JP2013155366A - Heat-dissipating resin composition and varnish containing the same - Google Patents
Heat-dissipating resin composition and varnish containing the same Download PDFInfo
- Publication number
- JP2013155366A JP2013155366A JP2012114814A JP2012114814A JP2013155366A JP 2013155366 A JP2013155366 A JP 2013155366A JP 2012114814 A JP2012114814 A JP 2012114814A JP 2012114814 A JP2012114814 A JP 2012114814A JP 2013155366 A JP2013155366 A JP 2013155366A
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- Prior art keywords
- powder
- resin
- heat
- resin composition
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 239000002966 varnish Substances 0.000 title claims description 47
- 239000011256 inorganic filler Substances 0.000 claims abstract description 129
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 35
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011354 acetal resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims description 138
- 239000011347 resin Substances 0.000 claims description 138
- 239000000843 powder Substances 0.000 claims description 107
- 239000003822 epoxy resin Substances 0.000 claims description 39
- 229920000647 polyepoxide Polymers 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 15
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 15
- 229920003986 novolac Polymers 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 229910052878 cordierite Inorganic materials 0.000 claims description 6
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052863 mullite Inorganic materials 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920003987 resole Polymers 0.000 claims description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 abstract description 19
- 239000010439 graphite Substances 0.000 abstract description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 27
- 230000017525 heat dissipation Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000000945 filler Substances 0.000 description 18
- 239000004065 semiconductor Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000011888 foil Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- -1 polyethylene Polymers 0.000 description 13
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920001955 polyphenylene ether Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 239000004697 Polyetherimide Substances 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
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- 229920002943 EPDM rubber Polymers 0.000 description 4
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
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- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Laminated Bodies (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Cooling Or The Like Of Electrical Apparatus (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Battery Mounting, Suspending (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、熱拡散性樹脂組成物および該組成物を含むワニスに関する。 The present invention relates to a heat-diffusing resin composition and a varnish containing the composition.
近年、高性能化、高機能化が進む電子機器に使用されるマイクロプロセッサー、画像処理チップ、メモリー等のＬＳＩ（Large Scale Integration）は高性能化が進み、それに伴い、発熱量も増加している。このためＬＳＩ等の電子部品を含む機器では、発熱に伴う電子部品の冷却が、熱による誤作動等を防止する上で重要になっている。この問題は昨今薄型化が進行する表示装置や照明器具等の機器において深刻化している。 In recent years, LSIs (Large Scale Integration) such as microprocessors, image processing chips, and memories that are used in electronic devices with higher performance and higher functionality have been improved in performance, and the amount of heat generated has increased accordingly. . For this reason, in devices including electronic parts such as LSI, cooling of electronic parts accompanying heat generation is important for preventing malfunction due to heat. This problem has become more serious in devices such as display devices and lighting fixtures that are becoming thinner.
これらの発熱する機器の冷却法としては、該機器を構成する部品の配置の最適化、金属製のヒートシンクや小型のファンモータ等の放熱器の利用が挙げられる。
ところがノート型パソコン、携帯電話等の薄型、小型化および軽量化が求められる電子機器では該電子機器内における電子部品の実装密度が飛躍的に高くなっており、限られた空間内における占有体積の問題から前記の放熱器等の利用が困難な場合がある。このような場合には、電子部品に金属材料や樹脂材料等の材料を接触させて、発生した熱をこれらの材料へ移動させて電子部品表面から放熱する方法がしばしばとられる。
As a cooling method for these devices that generate heat, optimization of arrangement of components constituting the device, use of a heat sink such as a metal heat sink or a small fan motor can be cited.
However, in electronic devices such as notebook computers and mobile phones that are required to be thin, downsized, and light in weight, the mounting density of electronic components in the electronic devices is dramatically increased, and the occupied volume in a limited space Due to problems, it may be difficult to use the radiator. In such a case, a method is often used in which a material such as a metal material or a resin material is brought into contact with the electronic component, and the generated heat is transferred to these materials to dissipate heat from the surface of the electronic component.
前記材料としては、樹脂材料が、その加工性、生産性および形状の自由度などから、電気機器、電子機器、精密機器、自動車部品等の用途に有用であり、これらの用途に従来使用されていた金属材料に代わる材料として期待されている。 As the material, a resin material is useful in applications such as electrical equipment, electronic equipment, precision equipment, and automobile parts because of its workability, productivity, and freedom of shape, and has been conventionally used in these applications. It is expected to be an alternative to metal materials.
金属材料の代替として樹脂材料を使用するためには、樹脂材料の熱拡散性および放熱性を改良する必要がある。樹脂材料に熱拡散性および放熱性を持たせる方法としては、樹脂と無機充填材とを混合する方法が知られている。 In order to use a resin material as an alternative to a metal material, it is necessary to improve the thermal diffusibility and heat dissipation of the resin material. As a method for imparting heat diffusibility and heat dissipation to a resin material, a method of mixing a resin and an inorganic filler is known.
このような樹脂と無機充填剤とを含む樹脂材料として、特許文献１には、液晶ポリマー等の耐高熱性の熱可塑性ポリマーと、窒化アルミニウム、酸化アルミニウム等の鉱物性結晶充填剤とを含む耐高熱性複合材料が開示されている。
また、特許文献２には、イミド変性エラストマーと放熱フィラーとを含む放熱シートが、特許文献３には、ポリイミド樹脂中に熱伝導性フィラーが分散された層を有するポリイミドフィルムが、特許文献４には、ポリビニルアセタール樹脂および熱硬化性樹脂を含有し、ＢステージとＣステージにおけるフロー量の差が特定の値である接着剤組成物が、特許文献５には、ポリビニルアセタール樹脂とエポキシ樹脂とを含むエポキシ樹脂組成物が、それぞれ記載されている。
As a resin material containing such a resin and an inorganic filler, Patent Document 1 discloses a high heat resistant thermoplastic polymer such as a liquid crystal polymer and a mineral crystal filler such as aluminum nitride and aluminum oxide. A high heat composite material is disclosed.
Patent Document 2 discloses a heat dissipating sheet containing an imide-modified elastomer and a heat dissipating filler. Patent Document 3 discloses a polyimide film having a layer in which a heat conductive filler is dispersed in a polyimide resin. Is an adhesive composition containing a polyvinyl acetal resin and a thermosetting resin and having a specific flow amount difference between the B stage and the C stage. Patent Document 5 discloses a polyvinyl acetal resin and an epoxy resin. Each of the epoxy resin compositions contained is described.
しかしながら、特許文献１に記載の発明では、融点および結晶性が高くて脆い液晶ポリマーを用いているため、複合材料の加工性が悪いという点で問題があった。 However, the invention described in Patent Document 1 has a problem in that the workability of the composite material is poor because a brittle liquid crystal polymer having a high melting point and high crystallinity is used.
また、特許文献２に記載の発明で用いているイミド変性エラストマーは、製造工程が複雑で容易に入手できない、特許文献３に記載のポリイミドフィルムは、融点が高く、加工性に乏しい、などの問題があった。 In addition, the imide-modified elastomer used in the invention described in Patent Document 2 has a complicated manufacturing process and is not easily available. The polyimide film described in Patent Document 3 has a high melting point and poor workability. was there.
さらに、前記特許文献１〜３に記載の発明で用いている樹脂は、比重や表面エネルギーが無機充填材と大きく異なるため、多量の無機充填材となじみにくく、安定した分散状態を保持しにくかった。 Furthermore, since the specific gravity and surface energy of the resin used in the inventions described in Patent Documents 1 to 3 are significantly different from those of the inorganic filler, it is difficult to be compatible with a large amount of the inorganic filler, and it is difficult to maintain a stable dispersion state. .
また、これらの従来の樹脂材料は、該材料を発熱する機器等に用いた場合には、該材料の熱拡散率が悪いことに起因する蓄熱によるふくらみ、亀裂、割れ、破損、爆発などが生じることがあった。この問題は、樹脂材料として、樹脂と、樹脂と混和性の悪い無機充填剤とを混合した組成物を使用する場合に顕著であった。 In addition, when these conventional resin materials are used in devices that generate heat, bulging, cracking, cracking, breakage, explosion, etc. due to heat storage caused by the poor thermal diffusivity of the material occur. There was a thing. This problem is remarkable when using a composition in which a resin and an inorganic filler having poor miscibility with the resin are used as the resin material.
これらのことから、安全性や信頼性に優れ、無機充填材の分散安定性が良好な、熱拡散性および放熱特性に優れた樹脂材料が求められている。 For these reasons, there is a demand for a resin material that has excellent safety and reliability, good dispersion stability of the inorganic filler, and excellent thermal diffusivity and heat dissipation characteristics.
特に樹脂と無機充填剤とを含む樹脂組成物では、樹脂と無機充填剤との密着性（相溶性）が低いと、無機充填剤の周囲に樹脂で覆われない部分、即ち空隙が生じる。具体的には、充填剤の凝集物が形成し得る隙間に樹脂が入り込めず、その隙間が空隙となる。気体で構成される隙間は、熱拡散率が低く、かつ無機充填剤の充填密度を低下させるため、組成物に空隙が生じると、該組成物の熱拡散率が低下する。
以上のことなどから、一定の熱拡散性を有する組成物を得るために、大量の無機充填剤が添加されてきたが、この場合、該組成物から得られる成形体の金属板、グラファイト板、樹脂製フィルム等への接着性が損なわれやすかった。
In particular, in a resin composition containing a resin and an inorganic filler, when the adhesiveness (compatibility) between the resin and the inorganic filler is low, a portion that is not covered with the resin, that is, a void is formed around the inorganic filler. Specifically, the resin cannot enter a gap where a filler aggregate can form, and the gap becomes a void. The gap formed by the gas has a low thermal diffusivity and lowers the packing density of the inorganic filler. Therefore, when voids are generated in the composition, the thermal diffusivity of the composition decreases.
From the above, in order to obtain a composition having a certain thermal diffusibility, a large amount of an inorganic filler has been added. In this case, a metal plate, a graphite plate of a molded body obtained from the composition, Adhesiveness to a resin film or the like was easily impaired.
また、汎用の樹脂、例えばアクリル、ポリオレフィン、ポリエステル、ナイロン、ウレタン等はその耐熱温度が１５０℃以下であるものが多く、発熱するデバイスに用いるためには耐熱性能が十分でないことが問題であった。
前記のように、耐熱性の樹脂として知られているポリイミドも放熱部材の用途に用いられているが、ポリイミドは通常熱硬化性であるため用途が限定されたり、構造上経時的に樹脂から水分を放出する可能性があり、無機充填剤である金属塩、金属酸化物、金属窒化物等の変性を招く恐れがあった。
In addition, general-purpose resins such as acrylic, polyolefin, polyester, nylon, and urethane often have a heat-resistant temperature of 150 ° C. or less, and there is a problem that the heat-resistant performance is not sufficient for use in a device that generates heat. .
As described above, polyimide, which is known as a heat-resistant resin, is also used for heat dissipation members. However, since polyimide is usually thermosetting, its use is limited, or the moisture from the resin over time due to its structure. There is a possibility that metal salt, metal oxide, metal nitride, etc., which are inorganic fillers, are modified.
特許文献４に記載の組成物は熱硬化性であるため、リワーク性に劣り、また、使用できる用途が限定されていた。 Since the composition of patent document 4 is thermosetting, it is inferior to rework property, and the use which can be used was limited.
また、特許文献５には、ポリビニルアセタール樹脂とエポキシ樹脂とを含むエポキシ樹脂組成物が記載されているが、熱拡散性が付与された組成物が求められていた。 Further, Patent Document 5 describes an epoxy resin composition containing a polyvinyl acetal resin and an epoxy resin, but a composition imparted with thermal diffusivity has been desired.
本発明は、このような事情に鑑みてなされたものであり、良好な熱拡散性と良好な耐熱性を有し、さらに、金属板、グラファイト板、樹脂製フィルム等への接着性に優れる熱拡散性樹脂組成物を提供することを目的とする。 The present invention has been made in view of such circumstances, and has good heat diffusibility and good heat resistance, and further has excellent adhesion to metal plates, graphite plates, resin films, and the like. It aims at providing a diffusible resin composition.
本発明者らは、特定の構成単位を有するポリビニルアセタール樹脂と特定量の無機フィラーとを含む組成物によれば、前記課題を解決できることを見出した。本発明はこのような知見に基づきなされたものである。
本発明の構成を以下に示す。
The present inventors have found that the above problem can be solved by a composition containing a polyvinyl acetal resin having a specific structural unit and a specific amount of an inorganic filler. The present invention has been made based on such findings.
The configuration of the present invention is shown below.
［項１］
ポリビニルアセタール樹脂（Ｉ）と無機フィラー（ＩＩ）とを含む熱拡散性樹脂組成物であって、
前記ポリビニルアセタール樹脂（Ｉ）が、下記構成単位Ａ、ＢおよびＣを有し、
前記組成物１００体積％に対し、前記無機フィラー（ＩＩ）を５〜８５体積％含む、熱可塑性である熱拡散性樹脂組成物。
[Claim 1]
A heat-diffusing resin composition comprising a polyvinyl acetal resin (I) and an inorganic filler (II),
The polyvinyl acetal resin (I) has the following structural units A, B and C,
A heat-diffusing resin composition that is thermoplastic and contains 5 to 85% by volume of the inorganic filler (II) with respect to 100% by volume of the composition.
［項２］
前記ポリビニルアセタール樹脂（Ｉ）が、さらに、下記構成単位Ｄを含む、項１に記載の熱拡散性樹脂組成物。
[Section 2]
Item 2. The thermal diffusable resin composition according to Item 1, wherein the polyvinyl acetal resin (I) further comprises the following structural unit D.
［項３］
前記構成単位ＡにおけるＲが水素または炭素数１〜３のアルキルである、項１または２に記載の熱拡散性樹脂組成物。
［項４］
前記構成単位ＡにおけるＲが水素である、項１〜３のいずれか１項に記載の熱拡散性樹脂組成物。
[Section 3]
Item 3. The heat-diffusing resin composition according to Item 1 or 2, wherein R in the structural unit A is hydrogen or alkyl having 1 to 3 carbon atoms.
[Claim 4]
Item 4. The heat-diffusing resin composition according to any one of Items 1 to 3, wherein R in the structural unit A is hydrogen.
［項５］
前記無機フィラー（ＩＩ）が、金属粉、金属酸化物粉、金属窒化物粉、金属水酸化物粉、金属炭化物粉、炭素材料粉および鉱物粉からなる群より選ばれる少なくとも１種の粉体を含む、項１〜４のいずれか１項に記載の熱拡散性樹脂組成物。
[Section 5]
The inorganic filler (II) is at least one powder selected from the group consisting of metal powder, metal oxide powder, metal nitride powder, metal hydroxide powder, metal carbide powder, carbon material powder, and mineral powder. Item 5. The heat-diffusing resin composition according to any one of Items 1 to 4.
［項６］
前記無機フィラー（ＩＩ）が、金粉、銀粉、銅粉、アルミニウム粉、ニッケル粉、窒化アルミニウム粉、酸化アルミニウム粉、酸化亜鉛粉、酸化マグネシウム粉、酸化ケイ素粉、ケイ酸塩粉、窒化ケイ素粉、炭化ケイ素粉、炭化タングステン粉、窒化ホウ素粉、水酸化アルミニウム粉、水酸化マグネシウム粉、酸化窒化アルミニウム粉、グラファイト粉、カーボンナノチューブ、ダイヤモンド粉、炭素繊維、フラーレン、コーディエライト粉およびムライト粉からなる群より選ばれる少なくとも１種の粉体を含む、項１〜５のいずれか１項に記載の熱拡散性樹脂組成物。
[Claim 6]
The inorganic filler (II) is gold powder, silver powder, copper powder, aluminum powder, nickel powder, aluminum nitride powder, aluminum oxide powder, zinc oxide powder, magnesium oxide powder, silicon oxide powder, silicate powder, silicon nitride powder, Consists of silicon carbide powder, tungsten carbide powder, boron nitride powder, aluminum hydroxide powder, magnesium hydroxide powder, aluminum oxynitride powder, graphite powder, carbon nanotube, diamond powder, carbon fiber, fullerene, cordierite powder and mullite powder Item 6. The heat-diffusing resin composition according to any one of Items 1 to 5, comprising at least one powder selected from the group.
［項７］
前記無機フィラー（ＩＩ）が窒化アルミニウム粉、酸化アルミニウム粉、酸化亜鉛粉、酸化マグネシウム粉、炭化ケイ素粉、コーディエライト粉、ムライト粉および窒化ホウ素粉からなる群より選ばれる少なくとも１種の粉体を含む、項１〜６のいずれか１項に記載の熱拡散性樹脂組成物。
[Claim 7]
The inorganic filler (II) is at least one powder selected from the group consisting of aluminum nitride powder, aluminum oxide powder, zinc oxide powder, magnesium oxide powder, silicon carbide powder, cordierite powder, mullite powder, and boron nitride powder. Item 7. The heat-diffusing resin composition according to any one of Items 1 to 6, comprising:
［項８］
エポキシ樹脂、ノボラック型フェノール樹脂、レゾール型フェノール樹脂およびポリウレタンからなる群より選ばれる少なくとも１種の樹脂（ＩＩＩ）をさらに含む、項１〜７のいずれか１項に記載の熱拡散性樹脂組成物。
[Section 8]
Item 8. The heat-diffusing resin composition according to any one of Items 1 to 7, further comprising at least one resin (III) selected from the group consisting of an epoxy resin, a novolak-type phenol resin, a resol-type phenol resin, and polyurethane. .
［項９］
前記樹脂（ＩＩＩ）が、ノボラック型フェノール樹脂およびレゾール型フェノール樹脂からなる群より選ばれる少なくとも１種の樹脂である、項８に記載の熱拡散性樹脂組成物。
[Claim 9]
Item 9. The heat-diffusing resin composition according to Item 8, wherein the resin (III) is at least one resin selected from the group consisting of a novolac-type phenol resin and a resol-type phenol resin.
［項１０］
シランカップリング剤をさらに含む、項１〜９のいずれか１項に記載の熱拡散性樹脂組成物。
[Section 10]
Item 10. The heat-diffusing resin composition according to any one of Items 1 to 9, further comprising a silane coupling agent.
［項１１］
熱拡散率が０．１ｍｍ2／ｓ以上である、項１〜１０のいずれか１項に記載の熱拡散性樹脂組成物。
[Section 11]
Item 11. The thermal diffusible resin composition according to any one of Items 1 to 10, wherein the thermal diffusivity is 0.1 mm 2 / s or more.
［項１２］
項１〜１１のいずれか１項に記載の熱拡散性樹脂組成物と、ケトン系溶媒、エステル系溶媒、芳香族系溶媒、アルコール系溶媒、エーテル系溶媒およびアミド系溶媒からなる群より選ばれる少なくとも１種の溶剤とを含むワニス。
[Claim 12]
The heat-diffusing resin composition according to any one of Items 1 to 11, and a group selected from the group consisting of a ketone solvent, an ester solvent, an aromatic solvent, an alcohol solvent, an ether solvent, and an amide solvent. A varnish containing at least one solvent.
［項１３］
前記溶剤の含有量が、ワニス１００重量％に対し、５０〜９５重量％である、項１２に記載のワニス。
[Claim 13]
Item 13. The varnish according to Item 12, wherein the content of the solvent is 50 to 95% by weight with respect to 100% by weight of the varnish.
本発明によれば、良好な熱拡散性と良好な耐熱性を有し、さらに、金属板、グラファイト板、樹脂製フィルム等への接着性に優れる熱拡散性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a heat diffusible resin composition having good heat diffusibility and good heat resistance, and having excellent adhesion to a metal plate, a graphite plate, a resin film, or the like. .
１．熱拡散性樹脂組成物
本発明の熱拡散性樹脂組成物（以下、単に「組成物」ともいう。）は、特定の構成単位を有するポリビニルアセタール樹脂（Ｉ）と特定量の無機フィラー（ＩＩ）とを含み、必要に応じて樹脂（ＩＩＩ）および／または添加剤を含有してもよい。
1. Thermally diffusible resin composition The thermally diffusible resin composition of the present invention (hereinafter also simply referred to as “composition”) comprises a polyvinyl acetal resin (I) having a specific structural unit and a specific amount of inorganic filler (II). And may contain a resin (III) and / or an additive as necessary.
また、本発明の組成物は、熱可塑性である。すなわち、加熱下で可塑性を有するため加工性やリワーク性が良好であり、押出成形や塗布工程等の作業性などに優れる。 The composition of the present invention is thermoplastic. That is, since it has plasticity under heating, workability and reworkability are good, and it is excellent in workability such as extrusion molding and coating process.
本発明の組成物によれば、該組成物から得られる成形体は、その厚みが薄くても、放熱特性および加工性に優れ、金属板、グラファイト板、樹脂性フィルム、特に金属板等との接着強度が高く、加工性に優れる。このため、本発明によれば、電子部品などの発熱体から発せられる熱が十分に除去され、軽量化、小型化可能な電子機器や、高エネルギー密度でも発熱によるトラブルが抑えられたバッテリーなどを提供することができる。 According to the composition of the present invention, the molded product obtained from the composition is excellent in heat dissipation characteristics and workability even when the thickness thereof is thin, and with metal plates, graphite plates, resinous films, particularly metal plates and the like. High adhesive strength and excellent workability. Therefore, according to the present invention, heat generated from a heating element such as an electronic component is sufficiently removed, and an electronic device that can be reduced in weight and size, a battery in which trouble due to heat generation is suppressed even at a high energy density, and the like. Can be provided.
１−１．ポリビニルアセタール樹脂（Ｉ）
前記ポリビニルアセタール樹脂（Ｉ）は、下記構成単位Ａ、ＢおよびＣを含む樹脂である。このような樹脂（Ｉ）は、靭性、耐熱性および耐衝撃性に優れ、汎用のポリマーに比較して密着性が高いため好ましい。
また、前記樹脂（Ｉ）を含む組成物は、アウトガスの問題が生じにくく、加工性やリワーク性に優れる。
1-1. Polyvinyl acetal resin (I)
The polyvinyl acetal resin (I) is a resin containing the following structural units A, B and C. Such a resin (I) is preferable because it is excellent in toughness, heat resistance and impact resistance, and has higher adhesion than a general-purpose polymer.
Moreover, the composition containing the resin (I) is less prone to outgassing and has excellent workability and reworkability.
前記構成単位Ａは、アセタール部位を有する構成単位であって、例えば、連続するポリビニルアルコール鎖単位とアルデヒド（Ｒ−ＣＨＯ）との反応により形成され得る。 The structural unit A is a structural unit having an acetal moiety, and can be formed, for example, by a reaction between a continuous polyvinyl alcohol chain unit and an aldehyde (R—CHO).
構成単位ＡにおけるＲは独立に、水素またはアルキルである。前記Ｒが嵩高い基（例えば炭素数が多い炭化水素基）であると、ポリビニルアセタール樹脂の軟化点が低下する傾向にある。また、前記Ｒが嵩高い基であるポリビニルアセタール樹脂は、溶媒への溶解性は高いが、一方で耐薬品性に劣ることがある。このため前記Ｒは、水素または炭素数１〜５のアルキルであることが好ましく、得られる組成物の靭性などの点から水素または炭素数１〜３のアルキルであることがより好ましく、水素、メチルまたはプロピルであることがさらに好ましく、得られる組成物の耐熱性などの点から水素であることが特に好ましい。 R in the structural unit A is independently hydrogen or alkyl. When R is a bulky group (for example, a hydrocarbon group having a large number of carbon atoms), the softening point of the polyvinyl acetal resin tends to decrease. Further, the polyvinyl acetal resin in which R is a bulky group has high solubility in a solvent, but may be inferior in chemical resistance. Therefore, R is preferably hydrogen or alkyl having 1 to 5 carbons, more preferably hydrogen or alkyl having 1 to 3 carbons from the viewpoint of the toughness of the resulting composition, and hydrogen, methyl Or it is more preferable that it is a propyl, and it is especially preferable that it is hydrogen from points, such as the heat resistance of the composition obtained.
前記樹脂（Ｉ）は、構成単位Ａ〜Ｃに加えて、下記構成単位Ｄを含むことが、無機フィラー（ＩＩ）、特に、金属水酸化物粉または鉱物粉等との密着性に優れる組成物を得ることができるなどの点から好ましい。
また、樹脂（Ｉ）が構成単位Ｄを含むと、グラファイト板等との接着性により優れる組成物を得ることができる。
The resin (I) contains the following structural unit D in addition to the structural units A to C, and is excellent in adhesion to the inorganic filler (II), particularly metal hydroxide powder or mineral powder. It is preferable from the point that can be obtained.
Moreover, when resin (I) contains the structural unit D, the composition which is excellent by adhesiveness with a graphite board etc. can be obtained.
前記樹脂（Ｉ）における構成単位Ａ、Ｂ、ＣおよびＤの総含有率は、該樹脂の全構成単位に対して８０〜１００ｍｏｌ％であることが好ましい。 The total content of the structural units A, B, C and D in the resin (I) is preferably 80 to 100 mol% with respect to all the structural units of the resin.
前記樹脂（Ｉ）に含まれ得るその他の構成単位としては、構成単位Ａ以外のビニルアセタール鎖単位（前記構成単位ＡにおけるＲが水素またはアルキル以外である構成単位）、下記分子間アセタール単位、および下記ヘミアセタール単位などが挙げられる。構成単位Ａ以外のビニルアセタール鎖単位の含有率は、ポリビニルアセタール樹脂の全構成単位に対して５ｍｏｌ％未満であることが好ましい。 Other structural units that can be included in the resin (I) include vinyl acetal chain units other than the structural unit A (constituent units in which R in the structural unit A is other than hydrogen or alkyl), the following intermolecular acetal units, and The following hemiacetal units are listed. The content of vinyl acetal chain units other than the structural unit A is preferably less than 5 mol% with respect to all the structural units of the polyvinyl acetal resin.
前記樹脂（Ｉ）において、構成単位Ａ〜Ｄは、規則性をもって配列（ブロック共重合体、交互共重合体など）していても、ランダムに配列（ランダム共重合体）していてもよいが、ランダムに配列していることが好ましい。 In the resin (I), the structural units A to D may be regularly arranged (block copolymer, alternating copolymer, etc.) or may be randomly arranged (random copolymer). It is preferable that they are arranged at random.
前記樹脂（Ｉ）における各構成単位は、該樹脂の全構成単位に対して、構成単位Ａの含有率が４９．９〜８０ｍｏｌ％であり、構成単位Ｂの含有率が０．１〜４９．９ｍｏｌ％であり、構成単位Ｃの含有率が０．１〜４９．９ｍｏｌ％であり、構成単位Ｄの含有率が０〜４９．９ｍｏｌ％であることが好ましい。
得られる組成物の、熱拡散率、および金属板、グラファイト板、樹脂製フィルム等との接着性の両立、さらには耐熱性の維持などの点から、より好ましくは、前記樹脂（Ｉ）の全構成単位に対して、構成単位Ａの含有率が４９．９〜８０ｍｏｌ％であり、構成単位Ｂの含有率が１〜３０ｍｏｌ％であり、構成単位Ｃの含有率が１〜３０ｍｏｌ％であり、構成単位Ｄの含有率が１〜３０ｍｏｌ％である。
Each structural unit in the resin (I) has a content of the structural unit A of 49.9 to 80 mol% and a content of the structural unit B of 0.1 to 49.3% with respect to all the structural units of the resin. It is preferably 9 mol%, the content of the structural unit C is 0.1 to 49.9 mol%, and the content of the structural unit D is preferably 0 to 49.9 mol%.
From the viewpoints of coexistence of thermal diffusivity and adhesiveness with a metal plate, a graphite plate, a resin film, and the like, and further maintenance of heat resistance of the composition obtained, more preferably, all of the resin (I) The content of the structural unit A is 49.9 to 80 mol%, the content of the structural unit B is 1 to 30 mol%, and the content of the structural unit C is 1 to 30 mol% with respect to the structural unit. The content rate of the structural unit D is 1-30 mol%.
耐薬品性、可撓性、耐摩耗性および機械的強度に優れる樹脂（Ｉ）を得るなどの点から、構成単位Ａの含有率は４９．９ｍｏｌ％以上であることが好ましい。
前記構成単位Ｂの含有率が０．１ｍｏｌ％以上であると、樹脂（Ｉ）の溶剤への溶解性が良くなるため好ましい。また、構成単位Ｂの含有率が４９．９ｍｏｌ％以下であると、樹脂（Ｉ）の耐薬品性、可撓性、耐摩耗性および機械的強度が低下しにくいため好ましい。
From the viewpoint of obtaining a resin (I) having excellent chemical resistance, flexibility, wear resistance and mechanical strength, the content of the structural unit A is preferably 49.9 mol% or more.
It is preferable that the content of the structural unit B is 0.1 mol% or more because the solubility of the resin (I) in the solvent is improved. Moreover, it is preferable for the content of the structural unit B to be 49.9 mol% or less because the chemical resistance, flexibility, wear resistance and mechanical strength of the resin (I) are unlikely to decrease.
前記構成単位Ｃは、樹脂（Ｉ）の溶剤への溶解性や得られる組成物の接着性などの点から、含有率が４９．９ｍｏｌ％以下であることが好ましい。また、ポリビニルアセタール樹脂の製造において、ポリビニルアルコール鎖をアセタール化する際、構成単位Ｂと構成単位Ｃが平衡関係となるため、構成単位Ｃの含有率は０．１ｍｏｌ％以上であることが好ましい。 The constituent unit C preferably has a content of 49.9 mol% or less from the viewpoint of the solubility of the resin (I) in a solvent and the adhesiveness of the resulting composition. Further, in the production of the polyvinyl acetal resin, when the polyvinyl alcohol chain is acetalized, the structural unit B and the structural unit C are in an equilibrium relationship. Therefore, the content of the structural unit C is preferably 0.1 mol% or more.
また、無機フィラー（ＩＩ）との密着強度に優れ、金属板やグラファイト板等との接着性に優れる組成物を得ることができるなどの点から、構成単位Ｄの含有率は前記範囲にあることが好ましい。構成単位Ｄの含有率が前記範囲にあると、樹脂（Ｉ）と、無機フィラー（ＩＩ）、特に極性の高い無機フィラーとの密着性を高めることができる。一方、構成単位Ｄの含有率の上限が前記範囲を超えると、カルボキシル基が他の官能基と反応して、ワニスを得難くなることがある。 Moreover, the content rate of the structural unit D exists in the said range from the point that it is excellent in the adhesive strength with inorganic filler (II), and can obtain the composition excellent in adhesiveness with a metal plate, a graphite plate, etc. Is preferred. When the content of the structural unit D is in the above range, adhesion between the resin (I) and the inorganic filler (II), particularly an inorganic filler having a high polarity, can be enhanced. On the other hand, when the upper limit of the content rate of the structural unit D exceeds the said range, a carboxyl group may react with another functional group and it may become difficult to obtain a varnish.
前記樹脂（Ｉ）における構成単位Ａ〜Ｃのそれぞれの含有率は、ＪＩＳ Ｋ ６７２８またはＪＩＳ Ｋ ６７２９に準じて測定することができる。 The content of each of the structural units A to C in the resin (I) can be measured according to JIS K 6728 or JIS K 6729.
また、前記樹脂（Ｉ）における構成単位Ｄの含有率は、以下に述べる方法で測定することができる。
１ｍｏｌ／リットル水酸化ナトリウム水溶液中で、樹脂（Ｉ）を、２時間、８０℃で加温する。この操作により、カルボキシル基にナトリウムが付加し、−ＣＯＯＮａを有するポリマーが得られる。該ポリマーから過剰な水酸化ナトリウムを抽出した後、脱水乾燥を行う。その後、炭化させて原子吸光分析を行い、ナトリウムの付加量を求めて定量する。
Moreover, the content rate of the structural unit D in the said resin (I) can be measured by the method described below.
Resin (I) is warmed at 80 ° C. for 2 hours in a 1 mol / liter aqueous sodium hydroxide solution. By this operation, sodium is added to the carboxyl group, and a polymer having —COONa is obtained. Excess sodium hydroxide is extracted from the polymer and then dehydrated and dried. Thereafter, carbonization is performed and atomic absorption analysis is performed, and the amount of sodium added is determined and quantified.
なお、構成単位Ｂ（ビニルアセテート鎖）の含有率を分析する際に、構成単位Ｄは、ビニルアセテート鎖として定量されるため、前記ＪＩＳ Ｋ ６７２８またはＪＩＳ Ｋ６７２９に準じて測定された構成単位Ｂの含有率より、定量した構成単位Ｄの含有率を差し引き、構成単位Ｂの含有率を補正する。 In addition, when analyzing the content rate of the structural unit B (vinyl acetate chain), since the structural unit D is quantified as a vinyl acetate chain, the structural unit B measured according to JIS K 6728 or JIS K6729 is used. The content rate of the structural unit D determined is subtracted from the content rate, and the content rate of the structural unit B is corrected.
前記樹脂（Ｉ）の重量平均分子量は、５０００〜３０００００であることが好ましく、１００００〜１５００００であることがより好ましい。重量平均分子量が前記範囲にある樹脂（Ｉ）を用いると、製造容易性、成形加工性および曲げ強度に優れる成形体（放熱部材）を得ることができるため好ましい。 The weight average molecular weight of the resin (I) is preferably 5,000 to 300,000, and more preferably 10,000 to 150,000. Use of the resin (I) having a weight average molecular weight in the above range is preferable because a molded body (heat radiating member) excellent in manufacturability, molding processability and bending strength can be obtained.
本発明において、樹脂（Ｉ）の重量平均分子量は、ＧＰＣ法により測定することができる。具体的な測定条件は以下の通りである。
検出器：８３０−ＲＩ （日本分光（株）製）
オ−ブン：西尾社製 ＮＦＬ−７００Ｍ
分離カラム：Ｓｈｏｄｅｘ ＫＦ−８０５Ｌ×２本
ポンプ：ＰＵ−９８０（日本分光（株）製）
温度：３０℃
キャリア：テトラヒドロフラン
標準試料：ポリスチレン
In the present invention, the weight average molecular weight of the resin (I) can be measured by the GPC method. Specific measurement conditions are as follows.
Detector: 830-RI (manufactured by JASCO Corporation)
Oven: NFL-700M manufactured by Nishio
Separation column: Shodex KF-805L x 2 Pump: PU-980 (manufactured by JASCO Corporation)
Temperature: 30 ° C
Carrier: Tetrahydrofuran Standard sample: Polystyrene
前記樹脂（Ｉ）のガラス転移温度は、好ましくは４０℃以上１５０℃以下であり、より好ましくは６０℃以上１３０℃以下である。ガラス転移温度がこの範囲にあると、本発明の組成物は、金属板、グラファイト板、樹脂性フィルム等への接着性が高く、耐熱性も良好である。
樹脂（Ｉ）のガラス転移温度は、示差走査熱量測定装置（ＤＳＣ）で測定することができる。
The glass transition temperature of the resin (I) is preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 60 ° C. or higher and 130 ° C. or lower. When the glass transition temperature is in this range, the composition of the present invention has high adhesion to a metal plate, graphite plate, resin film, etc., and good heat resistance.
The glass transition temperature of the resin (I) can be measured with a differential scanning calorimeter (DSC).
前記樹脂（Ｉ）のオストワルド粘度は、１〜１００ｍＰａ・ｓであることが好ましい。オストワルド粘度が前記範囲にある樹脂（Ｉ）を用いると、製造容易性、靭性に優れる成形体（放熱部材）が得られるため好ましい。
オストワルド粘度は、樹脂（Ｉ）５ｇをジクロロエタン１００ｍｌに溶解した溶液を用い、２０℃で、Ｏｓｔｗａｌｄ−Ｃａｎｎｏｎ Ｆｅｎｓｋｅ Ｖｉｓｃｏｍｅｔｅｒを用いて測定することができる。
The Ostwald viscosity of the resin (I) is preferably 1 to 100 mPa · s. It is preferable to use the resin (I) having an Ostwald viscosity in the above range because a molded body (heat radiating member) having excellent manufacturability and toughness can be obtained.
The Ostwald viscosity can be measured by using an Ostwald-Cannon Fenske Viscometer at 20 ° C. using a solution obtained by dissolving 5 g of resin (I) in 100 ml of dichloroethane.
前記樹脂（Ｉ）としては、具体的には、ポリビニルブチラール、ポリビニルホルマール、ポリビニルアセトアセタールおよびこれらの誘導体等が挙げられ、組成物の耐熱性などの点から、ポリビニルホルマールが好ましい。
前記樹脂（Ｉ）としては、前記樹脂を単独で用いてもよく、構成単位の結合の順番や結合の数等が異なる樹脂を２種以上併用してもよい。
前記樹脂（Ｉ）は、合成して得てもよく、市販品でもよい。
Specific examples of the resin (I) include polyvinyl butyral, polyvinyl formal, polyvinyl acetoacetal, and derivatives thereof. Polyvinyl formal is preferable from the viewpoint of heat resistance of the composition.
As said resin (I), the said resin may be used independently and 2 or more types of resin from which the order of the coupling | bonding of a structural unit, the number of coupling | bonding, etc. differ may be used together.
The resin (I) may be obtained by synthesis or may be a commercially available product.
前記構成単位Ａ、ＢおよびＣを含む樹脂の合成方法は、特に制限されないが、例えば、特開２００９−２９８８３３号公報に記載の方法を挙げることができる。また、前記構成単位Ａ、Ｂ、ＣおよびＤを含む樹脂の合成方法は、特に制限されないが、例えば、特開２０１０−２０２８６２号公報に記載の方法を挙げることができる。 The method for synthesizing the resin containing the structural units A, B and C is not particularly limited, and examples thereof include a method described in JP-A-2009-298833. In addition, a method for synthesizing the resin including the structural units A, B, C, and D is not particularly limited, and examples thereof include a method described in JP2010-202862A.
前記樹脂（Ｉ）の市販品としては、ポリビニルホルマールとして、ビニレック Ｃ、ビニレック Ｋ、ビニレック Ｌ（ＪＮＣ（株）製）などが挙げられ、ポリビニルブチラールとして、エスレックＢ・Ｋ （積水化学工業（株）製）などが挙げられる。 Commercially available products of the resin (I) include, as polyvinyl formal, vinylec C, vinylec K, vinylec L (manufactured by JNC Co., Ltd.), etc., and as polyvinyl butyral, ESREC BK (Sekisui Chemical Co., Ltd.) Manufactured).
１−２．樹脂（ＩＩＩ）
本発明の組成物は目的に応じた物性を得るために、前記樹脂（Ｉ）以外の樹脂（ＩＩＩ）を含有してもよい。このような樹脂（ＩＩＩ）としては、特に制限されないが、リサイクルや廃棄時に腐食性の酸性ガスの発生が少ないなどの点からハロゲン元素を有さない樹脂が好ましく、具体的には、エポキシ樹脂、アクリル樹脂、ポリオレフィン樹脂、ポリイミド樹脂、ポリアミド樹脂、フェノール樹脂およびポリカーボネート樹脂が挙げられる。
1-2. Resin (III)
The composition of the present invention may contain a resin (III) other than the resin (I) in order to obtain physical properties according to the purpose. Such a resin (III) is not particularly limited, but is preferably a resin that does not contain a halogen element from the viewpoint of less generation of corrosive acidic gas during recycling and disposal. Specifically, an epoxy resin, Acrylic resin, polyolefin resin, polyimide resin, polyamide resin, phenol resin and polycarbonate resin can be mentioned.
前記エポキシ樹脂としては、特に制限されないが、分子内に２個以上のエポキシ基を有する化合物であることが好ましく、ビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、イソシアネート変性エポキシ樹脂、ウレタン変性エポキシ樹脂、脂環式エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フルオレン型エポキシ樹脂などが挙げられる。 Although it does not restrict | limit especially as said epoxy resin, It is preferable that it is a compound which has a 2 or more epoxy group in a molecule | numerator, A bisphenol type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a glycidyl amine type epoxy Examples thereof include resins, isocyanate-modified epoxy resins, urethane-modified epoxy resins, alicyclic epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and fluorene type epoxy resins.
前記ビスフェノール型エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂などが挙げられる。 Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin.
ビスフェノールＡ型エポキシ樹脂としては、三菱化学（株）製、ｊＥＲ８２７、ｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１００４、ｊＥＲ１０５５、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０；ＤＩＣ（株）製、エピクロン８４０、エピクロン８５０、エピクロン８６０、エピクロン１０５０、エピクロン１０５５、エピクロン２０５０、エピクロン３０５０；新日鐵化学（株）製、エポトートＹＤ−１２７、エポトートＹＤ−１２８、エポトートＹＤ−１３４；などが挙げられる。 As the bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1004, jER1055, jER1007, jER1009, jER1010; DIC Corporation, Epicron 840, Epicron 850, Epicron 860, Epicron 1050, Epicron 1055, Epicron 2050, Epicron 3050; manufactured by Nippon Steel Chemical Co., Ltd., Epototo YD-127, Epototo YD-128, Epototo YD-134;
ビスフェノールＦ型エポキシ樹脂としては、三菱化学（株）製、ｊＥＲ８０６、ｊＥＲ８０７、ｊＥＲ４００４Ｐ、ｊＥＲ４００５Ｐ、ｊＥＲ４００７Ｐ、ｊＥＲ４０１０Ｐ；ＤＩＣ（株）製、エピクロン８３０；新日鐵化学（株）製、エポトートＹＤ−１７０、エポトートＹＤ−２００１、エポトートＹＤ−２００４、エポトートＹＤ−２００５ＲＬ；などが挙げられる。 As the bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation, jER806, jER807, jER4004P, jER4005P, jER4007P, jER4010P; manufactured by DIC Corporation, Epicron 830; manufactured by Nippon Steel Chemical Co., Ltd., Epototo YD-170, Epototo YD-2001, Epototo YD-2004, Epototo YD-2005RL;
ビスフェノールＳ型エポキシ樹脂としては、ＤＩＣ（株）製、エピクロンＥＸＡ-１５１４、エピクロンＥＸＡ-１５１５などが挙げられる。 Examples of the bisphenol S-type epoxy resin include DIC Corporation, Epicron EXA-1514, Epicron EXA-1515, and the like.
前記フェノールノボラック型エポキシ樹脂としては、三菱化学（株）製、ｊＥＲ１５２、ｊＥＲ１５４；ＤＩＣ（株）製、エピクロンＮ−７４０、エピクロンＮ−７７０、エピクロンＮ−７７５；新日鐵化学（株）製、エポトートＹＤＰＮ−６３８；などが挙げられる。 Examples of the phenol novolac type epoxy resin include: Mitsubishi Chemical Corporation, jER152, jER154; DIC Corporation, Epicron N-740, Epicron N-770, Epicron N-775; Nippon Steel Chemical Co., Ltd. Epototo YDPN-638; and the like.
前記クレゾールノボラック型エポキシ樹脂としては、ＤＩＣ（株）製、エピクロンＮ−６６０、エピクロンＮ−６６５、エピクロンＮ−６７０、エピクロンＮ−６７３、エピクロンＮ−６９５；日本化薬（株）製、ＥＯＣＮ−１０２０、ＥＯＣＮ−１０２Ｓ、ＥＯＣＮ−１０４Ｓ；などが挙げられる。 Examples of the cresol novolac type epoxy resin include DIC Corporation, Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-695; Nippon Kayaku Co., Ltd., EOCN- 1020, EOCN-102S, EOCN-104S; and the like.
前記グリシジルアミン型エポキシ樹脂としては、住友化学（株）製、ＥＬＭ−１２０、ＥＬＭ−４３４、ＥＬＭ−４３４ＨＶ；ＤＩＣ（株）製、エピクロン４３０−Ｌ、エピクロン４３０；新日鐵化学（株）製、エポトートＹＨ−４３４、エポトートＹＨ−４３４Ｌ；三菱化学（株）製、ｊＥＲ６０４；日本化薬（株）製、ＧＡＮ、ＧＯＴ；などが挙げられる。 Examples of the glycidylamine type epoxy resin include Sumitomo Chemical Co., Ltd., ELM-120, ELM-434, ELM-434HV; DIC Corporation, Epicron 430-L, Epicron 430; Nippon Steel Chemical Co., Ltd. , Epototo YH-434, Epototo YH-434L; manufactured by Mitsubishi Chemical Corporation, jER604; manufactured by Nippon Kayaku Co., Ltd., GAN, GOT;
前記イソシアネート変性エポキシ樹脂やウレタン変性エポキシ樹脂としては、旭化成イーマテリアル（株）製、ＡＥＲ４１５２；（株）ＡＤＥＫＡ製、ＡＣＲ１３４８；などが挙げられる。
前記脂環式エポキシ樹脂としては、（株）ダイセル製、セロキサイド２０２１、セロキサイド２０８０などが挙げられる。
Examples of the isocyanate-modified epoxy resin and urethane-modified epoxy resin include Asahi Kasei E-material Co., Ltd., AER4152; ADEKA Co., Ltd., ACR1348;
Examples of the alicyclic epoxy resin include Daicel Corporation, Celoxide 2021, Celoxide 2080, and the like.
前記ビフェニル型エポキシ樹脂としては、三菱化学（株）製、ｊＥＲＸＹ４０００、ｊＥＲＹＬ６１２１Ｈ、ｊＥＲＹＬ６６４０；日本化薬（株）製、ＮＣ−３０００；などが挙げられる。 Examples of the biphenyl type epoxy resin include Mitsubishi Chemical Co., Ltd., jERXY4000, jERYL6121H, jERYL6640; Nippon Kayaku Co., Ltd., NC-3000.
前記ナフタレン型エポキシ樹脂としては、ＤＩＣ（株）製、エピクロンＨＰ４０３２；日本化薬（株）製、ＮＣ−７０００、ＮＣ−７３００などが挙げられる。 Examples of the naphthalene type epoxy resin include DIC Corporation, Epicron HP4032, Nippon Kayaku Co., Ltd., NC-7000, NC-7300, and the like.
前記ジシクロペンタジエン型エポキシ樹脂としては、ＤＩＣ（株）製、エピクロンＨＰ７２００、エピクロンＨＰ７２００Ｌ、エピクロンＨＰ７２００Ｈ；日本化薬（株）製、ＸＤ−１０００−１Ｌ、ＸＤ−１０００−２Ｌ；などが挙げられる。 Examples of the dicyclopentadiene type epoxy resin include DIC Corporation, Epicron HP7200, Epicron HP7200L, Epicron HP7200H; Nippon Kayaku Co., Ltd., XD-1000-1L, XD-1000-2L; and the like.
使用するエポキシ樹脂に特に制限はないが、前記樹脂（Ｉ）と容易に混ざるエポキシ樹脂が好ましく、前記樹脂（Ｉ）と混合し易い、ビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂が特に好ましい。
これらのエポキシ樹脂は、単独で用いてもよく、または２種類以上を併用してもよい。
Although there is no restriction | limiting in particular in the epoxy resin to be used, The epoxy resin mixed easily with the said resin (I) is preferable, and the bisphenol type | mold epoxy resin and alicyclic epoxy resin which are easy to mix with the said resin (I) are especially preferable.
These epoxy resins may be used alone or in combination of two or more.
前記アクリル樹脂としては、特に制限されないが、例えば、α,β−不飽和酸およびその誘導体から得られるポリマーが挙げられ、具体的には、ポリアクリレート、ポリメタクリレート、ポリアクリルアミドなどが挙げられる。 Although it does not restrict | limit especially as said acrylic resin, For example, the polymer obtained from (alpha), (beta) -unsaturated acid and its derivative (s) is mentioned, Specifically, polyacrylate, polymethacrylate, polyacrylamide, etc. are mentioned.
前記ポリオレフィン樹脂としては、特に制限されないが、例えば、ポリエチレン、ポリプロピレン、ポリイソブチレン、ポリブテン、ポリメチルペンテン、ポリ環状オレフィン、ポリブタジエン、アタクチックまたはシンジオタクチックなポリスチレン、ポリ（ｐ−メチルスチレン）、ポリ（α−メチルスチレン）が挙げられる。さらに、前記ポリオレフィン樹脂として、ＡＳ（アクリロニトリル−スチレンコポリマー）、ＡＢＳ（アクリロニトリル−ブタジエン−スチレンコポリマー）、ＭＢＳ（メタクリル酸メチル−ブタジエン−スチレンコポリマー）、ＡＳＡ（アクリロニトリル−スチレン−アクリレートコポリマー）、ＡＥＳ（アクリロニトリル−エチレン−スチレンコポリマー）、スチレンまたはα−メチルスチレンとジエンまたはアクリル系誘導体とのコポリマーなどが挙げられる。 The polyolefin resin is not particularly limited. For example, polyethylene, polypropylene, polyisobutylene, polybutene, polymethylpentene, polycyclic olefin, polybutadiene, atactic or syndiotactic polystyrene, poly (p-methylstyrene), poly ( α-methylstyrene). Further, as the polyolefin resin, AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MBS (methyl methacrylate-butadiene-styrene copolymer), ASA (acrylonitrile-styrene-acrylate copolymer), AES (acrylonitrile). -Ethylene-styrene copolymer), copolymers of styrene or α-methylstyrene and diene or acrylic derivatives, and the like.
前記ポリイミド樹脂としては、特に制限されないが、特開平７−１５２０３７号公報に記載のポリイミド樹脂、ポリエーテルイミド樹脂、ポリアミド−イミド樹脂などが挙げられる。 The polyimide resin is not particularly limited, and examples thereof include a polyimide resin, a polyetherimide resin, and a polyamide-imide resin described in JP-A-7-152037.
前記ポリアミド樹脂としては、特に制限されないが、ジアミンとジカルボン酸および／またはアミノカルボン酸または対応するラクタムから得られるポリアミドおよびコポリアミドなどが挙げられ、具体的には、ポリアミド４、ポリアミド６、ポリアミド６／６、６／１０、６／９、６／１２または４／６、ポリアミド１１、ポリアミド１２、ｍ−キシレンジアミンとアジピン酸との縮合によって得られるポリアミドＭＸＤ６、ヘキサメチレンジアミンとイソフタル酸および／またはテレフタル酸との縮合によって得られる変性ポリアミド６Ｔ、ＥＰＤＭ（エチレン−プロピレン−ジエンゴム）またはＡＢＳで改質されたポリアミドまたはコポリアミド、樹脂成形加工中に縮合されるポリアミド（ＲＩＭポリアミド系）などが挙げられる。 The polyamide resin is not particularly limited, and examples thereof include polyamides and copolyamides obtained from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams. Specific examples include polyamide 4, polyamide 6, polyamide 6 and the like. / 6, 6/10, 6/9, 6/12 or 4/6, polyamide 11, polyamide 12, polyamide MXD6 obtained by condensation of m-xylenediamine and adipic acid, hexamethylenediamine and isophthalic acid and / or Modified polyamide 6T obtained by condensation with terephthalic acid, polyamide or copolyamide modified with EPDM (ethylene-propylene-diene rubber) or ABS, polyamide condensed during resin molding (RIM polyamide), etc. .
前記フェノール樹脂としては、特に制限されないが、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、キシリレンノボラック樹脂、ビスフェノールＡノボラック樹脂、トリフェニルメタンノボラック樹脂、ビフェニルノボラック樹脂、ジシクロペンタジエンフェノールノボラック樹脂、テルペンフェノールノボラック樹脂などが挙げられる。 Although it does not restrict | limit especially as said phenol resin, A novolak type phenol resin, a resol type phenol resin, a xylylene novolak resin, a bisphenol A novolak resin, a triphenylmethane novolak resin, a biphenyl novolak resin, a dicyclopentadiene phenol novolak resin, a terpene phenol Examples thereof include novolac resin.
前記ポリカーボネート樹脂としては、特に制限されないが、特開２０１０−５９３０７号公報に記載のポリカーボネート樹脂などが挙げられる。 Although it does not restrict | limit especially as said polycarbonate resin, The polycarbonate resin etc. which are described in Unexamined-Japanese-Patent No. 2010-59307 are mentioned.
前記樹脂（ＩＩＩ）としては、さらに、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルピロリドン、ポリステアリン酸ビニル、ポリ安息香酸ビニル、ポリマレイン酸ビニル、ポリビニルブチレート、環状エーテルのホモポリマーおよびコポリマー、ポリアルキレングリコール、ポリ酸化エチレン、ポリ酸化プロピレンまたはビスグリシジルエーテルとそのコポリマー、ポリオキシメチレンやコモノマーとして酸化エチレンを含有するポリオキシメチレンのようなポリアセタール、熱可塑性ポリウレタン、ポリアクリレートまたはＭＢＳで改質されたポリアセタール、ポリフェニレンエーテル、耐衝撃性ポリスチレン等で変性された変性ポリフェニレンエーテル、ポリエーテルまたはポリエステルをソフトセグメントとして有し、脂肪族または芳香族ポリイソシアネートを使用して得られるポリウレタン、ポリベンズイミダゾール、ポリアリルスルホン、ポリアリルケトン、ポリサルフォン、ポリエーテルサルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリフェニレンスルフィド、ポリフェニレンサルファイドスルフォン、光学的異方性溶融相を形成し得る溶融加工性ポリエステル、メラミン樹脂、尿素樹脂、ポリテトラフルオロエチレン、エチレン／テトラフルオロエチレンコポリマー、テトラフルオロエチレン／パーフルオロビニルエーテルコポリマーなどのフッ素樹脂などが挙げられる。 Examples of the resin (III) include polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl stearate, polyvinyl benzoate, vinyl maleate, polyvinyl butyrate, homopolymers and copolymers of cyclic ethers, polyalkylene glycols, Polyethylene oxide, polypropylene oxide or bisglycidyl ether and copolymers thereof, polyoxymethylene and polyacetals such as polyoxymethylene containing ethylene oxide as a comonomer, thermoplastic polyurethanes, polyacetals modified with polyacrylate or MBS, polyphenylene It has a modified polyphenylene ether, polyether or polyester modified with ether, impact-resistant polystyrene, etc. as a soft segment and is aliphatic. Polyurethane, polybenzimidazole, polyallylsulfone, polyallylketone, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyphenylene sulfide, polyphenylene sulfide sulfone, optics obtained using aromatic polyisocyanate And melt-processable polyester capable of forming a thermally anisotropic melt phase, melamine resin, urea resin, polytetrafluoroethylene, ethylene / tetrafluoroethylene copolymer, tetrafluoroethylene / perfluorovinyl ether copolymer and other fluororesins.
また、前記樹脂（ＩＩＩ）として、ジカルボン酸とジオールおよび／またはヒドロキシカルボン酸とから得られるポリエステル、ラクトンから得られるポリエステルなども挙げられ、このようなポリエステルとして、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリシクロヘキサンジメタノールテレフタレート（ＰＣＴ）、これらを更にポリカーボネートまたはＭＢＳなどで改質したポリエステルが挙げられる。 Examples of the resin (III) include polyesters obtained from dicarboxylic acids and diols and / or hydroxycarboxylic acids, and polyesters obtained from lactones. Examples of such polyesters include polyethylene terephthalate (PET) and polyester. Examples include butylene terephthalate (PBT), polycyclohexanedimethanol terephthalate (PCT), and polyester obtained by modifying these with polycarbonate or MBS.
さらに、前記樹脂（ＩＩＩ）として、セルロース、ゴム、ゼラチン等の天然ポリマーまたはこれらを化学的に改質したものの同族誘導体なども挙げられ、このようなポリマーとして、例えば、酢酸セルロース、プロピオン酸セルロース、セルロースエーテル、メチルセルロース、ロジン、ロジンエステルまたはこれらの誘導体が挙げられる。 Furthermore, examples of the resin (III) include natural polymers such as cellulose, rubber, and gelatin, or homologous derivatives of those chemically modified. Examples of such polymers include cellulose acetate, cellulose propionate, Examples thereof include cellulose ether, methyl cellulose, rosin, rosin ester, and derivatives thereof.
前記樹脂（ＩＩＩ）としては、上述のポリマーの混合物（ポリマーブレンド）であってもよく、例えば、ＰＰ／ＥＰＤＭ、ＰＡ６／ＥＰＤＭまたはＡＢＳ、ＰＣ／ＡＢＳ、ＰＢＴ／ＡＢＳ、ＰＣ／ＡＳ、ＰＣ／ＰＢＴ、ＰＯＭ／熱可塑性ＰＵＲ、ＰＣ／熱可塑性ＰＵＲ、ＰＯＭ／ＰＭＭＡ、ＰＯＭ／ＭＢＳ、ＰＰＥ／ＨＩＰＳ、ＰＰＥ／（ＰＡ６／６）、ＰＡ／ＨＤＰＥ、ＰＡ／ＰＰ、ＰＡ／ＰＰＥ、ＰＰＥ／ＰＰＳ、ＰＰＳ／ＰＥＩ、ＰＥＩ／ＰＥＥＫが挙げられる。（ＰＰ：ポリプロピレン、ＰＡ：ポリアミド、ＰＣ：ポリカーボネート、ＰＯＭ：ポリオキシメチレン、ＰＵＲ：ポリウレタンゴム、ＰＭＭＡ：ポリメタクリル酸メチル、ＰＰＥ：ポリフェニレンエーテル、ＨＩＰＳ：耐衝撃性ポリスチレン、ＨＤＰＥ：高密度ポリエチレン、ＰＰＳ：ポリフェニレンスルフィド、ＰＥＩ：ポリエーテルイミド、ＰＥＥＫ：ポリエーテルエーテルケトン） The resin (III) may be a mixture (polymer blend) of the above-mentioned polymers. For example, PP / EPDM, PA6 / EPDM or ABS, PC / ABS, PBT / ABS, PC / AS, PC / PBT , POM / thermoplastic PUR, PC / thermoplastic PUR, POM / PMMA, POM / MBS, PPE / HIPS, PPE / (PA6 / 6), PA / HDPE, PA / PP, PA / PPE, PPE / PPS, PPS / PEI, PEI / PEEK. (PP: Polypropylene, PA: Polyamide, PC: Polycarbonate, POM: Polyoxymethylene, PUR: Polyurethane rubber, PMMA: Polymethyl methacrylate, PPE: Polyphenylene ether, HIPS: High impact polystyrene, HDPE: High density polyethylene, PPS : Polyphenylene sulfide, PEI: Polyetherimide, PEEK: Polyetheretherketone)
前記樹脂（ＩＩＩ）は、単独で用いてもよく、２種以上を併用してもよい The resin (III) may be used alone or in combination of two or more.
前記樹脂（ＩＩＩ）としては、優れた特性を有する組成物を得るために、前記樹脂（Ｉ）と良く混合するものが好ましい。このような樹脂としては樹脂（Ｉ）と架橋構造を形成することのできる樹脂が挙げられる。詳しくはエポキシ樹脂、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、ポリウレタン等である。さらに好ましくはノボラック型フェノール樹脂、レゾール型フェノール樹脂である。
前記樹脂（ＩＩＩ）は合成して得てもよく、市販品でもよい。
The resin (III) is preferably one that is well mixed with the resin (I) in order to obtain a composition having excellent characteristics. Examples of such a resin include a resin capable of forming a crosslinked structure with the resin (I). Specifically, epoxy resin, novolac type phenol resin, resol type phenol resin, polyurethane and the like. More preferred are novolac type phenol resins and resol type phenol resins.
The resin (III) may be obtained by synthesis or may be a commercially available product.
前記樹脂（ＩＩＩ）は、前記樹脂（Ｉ）の熱可塑性などの特性を損なわない範囲で添加することが好ましく、本発明の組成物に含まれる樹脂の合計１００重量％に対して、１〜１０重量％がより好ましく、１〜５重量％がさらに好ましい。 The resin (III) is preferably added within a range that does not impair the properties such as thermoplasticity of the resin (I), and is 1 to 10% relative to 100% by weight of the total resin contained in the composition of the present invention. % By weight is more preferable, and 1 to 5% by weight is more preferable.
１−３．無機フィラー（ＩＩ）
本発明の組成物は、無機フィラー（ＩＩ）を含むことで、該組成物の熱拡散性および耐熱特性が向上する。
1-3. Inorganic filler (II)
When the composition of the present invention contains the inorganic filler (II), the thermal diffusibility and heat resistance characteristics of the composition are improved.
前記無機フィラー（ＩＩ）としては、特に制限されないが、熱伝導性フィラーが好ましく、金属粉、金属酸化物粉、金属窒化物粉、金属水酸化物粉、金属酸窒化物粉、金属炭化物粉などの金属または金属化合物含有フィラー、炭素材料フィラーおよび鉱物粉等が挙げられる。 Although it does not restrict | limit especially as said inorganic filler (II), A heat conductive filler is preferable, metal powder, metal oxide powder, metal nitride powder, metal hydroxide powder, metal oxynitride powder, metal carbide powder, etc. Metal or metal compound-containing filler, carbon material filler, mineral powder, and the like.
前記金属粉としては、金、銀、銅、アルミニウム、ニッケルなどの金属およびこれら金属を含有する合金からなる粉などが挙げられる。前記金属酸化物粉としては、酸化アルミニウム粉、酸化亜鉛粉、酸化マグネシウム粉、酸化ケイ素粉、酸化チタン粉、ケイ酸塩粉などが挙げられる。前記金属窒化物粉としては、窒化アルミニウム粉、窒化ホウ素粉、窒化ケイ素粉などが挙げられる。前記金属水酸化物粉としては、水酸化アルミニウム粉、水酸化マグネシウム粉などが挙げられる。前記金属酸窒化物としては、酸化窒化アルミニウム粉などが挙げられ、前記金属炭化物粉としては、炭化ケイ素粉、炭化タングステン粉などが挙げられる。 As said metal powder, the powder etc. which consist of metals, such as gold | metal | money, silver, copper, aluminum, nickel, and the alloy containing these metals, etc. are mentioned. Examples of the metal oxide powder include aluminum oxide powder, zinc oxide powder, magnesium oxide powder, silicon oxide powder, titanium oxide powder, and silicate powder. Examples of the metal nitride powder include aluminum nitride powder, boron nitride powder, and silicon nitride powder. Examples of the metal hydroxide powder include aluminum hydroxide powder and magnesium hydroxide powder. Examples of the metal oxynitride include aluminum oxynitride powder, and examples of the metal carbide powder include silicon carbide powder and tungsten carbide powder.
これらの中でも、熱拡散性および入手容易性などの点から窒化アルミニウム粉、窒化ホウ素粉、酸化アルミニウム粉、酸化亜鉛粉、酸化マグネシウム粉、水酸化アルミニウム粉、炭化ケイ素粉および炭化タングステン粉が好ましく、酸化亜鉛粉、酸化アルミニウム粉、窒化アルミニウム粉、窒化ホウ素粉、酸化マグネシウム粉および炭化ケイ素粉がより好ましい。 Among these, aluminum nitride powder, boron nitride powder, aluminum oxide powder, zinc oxide powder, magnesium oxide powder, aluminum hydroxide powder, silicon carbide powder and tungsten carbide powder are preferable from the viewpoint of thermal diffusibility and availability. Zinc oxide powder, aluminum oxide powder, aluminum nitride powder, boron nitride powder, magnesium oxide powder and silicon carbide powder are more preferable.
前記金属または金属化合物含有フィラーとしては、窒化アルミニウム粉、酸化アルミニウム粉、および針状（特にテトラポット形状）の酸化亜鉛粉を用いることが好ましい。
酸化亜鉛は、窒化アルミニウムに比べ、熱拡散率は低いが、針状またはテトラポット形状の酸化亜鉛粉を用いると、粒子状の酸化亜鉛粉を用いる場合より放熱特性に優れる組成物が得られる。
また、酸化アルミニウムは、窒化アルミニウムや酸化亜鉛に比べ、熱拡散率は低いが、化学的に安定であり、水や酸により反応したり、水や酸に溶解したりしないので、高い耐候性を有する組成物を得ることができる。
前記無機フィラーとして窒化アルミニウム粉を用いると、放熱特性により優れる組成物を得ることができる。
As the metal or metal compound-containing filler, it is preferable to use aluminum nitride powder, aluminum oxide powder, and needle-shaped (particularly tetrapot-shaped) zinc oxide powder.
Zinc oxide has a lower thermal diffusivity than aluminum nitride. However, when needle-like or tetrapot-shaped zinc oxide powder is used, a composition having better heat dissipation characteristics than when using particulate zinc oxide powder is obtained.
Aluminum oxide has lower thermal diffusivity than aluminum nitride and zinc oxide, but is chemically stable and does not react or dissolve in water or acid, so it has high weather resistance. The composition which has can be obtained.
When aluminum nitride powder is used as the inorganic filler, a composition having better heat dissipation characteristics can be obtained.
前記炭素材料フィラーとしては、グラファイト粉（天然黒鉛、人造黒鉛、膨張黒鉛、ケッチェンブラック）、カーボンナノチューブ、ダイヤモンド粉、炭素繊維およびフラーレンなどが挙げられ、これらの中でも熱拡散性に優れるなどの点から、グラファイト粉、カーボンナノチューブおよびダイヤモンド粉が好ましい。 Examples of the carbon material filler include graphite powder (natural graphite, artificial graphite, expanded graphite, ketjen black), carbon nanotube, diamond powder, carbon fiber, and fullerene. Among these, the heat diffusibility is excellent. From the above, graphite powder, carbon nanotube and diamond powder are preferable.
前記鉱物粉としては、熱拡散率が高いなどの点からコーディエライト粉およびムライト粉が好ましい。 As the mineral powder, cordierite powder and mullite powder are preferable in view of high thermal diffusivity.
前記無機フィラー（ＩＩ）の形状としては、特に制限されないが、粒子状（球状、楕円球状を含む）、偏平状、柱状、針状（テトラポット形状、樹枝状を含む）および不定形状などが挙げられる。これらの形状は、レーザー回折/散乱式粒子径分布測定装置やＳＥＭ（走査型電子顕微鏡）を用いて確認することができる。 The shape of the inorganic filler (II) is not particularly limited, and examples thereof include particles (including spherical and elliptical spheres), flat shapes, columnar shapes, needle shapes (including tetrapot shapes and dendritic shapes), and irregular shapes. It is done. These shapes can be confirmed using a laser diffraction / scattering particle size distribution measuring device or SEM (scanning electron microscope).
前記金属または金属化合物含有フィラー、および鉱物粉の一次粒子の平均径は、目的に応じて適宜選択すればよいが、熱拡散性などの点から、好ましくは０．００１〜３０μｍであり、より好ましくは０．０１〜１０μｍである。 The average diameter of the primary particles of the metal or metal compound-containing filler and mineral powder may be appropriately selected according to the purpose, but is preferably 0.001 to 30 μm, more preferably from the viewpoint of thermal diffusibility and the like. Is 0.01 to 10 μm.
なお、金属または金属化合物含有フィラー、および鉱物粉の一次粒子の平均径とは、該フィラーが粒子状の場合は、粒子の直径（楕円球状の場合は長軸の長さ）のことをいい、該フィラーが扁平状の場合は、最も長い辺のことをいい、該フィラーが柱状の場合は、円の直径（楕円の長軸）または柱の長さのうちいずれか長い方のことをいい、該フィラーが針状の場合は、針の長さのことをいう。 In addition, the average diameter of the primary particles of the metal or metal compound-containing filler and mineral powder refers to the diameter of the particle (the length of the major axis in the case of an oval sphere) when the filler is in the form of particles, When the filler is flat, it refers to the longest side, and when the filler is columnar, it refers to the longer of the circle diameter (ellipse major axis) or the column length, When the filler is needle-shaped, it means the length of the needle.
前記炭素材料フィラーの一次粒子の平均径は、形成したい最終製品の大きさ、本発明の組成物の厚み等に応じて適宜選択すればよいが、熱拡散性などの点から、好ましくは０．００１〜２０μｍであり、より好ましくは０．００２〜１０μｍである。炭素材料からなるフィラーの平均径は、レーザー回折/散乱式粒子径分布測定装置やＳＥＭ（走査型電子顕微鏡）などを用いて確認することができる。なお、カーボンナノチューブや炭素繊維の平均径とは、チューブや繊維の長さのことをいう。 The average diameter of the primary particles of the carbon material filler may be appropriately selected according to the size of the final product to be formed, the thickness of the composition of the present invention, etc., but is preferably from the viewpoint of thermal diffusibility. It is 001-20 micrometers, More preferably, it is 0.002-10 micrometers. The average diameter of the filler made of the carbon material can be confirmed using a laser diffraction / scattering particle size distribution measuring device, SEM (scanning electron microscope) or the like. In addition, the average diameter of a carbon nanotube or carbon fiber means the length of a tube or fiber.
前記無機フィラー（ＩＩ）は、平均径や形状が所望の範囲にある市販品をそのまま用いてもよく、平均径や形状が所望の範囲になるように市販品を粉砕、分級、加熱等したものを用いてもよい。 The inorganic filler (II) may be a commercially available product having an average diameter or shape in a desired range, or is obtained by pulverizing, classifying, heating, or the like so that the average diameter or shape is in a desired range. May be used.
前記無機フィラー（ＩＩ）としては、分散処理、防水処理などの表面処理された市販品をそのまま用いてもよく、該市販品から表面処理剤を除去したものを用いてもよい。また、表面処理されていない市販品を表面処理して用いてもよい。特に窒化アルミニウムおよび酸化マグネシウムは空気中の水分により劣化しやすいので、防水処理されたものを使用することが望ましい。
前記無機フィラー（ＩＩ）としては、上述のフィラーを単独で用いてもよく、２種以上を併用してもよい。
As the inorganic filler (II), a commercially available product subjected to a surface treatment such as a dispersion treatment or a waterproof treatment may be used as it is, or a product obtained by removing a surface treatment agent from the commercially available product may be used. Moreover, you may use the surface-treated commercial item which is not surface-treated. In particular, since aluminum nitride and magnesium oxide are easily deteriorated by moisture in the air, it is desirable to use a waterproofed one.
As said inorganic filler (II), the above-mentioned filler may be used independently and 2 or more types may be used together.
前記無機フィラー（ＩＩ）の配合量は、本発明の組成物１００体積％に対し、５〜８５体積％である。
本発明の組成物を発熱源から熱を外部に伝達する用途で使用する場合には、熱拡散率が高い組成物が得られるなどの点で、前記無機フィラー（ＩＩ）の配合量は２０〜８５％であることが好ましい。
The compounding quantity of the said inorganic filler (II) is 5-85 volume% with respect to 100 volume% of compositions of this invention.
When the composition of the present invention is used for the purpose of transferring heat from a heat source to the outside, the blending amount of the inorganic filler (II) is 20 to 20 in that a composition having a high thermal diffusivity is obtained. It is preferably 85%.
本発明の組成物は、前記樹脂（Ｉ）を含むため、無機フィラー（ＩＩ）の配合量が本発明の組成物１００体積％に対し、好ましくは５０〜８０体積％、より好ましくは６０〜７０体積％であっても、金属板、グラファイト板、樹脂製フィルム等への接着性が良好であり、加工時の剥がれ、割れ等の発生が少ないなどに優れる組成物を得ることができる。 Since the composition of this invention contains the said resin (I), the compounding quantity of inorganic filler (II) becomes like this. Preferably it is 50-80 volume% with respect to 100 volume% of the composition of this invention, More preferably, it is 60-70. Even if it is volume%, the adhesiveness to a metal plate, a graphite plate, a resin-made film etc. is favorable, and the composition which is excellent in peeling at the time of a process, generation | occurrence | production of a crack, etc. can be obtained.
前記無機フィラー（ＩＩ）が本発明の組成物中に４０体積％以上の割合で含まれていると、金属板、グラファイト板、樹脂性フィルム等への接着性を維持しつつ、熱拡散性が向上した組成物が得られるため好ましい。
前記無機フィラー（ＩＩ）の配合量が８０体積％以下の割合で含まれていると、金属板、グラファイト板、樹脂性フィルム等への接着性と熱拡散率にバランスよく優れる組成物が得られ、前記無機フィラーの配合量が５体積％以上の割合で含まれていると、熱拡散性が高い組成物が得られるため好ましい。
When the inorganic filler (II) is contained in the composition of the present invention at a ratio of 40% by volume or more, the thermal diffusibility is maintained while maintaining the adhesion to a metal plate, a graphite plate, a resinous film, and the like. This is preferable because an improved composition can be obtained.
When the blending amount of the inorganic filler (II) is contained in a proportion of 80% by volume or less, a composition having a good balance between adhesion to a metal plate, a graphite plate, a resinous film and the like and thermal diffusivity can be obtained. It is preferable that the amount of the inorganic filler is 5% by volume or more because a composition having high thermal diffusivity can be obtained.
本発明の組成物を発熱源からの遠赤外線を利用して熱を外部に伝達する用途で使用する場合には、熱拡散と熱放射をあわせた効果が高い組成物が得られるなどの点で前記無機フィラー（ＩＩ）の配合量は５％以上であることが好ましい。 When the composition of the present invention is used for the purpose of transferring heat to the outside using far infrared rays from a heat source, a composition having a high effect of combining heat diffusion and heat radiation can be obtained. The blending amount of the inorganic filler (II) is preferably 5% or more.
１−４．添加剤
前記添加剤としては、本発明の効果を損なわない限り特に制限されないが、酸化防止剤、シランカップリング剤、銅害防止剤、金属不活性化剤、防錆剤、粘着性付与剤、老化防止剤、消泡剤、帯電防止剤、耐候剤、硬化剤、硬化助剤などが挙げられる。
1-4. Additives The additives are not particularly limited as long as the effects of the present invention are not impaired, but are antioxidants, silane coupling agents, copper damage inhibitors, metal deactivators, rust inhibitors, tackifiers, Examples thereof include anti-aging agents, antifoaming agents, antistatic agents, weathering agents, curing agents, and curing aids.
本発明の組成物を金属板に接触させる場合であって、無機フィラー（ＩＩ）と樹脂（Ｉ）との密着性を向上させるために、シランカップリング剤を添加することが好ましい。 In the case of bringing the composition of the present invention into contact with a metal plate, it is preferable to add a silane coupling agent in order to improve the adhesion between the inorganic filler (II) and the resin (I).
シランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、ビニルトリクロロシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３,４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−ウレイドプロピルトリエトキシシラン、Ｎ−（１,３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ,Ｎ'−ビス（３−（トリメトキシシリル）プロピル）エチレンジアミン、ポリオキシエチレンプロピルトリアルコキシシラン、ポリエトキシジメチルシロキサン、ｐ−スチリルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシランなどが挙げられる。 Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxy Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N ′ -Bis (3- (trimethoxysilyl) propyl) ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxydimethylsiloxane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethyl Kishishiran and the like.
前記シランカップリング剤としては、ＪＮＣ（株）製のシランカップリング剤（商品名 Ｓ３３０、Ｓ５１０、Ｓ５２０、Ｓ５３０）などが好ましい。 As the silane coupling agent, a silane coupling agent (trade names S330, S510, S520, S530) manufactured by JNC Corporation is preferable.
前記シランカップリング剤の添加量は、前記樹脂（Ｉ）と無機フィラー（ＩＩ）との密着性を向上させることができるなどの点から、本発明の組成物に含まれる樹脂の総量１００重量部に対して好ましくは０．１〜１０重量部である。 The addition amount of the silane coupling agent is such that the adhesion between the resin (I) and the inorganic filler (II) can be improved, and the total amount of the resin contained in the composition of the present invention is 100 parts by weight. The amount is preferably 0.1 to 10 parts by weight.
前記組成物を構成する樹脂（Ｉ）は、古くからエナメル線などに使用されており、金属と接触することにより劣化したり、金属を劣化させ難い樹脂ではあるが、本発明の組成物を金属板に接触させる場合であって、該組成物を成形した成形体と金属板との積層体を高温多湿環境で使用する場合などでは、銅害防止剤や金属不活性化剤を本発明の組成物に添加することが好ましい。
前記銅害防止剤としては、例えば、特開平５−４８２６５号公報に記載の化合物を挙げることができる。
The resin (I) constituting the composition has been used for enameled wire for a long time, and is a resin that is deteriorated by contact with a metal or hardly deteriorates, but the composition of the present invention is a metal. In the case of using a laminate of a molded body obtained by molding the composition and a metal plate in a high-temperature and high-humidity environment, etc., a copper damage inhibitor or a metal deactivator is added to the composition of the present invention. It is preferable to add to the product.
Examples of the copper damage inhibitor include compounds described in JP-A-5-48265.
前記銅害防止剤としては、（株）ＡＤＥＫＡ製、Ｍａｒｋ ＺＳ−２７，Ｍａｒｋ ＣＤＡ−１６；三光化学工業（株）製、ＳＡＮＫＯ−ＥＰＯＣＬＥＡＮ；ＢＡＳＦ社製、Ｉｒｇａｎｏｘ ＭＤ１０２４；などが好ましい。 As the copper damage inhibitor, ADEKA Corporation, Mark ZS-27, Mark CDA-16; Sanko Chemical Industry Co., Ltd., SANKO-EPOCLEAN; BASF Corporation, Irganox MD1024;
前記銅害防止剤の添加量は、本発明の組成物の金属板と接触する部分の樹脂の劣化を防止できるなどの点から、該組成物に含まれる樹脂の総量１００重量部に対して、好ましくは０．１〜３重量部である。 The amount of the copper damage inhibitor added is such that it can prevent deterioration of the resin in contact with the metal plate of the composition of the present invention, and the total amount of the resin contained in the composition is 100 parts by weight. Preferably it is 0.1-3 weight part.
２．熱拡散性樹脂組成物の調製方法
本発明の組成物は、例えば、前記樹脂（Ｉ）、無機フィラー（ＩＩ）、ならびに必要に応じて用いられる前記樹脂（ＩＩＩ）および／または添加剤を混練機などで混練することで得ることができる。また、下記ワニスから溶剤を除去することで得ることもできる。組成物中の無機フィラー（ＩＩ）の凝集状態や分散状態を制御でき、熱拡散率の高い組成物を得ることができるなどの点からワニスから溶剤を除去することで得られる組成物が好ましい。
2. Preparation method of heat-diffusible resin composition The composition of the present invention comprises, for example, a kneader comprising the resin (I), the inorganic filler (II), and the resin (III) and / or additives used as necessary. It can be obtained by kneading. Moreover, it can also obtain by removing a solvent from the following varnish. A composition obtained by removing the solvent from the varnish is preferable in that the aggregation state and dispersion state of the inorganic filler (II) in the composition can be controlled and a composition having a high thermal diffusivity can be obtained.
なお、用いる無機フィラー（ＩＩ）は、予めシランカップリング剤で処理されていてもよい。無機フィラー（ＩＩ）の処理は任意の方法で行えばよいが、シランカップリング剤を含む水溶液に、無機フィラー（ＩＩ）を添加することでスラリーを得て、該スラリーから水を除去して固形物を得、必要により該固形物をすりつぶして粒子にする方法などが挙げられる。 In addition, the inorganic filler (II) to be used may be previously treated with a silane coupling agent. The treatment of the inorganic filler (II) may be performed by any method, but the slurry is obtained by adding the inorganic filler (II) to the aqueous solution containing the silane coupling agent, and the solid is removed by removing water from the slurry. A method of obtaining a product and, if necessary, grinding the solid to form particles is exemplified.
３．熱拡散性樹脂組成物の物性等
本発明の組成物において、無機フィラー（ＩＩ）の配合量に比して、熱拡散率が高いのは、前記樹脂（Ｉ）と無機フィラー（ＩＩ）との密着性（相溶性）が高く、無機フィラー（ＩＩ）の周囲を樹脂（Ｉ）が隙間なく覆い、空隙の形成を抑制できるからであると考えられる。つまり、樹脂（Ｉ）に含まれる構成単位Ｃ（および構成単位Ｄ）が、無機フィラー（ＩＩ）表面の官能基と相互作用することで、樹脂（Ｉ）と無機フィラー（ＩＩ）の密着性が高まり、無機フィラーの周囲をポリビニルアセタール樹脂が隙間なく覆うことで、空隙の形成を抑制できると考えられる。気体で構成される隙間は、組成物の熱拡散率を低下させたり、フィラーの充填密度を低下させるため、空隙の形成を抑制することで、熱拡散率の高い組成物を得ることができると考えられる。
3. Physical properties of heat diffusing resin composition, etc. In the composition of the present invention, the thermal diffusivity is higher than that of the inorganic filler (II) because the resin (I) and the inorganic filler (II) It is considered that the adhesiveness (compatibility) is high, and the resin (I) covers the periphery of the inorganic filler (II) without any gap, and the formation of voids can be suppressed. That is, the structural unit C (and the structural unit D) contained in the resin (I) interacts with the functional group on the surface of the inorganic filler (II), whereby the adhesion between the resin (I) and the inorganic filler (II) is improved. It is considered that the formation of voids can be suppressed by covering the periphery of the inorganic filler with the polyvinyl acetal resin without a gap. Since the gap composed of gas lowers the thermal diffusivity of the composition or lowers the packing density of the filler, it is possible to obtain a composition having a high thermal diffusivity by suppressing the formation of voids. Conceivable.
特に、ポリビニルアセタール樹脂以外の樹脂と無機フィラーとからなる組成物に比べ、無機フィラーの配合量が少なくても熱拡散性に優れる組成物を得ることができる。このため、本発明の組成物は、熱拡散性および金属板、グラファイト板、樹脂性フィルム等との接着性にバランスよく優れる。 In particular, a composition excellent in thermal diffusivity can be obtained even if the amount of inorganic filler is small compared to a composition comprising a resin other than polyvinyl acetal resin and an inorganic filler. For this reason, the composition of this invention is excellent in heat diffusivity and adhesiveness with a metal plate, a graphite plate, a resin film, etc. with sufficient balance.
本発明の組成物の熱拡散率は０．０５ｍｍ2／ｓ以上であり、好ましくは０．１ｍｍ2／ｓ以上である。
本発明の組成物の熱拡散率が前記範囲にあることで、放熱性に優れる組成物を得ることができる。
なお、本発明の組成物の熱拡散率は、大きければ大きいほどよいため、その上限は、特に制限されないが、１ｍｍ2／ｓであってもよい。
The thermal diffusivity of the composition of the present invention is 0.05 mm 2 / s or more, preferably 0.1 mm 2 / s or more.
The composition excellent in heat dissipation can be obtained because the thermal diffusivity of the composition of this invention exists in the said range.
In addition, since the thermal diffusivity of the composition of this invention is so good that it is large, the upper limit in particular is not restrict | limited, 1 mm < 2 > / s may be sufficient.
本発明の組成物の熱拡散率は、具体的には、下記実施例に記載の方法で測定することができる。 Specifically, the thermal diffusivity of the composition of the present invention can be measured by the method described in the Examples below.
本発明の組成物は、熱拡散性が高いだけでなく、耐熱性も高い点で好ましい。このような耐熱性は、例えば組成物に含まれる前記樹脂（Ｉ）の構成単位ＡのＲとして、鎖長の短いアルキル基を選ぶことによって向上させることができる。特に構成単位Ａ中のＲが水素である場合に最も耐熱性がよい。 The composition of the present invention is preferable in that it has not only high thermal diffusibility but also high heat resistance. Such heat resistance can be improved, for example, by selecting an alkyl group having a short chain length as R of the structural unit A of the resin (I) contained in the composition. In particular, the heat resistance is best when R in the structural unit A is hydrogen.
本発明の組成物を、回路基板などに半導体素子などを実装する際の接着剤として使用する際には、該組成物は、５０℃での粘弾性が１×１０8Ｐａ以上であることが実装条件下での寸法安定性が良好な点で好ましい。
本発明の組成物の粘弾性は、固体粘弾性測定装置により測定されうる。
When the composition of the present invention is used as an adhesive for mounting a semiconductor element or the like on a circuit board or the like, the composition should have a viscoelasticity at 50 ° C. of 1 × 10 8 Pa or more. This is preferable in terms of good dimensional stability under mounting conditions.
The viscoelasticity of the composition of the present invention can be measured by a solid viscoelasticity measuring device.
４．ワニス
本発明のワニスは、前記組成物と溶剤とを含む。
4). Varnish The varnish of the present invention contains the composition and a solvent.
４−１．溶剤
前記溶剤としては、前記樹脂（Ｉ）を溶解できるものであれば特に制限されないが、無機フィラー（ＩＩ）を分散させることができるものであることが好ましく、ケトン系溶媒、エステル系溶媒、芳香族系溶媒、アルコール系溶媒、エーテル系溶媒およびアミド系溶媒からなる群より選ばれる少なくとも１種の溶剤がより好ましい。
4-1. Solvent The solvent is not particularly limited as long as it can dissolve the resin (I), but is preferably one that can disperse the inorganic filler (II), and is preferably a ketone solvent, an ester solvent, an aroma. More preferred is at least one solvent selected from the group consisting of group solvents, alcohol solvents, ether solvents and amide solvents.
前記溶剤としては、具体的に、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｎ−オクタノール、ジアセトンアルコール、ベンジルアルコールなどのアルコール系溶媒；メチルセロソルブ、エチルセロソルブ、ブチルセロソルブなどのセロソルブ系溶媒；アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、イソホロンなどのケトン系溶媒；Ｎ,Ｎ−ジメチルアセトアミド、Ｎ,Ｎ−ジメチルホルムアミド、Ｎ,Ｎ−ジメチルメトキシアセトアミド、１−メチル−２−ピロリドン、ヘキサメチルホスホリルアミドなどのアミド系溶媒；酢酸メチル、酢酸エチルなどのエステル系溶媒；ジオキサン、テトラヒドロフランなどのエーテル系溶媒；ジクロロメタン、メチレンクロライド、クロロホルムなどの塩素化炭化水素系溶媒；トルエン、ピリジン、メシチレン、キシレンなどの芳香族系溶媒；ジメチルスルホン、スルホラン、ジメチルスルホキシド；酢酸；テルピネオール；ブチルカルビトール；ブチルカルビトールアセテート等が挙げられる。 Specific examples of the solvent include alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, n-octanol, diacetone alcohol, benzyl alcohol; methyl cellosolve, ethyl cellosolve Cellosolve solvents such as butyl cellosolve; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, isophorone; N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylmethoxyacetamide, 1-methyl Amide solvents such as 2-pyrrolidone and hexamethylphosphorylamide; Ester solvents such as methyl acetate and ethyl acetate; Ether solvents such as dioxane and tetrahydrofuran; Chlorinated hydrocarbon solvents such as lenchloride and chloroform; aromatic solvents such as toluene, pyridine, mesitylene and xylene; dimethyl sulfone, sulfolane, dimethyl sulfoxide; acetic acid; terpineol; butyl carbitol; butyl carbitol acetate It is done.
５．ワニスの調製方法
本発明のワニスの調製方法は、特に制限されないが、例えば、前記樹脂（Ｉ）を前記溶剤に溶解させ、樹脂溶液を得るステップ、および得られた樹脂溶液に無機フィラー（ＩＩ）を添加して、撹拌するステップを含む方法が好ましい。
5. Method for Preparing Varnish The method for preparing the varnish of the present invention is not particularly limited. For example, a step of dissolving the resin (I) in the solvent to obtain a resin solution, and an inorganic filler (II) in the obtained resin solution A method comprising adding and stirring is preferred.
本発明のワニス中における樹脂固形分濃度は１〜５０重量％であることが好ましく、３〜３０重量％であることがより好ましい。本発明のワニス中における樹脂固形分濃度が前記範囲にあると、後述の撹拌の条件を適切に制御することができる。 The resin solid content concentration in the varnish of the present invention is preferably 1 to 50% by weight, and more preferably 3 to 30% by weight. When the resin solid content concentration in the varnish of the present invention is within the above range, the conditions of stirring described later can be appropriately controlled.
前記樹脂溶液は、粉体で入手できる樹脂（Ｉ）に溶剤を添加して、必要により適切な温度に加温しながら攪拌することで得られる溶液が好ましい。 The resin solution is preferably a solution obtained by adding a solvent to the resin (I) available in powder form and stirring while heating to an appropriate temperature as necessary.
得られた樹脂溶液に添加される無機フィラー（ＩＩ）は、予めシランカップリング剤で処理されていてもよい。無機フィラー（ＩＩ）の処理は任意の方法で行えばよいが、シランカップリング剤を含む水溶液に、無機フィラー（ＩＩ）を添加することでスラリーを得て、該スラリーから水を除去して固形物を得、必要により該固形物をすりつぶして粒子にする方法などが挙げられる。 The inorganic filler (II) added to the obtained resin solution may be previously treated with a silane coupling agent. The treatment of the inorganic filler (II) may be performed by any method, but the slurry is obtained by adding the inorganic filler (II) to the aqueous solution containing the silane coupling agent, and the solid is removed by removing water from the slurry. A method of obtaining a product and, if necessary, grinding the solid to form particles is exemplified.
前記無機フィラー（ＩＩ）を添加したワニスを撹拌することにより、無機フィラー（ＩＩ）をワニス中に分散させることが好ましい。本発明のワニスは、撹拌により、無機フィラー（ＩＩ）の凝集状態または分散状態を制御したものであることが好ましい。具体的には、ワニス中の無機フィラー（ＩＩ）が、２次粒子を形成しているなどのある程度のフレキシビリティを持ってつながっている状態のワニスであることが好ましい。 It is preferable to disperse the inorganic filler (II) in the varnish by stirring the varnish to which the inorganic filler (II) is added. It is preferable that the varnish of this invention controls the aggregation state or dispersion state of inorganic filler (II) by stirring. Specifically, the varnish is preferably in a state where the inorganic filler (II) in the varnish is connected with a certain degree of flexibility such as forming secondary particles.
前記撹拌は、攪拌モーター、らいかい機、三本ロール、ボールミル、自転公転ミル、遊星ミルなど、通常の撹拌機や分散機で行えばよい。撹拌のせん断強度は、１０Ｐａ〜１０００Ｐａとすることが好ましい。撹拌するときのせん断強度が大きすぎると、無機フィラー（ＩＩ）の２次粒子が形成されないことがある。一方、撹拌するときのせん断強度が小さすぎると、無機フィラーの巨大な凝集体が形成されることがあり、得られるワニスからフィルムを形成しにくくなる場合がある。また、撹拌時の温度は特に限定されず、１０〜５０℃にすればよい。 The agitation may be performed with a normal agitator or disperser such as an agitation motor, a raking machine, a three roll, a ball mill, a rotation and revolution mill, or a planetary mill. The shear strength of stirring is preferably 10 Pa to 1000 Pa. If the shear strength when stirring is too large, secondary particles of the inorganic filler (II) may not be formed. On the other hand, if the shear strength when stirring is too small, huge aggregates of inorganic filler may be formed, and it may be difficult to form a film from the resulting varnish. Moreover, the temperature at the time of stirring is not specifically limited, What is necessary is just to be 10-50 degreeC.
６．用途
本発明の組成物やワニスは、導体層の接着に好ましく用いられる。例えば、基材樹脂フィルムと金属箔（好ましくは銅箔）との積層体である回路用基板、放熱基板および部品内蔵基板における、基材樹脂フィルムと金属箔との接着に用いることができる。また、回路用基板等の基材を、本発明の組成物からなるフィルムとしてもよい。
本発明の組成物やワニスから得られる層の厚みは用途に応じて適宜設定されればよく特に制限されないが、０．０５〜２００μｍであることが好ましい。
6). Use The composition and varnish of the present invention are preferably used for adhesion of a conductor layer. For example, it can be used for adhesion between a base resin film and a metal foil in a circuit board, a heat dissipation board, and a component-embedded board that are a laminate of a base resin film and a metal foil (preferably a copper foil). Moreover, base materials, such as a circuit board, are good also as a film which consists of a composition of this invention.
The thickness of the layer obtained from the composition or varnish of the present invention is not particularly limited as long as it is appropriately set depending on the application, but is preferably 0.05 to 200 μm.
本発明の組成物やワニスを導体層の接着に用いる場合には、例えば、該組成物やワニスを被接着体に塗布してもよいし、該組成物やワニスからフィルム成形して、そのフィルムを被接着体に接触させてもよい。フィルムの製造方法としては、例えば、本発明の組成物やワニスを、離型処理されたシートに塗布および固化して、それを剥離してフィルムを得る方法を挙げることができる。
フィルムを用いる場合には、フィルムの厚みは、好ましくは１０〜２００μｍである。
When the composition or varnish of the present invention is used for adhesion of a conductor layer, for example, the composition or varnish may be applied to an adherend, or a film is formed from the composition or varnish, and the film May be brought into contact with the adherend. Examples of the method for producing a film include a method in which the composition or varnish of the present invention is applied to a release-treated sheet and solidified, and then peeled to obtain a film.
When using a film, the thickness of the film is preferably 10 to 200 μm.
前記回路基板などの積層体は、フレキシブル体でも、リジッド体であってもよく、目的に応じて、厚みや、材質を選択して適宜設定される。
また、積層体に含まれる金属箔は、エッチング等でパターニングされて、半導体素子が実装される導体回路となりうる。
The laminate such as the circuit board may be a flexible body or a rigid body, and is appropriately set by selecting a thickness and a material according to the purpose.
Moreover, the metal foil contained in the laminate can be patterned by etching or the like to form a conductor circuit on which a semiconductor element is mounted.
本発明の組成物やワニスから得られる成形体は熱拡散率が高いので、本発明の組成物やワニスを用いて得た回路基板等に素子（ＬＳＩチップなど）などを実装して得られる電子部品において、該電子部品を使用する（電流を流す）際に素子から発生した熱を放散させやすい。このため、本発明の組成物やワニスは、各種半導体チップ、特にパワーデバイス用途などの発熱量の大きい半導体チップを実装する放熱基板の熱拡散性接着材料として好ましく用いられる。 Since a molded product obtained from the composition or varnish of the present invention has a high thermal diffusivity, an electronic device obtained by mounting an element (such as an LSI chip) on a circuit board or the like obtained using the composition or varnish of the present invention. In a component, it is easy to dissipate heat generated from the element when the electronic component is used (current is supplied). For this reason, the composition and varnish of the present invention are preferably used as a heat-diffusing adhesive material for a heat-dissipating substrate for mounting various semiconductor chips, particularly semiconductor chips having a large calorific value for power device applications.
また、本発明の組成物やワニスは、半導体パッケージと放熱部材とを接着する接着剤として好適に使用できる。特に半導体チップがパワーデバイスである場合、該半導体チップを含む装置は熱拡散性に優れる放熱部材を含むことが好ましい。 Moreover, the composition and varnish of this invention can be used conveniently as an adhesive agent which adhere | attaches a semiconductor package and a heat radiating member. In particular, when the semiconductor chip is a power device, the device including the semiconductor chip preferably includes a heat dissipation member having excellent thermal diffusibility.
前記放熱部材の例として、放熱板、ヒートシンクおよび冷却配管が挙げられる。放熱部材は、単独で用いても、複数組み合わせて用いてもよい。
前記放熱板は、熱拡散性に優れた金属板やグラファイト板であれば、特に制限されない。放熱板の例としては、アルミニウム、アルミニウム合金、銅、鉄、ステンレス系合金、インバー系多層金属等からなる金属板または複合積層板が挙げられる。放熱板の厚さは、材質にもよるが、例えば０．０５〜３．０ｍｍ程度である。
Examples of the heat radiating member include a heat radiating plate, a heat sink, and a cooling pipe. The heat dissipating members may be used alone or in combination.
The heat dissipation plate is not particularly limited as long as it is a metal plate or a graphite plate excellent in thermal diffusivity. Examples of the heat radiating plate include a metal plate or a composite laminated plate made of aluminum, aluminum alloy, copper, iron, stainless steel alloy, Invar multilayer metal, or the like. Although the thickness of a heat sink is based also on a material, it is about 0.05-3.0 mm, for example.
また、前記放熱部材は、金属板とグラファイト板とを本発明の組成物を介して積層した積層体であってもよい。 Moreover, the laminated body which laminated | stacked the metal plate and the graphite board through the composition of this invention may be sufficient as the said heat radiating member.
本発明の組成物やワニスを半導体パッケージと放熱部材とを接着する接着剤として使用する場合や放熱部材である積層体の形成に使用する場合、該組成物やワニスを被接着体に塗布、必要により乾燥させて半導体パッケージと放熱部材、金属板とグラファイト板とを接着してもよいし、本発明の組成物やワニスからドライフィルムを形成し、当該フィルムを半導体パッケージと放熱部材との間に配置することで、半導体パッケージと放熱部材、金属板とグラファイト板とを接着してもよい。 When the composition or varnish of the present invention is used as an adhesive for adhering a semiconductor package and a heat radiating member, or when used to form a laminate that is a heat radiating member, the composition or varnish is applied to the adherend. The semiconductor package and the heat radiating member, the metal plate and the graphite plate may be adhered to each other, or a dry film is formed from the composition or varnish of the present invention, and the film is interposed between the semiconductor package and the heat radiating member. By disposing, the semiconductor package and the heat dissipation member, the metal plate and the graphite plate may be bonded.
前記ドライフィルムを用いて半導体パッケージと放熱部材とを接着する温度は、半導体パッケージと放熱部材とを接着できる温度であればよいが、例えば１００〜２００℃程度である。 Although the temperature which adhere | attaches a semiconductor package and a heat radiating member using the said dry film should just be the temperature which can adhere | attach a semiconductor package and a heat radiating member, it is about 100-200 degreeC, for example.
なお、本発明における半導体素子には、各種半導体チップが含まれ、パワーデバイス等も含まれる。
また、本発明におけるパワーデバイスとは、高出力容量のダイオード、トランジスタおよびＩＣ等の、出力容量が１００ＶＡ以上の電力用半導体素子である。
The semiconductor element in the present invention includes various semiconductor chips, and includes power devices and the like.
The power device in the present invention is a power semiconductor element having an output capacity of 100 VA or more, such as a high output capacity diode, transistor, and IC.
以下、実施例を挙げて本発明を説明する。しかし、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the examples.
本発明の実施例に用いた材料は次のとおりである。
＜樹脂＞
・「ＰＶＦ−Ｃ１」：ポリビニルホルマール樹脂、ＪＮＣ（株）製、ビニレック Ｃ（商品名）、ガラス転移点 １１１℃
・「ＰＶＦ−Ｃ２」：ポリビニルホルマール樹脂、ＪＮＣ（株）製、ビニレック Ｃ（商品名）、ガラス転移点 １０４℃
・「ＰＶＦ−Ｌ」：ポリビニルホルマール樹脂、ＪＮＣ（株）製、ビニレック Ｌ（商品名）、ガラス転移点 １０７℃
・「ＰＶＢ」：ポリビニルブチラール樹脂、積水化学工業（株）製、エスレックＢ・Ｋ（ＫＳ） ＢＭ−１（商品名）
・「ＰＭＭＡ」：ポリメチルメタクリレート、（株）三羽研究所製、ＭＡ−８３０ 高分子量タイプ
・「ＰＶＡ」：ポリビニルアルコール、和光純薬工業（株）、試薬特級、けん化度７８〜８２ｍｏｌ％
The materials used in the examples of the present invention are as follows.
<Resin>
・ "PVF-C1": polyvinyl formal resin, manufactured by JNC Corporation, Vinylec C (trade name), glass transition point 111 ° C
・ "PVF-C2": polyvinyl formal resin, manufactured by JNC Corporation, Vinylec C (trade name), glass transition point 104 ° C
"PVF-L": polyvinyl formal resin, manufactured by JNC Corporation, Vinylec L (trade name), glass transition point 107 ° C
・ "PVB": Polyvinyl butyral resin, manufactured by Sekisui Chemical Co., Ltd., S-Rec BK (KS) BM-1 (trade name)
-"PMMA": Polymethylmethacrylate, manufactured by Sanba Laboratory, MA-830 high molecular weight type "PVA": Polyvinyl alcohol, Wako Pure Chemical Industries, Ltd., reagent grade, saponification degree 78-82 mol%
前記「ＰＶＦ−Ｃ１」、「ＰＶＦ−Ｃ２」および「ＰＶＦ−Ｌ」の構造および物性を下記表１に記載する。 The structures and physical properties of the “PVF-C1”, “PVF-C2” and “PVF-L” are shown in Table 1 below.
＜溶剤＞
・「ＮＭＰ」：１−メチル−２−ピロリドン、和光純薬工業（株）製、和光特級
・「シクロペンタノン」：和光純薬工業（株）製、和光一級
<Solvent>
・ “NMP”: 1-methyl-2-pyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade ・ “Cyclopentanone”: manufactured by Wako Pure Chemical Industries, Ltd., Wako First Grade
＜無機フィラー＞
・酸化亜鉛粉：（株）アムテック製、パナテトラ ＷＺ−０５１１（商品名、テトラポット形状、平均径（針の長さ）：約１０μｍ）
・炭化ケイ素粉：（シグマアルドリッチ社、試薬グレード、２００−４５０メッシュ）
・酸化アルミニウム粉：昭和電工（株）製 アルミナ（低ソーダ）ＡＬ−４７−Ｈ（商品名、粒子状、平均径：２．１μｍ）
・窒化アルミニウム粉：(株)トクヤマ製、窒化アルミニウム Ｈグレード（商品名、粒子状、平均径（Ａｌ）：１μｍ）
・コーディエライト：丸ス釉薬合資会社製、ＳＳ−６００
・電融ムライト：太平洋ランダム株式会社製、７０Ｍ
・窒化ホウ素：電気化学工業（株）製、ＳＰ３−７
・チタンブラック：三菱マテリアル（株）製、１３Ｍ−Ｃ
<Inorganic filler>
-Zinc oxide powder: Panatetra WZ-0511 (trade name, tetrapot shape, average diameter (needle length): about 10 μm), manufactured by Amtec Co., Ltd.
Silicon carbide powder: (Sigma Aldrich, reagent grade, 200-450 mesh)
Aluminum oxide powder: Alumina (low soda) AL-47-H manufactured by Showa Denko KK (trade name, particulate, average diameter: 2.1 μm)
・ Aluminum nitride powder: Aluminum nitride H grade (trade name, particulate, average diameter (Al): 1 μm), manufactured by Tokuyama Corporation
-Cordierite: Made by Marusu Shakuyaku limited liability company, SS-600
-Electromelting mullite: 70M made by Taiheiyo Random Co., Ltd.
Boron nitride: manufactured by Electrochemical Industry Co., Ltd., SP3-7
-Titanium black: 13M-C, manufactured by Mitsubishi Materials Corporation
＜熱拡散率の評価＞
下記実施例および比較例で得られた測定用サンプルの、熱拡散率は下記のように求めた。
下記実施例１〜１５および比較例１〜７で得られた測定用サンプルを約９．８ｍｍの正方形の平板に切り抜き、両面にカーボンスプレー（日本船舶工具有限会社製：ＤＧＦ）を塗装した後（膜厚；１μｍ）、ＮＥＴＺＳＣＨ社製、ＬＦＡ−４４７型キセノンフラッシュ熱拡散率測定装置のサンプルホルダーにセットした。該サンプルホルダーが２５℃なった後でキセノンランプを所定の強度でセットした測定用サンプルに照射し、該測定用サンプルのランプ照射面と反対の面からの熱放射強度の時間変化を測定し、付属のソフトウエアで解析することにより、熱拡散率を求めた。検出器のゲインなどの測定条件は自動とし、解析は、アルミニウム箔の熱拡散率が樹脂組成物の熱拡散率に比較して無視できるほど大きいため、測定用サンプルの厚みからアルミニウム箔の厚みを差し引き、樹脂組成物のみの厚みを有する１層の板として熱拡散率を求めた。
<Evaluation of thermal diffusivity>
The thermal diffusivity of the measurement samples obtained in the following examples and comparative examples was determined as follows.
After cutting the measurement samples obtained in Examples 1 to 15 and Comparative Examples 1 to 7 into a square plate of about 9.8 mm, and coating carbon spray (made by Nippon Ship Tool Co., Ltd .: DGF) on both sides ( (Film thickness: 1 μm), set in a sample holder of an LFA-447 type xenon flash thermal diffusivity measuring apparatus manufactured by NETZSCH. After the sample holder reaches 25 ° C., irradiate a measurement sample with a xenon lamp set at a predetermined intensity, measure the temporal change in thermal radiation intensity from the surface opposite to the lamp irradiation surface of the measurement sample, The thermal diffusivity was obtained by analyzing with the attached software. Measurement conditions such as detector gain are automatic, and the analysis shows that the thermal diffusivity of the aluminum foil is negligible compared to the thermal diffusivity of the resin composition. The thermal diffusivity was determined as a single-layer plate having a thickness of only the resin composition.
本発明の組成物の特性の評価はシート形状における熱拡散率を用いて行ったが、シート形状以外、たとえば粒状、塊状、繊維状であっても該組成物の熱特性は変わらない。また、３次元的な加工を行っても熱特性は変わらない。
本測定による熱拡散率が大きいほど発熱源から組成物を通じて外部に放出できる熱量が多いことを示す。
Although the evaluation of the characteristics of the composition of the present invention was performed using the thermal diffusivity in the sheet shape, the thermal characteristics of the composition do not change even if the composition is other than the sheet shape, for example, in the form of granules, lumps, or fibers. Further, the thermal characteristics do not change even when three-dimensional processing is performed.
The larger the thermal diffusivity by this measurement, the more heat that can be released from the heat source to the outside through the composition.
＜実装放熱特性の評価＞
厚み５０μｍ、大きさ４０ｍｍ×４０ｍｍの測定用サンプルのアルミニウム箔面側とセラミックヒーター（坂口電熱（株）製、マイクロセラミックヒーターＭＳ−３）を両面テープ（住友スリーエム（株）製、熱伝導性接着剤転写テープＮｏ．９８８５、１０ｍｍ×１０ｍｍ）を用いて貼り合わせた。セラミックヒーターの測定用サンプルを張り合わせる面の裏面にＫ熱電対（理化工業（株）製、ＳＴ−５０）を取り付け、データロガーを用いてパソコンにてその温度を記録した。貼り合わせ強度はプッシュプルスケールＰＳ−５０Ｎ（(株)イマダ製）で測定したところ４０Ｎ／ｃｍ2であった。このヒーターを取り付けた測定用サンプルを４０℃に設定した恒温槽中央に静置し、セラミックヒーターの温度が４０℃で一定になったことを確認した後、セラミックヒーターに直流安定化電源を用いて１．１Ｖ、電流１．４Ａを印加し、５００秒後および９００秒後のセラミックヒーター表面の温度を測定した。セラミックヒーターは一定の熱量を発生しているので、取り付けてある放熱部材の放熱効果が高いほど、セラミックヒーターの温度は低下する。すなわち、セラミックヒーターの温度が低くなる放熱部材ほど放熱効果が高いといえる。
<Evaluation of mounting heat dissipation characteristics>
Double-sided tape (Sumitomo 3M, manufactured by Sumitomo 3M Co., Ltd.) with aluminum foil surface side of the sample for measurement having a thickness of 50 μm and a size of 40 mm × 40 mm and a ceramic heater (manufactured by Sakaguchi Electric Heat Co., Ltd., Micro Ceramic Heater MS-3) Adhesive transfer tape No. 9885, 10 mm × 10 mm) was used. A K thermocouple (manufactured by Rika Kogyo Co., Ltd., ST-50) was attached to the back surface of the ceramic heater measurement sample, and the temperature was recorded on a personal computer using a data logger. The bonding strength was 40 N / cm 2 when measured with a push-pull scale PS-50N (manufactured by Imada Co., Ltd.). The measurement sample attached with this heater is left in the center of a constant temperature bath set to 40 ° C., and after confirming that the temperature of the ceramic heater is constant at 40 ° C., a DC stabilized power source is used for the ceramic heater. 1.1 V and a current of 1.4 A were applied, and the temperature of the ceramic heater surface after 500 seconds and 900 seconds was measured. Since the ceramic heater generates a certain amount of heat, the higher the heat dissipation effect of the attached heat dissipation member, the lower the temperature of the ceramic heater. That is, it can be said that the heat dissipation member having a lower temperature of the ceramic heater has a higher heat dissipation effect.
＜接着性の評価＞
ＪＩＳ−Ｋ５６００−５−６に記載されたクロスカット法に準じ、縦・横それぞれの方向に２ｍｍ間隔でカッターナイフを用いて測定用サンプルの組成物表面に６本ずつ傷をつけ、計２５の区画を作成し、セロハンテープを貼り付けて引き剥がし、この時に組成物がアルミニウム箔から剥離する程度を観察した。
評価はＪＩＳ−Ｋ５６００−５−６に従って結果を０（良好）〜５（不良）の段階に分類した。また、剥離した区画の数ｘを「ｘ／２５」と示す。
<Evaluation of adhesiveness>
According to the cross-cut method described in JIS-K5600-5-6, the composition surface of the sample for measurement was scratched 6 by 6 using a cutter knife at intervals of 2 mm in both the vertical and horizontal directions. A compartment was created, and a cellophane tape was applied and peeled off. At this time, the degree to which the composition peeled from the aluminum foil was observed.
Evaluation was classified according to JIS-K5600-5-6, from 0 (good) to 5 (bad). Further, the number x of the separated sections is indicated as “x / 25”.
＜耐熱性の評価＞
作成した測定用サンプルをアルミニウム箔ごと直径６ｍｍに切り抜き、パーキンエルマー社製、ダイアモンドＤＳＣでガラス転移点を測定して耐熱性を評価した。昇降温速度は１０℃/min、降温時の変曲点と低温側ベースラインの交点をガラス転移点（Ｔｇ）として算出した。ガラス転移点（Ｔｇ）が低い素材の場合、熱によって容易に軟化・溶融してしまうため、これらの温度が高いほど熱に対して安定な素材である。
<Evaluation of heat resistance>
The prepared measurement sample was cut out to a diameter of 6 mm together with the aluminum foil, and the glass transition point was measured by Diamond DSC manufactured by Perkin Elmer Co., Ltd. to evaluate the heat resistance. The temperature increase / decrease rate was 10 ° C./min, and the intersection of the inflection point and the low temperature side baseline at the time of temperature decrease was calculated as the glass transition point (Tg). In the case of a material having a low glass transition point (Tg), since it is easily softened and melted by heat, the higher the temperature, the more stable the material against heat.
［実施例１］
２００ｍｌの三つ口フラスコにＮＭＰを８０ｇ入れ、フッ素樹脂製の攪拌羽根を上部からセットし、モーターにより攪拌羽根を回転させた。回転数はワニスの粘度により適時調節した。このフラスコにガラス製の漏斗を用いてポリビニルホルマール樹脂（ＰＶＦ−Ｃ１）を１０ｇ投入した。漏斗に付着したＰＶＦ−Ｃ１を２０ｇのＮＭＰで洗い流した後、漏斗を取り外し、ガラス栓をした。得られた溶液を８０℃に設定したウォーターバスで４時間攪拌しながら加熱し、ＰＶＦ−Ｃ１をＮＭＰに完全に溶解させた。攪拌後のフラスコをウォーターバスから取り出し、室温に戻した後、無機フィラーとして酸化亜鉛粉を乾燥した漏斗を用いて４２．８ｇ投入し、一夜攪拌することで、ワニスを得た。
[Example 1]
80 g of NMP was put into a 200 ml three-necked flask, a stirring blade made of fluororesin was set from above, and the stirring blade was rotated by a motor. The number of revolutions was adjusted as appropriate according to the viscosity of the varnish. 10 g of polyvinyl formal resin (PVF-C1) was charged into the flask using a glass funnel. After the PVF-C1 adhering to the funnel was washed away with 20 g of NMP, the funnel was removed and a glass stopper was attached. The obtained solution was heated with stirring in a water bath set at 80 ° C. for 4 hours to completely dissolve PVF-C1 in NMP. The flask after stirring was taken out from the water bath and returned to room temperature, and then 42.8 g was charged using a funnel dried with zinc oxide powder as an inorganic filler, and stirred overnight to obtain a varnish.
得られたワニスを、アルミニウム箔(厚み５０μｍ)上にキャストし、得られた塗膜を１３０℃で３０分間乾燥させて、溶剤を除去することで、アルミニウム箔付フィルム状の樹脂組成物（測定用サンプル）を作成した。 The obtained varnish was cast on an aluminum foil (thickness 50 μm), and the resulting coating film was dried at 130 ° C. for 30 minutes to remove the solvent, thereby removing the solvent from the film-like resin composition with aluminum foil (measurement) Sample).
［実施例２〜１５］
樹脂の種類、無機フィラーの種類、無機フィラーの添加量を表２に示すように変更した以外は実施例１と同様にしてワニスおよび測定用サンプルを調製した。
[Examples 2 to 15]
A varnish and a measurement sample were prepared in the same manner as in Example 1 except that the resin type, inorganic filler type, and inorganic filler addition amount were changed as shown in Table 2.
［比較例１］
無機フィラーを添加しない以外は実施例１と同様にしてワニスおよび測定用サンプルを調製した。
[Comparative Example 1]
A varnish and a measurement sample were prepared in the same manner as in Example 1 except that the inorganic filler was not added.
［比較例２］
無機フィラーを添加せず、樹脂としてＰＶＦ−Ｃ２を用いた以外は実施例１と同様にして、ワニスおよび測定用サンプルを調製した。
[Comparative Example 2]
A varnish and a measurement sample were prepared in the same manner as in Example 1 except that PVF-C2 was used as a resin without adding an inorganic filler.
［比較例３〜４］
樹脂としてＰＶＦ−ＬまたはＰＶＢを用いた以外は比較例２と同様にして、ワニスおよび測定用サンプルを調製した。
[Comparative Examples 3 to 4]
A varnish and a measurement sample were prepared in the same manner as in Comparative Example 2 except that PVF-L or PVB was used as the resin.
［比較例５〜６］
樹脂としてＰＭＭＡまたはＰＶＡを用い、フィラーとして酸化アルミニウム粉を用いた以外は実施例１と同様にして、ワニスおよび測定用サンプルを調製した。
[Comparative Examples 5-6]
A varnish and a measurement sample were prepared in the same manner as in Example 1 except that PMMA or PVA was used as the resin and aluminum oxide powder was used as the filler.
［比較例７］
三つ口フラスコにシクロペンタノン（４５ｇ）に入れ、フッ素樹脂製の攪拌羽根を上部からセットし、モーターにより攪拌羽根を回転させた。回転数はワニスの粘度により適時調節した。このフラスコにガラス製の漏斗を用いてＰＶＢ（２．２７３ｇ）、クレゾールノボラックエポキシ樹脂（ＤＩＣ社製、エピクロン Ｎ−６６０、エポキシ当量 ２０２〜２１２；１．７７３ｇ）、フェノールノボラック樹脂（ＤＩＣ社製、フェノライト ＴＤ−２０９０、水酸基当量 １０５；０．９４１ｇ）、およびトリフェニルホスフィン（０．０１４ｇ）を投入した。得られた液（混合物Ａとシクロペンタノンの混合物）を８０℃に設定したウォーターバスで４時間攪拌しながら加熱し、固形分をシクロペンタノンに完全に溶解させて溶液を得た。
攪拌後のフラスコをウォーターバスから取り出し、室温に戻した。得られた溶液に、混合物Ａの固形分濃度が１０重量％となるようにシクロペンタノンを加え、得られた液（３．２５２ｇ）に窒化ホウ素を（０．０１６７ｇ）添加してさらに２時間攪拌しＰＶＢ１００重量％に対して窒化ホウ素１２重量％のワニスを調製した。
[Comparative Example 7]
Cyclopentanone (45 g) was placed in a three-necked flask, a fluororesin stirring blade was set from above, and the stirring blade was rotated by a motor. The number of revolutions was adjusted as appropriate according to the viscosity of the varnish. Using a glass funnel, PVB (2.273 g), cresol novolac epoxy resin (manufactured by DIC, Epicron N-660, epoxy equivalent 202-212; 1.773 g), phenol novolac resin (manufactured by DIC, Phenolite TD-2090, hydroxyl equivalent 105 (0.941 g), and triphenylphosphine (0.014 g) were added. The obtained liquid (mixture of mixture A and cyclopentanone) was heated with stirring in a water bath set at 80 ° C. for 4 hours, and the solid content was completely dissolved in cyclopentanone to obtain a solution.
The stirred flask was removed from the water bath and returned to room temperature. Cyclopentanone is added to the obtained solution so that the solid content concentration of the mixture A becomes 10% by weight, and boron nitride (0.0167 g) is added to the obtained liquid (3.252 g), and further 2 hours. The mixture was stirred to prepare a varnish of 12% by weight of boron nitride based on 100% by weight of PVB.
次に、得られたワニスをアルミニウム箔(厚み５０μｍ)上にキャストして得られた塗膜を８０℃で３０分間、続いて１２０℃で３０分、さらに１８０℃で２時間乾燥させて、溶剤を除去することで、アルミニウム箔付フィルム状の樹脂組成物（測定用サンプル）を調製した。 Next, the coating film obtained by casting the obtained varnish on an aluminum foil (thickness 50 μm) was dried at 80 ° C. for 30 minutes, then at 120 ° C. for 30 minutes, and further at 180 ° C. for 2 hours to obtain a solvent. The film-like resin composition with aluminum foil (sample for measurement) was prepared by removing.
下記表２に実施例１〜１５および比較例１〜７で調製した樹脂組成物の構成、熱拡散率および接着性の評価結果を示す。 Table 2 below shows the composition, thermal diffusivity and adhesion evaluation results of the resin compositions prepared in Examples 1 to 15 and Comparative Examples 1 to 7.
実施例で得られる樹脂組成物は、比較例１、２、３、４および７で得られた組成物よりも良好な熱拡散率（０．１ｍｍ2／ｓ以上）を有することがわかる。 It can be seen that the resin compositions obtained in the examples have better thermal diffusivity (0.1 mm 2 / s or more) than the compositions obtained in Comparative Examples 1, 2, 3, 4 and 7.
実施例１０で得られた樹脂組成物は、汎用の酸化アルミニウムを用いても、熱拡散率は大となった。
従来の樹脂を使用した場合、無機フィラーの含有量が８０体積％では、均一なキャスト成形すら難しいと考えられる。
このような実施例１０で得られる樹脂組成物は、他の部材等で該樹脂組成物をコーティングして用いる、該組成物を圧着して用いるなどの用途で好適に用いられる。
The resin composition obtained in Example 10 had a large thermal diffusivity even when a general-purpose aluminum oxide was used.
When a conventional resin is used, it is considered that even uniform casting is difficult when the inorganic filler content is 80% by volume.
The resin composition obtained in Example 10 is suitably used for applications such as coating the resin composition with another member or the like, or using the composition by pressure bonding.
下記表３に実施例８、１３、１４で作成した測定用サンプルと該測定用サンプルの調製に使用したアルミニウム箔の実装放熱特性の測定結果を示す。 Table 3 below shows the measurement results of the mounting heat dissipation characteristics of the measurement samples prepared in Examples 8, 13, and 14 and the aluminum foil used for the preparation of the measurement samples.
実施例８、１３、１４とアルミ箔の実装放熱特性測定の結果、実施例８、１３、１４の測定用サンプルは、トランジスタの温度を未処理のアルミ箔に比較して１０℃近く低下させた。 As a result of measuring the mounting heat dissipation characteristics of Examples 8, 13, and 14 and the aluminum foil, the measurement samples of Examples 8, 13, and 14 lowered the temperature of the transistor by nearly 10 ° C. compared to the untreated aluminum foil. .
下記表４に実施例４で作成した樹脂組成物および比較例５、６で作成した樹脂組成物のガラス転移点を示す。 Table 4 below shows the glass transition points of the resin composition prepared in Example 4 and the resin compositions prepared in Comparative Examples 5 and 6.
実施例４と比較例５および６の測定用サンプルのＤＳＣ測定の結果から、実施例４の測定用サンプルは比較例５および６の測定用サンプルに比較して高いガラス転移点を有し、物理的耐熱性が高いと言える。 From the results of DSC measurement of the measurement samples of Example 4 and Comparative Examples 5 and 6, the measurement sample of Example 4 has a higher glass transition point than the measurement samples of Comparative Examples 5 and 6, and It can be said that the heat resistance is high.
本発明の組成物は、電子機器、モーター、バッテリー、照明等の発熱するデバイスの熱源から放熱機構までの伝熱パスにおいて接着剤として用いることができる。具体的には、例えば、回路用基板、放熱基板、部品内蔵基板、ヒートシンク等に適用されうる。また、放熱、均熱特性を示す金属板とグラファイト板とを積層した放熱部材を形成するための接着剤などとしても使用できる。 The composition of the present invention can be used as an adhesive in a heat transfer path from a heat source of a device that generates heat such as an electronic device, a motor, a battery, and a lighting to a heat dissipation mechanism. Specifically, for example, it can be applied to a circuit board, a heat dissipation board, a component built-in board, a heat sink, and the like. Further, it can be used as an adhesive for forming a heat dissipation member in which a metal plate exhibiting heat dissipation and soaking characteristics and a graphite plate are laminated.
Claims (13)
前記ポリビニルアセタール樹脂（Ｉ）が、下記構成単位Ａ、ＢおよびＣを有し、
前記組成物１００体積％に対し、前記無機フィラー（ＩＩ）を５〜８５体積％含む、熱可塑性である熱拡散性樹脂組成物。
The polyvinyl acetal resin (I) has the following structural units A, B and C,
A heat-diffusing resin composition that is thermoplastic and contains 5 to 85% by volume of the inorganic filler (II) with respect to 100% by volume of the composition.
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| JP2012000241A JP2012136022A (en) | 2012-01-04 | 2012-01-04 | Heat dissipating member, electronic device and battery |
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| JP2012114814A JP5920011B2 (en) | 2012-01-04 | 2012-05-18 | Thermally diffusible resin composition and varnish containing the composition |
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| JP2012102712A Active JP6136104B2 (en) | 2012-01-04 | 2012-04-27 | Heat dissipation member, electronic device and battery |
| JP2012114814A Active JP5920011B2 (en) | 2012-01-04 | 2012-05-18 | Thermally diffusible resin composition and varnish containing the composition |
| JP2012281105A Expired - Fee Related JP6212858B2 (en) | 2012-01-04 | 2012-12-25 | Heat dissipation member, electronic device and battery |
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| WO2019230969A1 (en) * | 2018-05-31 | 2019-12-05 | 積水化学工業株式会社 | Heat dissipation composition, heat dissipation member, and filler aggregate for heat dissipation member |
| WO2020189644A1 (en) * | 2019-03-18 | 2020-09-24 | 積水化学工業株式会社 | Dispersant for fillers and dispersion liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013157590A (en) | 2013-08-15 |
| JP2012136022A (en) | 2012-07-19 |
| TWI566947B (en) | 2017-01-21 |
| JP5920011B2 (en) | 2016-05-18 |
| JP6212858B2 (en) | 2017-10-18 |
| TW201328882A (en) | 2013-07-16 |
| JP6136104B2 (en) | 2017-05-31 |
| JP2017130670A (en) | 2017-07-27 |
| JP2013157599A (en) | 2013-08-15 |
| JP6168250B2 (en) | 2017-07-26 |
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