAHHPQKNPTZEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Description
本発明は、極めて高い熱伝導率を有する高熱伝導性コンパウンドに関する。 The present invention relates to a high thermal conductivity compound having an extremely high thermal conductivity.
電子機器に使用されている半導体部品の中には、コンピュータのＣＰＵや電源制御用のパワー半導体のように使用中に発熱をともなう部品がある。これらの半導体部品を熱から保護し、正常に機能させるためには、発生した熱をヒートシンク等の放熱部品へ伝導させ放熱する方法がある。熱伝導性コンパウンドは、これら半導体部品と放熱部品を密着させるように両者の間に塗布され、熱の伝導を高めるために用いられる。これら接合部の熱伝導は、熱伝導性コンパウンドの熱伝導率が高いほど優れ、また、塗布性が良いほど（塗膜が薄いほど、密着性が高いほど）高くなる。近年、特にコンピュータの性能向上はめざましく、ＣＰＵの放熱対策には熱伝導率の高い熱伝導性コンパウンドが求められている。 Among semiconductor components used in electronic devices, there are components that generate heat during use, such as a CPU for a computer and a power semiconductor for power control. In order to protect these semiconductor components from heat and to function normally, there is a method of conducting the generated heat to a heat radiating component such as a heat sink to dissipate heat. The thermally conductive compound is applied between the semiconductor component and the heat radiating component so that the semiconductor component and the heat radiating component are in close contact with each other, and is used to increase heat conduction. The thermal conductivity of these joints is better as the thermal conductivity of the thermal conductive compound is higher, and is higher as the coating property is better (the thinner the coating film, the higher the adhesion). In recent years, the performance of computers has been particularly improved, and a thermal conductive compound having a high thermal conductivity has been demanded as a heat dissipation measure for CPUs.
熱伝導性コンパウンドは、基油に熱伝導率の高い充填剤を多量に分散することで熱伝導率を高めたグリース状組成物である。充填剤としては酸化亜鉛、酸化アルミニウムなどの金属酸化物や、窒化珪素、窒化アルミ、窒化ホウ素などの窒化物、アルミニウムや銅、銀などの金属粉末が使用されている。この内、アルミニウムや銅、銀などの金属粉末は非常に熱伝導性が高く、より高い熱伝導性のコンパウンドの充填剤として用いられる場合がある（特許文献１参照）。
しかし、アルミニウムや銅、銀などの金属粉末は高熱伝導性ではあるものの、比較的柔らかい材質であるために、製造時のロールミル処理工程において金属粒子が潰れる場合がある。粒子が潰れた場合にはコンパウンドのちょう度が低くなり、コンパウンドを調製できなくなる場合があり、この潰れを改善する技術が望まれている。 However, although metal powders such as aluminum, copper, and silver are highly heat-conductive, they are relatively soft materials, and therefore, metal particles may be crushed in a roll mill treatment process during manufacturing. When the particles are crushed, the consistency of the compound is lowered, and the compound may not be prepared. A technique for improving the crushed is desired.
また、熱伝導性コンパウンドの熱伝導率は充填剤の量が多いほど高くなるが、充填剤の量が多すぎるとちょう度が低くなり十分な塗布性が得られなくなる場合がある。この場合、塗膜の膜厚が増えたり気泡が混入したりすることで、熱伝導性が低下するおそれがある。そのため、ちょう度が高く、塗布性を良好に保ちつつ、充填剤の量を多くできる技術が求められている。
本発明の目的は、高熱伝導性でありながら、ちょう度が高く、塗布性が良好な熱伝導性コンパウンドを提供することである。
Further, the thermal conductivity of the thermally conductive compound increases as the amount of the filler increases. However, if the amount of the filler is too large, the consistency decreases and sufficient coatability may not be obtained. In this case, there is a possibility that the thermal conductivity is lowered by increasing the film thickness of the coating film or mixing bubbles. Therefore, there is a demand for a technique that can increase the amount of filler while maintaining a high consistency and good coatability.
An object of the present invention is to provide a heat conductive compound having a high consistency and a good coating property while having a high heat conductivity.
そこで、本発明者らは、２００Ｗ／ｍ・Ｋ以上の熱伝導率を有する特定粒径の粗粒金属粉末と新モース硬度が６以上である硬度の高い特定粒径の粗粒無機充填剤とを併用し、さらに特定粒径の細粒無機充填剤及び特定の表面改質剤を組み合わせ、それぞれ特定量含有させた熱伝導性コンパウンドにすることで、粗粒金属粉末を潰れにくくし、ちょう度が高く、かつ優れた熱伝導率を有する熱伝導性コンパウンドが得られることを見出した。 Therefore, the inventors of the present invention provide a coarse metal powder having a specific particle size having a thermal conductivity of 200 W / m · K or more, a coarse inorganic filler having a specific particle size having a high hardness with a new Mohs hardness of 6 or more, and In combination, a fine inorganic filler with a specific particle size and a specific surface modifier are combined to make a heat conductive compound containing a specific amount of each, making the coarse metal powder difficult to crush and consistency. It was found that a thermally conductive compound having a high thermal conductivity and an excellent thermal conductivity can be obtained.
すなわち、本発明は、（Ａ）熱伝導率が２００Ｗ／ｍ・Ｋ以上で平均粒径５〜５０μｍの金属粉末、（Ｂ）新モース硬度が６以上で平均粒径５〜５０μｍの粗粒無機充填剤、（Ｃ）平均粒径０．１５〜２μｍの細粒無機充填剤、（Ｄ）基油、及び（Ｅ）（ポリ）グリセリルエーテル、並びにアルケニルコハク酸イミド及びそのホウ素誘導体から選ばれる１種以上の表面改質剤を含有する高熱伝導性コンパウンドであって、（Ａ）、（Ｂ）及び（Ｃ）の合計含有量がコンパウンド全量中８８〜９７質量％の範囲であり、かつ（Ａ）と（Ｂ）の合計含有量と（Ｃ）の含有量の質量比が２０：８０〜８５：１５の範囲であり、（Ｄ）の含有量がコンパウンド全量中１２質量％未満であり、さらに（Ｅ）の含有量がコンパウンド全量中それぞれ０．０８〜４質量％である割合となるように（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、及び（Ｅ）成分が配合されたものであることを特徴とする高熱伝導性コンパウンドを提供するものである。 That is, the present invention comprises (A) a metal powder having a thermal conductivity of 200 W / m · K or more and an average particle size of 5 to 50 μm, and (B) a coarse inorganic material having a new Mohs hardness of 6 or more and an average particle size of 5 to 50 μm. 1 selected from a filler, (C) a fine inorganic filler having an average particle size of 0.15 to 2 μm, (D) a base oil, and (E) (poly) glyceryl ether, and an alkenyl succinimide and a boron derivative thereof. A high thermal conductivity compound containing at least a seed surface modifier, wherein the total content of (A), (B) and (C) is in the range of 88 to 97% by mass in the total amount of the compound, and (A ) And (B) and the mass ratio of the content of (C) is in the range of 20:80 to 85:15, the content of (D) is less than 12% by mass in the total amount of the compound, The content of (E) is 0.08 in the total amount of the compound. As the ratio is 4 wt% (A), provides a high thermal conductivity compound, wherein (B), (C), in which (D), and component (E) is blended Is.
また、本発明は、上記高熱伝導性コンパウンドにおいて、さらに、（Ｅ）（ポリ）グリセリルエーテル、並びにアルケニルコハク酸イミド及びそのホウ素誘導体から選ばれる１種以上の表面改質剤がコンパウンド全量中それぞれ０．０８〜４質量％含有する高熱伝導性コンパウンドを提供するものである。
また、本発明は、上記高熱伝導性コンパウンドにおいて、金属粉末（Ａ）がアルミニウム粉末であり、粗粒無機充填剤（Ｂ）が酸化亜鉛粉末であり、金属粉末（Ａ）と粗粒無機充填剤（Ｂ）の含有量の質量比が９５：５〜５：９５の範囲であり、細粒無機充填剤（Ｃ）が酸化亜鉛粉末である高熱伝導性コンパウンドを提供するものである。
In the high thermal conductivity compound, the present invention may further comprise (E) (poly) glyceryl ether, and one or more surface modifiers selected from alkenyl succinimide and its boron derivative in each of the total amount of the compound. The present invention provides a high thermal conductive compound containing 0.08 to 4% by mass.
Moreover, the present invention provides the high thermal conductive compound, wherein the metal powder (A) is an aluminum powder, the coarse inorganic filler (B) is a zinc oxide powder, the metal powder (A) and the coarse inorganic filler. The mass ratio of the content of (B) is in the range of 95: 5 to 5:95, and a highly thermally conductive compound in which the fine inorganic filler (C) is zinc oxide powder is provided.
また、本発明は、上記高熱伝導性コンパウンドにおいて、基油が、鉱油、合成炭化水素油、ジエステル、ポリオールエステル、及びフェニルエーテルから選ばれる少なくとも１種以上である高熱伝導性コンパウンドを提供するものである。
また、本発明は、上記高熱伝導性コンパウンドにおいて、基油がジエステル及びポリオールエステルから選ばれる１種以上を含有し、その含有量が基油中に２〜９０質量％である高熱伝導性コンパウンドを提供するものである。
また、本発明は、（Ａ）熱伝導率が２００Ｗ／ｍ・Ｋ以上で平均粒径５〜５０μｍの金属粉末、（Ｂ）新モース硬度が６以上で平均粒径５〜５０μｍの粗粒無機充填剤、（Ｃ）平均粒径０．１５〜２μｍの細粒無機充填剤、（Ｄ）基油、及び（Ｅ）（ポリ）グリセリルエーテル、並びにアルケニルコハク酸イミド及びそのホウ素誘導体から選ばれる１種以上の表面改質剤を、（Ａ）、（Ｂ）及び（Ｃ）の合計含有量がコンパウンド全量中８８〜９７質量％の範囲であり、かつ（Ａ）と（Ｂ）の合計含有量と（Ｃ）の含有量の質量比が２０：８０〜８５：１５の範囲であり、（Ｄ）の含有量がコンパウンド全量中１２質量％未満であり、さらに（Ｅ）の含有量がコンパウンド全量中それぞれ０．０８〜４質量％である割合になるように配合することを特徴とする高熱伝導性コンパウンドの製造方法を提供するものである。
The present invention also provides a high thermal conductivity compound, wherein the base oil is at least one selected from mineral oil, synthetic hydrocarbon oil, diester, polyol ester, and phenyl ether. is there.
Further, the present invention provides a high thermal conductivity compound in which the base oil contains one or more selected from diesters and polyol esters, and the content thereof is 2 to 90% by mass in the base oil. It is to provide.
The present invention also provides: (A) a metal powder having a thermal conductivity of 200 W / m · K or more and an average particle size of 5 to 50 μm; and (B) a coarse inorganic material having a new Mohs hardness of 6 or more and an average particle size of 5 to 50 μm. 1 selected from a filler, (C) a fine inorganic filler having an average particle size of 0.15 to 2 μm, (D) a base oil, and (E) (poly) glyceryl ether, and an alkenyl succinimide and a boron derivative thereof. The total content of (A), (B) and (C) is in the range of 88 to 97% by mass in the total amount of the compound, and the total content of (A) and (B). And the mass ratio of the content of (C) is in the range of 20:80 to 85:15, the content of (D) is less than 12% by mass in the total amount of the compound, and the content of (E) is the total amount of the compound It mix | blends so that it may become a ratio which is 0.08-4 mass% inside, respectively. The present invention provides a method for producing a high thermal conductivity compound.
本発明の高熱伝導性コンパウンドは、塗布性を損なうことなくより優れた熱伝導性を発揮できる。本発明の高熱伝導性コンパウンドは、熱対策の必要な電子部品の放熱性を向上でき、特にＣＰＵやパワー半導体等の放熱材料として好適である。 The high thermal conductivity compound of the present invention can exhibit better thermal conductivity without impairing the coating property. The high thermal conductivity compound of the present invention can improve the heat dissipation of electronic components that require heat countermeasures, and is particularly suitable as a heat dissipation material for CPUs and power semiconductors.
本発明に用いられる無機充填剤は、高充填させるために粗粒無機充填剤と細粒無機充填剤を組み合わせて配合する。
金属粉末（Ａ）は、熱伝導率が２００Ｗ／ｍ・Ｋ以上で、平均粒径が５〜５０μｍである。熱伝導率が２００Ｗ／ｍ・Ｋ以上の金属粉末としては、アルミニウムや銅や銀などの金属粉末が例示されるが、特にアルミニウム粉末が好ましい。金属粉末（Ａ）の平均粒径は、５〜４０μｍが好ましく、８〜３０μｍが特に好ましい。
The inorganic filler used in the present invention is blended with a combination of a coarse inorganic filler and a fine inorganic filler for high filling.
The metal powder (A) has a thermal conductivity of 200 W / m · K or more and an average particle size of 5 to 50 μm. Examples of the metal powder having a thermal conductivity of 200 W / m · K or more include metal powders such as aluminum, copper, and silver, and aluminum powder is particularly preferable. 5-40 micrometers is preferable and, as for the average particle diameter of metal powder (A), 8-30 micrometers is especially preferable.
粗粒無機充填剤（Ｂ）は、新モース硬度が６以上で平均粒径５〜５０μｍの粗粒無機充填剤である。粗粒無機充填剤（Ｂ）を含まない場合や新モース硬度が６よりも低い場合には、ロールミル処理時に金属粉末（Ａ）が潰れ、コンパウンドのちょう度が低くなったりコンパウンドを調製できなくなる場合がある。新モース硬度は、７以上が好ましく、７．５以上が特に好ましい。新モース硬度が６以上の粗粒無機充填剤としては、例えば、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化チタン、窒化アルミニウム、炭化ケイ素、シリカなどの粉末が例示される。より好ましくは酸化亜鉛粉末が挙げられる。粗粒無機充填剤（Ｂ）の平均粒径は、５〜４０μｍが好ましく、８〜３０μｍがより好ましく、８〜２５μｍが特に好ましい。粗粒無機充填剤（Ｂ）の最大粒径は、１００μｍ以下が好ましく、７５μｍ以下がより好ましく、５０μｍ以下が特に好ましい。 The coarse inorganic filler (B) is a coarse inorganic filler having a new Mohs hardness of 6 or more and an average particle diameter of 5 to 50 μm. When the coarse inorganic filler (B) is not included, or when the new Mohs hardness is lower than 6, the metal powder (A) is crushed during the roll mill treatment, and the consistency of the compound is lowered or the compound cannot be prepared. There is. The new Mohs hardness is preferably 7 or more, particularly preferably 7.5 or more. Examples of the coarse inorganic filler having a new Mohs hardness of 6 or more include powders such as zinc oxide, aluminum oxide, magnesium oxide, titanium oxide, aluminum nitride, silicon carbide, and silica. More preferably, a zinc oxide powder is mentioned. The average particle diameter of the coarse inorganic filler (B) is preferably 5 to 40 μm, more preferably 8 to 30 μm, and particularly preferably 8 to 25 μm. The maximum particle size of the coarse inorganic filler (B) is preferably 100 μm or less, more preferably 75 μm or less, and particularly preferably 50 μm or less.
また、金属粉末（Ａ）及び粗粒無機充填剤（Ｂ）、すなわち粗粒の平均粒径は、５０μｍを越えると塗膜が厚くなり熱伝導性が低下する傾向にある。一方、金属粉末（Ａ）及び粗粒無機充填剤（Ｂ）の平均粒径を５μｍ以上とすることや、細粒無機充填剤（Ｃ）の平均粒径を２μｍ以下とすることで、無機充填剤を最密充填しやすくなり、結果として十分な熱伝導率を得やすくなる。 When the average particle size of the metal powder (A) and the coarse inorganic filler (B), that is, the coarse particles exceeds 50 μm, the coating film becomes thick and the thermal conductivity tends to be lowered. On the other hand, by setting the average particle size of the metal powder (A) and the coarse inorganic filler (B) to 5 μm or more, or by setting the average particle size of the fine inorganic filler (C) to 2 μm or less, the inorganic filling It becomes easy to close-pack the agent, and as a result, sufficient thermal conductivity is easily obtained.
細粒無機充填剤（Ｃ）は、平均粒径が０．１５〜２μｍの細粒無機充填剤である。細粒無機充填剤（Ｃ）の平均粒径は、０．２〜１．８μｍが好ましく、０．３〜１．５μｍが特に好ましい。細粒無機充填剤（Ｃ）の平均粒径は、０．１５μｍ以上とすることで、無機充填剤の総表面積を適度に保つことができため、液体成分（基油と表面改質剤）を十分に保持することができたり、適度なちょう度とすることが出来るなどコンパウンドを調製しやすくなる。細粒無機充填剤（Ｃ）の平均粒径が２μｍ以下とすることで、無機充填剤を最密充填しやすくなり、結果として十分な熱伝導率を得やすくなる。細粒無機充填剤（Ｃ）としては、酸化亜鉛、酸化アルミニウム、窒化ホウ素（六方晶）などの粉末が例示される。より好ましくは酸化亜鉛粉末が挙げられる。 The fine inorganic filler (C) is a fine inorganic filler having an average particle size of 0.15 to 2 μm. The average particle size of the fine inorganic filler (C) is preferably 0.2 to 1.8 μm, particularly preferably 0.3 to 1.5 μm. By setting the average particle size of the fine inorganic filler (C) to 0.15 μm or more, the total surface area of the inorganic filler can be kept moderate, so that the liquid components (base oil and surface modifier) The compound can be easily prepared, for example, it can be held sufficiently or can have an appropriate consistency. By setting the average particle size of the fine inorganic filler (C) to 2 μm or less, it becomes easy to close-pack the inorganic filler, and as a result, sufficient thermal conductivity is easily obtained. Examples of the fine inorganic filler (C) include powders of zinc oxide, aluminum oxide, boron nitride (hexagonal crystal) and the like. More preferably, a zinc oxide powder is mentioned.
また、金属粉末（Ａ）と粗粒無機充填剤（Ｂ）の合計含有量と細粒無機充填剤（Ｃ）の含有量の質量比は、２０：８０〜８５：１５の範囲であり、好ましくは３０：７０〜８０：２０の範囲であり、特に好ましくは３５：６５〜７０：３０の範囲である。細粒無機充填剤（Ｃ）が多すぎると、無機充填剤の表面積が大きくなりすぎて液体成分（基油と表面改質剤）が不足し、ちょう度が低くなったりコンパウンドを調製できなくなる場合がある。一方、細粒無機充填剤（Ｃ）が少な過ぎると、無機充填剤を最密充填できなくなり、結果として離油が生じたり十分な熱伝導率が得られない場合がある。 Moreover, the mass ratio of the total content of the metal powder (A) and the coarse inorganic filler (B) and the fine inorganic filler (C) is in the range of 20:80 to 85:15, preferably Is in the range of 30:70 to 80:20, particularly preferably in the range of 35:65 to 70:30. When there are too many fine-grained inorganic fillers (C), the surface area of the inorganic fillers becomes too large and the liquid components (base oil and surface modifier) are insufficient, resulting in low consistency or inability to prepare compounds. There is. On the other hand, when there are too few fine inorganic fillers (C), it becomes impossible to close-pack with an inorganic filler, and as a result, oil separation may occur or sufficient thermal conductivity may not be obtained.
金属粉末（Ａ）と粗粒無機充填剤（Ｂ）の含有割合は、質量比で好ましくは９５：５〜５：９５であり、より好ましくは９０：１０〜５：９５であり、特に好ましくは８５：１５〜５：９５である。 The content ratio of the metal powder (A) and the coarse inorganic filler (B) is preferably 95: 5 to 5:95, more preferably 90:10 to 5:95, and particularly preferably, by mass ratio. 85: 15-5: 95.
無機充填剤の充填率は高いほど熱伝導性に優れており、本発明においては、（Ａ）、（Ｂ）及び（Ｃ）の合計含有量がコンパウンド全量中８８〜９７質量％であり、好ましくは９０〜９６質量％である。８８質量％以上とすることで４．５Ｗ／ｍ・Ｋ以上の高熱伝導率が得やすくなり、また離油を生じたり基油が滲み出たりすることを抑制しやすくなる。一方、９７質量％以下とすることでちょう度の低下を抑制し、コンパウンドを調製しやすくできる。 The higher the filling rate of the inorganic filler, the better the thermal conductivity. In the present invention, the total content of (A), (B) and (C) is 88 to 97% by mass in the total amount of the compound, preferably Is 90-96 mass%. By setting it as 88 mass% or more, it becomes easy to obtain high thermal conductivity of 4.5 W / m · K or more, and it becomes easy to suppress oil separation or base oil oozing out. On the other hand, by setting it as 97 mass% or less, the fall of the consistency can be suppressed and a compound can be prepared easily.
基油（Ｄ）としては、種々の基油が使用でき、例えば、鉱油、合成炭化水素油、エステル、ポリエーテル、リン酸エステル、シリコーン油及びフッ素油などが挙げられる。基油の分離を防止する点においては、表面張力の低いシリコーン油及びフッ素油は、あまり好ましくない。基油は１種単独で使用しても、２種以上を組み合わせて使用しても良い。
合成炭化水素油としては、例えば、エチレンやプロピレン、ブテン、及びこれらの誘導体などを原料として製造されたアルファオレフィンを、単独または２種以上混合して重合したものが挙げられる。具体的には、１−デセンのオリゴマーであるポリアルファオレフィン（ＰＡＯ）や、１−ブテンやイソブチレンのオリゴマーであるポリブテン、エチレンとアルファオレフィンのコオリゴマー等が挙げられる。また、アルキルベンゼンやアルキルナフタレン等を用いることもできる。
Various base oils can be used as the base oil (D), and examples thereof include mineral oil, synthetic hydrocarbon oil, ester, polyether, phosphate ester, silicone oil, and fluorine oil. In terms of preventing separation of the base oil, silicone oil and fluorine oil having a low surface tension are less preferred. A base oil may be used individually by 1 type, or may be used in combination of 2 or more type.
Examples of the synthetic hydrocarbon oil include those obtained by polymerizing alpha olefins produced using ethylene, propylene, butene, and derivatives thereof as a raw material alone or in combination of two or more. Specific examples include polyalphaolefin (PAO) which is an oligomer of 1-decene, polybutene which is an oligomer of 1-butene and isobutylene, and a co-oligomer of ethylene and alphaolefin. Moreover, alkylbenzene, alkylnaphthalene, etc. can also be used.
エステルとしては、ジエステルやポリオールエステルが挙げられる。
ジエステルとしては、アジピン酸、アゼライン酸、セバシン酸、ドデカン二酸等の二塩基酸のエステルが挙げられる。
ポリオールエステルとしては、β位の炭素上に水素原子が存在していないネオペンチルポリオールのエステルで、具体的にはネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール等のカルボン酸エステルなどが挙げられる。また、エチレングリコール、プロピレングリコール、ブチレングリコール、２−ブチル−２−エチルプロパンジオール、２，４−ジエチル−ペンタンジオールなどの脂肪族２価アルコールと、直鎖または分岐の飽和脂肪酸とのエステルも用いることができる。
Examples of esters include diesters and polyol esters.
Examples of the diester include esters of dibasic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
The polyol ester is an ester of neopentyl polyol having no hydrogen atom on the β-position carbon, and specifically includes carboxylic acid esters such as neopentyl glycol, trimethylolpropane, and pentaerythritol. Further, esters of aliphatic dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 2-butyl-2-ethylpropanediol, 2,4-diethyl-pentanediol and linear or branched saturated fatty acids are also used. be able to.
ポリエーテルとしては、ポリグリコールやフェニルエーテルなどが挙げられる。
ポリグリコールとしては、ポリエチレングリコールやポリプロピレングリコール、及びこれらの誘導体などが挙げられる。
フェニルエーテルとしては、下記一般式（１）のアルキル化ジフェニルエーテル等が挙げられる。
Examples of the polyether include polyglycol and phenyl ether.
Examples of the polyglycol include polyethylene glycol, polypropylene glycol, and derivatives thereof.
Examples of the phenyl ether include alkylated diphenyl ether represented by the following general formula (1).
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９及びＲ１０は、水素原子又は炭素数１〜２２の炭化水素基であり、Ｒ１〜Ｒ１０のうち、少なくとも１つは炭素数８〜２２の炭化水素基である。）
リン酸エステルとしては、トリエチルホスフェート、トリブチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート等が挙げられる。
高熱伝導性コンパウンドは発熱部に塗布されるため、長時間高温にさらされる。このため、基油としては熱酸化安定性に優れることが望ましい。
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, (At least one of R 1 to R 10 is a hydrocarbon group having 8 to 22 carbon atoms.)
Examples of phosphate esters include triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate.
Since the high thermal conductivity compound is applied to the heat generating portion, it is exposed to a high temperature for a long time. For this reason, it is desirable that the base oil has excellent thermal oxidation stability.
基油の動粘度は、４０℃で１０ｍｍ２／ｓ〜５００ｍｍ２／ｓであることが好ましく、２０ｍｍ２／ｓ〜４５０ｍｍ２／ｓであることが特に好ましい。粘度が低すぎると、高温になった時に、蒸発、離油などが生じる恐れがある。また、粘度が高すぎるとちょう度が低くなりコンパウンドが硬くなる恐れがある。
ジエステルやポリオールエステルは、他の基油成分と組み合わせて用いることでちょう度を高くすることができる。その際、組み合わせるジエステルやポリオールエステルは、１種であってもよいし、２種以上組み合わせてもよい。また、ジエステルやポリオールエステルの割合は、ジエステルやポリオールエステルを含む全ての基油成分１００質量％に対して２〜９０質量％が好ましく、より好ましくは２〜５０質量％であり、さらに好ましくは４〜３０質量％である。上記範囲でジエステルやポリオールエステルを配合することで、より高いちょう度とすることができる。
The kinematic viscosity of the base oil is preferably 10mm 2 / s~500mm 2 / s at 40 ° C., particularly preferably 20mm 2 / s~450mm 2 / s. If the viscosity is too low, evaporation or oil separation may occur at high temperatures. On the other hand, if the viscosity is too high, the consistency is lowered and the compound may be hardened.
Diesters and polyol esters can increase the consistency when used in combination with other base oil components. In that case, 1 type may be sufficient as the diester and polyol ester to combine, and 2 or more types may be combined. Further, the ratio of the diester or polyol ester is preferably 2 to 90% by mass, more preferably 2 to 50% by mass, and still more preferably 4 to 100% by mass of all base oil components including the diester or polyol ester. -30 mass%. By blending a diester or a polyol ester within the above range, a higher consistency can be achieved.
基油の含有量としては１２質量％未満、好ましくは２〜１２質量％であり、含有量がこれ以上の場合は、ちょう度が高くなりすぎ、コンパウンドが流れ出てしまう場合がある。さらに離油を生じたり、熱伝導性が低下する場合がある。
本発明に用いられる表面改質剤（Ｅ）は、無機充填剤粉末の表面に吸着して基油との親和性を向上させることにより、無機充填剤の充填量を増加させ熱伝導性を向上させたり、ちょう度を高めて塗布性を向上させる働きがある。なお、表面改質剤（Ｅ）を用いることで、塗膜をより一層薄くすることができ、発熱部品から放熱部品への熱伝導を効率よく行うことができる。
The content of the base oil is less than 12% by mass, preferably 2 to 12% by mass. When the content is more than this, the consistency becomes too high and the compound may flow out. In addition, oil separation may occur and thermal conductivity may decrease.
The surface modifier (E) used in the present invention improves the thermal conductivity by increasing the filling amount of the inorganic filler by adsorbing to the surface of the inorganic filler powder and improving the affinity with the base oil. It has the function of improving the coating properties by increasing the consistency. In addition, by using surface modifier (E), a coating film can be made still thinner and the heat conduction from a heat-emitting component to a heat radiating component can be performed efficiently.
さらに、本発明に用いられる表面改質剤（Ｅ）は、従来表面改質剤として用いられている物質と比較すると耐熱性が高い。そのため、油分の熱・酸化安定性が良好で、耐熱性の高いコンパウンドを得ることができる。 Furthermore, the surface modifier (E) used in the present invention has high heat resistance as compared with substances conventionally used as surface modifiers. Therefore, it is possible to obtain a compound having good heat and oxidation stability of oil and high heat resistance.
表面改質剤の種類としては、（ポリ）グリセリルエーテル、およびアルケニルコハク酸イミドやそのホウ素誘導体が好ましく使用できる。
（ポリ）グリセリルエーテルは、一般式（２）で表わされる化合物である。
As the type of the surface modifier, (poly) glyceryl ether, alkenyl succinimide and its boron derivative can be preferably used.
(Poly) glyceryl ether is a compound represented by the general formula (2).
一般式（２）において、Ｒ１１は炭素数８以上の炭化水素基を表わし、例えば、炭素数８以上のアルキル基、アルケニル基、アリール基が挙げられ、炭素数８以上のアルキル基、アルケニル基が好ましい。Ｒ１１の炭素数は、８〜３０が好ましく、１０〜２６がより好ましく、１２〜２２が特に好ましい。また、一般式（２）において、ｐはグリセリンの重合度を表わす係数であって、１以上の数であり、好ましくは１〜５の数である。なお、ｐが１以上の場合は、ｐは平均値である。ｐが５を越えると基油への溶解性が悪くなる。
In the general formula (2), R 11 represents a hydrocarbon group having 8 or more carbon atoms, and examples thereof include an alkyl group, alkenyl group, and aryl group having 8 or more carbon atoms, and an alkyl group and alkenyl group having 8 or more carbon atoms. Is preferred. The number of carbon atoms in R 11 is preferably 8 to 30, more preferably from 10 to 26, particularly preferably 12 to 22. Moreover, in General formula (2), p is a coefficient showing the polymerization degree of glycerol, is a number of 1 or more, preferably a number of 1-5. In addition, when p is 1 or more, p is an average value. If p exceeds 5, the solubility in the base oil will deteriorate.
アルケニルコハク酸イミドおよびそのホウ素誘導体は、一般式（３）で表わされる化合物である。
（式中、Ｒ１２は炭素数１〜５０のアルケニル基又はポリアルケニル基であり、２個のＲ１２は同一でも異なっていてもよく、Ｒ１３は炭素数２〜５のアルキレン基であり、ｑは１〜１０であり、ｑ＋１個のＲ１３は同一でも異なっていてもよい。Ｘはホウ素含有置換基である。）
一般式（３）においてＲ１２は炭素数１〜５０のアルケニル基又はポリアルケニル基であり、２個のＲ１２は同一でも異なっていてもよい。アルケニル基としては、プロペニル基、ブテニル基、ペンテニル基などが挙げられ、ポリアルケニル基としては、ポリプロペニル基、ポリブテニル基、ポリペンテニル基などが挙げられる。Ｒ１３は炭素数２〜５のアルキレン基である。ｑは１〜１０であり、ｑ＋１個のＲ１３は同一でも異なっていてもよい。Ｘはホウ素含有置換基であり、Ｘとしては、例えば化学式（４）の基が例示できる。
(In the formula, R 12 is an alkenyl group or polyalkenyl group having 1 to 50 carbon atoms, two R 12 groups may be the same or different, and R 13 is an alkylene group having 2 to 5 carbon atoms, q is 1 to 10, and q + 1 R 13 may be the same or different.X is a boron-containing substituent.)
In the general formula (3), R 12 is an alkenyl group or polyalkenyl group having 1 to 50 carbon atoms, and two R 12 may be the same or different. Examples of the alkenyl group include a propenyl group, a butenyl group, and a pentenyl group. Examples of the polyalkenyl group include a polypropenyl group, a polybutenyl group, and a polypentenyl group. R 13 is an alkylene group having 2 to 5 carbon atoms. q is 1 to 10, and q + 1 R 13 may be the same or different. X is a boron-containing substituent, and examples of X include a group of the chemical formula (4).
このとき、ポリアルケニル基の分子量は７０〜５００００程度のものが好ましく、２００〜５０００がより好ましく、５００〜３０００が特に好ましい。
表面改質剤（Ｅ）は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
また、ポリグリセリルエーテルと、アルケニルコハク酸イミドやそのホウ素誘導体は、組み合わせて使用することで、さらにちょう度を高めることができる。この組み合わせは、９５：５〜２０：８０、好ましくは９０：１０〜４０：６０、さらに好ましくは８０：２０〜６０：４０とすることで、ちょう度をより一層高くすることができる。
本発明に用いる表面改質剤（Ｅ）は、高熱伝導性コンパウンド全量中０．０８〜４．０質量％含有することが好ましい。さらに好ましくは０．１〜２．０質量％であり、特に好ましくは０．１〜１．０質量％であり、最も好ましくは０．１〜０．５質量％である。表面改質剤（Ｅ）は、含有量が０．０８質量％以上とすることで、効果を得ることができる。一方、含有量は４．０質量％より多くしても、添加量に見合うだけの効果の向上は得られず経済的でない。
At this time, the molecular weight of the polyalkenyl group is preferably about 70 to 50000, more preferably 200 to 5000, and particularly preferably 500 to 3000.
A surface modifier (E) may be used individually by 1 type, and may be used in combination of 2 or more type.
Further, the use of polyglyceryl ether, alkenyl succinimide and its boron derivative in combination can further increase the consistency. This combination can further increase the consistency by setting 95: 5 to 20:80, preferably 90:10 to 40:60, and more preferably 80:20 to 60:40.
The surface modifier (E) used in the present invention is preferably contained in an amount of 0.08 to 4.0% by mass in the total amount of the high thermal conductivity compound. More preferably, it is 0.1-2.0 mass%, Most preferably, it is 0.1-1.0 mass%, Most preferably, it is 0.1-0.5 mass%. An effect can be acquired because content of a surface modifier (E) shall be 0.08 mass% or more. On the other hand, even if the content is more than 4.0% by mass, the improvement of the effect corresponding to the addition amount cannot be obtained and it is not economical.
また、本発明の高熱伝導性コンパウンドには必要に応じて、公知の添加剤を適宜配合することができる。これらとしては、例えば、酸化防止剤としてはフェノール系、アミン系、イオウ・リン系等の化合物が、さび止め剤としてはスルホン酸塩、カルボン酸、カルボン酸塩等の化合物が、腐食防止剤としてはベンゾトリアゾールおよびその誘導体等の化合物、チアジアゾール系化合物が、増粘剤・増ちょう剤としてはポリブテン、ポリメタクリレート、脂肪酸塩、ウレア化合物、石油ワックス、ポリエチレンワックス等が挙げられる。これらの添加剤の配合量は、通常の配合量であればよい。 Moreover, a well-known additive can be suitably mix | blended with the high heat conductive compound of this invention as needed. These include, for example, compounds such as phenols, amines and sulfur / phosphorus as antioxidants, and compounds such as sulfonates, carboxylic acids and carboxylates as corrosion inhibitors as rust inhibitors. Are compounds such as benzotriazole and derivatives thereof, and thiadiazole compounds, and examples of the thickener and thickener include polybutene, polymethacrylate, fatty acid salt, urea compound, petroleum wax, polyethylene wax and the like. The amount of these additives may be a normal amount.
本発明の高熱伝導性コンパウンドの製造に関しては、均一に成分を混合できればその方法にはよらない。一般的な製造方法としては、乳鉢、プラネタリーミキサー、２軸式押出機などにより混練りを行い、グリース状にした後、さらに三本ロールにて均一に混練りする方法がある。
本発明の高熱伝導性コンパウンドの不混和ちょう度は概ね２００以上であれば使用可能である。本発明の高熱伝導性コンパウンドの不混和ちょう度は、好ましくは２３０以上であり、より好ましくは２５０以上であり、特に好ましくは２８０以上である。
本発明の高熱伝導性コンパウンドは、極めて優れた熱伝導性を発揮することができ、具体的には、好ましくは４．５Ｗ／ｍ・Ｋ以上の熱伝導性を発揮することができ、より好ましくは４．７Ｗ／ｍ・Ｋ以上の熱伝導性を発揮することができ、さらに好ましくは５．０Ｗ／ｍ・Ｋ以上の熱伝導性を発揮することができ、特に好ましくは５．３Ｗ／ｍ・Ｋ以上の熱伝導性を発揮することができる。
Regarding the production of the high thermal conductivity compound of the present invention, the method is not limited as long as the components can be mixed uniformly. As a general production method, there is a method of kneading with a mortar, a planetary mixer, a twin-screw extruder, or the like to form a grease and then uniformly kneading with three rolls.
The immiscible penetration of the high thermal conductivity compound of the present invention can be used if it is approximately 200 or more. The immiscibility of the high thermal conductivity compound of the present invention is preferably 230 or more, more preferably 250 or more, and particularly preferably 280 or more.
The high thermal conductivity compound of the present invention can exhibit extremely excellent thermal conductivity, specifically, preferably can exhibit thermal conductivity of 4.5 W / m · K or more, and more preferably Can exhibit a thermal conductivity of 4.7 W / m · K or more, more preferably 5.0 W / m · K or more, and particularly preferably 5.3 W / m. -It can exhibit thermal conductivity of K or higher.
以下、実施例により本発明を詳述するが、本発明はこれによって何等限定されるものではない。
実施例及び比較例に用いた充填剤と基油および表面改質剤を表１〜３に示す。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by this.
Tables 1 to 3 show fillers, base oils and surface modifiers used in Examples and Comparative Examples.
（実施例１〜８）
下記表４に実施例１〜８の組成を示す。なお、表中のその他※は、アミン系酸化防止剤を示す。
表４の組成になるように各成分を配合して、熱伝導性コンパウンドを以下の方法で調製した。
製造方法：基油に表面改質剤、酸化防止剤等の各種添加剤を溶解し、無機充填剤とともにプラネタリーミキサーまたは自動乳鉢に入れた。室温〜６０℃で６０分混練りを行いよく混合し、グリース状とした。その後、三本ロールによる混練りを２回実施して熱伝導性コンパウンドを調製した。
(Examples 1-8)
Table 4 below shows the compositions of Examples 1 to 8. In addition, other * in the table indicates an amine-based antioxidant.
Each component was mix | blended so that it might become a composition of Table 4, and the heat conductive compound was prepared with the following method.
Production method: Various additives such as surface modifiers and antioxidants were dissolved in the base oil, and placed in a planetary mixer or automatic mortar together with an inorganic filler. The mixture was kneaded at room temperature to 60 ° C. for 60 minutes and mixed well to obtain a grease. Thereafter, kneading with a three roll was carried out twice to prepare a heat conductive compound.
得られた熱伝導性コンパウンドを用いて、以下に示す性能を評価した。
ちょう度：ＪＩＳ−Ｋ２２２０に準拠して不混和ちょう度を測定した。ちょう度の値が大きいほどコンパウンドが軟らかくなり、逆に小さいほど硬くなる。
離油度：ＪＩＳ−Ｋ２２２０に準拠して測定した。
熱伝導率：熱線法により０℃で測定した。
The performance shown below was evaluated using the obtained heat conductive compound.
Consistency: An immiscible consistency was measured in accordance with JIS-K2220. The greater the consistency value, the softer the compound, and vice versa.
Oil separation: measured in accordance with JIS-K2220.
Thermal conductivity: measured at 0 ° C. by a hot wire method.
（比較例１〜８）
下記表５の組成になるように各成分を配合して、熱伝導性コンパウンドを実施例と同様の方法で調製した。
Each component was mix | blended so that it might become a composition of following Table 5, and the heat conductive compound was prepared by the method similar to an Example.
表６に実施例１〜８と比較例１〜８の不混和ちょう度、熱伝導率、離油度を示す。
表６からわかるように実施例１〜８は、充填剤を高充填させて熱伝導性を高めても、ちょう度が高く塗布性に優れるとともに、離油の発生もみられない。
一方、金属粉末（Ａ）を用いない比較例１、２では、熱伝導率が本願実施例に比べ低くなってしまう。粗粒無機充填剤（Ｂ）を除いた比較例３は、製造過程で金属粉末（Ａ）の粒子が潰れてしまいグリース状にならない。表面改質剤が少なすぎるとコンパウンドが硬くなるかグリース状にならない（比較例４）。無機充填剤の量が少ない比較例５では、高いちょう度が得られるが、熱伝導率は低下してしまう。シラン系の表面改質剤やノニオン系の界面活性剤を用いた比較例６〜８では、ちょう度が低いか充填率を上げるとグリース状にならない。
As can be seen from Table 6, in Examples 1 to 8, even if the filler is highly filled to increase the thermal conductivity, the consistency is high and the coating property is excellent, and the occurrence of oil separation is not observed.
On the other hand, in Comparative Examples 1 and 2 in which the metal powder (A) is not used, the thermal conductivity is lower than that in the present example. In Comparative Example 3 excluding the coarse inorganic filler (B), the particles of the metal powder (A) are crushed during the production process and do not become grease. If the surface modifier is too little, the compound will be hard or not greased (Comparative Example 4). In Comparative Example 5 where the amount of the inorganic filler is small, a high consistency is obtained, but the thermal conductivity is lowered. In Comparative Examples 6 to 8 using a silane-based surface modifier or a nonionic surfactant, the grease does not become a grease when the consistency is low or the filling rate is increased.
また、実施例６の熱伝導性コンパウンドについては、下記の薄膜化測定方法により、薄膜の膜厚を測定した。膜厚は７４μｍであった。
<薄膜化測定方法>
熱伝導性コンパウンド０．０５ｍｌを表面粗さがＲａ＝０．５μｍの２枚のアルミニウム板に挟み、３ｋｇの荷重をかけて押し潰し、３００秒後の拡がり面積を測定し、膜厚を算出した。
Moreover, about the heat conductive compound of Example 6, the film thickness of the thin film was measured with the following thin film measurement method. The film thickness was 74 μm.
<Thin film measurement method>
A heat conductive compound of 0.05 ml was sandwiched between two aluminum plates with a surface roughness Ra = 0.5 μm and crushed by applying a load of 3 kg, and the spreading area after 300 seconds was measured to calculate the film thickness. .
Claims (5)
（Ｂ）新モース硬度が６以上で平均粒径５〜５０μｍの粗粒無機充填剤、
（Ｃ）平均粒径０．１５〜２μｍの細粒無機充填剤、
（Ｄ）基油、及び
（Ｅ）（ポリ）グリセリルエーテル、並びにアルケニルコハク酸イミド及びそのホウ素誘導体から選ばれる１種以上の表面改質剤を含有する高熱伝導性コンパウンドであって、
（Ａ）、（Ｂ）及び（Ｃ）の合計含有量がコンパウンド全量中８８〜９７質量％の範囲であり、かつ（Ａ）と（Ｂ）の合計含有量と（Ｃ）の含有量の質量比が２０：８０〜８５：１５の範囲であり、（Ｄ）の含有量がコンパウンド全量中１２質量％未満であり、さらに（Ｅ）の含有量がコンパウンド全量中それぞれ０．０８〜４質量％である割合となるように（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、及び（Ｅ）成分が配合されたものであることを特徴とする高熱伝導性コンパウンド。 (A) a metal powder having a thermal conductivity of 200 W / m · K or more and an average particle size of 5 to 50 μm,
(B) a coarse inorganic filler having a new Mohs hardness of 6 or more and an average particle size of 5 to 50 μm,
(C) a fine inorganic filler having an average particle size of 0.15 to 2 μm,
(D) a base oil, and (E) (poly) glyceryl ether, and a high thermal conductivity compound containing one or more surface modifiers selected from alkenyl succinimide and boron derivatives thereof,
The total content of (A), (B) and (C) is in the range of 88 to 97% by mass in the total amount of the compound, and the total content of (A) and (B) and the mass of the content of (C) The ratio is in the range of 20:80 to 85:15, the content of (D) is less than 12% by mass in the total amount of the compound, and the content of (E) is 0.08 to 4% by mass in the total amount of the compound, respectively. (A), (B), (C), (D), and (E) component are mix | blended so that it may become a ratio which is these, The high heat conductive compound characterized by the above-mentioned.
（Ｂ）新モース硬度が６以上で平均粒径５〜５０μｍの粗粒無機充填剤、(B) a coarse inorganic filler having a new Mohs hardness of 6 or more and an average particle size of 5 to 50 μm,
（Ｃ）平均粒径０．１５〜２μｍの細粒無機充填剤、(C) a fine inorganic filler having an average particle size of 0.15 to 2 μm,
（Ｄ）基油、及び(D) base oil, and
（Ｅ）（ポリ）グリセリルエーテル、並びにアルケニルコハク酸イミド及びそのホウ素誘導体から選ばれる１種以上の表面改質剤を、(E) (poly) glyceryl ether, and one or more surface modifiers selected from alkenyl succinimides and boron derivatives thereof,
（Ａ）、（Ｂ）及び（Ｃ）の合計含有量がコンパウンド全量中８８〜９７質量％の範囲であり、かつ（Ａ）と（Ｂ）の合計含有量と（Ｃ）の含有量の質量比が２０：８０〜８５：１５の範囲であり、（Ｄ）の含有量がコンパウンド全量中１２質量％未満であり、さらに（Ｅ）の含有量がコンパウンド全量中それぞれ０．０８〜４質量％である割合になるように配合することを特徴とする高熱伝導性コンパウンドの製造方法。The total content of (A), (B) and (C) is in the range of 88 to 97% by mass in the total amount of the compound, and the total content of (A) and (B) and the mass of the content of (C) The ratio is in the range of 20:80 to 85:15, the content of (D) is less than 12% by mass in the total amount of the compound, and the content of (E) is 0.08 to 4% by mass in the total amount of the compound, respectively. The manufacturing method of the high heat conductive compound characterized by mix | blending so that it may become a ratio.
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| JP5489409B2 (en) | 2007-04-10 | 2014-05-14 | コスモ石油ルブリカンツ株式会社 | High thermal conductivity compound |
| JP5269366B2 (en) * | 2007-08-22 | 2013-08-21 | コスモ石油ルブリカンツ株式会社 | Heat-resistant thermal grease |
| JP5378861B2 (en) * | 2009-03-31 | 2013-12-25 | 古河電気工業株式会社 | Optical fiber laser |
| JP5318733B2 (en) * | 2009-11-26 | 2013-10-16 | コスモ石油ルブリカンツ株式会社 | Thermally conductive grease |
| JP5781407B2 (en) * | 2011-09-05 | 2015-09-24 | コスモ石油ルブリカンツ株式会社 | Thermally conductive compound |
| JP5944306B2 (en) * | 2012-12-21 | 2016-07-05 | コスモ石油ルブリカンツ株式会社 | High thermal conductive grease |
| CN115244138A (en) * | 2020-03-11 | 2022-10-25 | 住友金属矿山株式会社 | Thermally conductive composition |
| JP2023151485A (en) * | 2022-03-31 | 2023-10-16 | コスモ石油ルブリカンツ株式会社 | Thermally conductive grease composition |
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| US5098609A (en) * | 1989-11-03 | 1992-03-24 | The Research Foundation Of State Univ. Of N.Y. | Stable high solids, high thermal conductivity pastes |
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