JP2014118484A - Thermal conductive silicone composition and thermal conductive member - Google Patents
Thermal conductive silicone composition and thermal conductive member Download PDFInfo
- Publication number
- JP2014118484A JP2014118484A JP2012274714A JP2012274714A JP2014118484A JP 2014118484 A JP2014118484 A JP 2014118484A JP 2012274714 A JP2012274714 A JP 2012274714A JP 2012274714 A JP2012274714 A JP 2012274714A JP 2014118484 A JP2014118484 A JP 2014118484A
- Authority
- JP
- Japan
- Prior art keywords
- component
- conductive silicone
- thermally conductive
- group
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 49
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000011231 conductive filler Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 8
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000012756 surface treatment agent Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 abstract description 33
- 239000004945 silicone rubber Substances 0.000 abstract description 33
- 239000000463 material Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000004382 potting Methods 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 3
- -1 alkyl titanate Chemical compound 0.000 description 72
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 239000000843 powder Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 19
- 239000010419 fine particle Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000005375 organosiloxane group Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- KSLSOBUAIFEGLT-UHFFFAOYSA-N 2-phenylbut-3-yn-2-ol Chemical compound C#CC(O)(C)C1=CC=CC=C1 KSLSOBUAIFEGLT-UHFFFAOYSA-N 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- RYUYSSZLUKUHNY-UHFFFAOYSA-N C(C1CO1)OC1=C(NC=C1)[Si](OC)(OC)OC Chemical compound C(C1CO1)OC1=C(NC=C1)[Si](OC)(OC)OC RYUYSSZLUKUHNY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N trimethylsilyl-trifluoromethansulfonate Natural products C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 description 1
- GRGVQLWQXHFRHO-AATRIKPKSA-N (e)-3-methylpent-3-en-1-yne Chemical compound C\C=C(/C)C#C GRGVQLWQXHFRHO-AATRIKPKSA-N 0.000 description 1
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- PFRLCKFENIXNMM-UHFFFAOYSA-N 3-trimethylsilylpropan-1-amine Chemical compound C[Si](C)(C)CCCN PFRLCKFENIXNMM-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- YZUYFNRZWIATPR-UHFFFAOYSA-H [OH-].[Mg+2].[C+4].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Mg+2].[C+4].[OH-].[OH-].[OH-].[OH-].[OH-] YZUYFNRZWIATPR-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、熱伝導性シリコーン組成物及びそれを硬化させた熱伝導性部材に関する。 The present invention relates to a thermally conductive silicone composition and a thermally conductive member obtained by curing the composition.
近年、トランジスター、ＩＣ、及びメモリー素子等の電子部品を搭載したプリント回路基板やハイブリッドＩＣの高密度・高集積化にともなって、これらを効率よく放熱するために各種の熱伝導性シリコーンゴム組成物が使用されている。このような熱伝導性シリコーンゴム組成物としては、ビニル基含有オルガノポリシロキサン、オルガノハイドロジェンポリシロキサン、アルミナ、石英粉末、マグネシア、窒化ホウ素、及び炭化ケイ素から選択される熱伝導性充填剤、アミノシラン、エポキシシラン、及びアルキルチタネートから選択される接着性付与剤、並びに白金系触媒からなる熱伝導性シリコーンゴム組成物（特開昭６１−１５７５６９号公報）、一分子中に脂肪族不飽和基を少なくとも０．１モル％含有するオルガノポリシロキサン、一分子中にケイ素原子に結合した水素原子を少なくとも２個有するオルガノハイドロジェンポリシロキサン、平均粒子径が１０〜５０μｍである球状アルミナ微粉末と平均粒子径が１０μｍ未満である球状又は非球状のアルミナ微粉末、及び白金又は白金系化合物からなる熱伝導性シリコーンゴム組成物（特開昭６３−２５１４６６号公報）、アルケニル基含有オルガノポリシロキサン、オルガノハイドロジェンポリシロキサン、平均粒子径が０．１〜５μｍである無定形アルミナ微粉末と平均粒子径が５〜５０μｍである球状アルミナ微粉末、及び白金系触媒からなる熱伝導性シリコーンゴム組成物（特開平０２−０４１３６２号公報）、一分子中にアルケニル基を平均して０．５個以上含んでいるアルケニル基含有オルガノポリシロキサン、一分子中にケイ素原子に結合した水素原子を少なくとも２個含んでなるオルガノハイドロジェンポリシロキサン、平均粒子径が５０μｍ以下であり、長短径比が１．０〜１．４である高純度のアルミナ微粉末、及び白金系触媒からなる熱伝導性シリコーンゴム組成物（特開平０５−１０５８１４号公報）が提案されている。 In recent years, various thermal conductive silicone rubber compositions have been developed to efficiently dissipate heat as printed circuit boards and hybrid ICs equipped with electronic components such as transistors, ICs, and memory devices have become dense and highly integrated. Is used. Examples of such a heat conductive silicone rubber composition include vinyl group-containing organopolysiloxane, organohydrogenpolysiloxane, alumina, quartz powder, magnesia, boron nitride, and silicon carbide. , An epoxy silane, and an alkyl titanate, and a thermally conductive silicone rubber composition comprising a platinum-based catalyst (JP-A-61-157569), an aliphatic unsaturated group in one molecule Organopolysiloxane containing at least 0.1 mol%, organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, spherical alumina fine powder having an average particle size of 10 to 50 μm and average particles Spherical or non-spherical alumina fine powder having a diameter of less than 10 μm And a thermally conductive silicone rubber composition (Japanese Unexamined Patent Publication No. 63-251466) comprising platinum or a platinum-based compound, an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, having an average particle size of 0.1 to 5 μm A thermally conductive silicone rubber composition (Japanese Patent Laid-Open No. 02-041362) comprising a certain amorphous alumina fine powder, a spherical alumina fine powder having an average particle diameter of 5 to 50 μm, and a platinum-based catalyst, an alkenyl group in one molecule Alkenyl group-containing organopolysiloxane containing 0.5 or more on average, organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule, and having an average particle size of 50 μm or less And a high-purity alumina fine powder having a major axis to minor axis ratio of 1.0 to 1.4, and a platinum-based catalyst. Thermally conductive silicone rubber composition (Japanese Unexamined Patent Publication No. 05-105814) have been proposed.
しかし、これらの熱伝導性シリコーンゴム組成物は、硬化途上で該組成物から揮発する低沸分や該組成物からブリードアウトするオイル分により、周囲の基材を汚染するという問題があった。また、熱伝導性部材として硬化して用いた場合に基材との密着性が悪いという問題があった。更に、硬化物にクラックが発生し、硬化物が破壊してしまうという問題があった。 However, these thermally conductive silicone rubber compositions have a problem that the surrounding base material is contaminated by a low boiling point component that volatilizes from the composition during curing or an oil component that bleeds out from the composition. In addition, when used as a thermally conductive member, there is a problem of poor adhesion to the substrate. Furthermore, there was a problem that cracks occurred in the cured product and the cured product was destroyed.
これに対し、一分子中に少なくとも２個のケイ素原子結合アルケニル基を有し、ケイ素原子結合の水酸基及びアルコキシ基を有しない、４量体〜２０量体の環状シロキサンの含有量が質量単位が１，０００ｐｐｍ以下であるオルガノポリシロキサン、一分子中に少なくとも２個のケイ素原子結合水素原子を有し、ケイ素原子結合のアルケニル基、水酸基及びアルコキシ基を有しないオルガノポリシロキサン、接着性付与剤、熱伝導性充填剤、及びヒドロシリル化反応用触媒からなる熱伝導性シリコーン組成物（特開２０１１−１５３２５２号公報）が提案されている。 On the other hand, the content of the cyclic siloxane of a tetramer to a 20-mer having at least two silicon-bonded alkenyl groups in one molecule and having no silicon-bonded hydroxyl group and alkoxy group is a mass unit. Organopolysiloxane having 1,000 ppm or less, organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and having no silicon-bonded alkenyl group, hydroxyl group and alkoxy group, an adhesion-imparting agent, A thermally conductive silicone composition (Japanese Patent Laid-Open No. 2011-153252) comprising a thermally conductive filler and a hydrosilylation reaction catalyst has been proposed.
しかし、この熱伝導性シリコーン組成物においても、熱伝導性部材として硬化して用いた場合に基材との密着性が悪く、硬化物にクラックが発生してしまい、硬化物が破壊してしまうという問題があった。 However, even in this thermally conductive silicone composition, when cured and used as a thermally conductive member, the adhesion to the substrate is poor, cracks occur in the cured product, and the cured product is destroyed. There was a problem.
本発明は上記課題を解決すべくなされたものであり、熱伝導性部材、特に電子材料のポッティング剤等として用いた場合に、基材への密着性に優れ、クラックを有しない硬化物を与える熱伝導性シリコーン組成物、及びそれを硬化させた熱伝導性部材を提供することにある。 The present invention has been made to solve the above-mentioned problems, and when used as a heat conductive member, particularly as a potting agent for electronic materials, provides a cured product having excellent adhesion to a substrate and having no cracks. It is providing the heat conductive silicone composition and the heat conductive member which hardened it.
本発明者らは上記の課題について鋭意検討した結果、本発明に到達した。すなわち、本発明の目的は、（Ａ）２５０℃で３０分間保持した前後の熱重量分析（ＴＧＡ）による質量変化が４．０質量％未満である、水酸化アルミニウム又は酸化マグネシウムの熱伝導性充填剤を含む、熱伝導性シリコーンゴム組成物によって達成される。 As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is, the object of the present invention is (A) Thermally conductive filling of aluminum hydroxide or magnesium oxide whose mass change by thermogravimetric analysis (TGA) before and after holding at 250 ° C. for 30 minutes is less than 4.0% by mass This is achieved by a thermally conductive silicone rubber composition containing an agent.
本発明の熱伝導性シリコーンゴム組成物は、
（Ｂ）一分子中に少なくとも２個のケイ素原子結合アルケニル基を有するオルガノポリシロキサン、
（Ｃ）一分子中に少なくとも２個のケイ素原子結合水素原子を有し、ケイ素原子結合アルケニル基、水酸基及びアルコキシを有しないオルガノポリシロキサン、及び
（Ｄ）ヒドロシリル化反応用触媒
を更に含むことが好ましい。
The thermally conductive silicone rubber composition of the present invention is
(B) an organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule;
(C) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and having no silicon-bonded alkenyl group, hydroxyl group and alkoxy, and (D) a catalyst for hydrosilylation reaction. preferable.
前記（Ｂ）成分は、分子鎖両末端にケイ素原子結合アルケニル基を有するオルガノポリシロキサンであることが好ましい。 The component (B) is preferably an organopolysiloxane having silicon-bonded alkenyl groups at both ends of the molecular chain.
前記（Ａ）成分の含有量は、（Ｂ）成分１００質量部に対して１００〜２，０００質量部であることが好ましい。 The content of the component (A) is preferably 100 to 2,000 parts by mass with respect to 100 parts by mass of the component (B).
前記（Ｃ）成分の含有量は、前記（Ｂ）成分中のアルケニル基１モルに対してケイ素原子結合水素原子が０．５〜１０モルとなる量であることが好ましい。 The content of the component (C) is preferably such that silicon-bonded hydrogen atoms are 0.5 to 10 moles per mole of the alkenyl group in the component (B).
本発明の熱伝導性シリコーン組成物は、（Ｅ）接着付与剤を更に含むことができる。 The heat conductive silicone composition of this invention can further contain (E) adhesion imparting agent.
前記（Ｃ）成分と前記（Ｅ）成分との合計量は、前記（Ｂ）成分と前記（Ｃ）成分と前記（Ｅ）成分との合計量に対して、０．５〜１０質量％であることが好ましい。 The total amount of the component (C) and the component (E) is 0.5 to 10% by mass with respect to the total amount of the component (B), the component (C), and the component (E). Preferably there is.
本発明の熱伝導性シリコーン組成物は、（Ｆ）（Ａ）成分以外の熱伝導性充填剤を更に含むことができる。 The heat conductive silicone composition of this invention can further contain heat conductive fillers other than (F) (A) component.
前記（Ａ）成分と（Ｆ）成分のいずれか１つの成分、又は両方の成分は、ケイ素表面処理剤によって表面処理されていることが好ましい。 It is preferable that any one component of the said (A) component and (F) component, or both components are surface-treated with the silicon surface treating agent.
また、本発明は、前記熱伝導性シリコーン組成物を硬化させた熱伝導性部材にも関する。 The present invention also relates to a heat conductive member obtained by curing the heat conductive silicone composition.
本発明の熱伝導性シリコーン組成物は、熱伝導性部材、特に電子材料のポッティング剤等として用いた場合に、基材への密着性に優れ、クラックを有しない硬化物を得ることができるという特徴がある。また、本発明の熱伝導性シリコーン組成物を用いて製造した放熱材料は、熱伝導性に優れ、不良品が少ないという特徴を有する。 When the heat conductive silicone composition of the present invention is used as a heat conductive member, particularly as a potting agent for electronic materials, it is possible to obtain a cured product having excellent adhesion to a substrate and having no cracks. There are features. Moreover, the heat dissipation material manufactured using the heat conductive silicone composition of this invention has the characteristics that it is excellent in heat conductivity and there are few inferior goods.
（Ａ）成分は本組成物に熱伝導性を付与するための熱伝導性充填剤であり、２５０℃で３０分間保持した前後の熱重量分析（ＴＧＡ）による質量変化が４．０質量％未満である、水酸化アルミニウム又は酸化マグネシウムである。（Ａ）成分は、水酸化アルミニウムであることが好ましい。一方、質量変化が４．０質量％以上であるものを用いた場合、得られる熱伝導性シリコーンゴムの高温安定性が悪化し、基材への密着不良や、クラック等の硬化物の破壊が発生し、得られる放熱材料の品質不良品につながるため、好ましくない。 Component (A) is a thermally conductive filler for imparting thermal conductivity to the composition, and its mass change by thermogravimetric analysis (TGA) before and after being held at 250 ° C. for 30 minutes is less than 4.0% by mass. Is aluminum hydroxide or magnesium oxide. The component (A) is preferably aluminum hydroxide. On the other hand, when a material having a mass change of 4.0% by mass or more is used, the high temperature stability of the obtained heat conductive silicone rubber is deteriorated, resulting in poor adhesion to the substrate and destruction of a cured product such as a crack. This is not preferable because it is generated and leads to defective quality of the obtained heat dissipation material.
（Ａ）成分の形状は特に限定されないが、例えば、球状、針状、円盤状、棒状、及び不定形状が挙げられ、好ましくは、球状又は不定形状である。また、（Ａ）成分の平均粒子径は限定されないが、顕微鏡観察又はレーザー回折散乱式粒度分布測定装置を用いて測定して、好ましくは、０．０１〜１００μｍの範囲内であり、より好ましくは、０．０１〜５０μｍの範囲内、特に好ましくは０．５〜２５μｍの範囲内である。 Although the shape of (A) component is not specifically limited, For example, spherical shape, needle shape, disk shape, rod shape, and indefinite shape are mentioned, Preferably it is spherical shape or indefinite shape. Moreover, although the average particle diameter of (A) component is not limited, Preferably it is in the range of 0.01-100 micrometers, as measured using a microscope observation or a laser diffraction scattering type particle size distribution measuring apparatus, More preferably , In the range of 0.01 to 50 μm, particularly preferably in the range of 0.5 to 25 μm.
また、本組成物において、（Ａ）成分はケイ素系表面処理剤により表面処理されていることが好ましい。このケイ素系表面処理剤としては、例えば、メチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、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、及び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等のアルコキシシラン；メチルトリクロルシラン、ジメチルジクロルシラン、及びトリメチルモノクロルシラン等のクロロシラン；ヘキサメチルジシラザン及びヘキサメチルシクロトリシラザン等のシラザン；並びに分子鎖両末端シラノール基封鎖ジメチルシロキサンオリゴマー、分子鎖両末端シラノール基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体オリゴマー、分子鎖両末端シラノール基封鎖メチルビニルシロキサンオリゴマー、及び分子鎖両末端シラノール基封鎖メチルフェニルシロキサンオリゴマー等のシロキサンオリゴマーが挙げられる。 In the present composition, the component (A) is preferably surface-treated with a silicon-based surface treatment agent. Examples of the silicon-based surface treatment agent include methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethylsilane. Alkoxysilanes such as methoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane; Silazanes such as hexamethyldisilazane and hexamethylcyclotrisilazane; and silanol-blocked dimethylsiloxane oligomers at both ends of the molecular chain, and dimethylsiloxane / methylvinylsilo blocked at both ends of the molecular chain San copolymer oligomer capped at both molecular terminals with silanol groups methylvinylsiloxane oligomer, and siloxane oligomers such capped at both molecular terminals with silanol groups methylphenylsiloxane oligomer and the like.
これらの表面処理方法としては、例えば、（Ａ）成分とケイ素系表面処理剤を直接混合して処理する方法（乾式処理方法）、ケイ素系表面処理剤をトルエン、メタノール、及びヘプタン等の有機溶剤と共に（Ａ）成分と混合して処理する方法（湿式処理方法）、並びに（Ｂ）成分とケイ素系表面処理剤との混合物中に（Ａ）成分を配合するか、又は、（Ｂ）成分と（Ａ）成分の混合物中にケイ素系表面処理剤を配合して（Ａ）成分の表面を処理する方法（ｉｎ−ｓｉｔｕ処理方法）が挙げられる。 As these surface treatment methods, for example, a method of directly mixing (A) component and a silicon-based surface treatment agent (dry treatment method), the silicon-based surface treatment agent is an organic solvent such as toluene, methanol, and heptane. And (A) component in a mixture of component (A) and processing (wet treatment method), and (B) component and silicon-based surface treatment agent, or (B) component and (A) The method (in-situ processing method) which mix | blends a silicon type surface treating agent in the mixture of a component, and processes the surface of (A) component is mentioned.
（Ａ）成分は、市販の水酸化アルミニウム又は酸化マグネシウムであって、本発明に規定する質量変化特性を有するものを選択することで得られる（例えば、住友化学社製 ＣＷＬ３２５ＬＶ等）ほか、例えば市販の水酸化アルミニウム又は酸化マグネシウムを熱処理することによって得ることができる。熱処理の条件は特に限定されないが、不活性ガス又は真空中、１００〜５００℃で処理することが好ましく、１５０℃から３００℃で処理することがより好ましい。不活性ガスとしては、窒素、ヘリウム、及びアルゴンが例示される。なお、この不活性ガス中に、水素ガス等の還元性ガスを含んでもよい。熱処理時間も特に限定されるものではないが、例えば、１０分〜１０時間、好ましくは３０分〜５時間の範囲とすることができる。 The component (A) is commercially available aluminum hydroxide or magnesium oxide, which can be obtained by selecting one having the mass change characteristic defined in the present invention (for example, CWL325LV manufactured by Sumitomo Chemical Co., Ltd.). It can be obtained by heat-treating aluminum hydroxide or magnesium oxide. Although the heat treatment conditions are not particularly limited, the treatment is preferably performed at 100 to 500 ° C. in an inert gas or vacuum, and more preferably at 150 to 300 ° C. Nitrogen, helium, and argon are illustrated as an inert gas. The inert gas may contain a reducing gas such as hydrogen gas. The heat treatment time is not particularly limited, but can be, for example, in the range of 10 minutes to 10 hours, preferably 30 minutes to 5 hours.
（Ａ）成分の含有量は（Ｂ）成分１００質量部に対して１００〜２，０００質量部の範囲内であり、好ましくは２００〜１，６００質量部の範囲内である。これは、（Ａ）成分の含有量が上記範囲の下限以上であると、得られるシリコーンゴムの熱伝導性が良好となるからであり、一方、上記範囲の上限以下であると、得られる組成物の取扱作業性が良好となるからである。 (A) Content of a component exists in the range of 100-2,000 mass parts with respect to 100 mass parts of (B) component, Preferably it exists in the range of 200-1,600 mass parts. This is because the thermal conductivity of the resulting silicone rubber is good when the content of the component (A) is at least the lower limit of the above range, and on the other hand, the composition obtained when it is below the upper limit of the above range. This is because the handling workability of the object is improved.
（Ｂ）成分のオルガノポリシロキサンは本組成物の主剤であり、一分子中に少なくとも２個のケイ素原子結合アルケニル基を有するものである。（Ｂ）成分中のケイ素原子結合アルケニル基としては、例えば、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、及びヘプテニル基が挙げられ、特に、ビニル基が好ましい。（Ｂ）成分中のアルケニル基以外のケイ素原子結合有機基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、及びヘプチル基等のアルキル基；フェニル基、トリル基、キシリル基、及びナフチル基等のアリール基；ベンジル基及びフェネチル基等のアラルキル基；並びにクロロメチル基、３−クロロプロピル基、及び３，３，３−トリフロロプロピル基等のハロゲン化アルキル基が挙げられ、特に、メチル基及びフェニル基が好ましい。このような（Ｂ）成分の分子構造は限定されず、例えば、直鎖状、一部分岐を有する直鎖状、及び分岐鎖状が挙げられ、特に、直鎖状が好ましい。 The (B) component organopolysiloxane is the main component of the present composition and has at least two silicon-bonded alkenyl groups in one molecule. Examples of the silicon atom-bonded alkenyl group in component (B) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is particularly preferable. Examples of silicon-bonded organic groups other than alkenyl groups in component (B) include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; phenyl groups, tolyl Aryl groups such as benzyl, phenethyl and the like; and halogenated alkyls such as chloromethyl, 3-chloropropyl and 3,3,3-trifluoropropyl Group, and methyl group and phenyl group are particularly preferable. The molecular structure of such component (B) is not limited, and examples thereof include a straight chain, a partially branched straight chain, and a branched chain, and a straight chain is particularly preferable.
（Ｂ）成分の２５℃における粘度は限定されないが、１０〜５００，０００ｍＰａ・ｓの範囲内であることが好ましく、５０〜１００，０００ｍＰａ・ｓの範囲内であることがより好ましい。これは、（Ｂ）成分の粘度が上記範囲の下限以上であると、得られるシリコーンゴムの物理的特性が良好となるからであり、一方、上記範囲の上限以下であると、得られる組成物の取扱作業性が向上するからである。なお、（Ｂ）成分の２５℃での粘度は、例えば、ＪＩＳ Ｋ７１１７−１に準拠してＢ型粘度計を用いて測定することにより求めることができる。 The viscosity of component (B) at 25 ° C. is not limited, but is preferably in the range of 10 to 500,000 mPa · s, more preferably in the range of 50 to 100,000 mPa · s. This is because when the viscosity of the component (B) is not less than the lower limit of the above range, the resulting silicone rubber has good physical properties, and on the other hand, it is not more than the upper limit of the above range. This is because the handling operability of the is improved. In addition, the viscosity at 25 degreeC of (B) component can be calculated | required by measuring using a B-type viscosity meter based on JISK7117-1, for example.
また、（Ｂ）成分は４量体〜２０量体の環状シロキサンの含有量が質量単位で１，０００ｐｐｍ以下であることが好ましい。これは、（Ｂ）成分中の４量体〜２０量体の環状シロキサンの含有量が上記範囲の上限以下であると、得られる組成物の硬化途上で、該組成物から揮発する低沸分をより減少することができるからである。このような環状シロキサンとしては、例えば、環状ジメチルシロキサンオリゴマー、環状メチルビニルシロキサンオリゴマー、環状メチルフェニルシロキサンオリゴマー、及び環状ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマーが挙げられる。（Ｂ）成分中の４量体〜２０量体の環状シロキサンの含有量はガスクロマトグラフィー等の分析により測定可能である。 In addition, the component (B) preferably contains a tetramer to a 20mer cyclic siloxane in a mass unit of 1,000 ppm or less. This is because the content of the tetramer to 20mer cyclic siloxane in the component (B) is not more than the upper limit of the above range, and the low-boiling fraction volatilized from the composition during curing of the resulting composition. It is because it can reduce more. Examples of such cyclic siloxanes include cyclic dimethylsiloxane oligomers, cyclic methylvinylsiloxane oligomers, cyclic methylphenylsiloxane oligomers, and cyclic dimethylsiloxane / methylvinylsiloxane copolymer oligomers. The content of the tetramer to 20mer cyclic siloxane in the component (B) can be measured by analysis such as gas chromatography.
このような（Ｂ）成分のオルガノポリシロキサンとしては、例えば、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサン共重合体、式：Ｒ１ ３ＳｉＯ１／２で示されるシロキサン単位と式：Ｒ１ ２Ｒ２ＳｉＯ１／２で示されるシロキサン単位と式：Ｒ１ ２ＳｉＯ２／２で示されるシロキサン単位と少量の式：ＳｉＯ４／２で示されるシロキサン単位からなるオルガノポリシロキサン共重合体、式：Ｒ１ ２Ｒ２ＳｉＯ１／２で示されるシロキサン単位と式：Ｒ１ ２ＳｉＯ２／２で示されるシロキサン単位と少量の式：ＳｉＯ４／２で示されるシロキサン単位からなるオルガノポリシロキサン共重合体、式：Ｒ１Ｒ２ＳｉＯ２／２で示されるシロキサン単位と少量の式：Ｒ１ＳｉＯ３／２で示されるシロキサン単位若しくは式：Ｒ２ＳｉＯ３／２で示されるシロキサン単位からなるオルガノポリシロキサン共重合体、及び、これらのオルガノポリシロキサンの二種以上の混合物が挙げられる。上式中、Ｒ１はアルケニル基以外の一価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、及びヘプチル基等のアルキル基；フェニル基、トリル基、キシリル基、及びナフチル基等のアリール基；ベンジル基及びフェネチル基等のアラルキル基；並びにクロロメチル基、３−クロロプロピル基、及び３，３，３−トリフロロプロピル基等のハロゲン化アルキル基が挙げられる。また、上式中、Ｒ２はアルケニル基であり、例えば、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、及びヘプテニル基が挙げられる。 Examples of the organopolysiloxane of component (B) include, for example, a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both molecular chain terminals, a trimethylsiloxy group-capped methylvinylpolysiloxane with both molecular chain terminals, Terminal trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends Dimethylvinylsiloxy-blocked dimethylsiloxane / methylvinylsiloxane copolymer, dimethylvinylsiloxy-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer , Wherein: the siloxane units of the formula R 1 3 SiO 1/2: siloxane units represented by the formula R 1 2 R 2 SiO 1/2: siloxane units and a small amount of which is represented by R 1 2 SiO 2/2 Organopolysiloxane copolymer comprising a siloxane unit represented by the formula: SiO 4/2 , a siloxane unit represented by the formula: R 1 2 R 2 SiO 1/2 and a siloxane represented by the formula: R 1 2 SiO 2/2 Unit and a small amount of formula: an organopolysiloxane copolymer comprising a siloxane unit represented by SiO 4/2 , a siloxane unit represented by a formula: R 1 R 2 SiO 2/2 and a small amount of formula: R 1 SiO 3/2 in the siloxane units or of the formula shown organopolysiloxane copolymers composed of siloxane units represented by R 2 SiO 3/2, and these Oruganopori Mixtures of two or more Rokisan thereof. In the above formula, R 1 is a monovalent hydrocarbon group other than an alkenyl group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, Aryl groups such as tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl and phenethyl groups; and halogenations such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl An alkyl group is mentioned. In the above formula, R 2 is an alkenyl group, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.
（Ｃ）成分のオルガノポリシロキサンは本組成物の架橋剤であり、一分子中に少なくとも２個のケイ素原子結合水素原子を有し、ケイ素原子結合のアルケニル基、水酸基及びアルコキシ基を有しないものである。（Ｃ）成分中のケイ素原子結合有機基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、及びヘプチル基等のアルキル基；フェニル基、トリル基、キシリル基、及びナフチル基等のアリール基；ベンジル基及びフェネチル基等のアラルキル基；並びにクロロメチル基、３−クロロプロピル基、及び３，３，３−トリフロロプロピル基等のハロゲン化アルキル基が挙げられ、特に、メチル基及びフェニル基が好ましい。このような（Ｃ）成分の分子構造は限定されず、例えば、直鎖状、一部分岐を有する直鎖状、分岐鎖状が挙げられ、特に、直鎖状が好ましい。 Component (C), the organopolysiloxane, is a cross-linking agent of the present composition, and has at least two silicon-bonded hydrogen atoms in one molecule, and does not have silicon-bonded alkenyl groups, hydroxyl groups, and alkoxy groups. It is. Examples of silicon-bonded organic groups in component (C) include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; phenyl groups, tolyl groups, and xylyl groups. And aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; and halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, and 3,3,3-trifluoropropyl group. In particular, a methyl group and a phenyl group are preferable. The molecular structure of such component (C) is not limited, and examples thereof include a straight chain, a partially branched straight chain, and a branched chain, and a straight chain is particularly preferable.
（Ｃ）成分の２５℃における粘度は限定されないが、１〜５００，０００ｍＰａ・ｓの範囲内であることが好ましく、５〜１００，０００ｍＰａ・ｓの範囲内であることがより好ましい。これは、（Ｃ）成分の粘度が上記範囲の下限以上であると、得られるシリコーンゴムの物理的特性が良好となるからであり、一方、上記範囲の上限以下であると、得られる組成物の取扱作業性が良好となるからである。なお、（Ｃ）成分の２５℃での粘度は、例えば、ＪＩＳ Ｋ７１１７−１に準拠してＢ型粘度計を用いて測定することにより求めることができる。 The viscosity of component (C) at 25 ° C. is not limited, but is preferably in the range of 1 to 500,000 mPa · s, and more preferably in the range of 5 to 100,000 mPa · s. This is because when the viscosity of the component (C) is not less than the lower limit of the above range, the resulting silicone rubber has good physical properties, and on the other hand, it is not more than the upper limit of the above range. This is because the handling workability is improved. In addition, the viscosity at 25 degreeC of (C) component can be calculated | required by measuring using a B-type viscosity meter based on JISK7117-1, for example.
このような（Ｃ）成分のオルガノポリシロキサンとしては、例えば、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルフェニルシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルフェニルポリシロキサン、式：Ｒ１ ３ＳｉＯ１／２で示されるシロキサン単位と式：Ｒ１ ２ＨＳｉＯ１／２で示されるシロキサン単位と式：ＳｉＯ４／２で示されるシロキサン単位からなるオルガノポリシロキサン共重合体、式：Ｒ１ ２ＨＳｉＯ１／２で示されるシロキサン単位と式：ＳｉＯ４／２で示されるシロキサン単位からなるオルガノポリシロキサン共重合体、式：Ｒ１ＨＳｉＯ２／２で示されるシロキサン単位と式：Ｒ１ＳｉＯ３／２で示されるシロキサン単位若しくは式：ＨＳｉＯ３／２で示されるシロキサン単位からなるオルガノポリシロキサン共重合体、及びこれらのオルガノポリシロキサンの二種以上の混合物が挙げられる。上式中、Ｒ１はアルケニル基以外の一価炭化水素基であり、前記と同様の基が例示される。 Examples of the organopolysiloxane of component (C) include, for example, molecular chain both ends trimethylsiloxy group-capped methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecule Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, both chain ends dimethylhydrogensiloxy group-capped dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-capped dimethylsiloxane / methyl Phenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane with both molecular chains, siloxane unit represented by formula: R 1 3 SiO 1/2 and formula: R 1 2 An organopolysiloxane copolymer comprising a siloxane unit represented by HSiO 1/2 and a siloxane unit represented by formula: SiO 4/2 , a siloxane unit represented by formula: R 1 2 HSiO 1/2 and formula: SiO 4 / An organopolysiloxane copolymer comprising a siloxane unit represented by formula 2 , a siloxane unit represented by formula: R 1 HSiO 2/2 and a siloxane unit represented by formula: R 1 SiO 3/2 or a formula: HSiO 3/2 And organopolysiloxane copolymers composed of the siloxane units shown, and mixtures of two or more of these organopolysiloxanes. In the above formula, R 1 is a monovalent hydrocarbon group other than an alkenyl group, and the same groups as described above are exemplified.
（Ｃ）成分の含有量は、（Ｂ）成分中のアルケニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．５〜１０モルの範囲内となる量であり、好ましくは０．５〜５モルの範囲内となる量であり、さらに好ましくは０．５〜３モルの範囲内となる量である。これは、（Ｃ）成分の含有量が上記範囲の下限以上であると、得られる組成物の硬化を十分に行うことができるようになるからであり、一方、上記範囲の上限以下であると、得られるシリコーンゴムの物理的特性の経時的変化を抑制することができるからである。 The content of component (C) is such that the silicon-bonded hydrogen atoms in this component are within the range of 0.5 to 10 mol, preferably 1 mol per alkenyl group in component (B), preferably The amount is in the range of 0.5 to 5 mol, and more preferably in the range of 0.5 to 3 mol. This is because when the content of the component (C) is not less than the lower limit of the above range, the resulting composition can be sufficiently cured, and on the other hand, not more than the upper limit of the above range. This is because the change over time in the physical properties of the resulting silicone rubber can be suppressed.
（Ｄ）成分は本組成物の硬化を促進するためのヒドロシリル化反応用触媒である。（Ｄ）成分としては、例えば、白金微粉末、白金黒、白金担持シリカ微粉末、白金担持活性炭、塩化白金酸、四塩化白金、塩化白金酸のアルコール溶液、白金とオレフィンとの錯体、白金とジビニルテトラメチルジシロキサン等のアルケニルシロキサンとの錯体等の白金系触媒；テトラキス（トリフェニルホスフィン）パラジウム等のパラジウム系触媒；及びロジウム系触媒、並びに、これらの金属系触媒を含有してなるポリスチレン樹脂、ナイロン樹脂、ポリカーボネート樹脂、及びシリコーン樹脂等の粒子径が１０μｍ未満の熱可塑性樹脂粉末が挙げられる。 Component (D) is a hydrosilylation reaction catalyst for promoting the curing of the composition. Examples of the component (D) include platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, platinum tetrachloride, an alcohol solution of chloroplatinic acid, a complex of platinum and olefin, platinum and Platinum-based catalysts such as complexes with alkenylsiloxanes such as divinyltetramethyldisiloxane; palladium-based catalysts such as tetrakis (triphenylphosphine) palladium; and rhodium-based catalysts, and polystyrene resins containing these metal-based catalysts A thermoplastic resin powder having a particle diameter of less than 10 μm, such as nylon resin, polycarbonate resin, and silicone resin.
（Ｄ）成分含有量は触媒量であり、例えば、（Ｂ）成分に対して（Ｄ）成分中の金属原子が質量単位で０．１〜５００ｐｐｍの範囲内となる量であることが好ましく、１〜５０ｐｐｍの範囲内となる量であることがより好ましい。これは、（Ｄ）成分の含有量が上記範囲の下限以上であると、得られる組成物の硬化性が良好となるからであり、一方、上記範囲の上限以下であっても、得られる組成物の硬化には十分であるからである。 (D) Component content is a catalyst amount, for example, it is preferable that the metal atom in (D) component with respect to (B) component is the quantity which is in the range of 0.1-500 ppm by mass unit, It is more preferable that the amount be in the range of 1 to 50 ppm. This is because if the content of the component (D) is equal to or higher than the lower limit of the above range, the resulting composition has good curability. This is because it is sufficient for curing the product.
（Ｅ）成分は本組成物に接着性を付与するための接着性付与剤である。この（Ｅ）成分は限定されないが、ケイ素原子結合アルコキシ基を有する有機ケイ素化合物であることが好ましい。（Ｅ）成分中のケイ素原子結合アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、及びブトキシ基が挙げられ、特に、メトキシ基が好ましい。また、（Ｅ）成分中のケイ素原子結合有機基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、及びオクチル基等のアルキル基；ビニル基、アリル基、及びヘキセニル基等のアルケニル基；フェニル基、トリル基、及びキシリル基等のアリール基；３，３，３−トリフロロプロピル基及び３−クロロプロピル基等のハロゲン化アルキル基；３−グリシドキシピロピル基、３−メタクリロキシプロピル基、３−アミノプロピル基、及びＮ−（２−アミノエチル）−３−アミノプロピル基等の官能性有機基；トリメトキシシリルエチル基及びメチルジメトキシシリルエチル基等のアルコキシシリルアルキル基；並びにケイ素原子結合水素原子が挙げられる。 The component (E) is an adhesiveness imparting agent for imparting adhesiveness to the composition. The component (E) is not limited, but is preferably an organosilicon compound having a silicon atom-bonded alkoxy group. Examples of the silicon atom-bonded alkoxy group in component (E) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is particularly preferable. Examples of the silicon atom-bonded organic group in component (E) include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and octyl groups; vinyl groups, allyl groups, and hexenyl groups. Alkenyl groups such as phenyl groups, tolyl groups, and xylyl groups; halogenated alkyl groups such as 3,3,3-trifluoropropyl groups and 3-chloropropyl groups; 3-glycidoxypyrrolyl groups , Functional organic groups such as 3-methacryloxypropyl group, 3-aminopropyl group, and N- (2-aminoethyl) -3-aminopropyl group; alkoxy such as trimethoxysilylethyl group and methyldimethoxysilylethyl group A silylalkyl group; and a silicon-bonded hydrogen atom.
このような（Ｅ）成分としては、３−グリシドキシピロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−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−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、及び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等のアルコキシシランの一種若しくは二種以上からなる部分加水分解縮合物；メチルポリシリケート、エチルポリシリケート、一般式：
で示されるオルガノシロキサンオリゴマー；一般式：
で示されるオルガノシロキサンオリゴマー；一般式：
で示されるオルガノシロキサンオリゴマー；一般式：
で示されるオルガノシロキサンオリゴマー；一般式：
で示されるオルガノシロキサンオリゴマー；一般式：
で示されるオルガノシロキサンオリゴマー；並びに一般式：
で示されるオルガノシロキサンオリゴマーが挙げられる。
Examples of such a component (E) include 3-glycidoxypyrrolyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- Partially hydrolyzed condensate comprising one or more alkoxysilanes such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane; methyl Polysilicate, ethyl polysilicate, general formula:
An organosiloxane oligomer represented by the general formula:
An organosiloxane oligomer represented by the general formula:
An organosiloxane oligomer represented by the general formula:
An organosiloxane oligomer represented by the general formula:
An organosiloxane oligomer represented by the general formula:
As well as the general formula:
The organosiloxane oligomer shown by these is mentioned.
（Ｅ）成分としては、特に、（ｉ）沸点が１００℃以上であるケイ素原子結合アルコキシ基を有する有機ケイ素化合物と（ｉｉ）一分子中に少なくとも１個のケイ素原子結合アルケニル基を有し、ケイ素原子結合水酸基を有するジオルガノシロキサンオリゴマーとの混合物、又は前記（ｉ）成分と（ｉｉ）成分との縮合反応物であることが好ましい。 As the component (E), in particular, (i) an organosilicon compound having a silicon atom-bonded alkoxy group having a boiling point of 100 ° C. or higher, and (ii) having at least one silicon atom-bonded alkenyl group in one molecule, It is preferably a mixture with a diorganosiloxane oligomer having a silicon atom-bonded hydroxyl group, or a condensation reaction product of the component (i) and the component (ii).
（ｉ）成分は沸点、すなわち、１気圧における沸点（標準沸点）が１００℃以上であるが、これは、沸点が１００℃以上であると、得られる組成物の硬化途上で、該組成物から揮発する低沸分をより減少することができるからである。このような（ｉ）成分としては、例えば、３−グリシドキシピロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−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−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、及び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が挙げられる。 The component (i) has a boiling point, that is, a boiling point at 1 atm (standard boiling point) of 100 ° C. or higher. This is because, when the boiling point is 100 ° C. or higher, in the course of curing of the resulting composition, This is because the low boiling point component that volatilizes can be further reduced. Examples of the component (i) include 3-glycidoxypyrrolyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
また、（ｉｉ）成分はケイ素原子結合水酸基（シラノール基）を有するジオルガノシロキサンオリゴマーであり、該シラノール基の含有量が多くとも９質量％であることが好ましい。これはその含有量が９質量％以下であると、得られる組成物の接着性が良好となるからである。このような（ｉｉ）成分としては、例えば、分子鎖両末端シラノール基封鎖メチルビニルシロキサンオリゴマー、分子鎖両末端シラノール基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合オリゴマー、及び分子鎖両末端シラノール基封鎖メチルビニルシロキサン・メチルフェニルシロキサン共重合オリゴマーが挙げられる。 The component (ii) is a diorganosiloxane oligomer having a silicon atom-bonded hydroxyl group (silanol group), and the content of the silanol group is preferably at most 9% by mass. This is because the adhesiveness of the composition obtained will become favorable that the content is 9 mass% or less. Examples of the component (ii) include, for example, molecular chain both-end silanol group-capped methyl vinyl siloxane oligomer, molecular chain both-end silanol group-capped dimethylsiloxane / methyl vinyl siloxane copolymer oligomer, and molecular chain both-end silanol group-capped methyl. Examples include vinylsiloxane / methylphenylsiloxane copolymer oligomers.
（Ｅ）成分は、上記（ｉ）成分と上記（ｉｉ）成分の混合物であってもよく、また、それらを縮合反応してなる反応物であってもよい。上記（ｉ）成分と上記（ｉｉ）成分を縮合反応する方法は限定されないが、水酸化カリウム及び水酸化ナトリウム等の塩基性触媒の存在下で反応を行うことが好ましい。 The component (E) may be a mixture of the component (i) and the component (ii), or may be a reaction product obtained by a condensation reaction between them. A method for performing the condensation reaction between the component (i) and the component (ii) is not limited, but the reaction is preferably performed in the presence of a basic catalyst such as potassium hydroxide or sodium hydroxide.
（Ｅ）成分の含有量は、（Ｂ）成分１００質量部に対して少なくとも０．０５質量部であり、好ましくは少なくとも０．１質量部である。これは、（Ｅ）成分の含有量が、上記範囲の下限以上であると、得られる組成物の接着性が良好となるからである。 The content of the component (E) is at least 0.05 parts by mass, preferably at least 0.1 parts by mass with respect to 100 parts by mass of the component (B). This is because the adhesiveness of the composition obtained will become favorable as content of (E) component is more than the minimum of the said range.
（Ｆ）成分は（Ａ）成分と同様に本組成物に熱伝導性を付与するための熱伝導性充填剤である。このような（Ｆ）成分としては、（Ａ）成分以外の熱伝導性充填剤、例えば、金、銀、銅、アルミニウム、ニッケル、真鍮、形状記憶合金、及び半田等の金属系粉末；セラミック、ガラス、石英、及び有機樹脂等の粉末表面に、金、銀、ニッケル、及び銅等の金属を蒸着又はメッキした粉末；酸化アルミニウム、酸化ベリリウム、酸化クロム、酸化亜鉛、酸化チタン、及び結晶性シリカ等の金属酸化物系粉末；窒化ホウ素、窒化ケイ素、及び窒化アルミニウム等の金属窒化物系粉末；炭化ホウ素、炭化チタン、及び炭化ケイ素等の金属炭化物系粉末；水酸化マグネシウム等の金属水酸化物系粉末；カーボンナノチューブ、カーボンマイクロファイバー、ダイヤモンド、及びグラファイト等の炭素系粉末；並びにこれらの２種以上の混合物が挙げられる。特に、（Ｆ）成分は、金属系粉末、金属酸化物系粉末、又は金属窒化物系粉末が好ましく、具体的には、銀粉末、アルミニウム粉末、酸化アルミニウム粉末、酸化亜鉛粉末、又は窒化アルミニウム粉末であることが好ましい。なお、これらの熱伝導性充填剤は、水酸化アルミニウムまたは酸化マグネシウムと異なり、水和水や吸湿に伴う充填剤の質量変化は、多くの場合、問題とならない。 The component (F) is a thermally conductive filler for imparting thermal conductivity to the composition in the same manner as the component (A). Examples of such component (F) include thermally conductive fillers other than component (A), for example, metal powders such as gold, silver, copper, aluminum, nickel, brass, shape memory alloy, and solder; ceramics, Powder obtained by depositing or plating a metal such as gold, silver, nickel, and copper on a powder surface such as glass, quartz, and organic resin; aluminum oxide, beryllium oxide, chromium oxide, zinc oxide, titanium oxide, and crystalline silica Metal oxide powders such as boron nitride, silicon nitride, and aluminum nitride; Metal carbide powders such as boron carbide, titanium carbide, and silicon carbide; Metal hydroxides such as magnesium hydroxide Carbon powders such as carbon nanotubes, carbon microfibers, diamond, and graphite; and mixtures of two or more thereof. It is. In particular, the component (F) is preferably a metal powder, a metal oxide powder, or a metal nitride powder. Specifically, the silver powder, aluminum powder, aluminum oxide powder, zinc oxide powder, or aluminum nitride powder. It is preferable that In these heat conductive fillers, unlike aluminum hydroxide or magnesium oxide, mass change of the filler due to hydration water or moisture absorption is not a problem in many cases.
（Ｆ）成分の形状は特に限定されないが、例えば、球状、針状、円盤状、棒状、及び不定形状が挙げられ、好ましくは、球状又は不定形状である。また、（Ｆ）成分の平均粒子径は限定されないが、好ましくは、０．０１〜１００μｍの範囲内であり、より好ましくは、０．０１〜５０μｍの範囲内である。 Although the shape of (F) component is not specifically limited, For example, spherical shape, needle shape, disk shape, rod shape, and indefinite shape are mentioned, Preferably it is spherical shape or indefinite shape. Moreover, although the average particle diameter of (F) component is not limited, Preferably, it exists in the range of 0.01-100 micrometers, More preferably, it exists in the range of 0.01-50 micrometers.
また、（Ｆ）成分はケイ素系表面処理剤により表面処理されていることが好ましい。このケイ素系表面処理剤としては、（Ａ）成分で挙げたケイ素処理剤と同じものを使用することができる。また、これらの表面処理方法としても、（Ａ）成分で挙げた方法と同じ方法で行うことができる。（Ａ）成分と（Ｆ）成分のいずれか１つの成分、又は両方の成分がケイ素表面処理剤によって表面処理されていることが好ましい。 The component (F) is preferably surface-treated with a silicon-based surface treatment agent. As the silicon-based surface treating agent, the same silicon treating agent as mentioned in the component (A) can be used. Moreover, also as these surface treatment methods, it can carry out by the same method as the method quoted by (A) component. It is preferable that any one component of (A) component and (F) component, or both components are surface-treated with the silicon surface treating agent.
（Ｆ）成分の含有量は（Ｂ）成分１００質量部に対して１００〜２，０００質量部の範囲内であり、好ましくは、２００〜１，６００質量部の範囲内である。これは、（Ｆ）成分の含有量が上記範囲の下限以上であると、得られるシリコーンゴムの熱伝導性が良好となるからであり、一方、上記範囲の上限以下であると、得られる組成物の取扱作業性が良好となるからである。 (F) Content of a component exists in the range of 100-2,000 mass parts with respect to 100 mass parts of (B) component, Preferably, it exists in the range of 200-1,600 mass parts. This is because the thermal conductivity of the resulting silicone rubber is good when the content of the component (F) is at least the lower limit of the above range, and on the other hand, the composition obtained when the content is below the upper limit of the above range. This is because the handling workability of the object is improved.
また、本組成物の取扱作業性を向上させるため、硬化抑制剤を含むことが好ましい。この硬化抑制剤としては、例えば、２−メチル−３−ブチン−２−オール、３，５−ジメチル−１−ヘキシン−３−オール、及び２−フェニル−３−ブチン−２−オール等のアルキンアルコール；３−メチル−３−ペンテン−１−イン、及び３，５−ジメチル−３−ヘキセン−１−イン等のエンイン化合物；並びにベンゾトリアゾールが挙げられる。これらの硬化抑制剤の含有量は、（Ｂ）成分に対して質量単位で１０〜５０，０００ｐｐｍの範囲内であることが好ましい。 Moreover, in order to improve the handling workability | operativity of this composition, it is preferable that a hardening inhibitor is included. Examples of the curing inhibitor include alkynes such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol. Examples include alcohols; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; and benzotriazole. The content of these curing inhibitors is preferably in the range of 10 to 50,000 ppm by mass with respect to component (B).
本発明の熱伝導性シリコーン組成物を調製する方法は特に限定されず、例えば、［１］（Ｂ）成分に（Ａ）成分を混合し、これに（Ｃ）成分を徐々に加え混合して調製する方法、［２］（Ａ）成分と（Ｃ）成分をあらかじめ混合し、（Ｂ）成分を徐々に加えて調製する方法を用いて調製することができるが、特に［１］の方法であることが好ましい。混合装置としては種々の装置が使用可能であるが、２本ロール、バンバリーミキサー、ニーダーミキサー、プラネタリーミキサー、ロスミキサー、ホバートミキサー、スピードミキサー等の周知の混練手段により均一に混合することにより調製することができる。特に、ロスミキサーの使用が好ましい。 The method for preparing the heat conductive silicone composition of the present invention is not particularly limited. For example, (1) component (A) is mixed with component (B), and component (C) is gradually added thereto and mixed. Preparation method [2] The component (A) and the component (C) can be mixed in advance, and the component (B) can be gradually added and prepared. Preferably there is. Various devices can be used as the mixing device, but it is prepared by mixing uniformly by a known kneading means such as a two-roll, a Banbury mixer, a kneader mixer, a planetary mixer, a loss mixer, a Hobart mixer, or a speed mixer. can do. In particular, the use of a loss mixer is preferable.
本発明の熱伝導性充填剤用表面処理剤及び熱伝導性シリコーン組成物には、本発明の目的を損なわない限り、その他の任意成分として、各種の添加剤、例えば、ヒュームド酸化チタン等の補強充填剤；珪藻土、アルミノ珪酸、酸化鉄、酸化亜鉛、及び炭酸カルシウム等の非補強充填剤；並びにこれらの充填剤をオルガノシラン、及びポリオルガノシロキサン等の有機ケイ素化合物で表面処理したものを配合してもよい。また、必要に応じてメチルエチルケトンやメチルイソブチルケトンなどの溶媒、顔料、染料、耐熱剤、難燃剤、内部離型剤、可塑剤、ミネラルオイル、及び無官能のシリコーンオイル等のシリコーン組成物に汎用される添加剤を配合してもよい。 In the surface treatment agent for heat conductive filler and the heat conductive silicone composition of the present invention, various additives such as fumed titanium oxide are reinforced as other optional components as long as the object of the present invention is not impaired. Fillers; non-reinforcing fillers such as diatomaceous earth, aluminosilicate, iron oxide, zinc oxide and calcium carbonate; and those surface-treated with organosilicon compounds such as organosilane and polyorganosiloxane May be. In addition, it is widely used for silicone compositions such as solvents such as methyl ethyl ketone and methyl isobutyl ketone, pigments, dyes, heat-resistant agents, flame retardants, internal mold release agents, plasticizers, mineral oils, and non-functional silicone oils as required. Additives may be blended.
以下、本発明を実施例により詳細に説明するが、本発明は実施例に限定されるものではない。また、実施例中の物性は２５℃における値である。なお、熱伝導性充填剤の粒子径は、各メーカーのカタログ値である。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to an Example. The physical properties in the examples are values at 25 ° C. In addition, the particle diameter of a heat conductive filler is a catalog value of each manufacturer.
［熱伝導性充填剤の質量変化（＝加熱減量％）］
各熱伝導性充填剤を、以下の測定条件で、２５０℃で３０分保持した後の質量減少率を測定した。
装置：株式会社島津製作所製熱重量測定装置 ＴＧＡ−５０）
昇温速度：室温から２５０℃まで１０℃／ｍｉｎ
温度条件：２５０℃到達後３０分保持
測定雰囲気：窒素ガス（流量５０ｍｌ／ｍｉｎ）
サンプル量：１０ｍｇ
[Mass change of thermally conductive filler (= heat loss%)]
Each heat conductive filler was measured for mass reduction rate after being held at 250 ° C. for 30 minutes under the following measurement conditions.
Device: Shimadzu Corporation thermogravimetric measuring device TGA-50)
Temperature increase rate: 10 ° C / min from room temperature to 250 ° C
Temperature condition: Hold for 30 minutes after reaching 250 ° C. Measurement atmosphere: Nitrogen gas (flow rate 50 ml / min)
Sample amount: 10mg
［高温保持試験後の熱伝導性シリコーンゴム（硬化物）の安定性評価］
各熱伝導性シリコーンゴム組成物を５０ｃｃガラスビーカーに４０ｃｃ充填し、熱循環式オーブンで１５０℃、１時間の条件で加熱硬化させることにより、熱伝導性シリコーンゴム（試料）を得た。得られた試料は、１８０℃で７２時間更に保管した後、外観を目視観察することにより、以下の基準で評価した。
○：保管後、ビーカー面からの剥離（密着不良）や試料の破壊（割れ等）が認められない。
×：保管後、ビーカー面からの剥離及び試料の破壊が明らかに認められる。
[Stability evaluation of thermally conductive silicone rubber (cured product) after high temperature holding test]
A heat conductive silicone rubber (sample) was obtained by filling 40 cc of each heat conductive silicone rubber composition in a 50 cc glass beaker and heating and curing in a heat circulating oven at 150 ° C. for 1 hour. The obtained sample was further stored at 180 ° C. for 72 hours, and then visually evaluated for the appearance, and evaluated according to the following criteria.
○: After storage, peeling from the beaker surface (adhesion failure) and destruction (cracking, etc.) of the sample are not observed.
X: After storage, peeling from the beaker surface and destruction of the sample are clearly observed.
［実施例１］
ロスミキサーにより、粘度４００ｍＰａ・ｓの分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン１００質量部、メチルトリメトキシシラン４．３質量部、及び平均粒子径２５μｍの加熱減量３．９質量％の不定形状水酸化アルミニウム微粒子（住友化学社製 ＣＷＬ３２５ＬＶ）３２０質量部を室温で混合した。その後、減圧下、１５０℃で１時間加熱混合してシリコーンゴムベースを調製した。次に、上記シリコーンゴムベースに、粘度５ｍＰａ・ｓの分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体１質量部（シリコーンゴムベースに含まれている上記ジメチルポリシロキサン中のビニル基１モルに対して、本成分中のケイ素原子結合水素原子が０．８モルとなる量）、２−フェニル−３−ブチン−２−オール０．１質量部、及び白金の１，３−ジビニルテトラメチルジシロキサン錯体（シリコーンゴムベースに含まれている上記ジメチルポリシロキサンに対して、本成分中の白金金属が質量単位で３０ｐｐｍとなる量）を添加し、室温で均一に混合して熱伝導性シリコーンゴム組成物１を調製した。
[Example 1]
Using a loss mixer, 100 parts by mass of dimethylpolysiloxane blocked with a dimethylvinylsiloxy group at both ends of a molecular chain having a viscosity of 400 mPa · s, 4.3 parts by mass of methyltrimethoxysilane, and 3.9% by mass with an average particle size of 25 μm. 320 parts by mass of fine aluminum hydroxide particles (CWL325LV, manufactured by Sumitomo Chemical Co., Ltd.) were mixed at room temperature. Thereafter, the mixture was heated and mixed at 150 ° C. for 1 hour under reduced pressure to prepare a silicone rubber base. Next, on the silicone rubber base, 1 part by mass of a dimethylsiloxane / methylhydrogensiloxane copolymer blocked with a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 5 mPa · s (in the dimethylpolysiloxane contained in the silicone rubber base) Amount of silicon atom-bonded hydrogen atom in this component to 0.8 mol) per mol of vinyl group, 0.1 part by mass of 2-phenyl-3-butyn-2-ol, and 1,3 of platinum -Add divinyltetramethyldisiloxane complex (the amount of platinum metal in this component to 30ppm by mass with respect to the dimethylpolysiloxane contained in the silicone rubber base) and mix evenly at room temperature. A thermally conductive silicone rubber composition 1 was prepared.
［比較例１］
実施例１の水酸化アルミニウム微粒子（ＣＷＬ３２５ＬＶ）の代わりに、平均粒子径１８μｍの加熱減量４．４質量％の不定形状水酸化アルミニウム微粒子（昭和電工社製 ハイジライトＨ−３１）を用いた以外は実施例１と同様にして、熱伝導性シリコーンゴム組成物２を調製した。
[Comparative Example 1]
Instead of the aluminum hydroxide fine particles (CWL325LV) of Example 1, non-uniform shaped aluminum hydroxide fine particles (Heidilite H-31 manufactured by Showa Denko KK) with an average particle diameter of 18 μm and a weight loss of 4.4% by mass were used. In the same manner as in Example 1, a heat conductive silicone rubber composition 2 was prepared.
［実施例２］
比較例１で用いた平均粒子径１８μｍの加熱減量４．４質量％の不定形状水酸化アルミニウム微粒子（昭和電工社製 ハイジライトＨ−３１）を、熱循環式オーブンで２５０℃−３時間乾燥させることにより、最終的に平均粒子径１８μｍの加熱減量１．４質量％の不定形状水酸化アルミニウム微粒子（以下、「空焼きしたＨ−３１」という）を調製した。
実施例１の水酸化アルミニウム微粒子（ＣＷＬ３２５ＬＶ）の代わりに、この「空焼きしたＨ−３１」を用いた以外は実施例１と同様にして、熱伝導性シリコーンゴム組成物３を調製した。
[Example 2]
The amorphous aluminum hydroxide fine particles of 4.4 mass% with an average particle diameter of 18 μm used in Comparative Example 1 (Heidilite H-31 manufactured by Showa Denko KK) are dried at 250 ° C. for 3 hours in a thermal circulation oven. As a result, amorphous aluminum hydroxide fine particles (hereinafter referred to as “air-baked H-31”) having an average particle diameter of 18 μm and a loss on heating of 1.4% by mass were prepared.
A thermally conductive silicone rubber composition 3 was prepared in the same manner as in Example 1 except that this “air-baked H-31” was used instead of the aluminum hydroxide fine particles (CWL325LV) of Example 1.
［比較例２］
実施例１の水酸化アルミニウム微粒子（ＣＷＬ３２５ＬＶ）の代わりに、平均粒子径９μｍの加熱減量４．１質量％の不定形状水酸化アルミニウム微粒子（日本軽金属社製 ＢＦ０８３）を用いた以外は実施例１と同様にして、熱伝導性シリコーンゴム組成物４を調製した。
[Comparative Example 2]
Example 1 is used except that in place of the aluminum hydroxide fine particles (CWL 325LV) of Example 1, irregular shaped aluminum hydroxide fine particles (BF083 manufactured by Nippon Light Metal Co., Ltd.) having an average particle size of 9 μm and a weight loss of 4.1% by mass are used. Similarly, a heat conductive silicone rubber composition 4 was prepared.
［比較例３］
実施例１の水酸化アルミニウム微粒子（ＣＷＬ３２５ＬＶ）の代わりに、平均粒子径３．６μｍの加熱減量４．９質量％の不定形状水酸化アルミニウム微粒子（昭和電工社製 ＨＰ３５０）を用いた以外は実施例１と同様にして、熱伝導性シリコーンゴム組成物５を調製した。
[Comparative Example 3]
Example except that in place of the aluminum hydroxide fine particles (CWL325LV) in Example 1, amorphous aluminum hydroxide fine particles (HP350, Showa Denko KK) having an average particle size of 3.6 μm and a weight loss of 4.9% by mass were used. In the same manner as in Example 1, a heat conductive silicone rubber composition 5 was prepared.
［実施例３］
比較例３で用いた平均粒子径３．６μｍの加熱減量４．９質量％の不定形状水酸化アルミニウム微粒子（昭和電工社製 ＨＰ３５０）を、熱循環式オーブンで２５０℃、３時間乾燥させることにより、最終的に３．６μｍの加熱減量２．１質量％の不定形状水酸化アルミニウム微粒子（以下、「空焼きしたＨＰ３５０」という）を調製した。
実施例１の水酸化アルミニウム微粒子（ＣＷＬ３２５ＬＶ）の代わりに、この「空焼きしたＨＰ３５０」を用いた以外は実施例１と同様にして、熱伝導性シリコーンゴム組成物６を調製した。
[Example 3]
By drying amorphous aluminum hydroxide fine particles (HP350 manufactured by Showa Denko KK) having an average particle size of 3.6 μm and a weight loss of 4.9% by mass used in Comparative Example 3 in a thermal circulation oven at 250 ° C. for 3 hours. Finally, an amorphous aluminum hydroxide fine particle (hereinafter referred to as “air-baked HP350”) having a loss on heating of 2.1 μ% by mass of 3.6 μm was prepared.
A thermally conductive silicone rubber composition 6 was prepared in the same manner as in Example 1 except that this “air-baked HP350” was used instead of the aluminum hydroxide fine particles (CWL325LV) of Example 1.
実施例１〜３及び比較例１〜３について、得られた熱伝導性シリコーンゴム組成物中の熱伝導性充填剤の種類、平均粒径、質量変化（＝加熱減量％）と熱伝導性シリコーンゴム（硬化物）の安定性評価の結果を、表１に示す。 About Examples 1-3 and Comparative Examples 1-3, the kind of heat conductive filler in the obtained heat conductive silicone rubber composition, an average particle diameter, mass change (= heating loss%), and heat conductive silicone Table 1 shows the results of the stability evaluation of the rubber (cured product).
表１に示すとおり、加熱減量が４．０質量％未満である熱伝導性充填剤を用いることにより、高温保持試験後の熱伝導性シリコーンゴム硬化物の容器（ビーカー）への密着不良や硬化物の破壊（クラック）等が極めて効果的に抑制されることが分かった。特に、実施例１と比較例４との対比から明らかなように、類似の水酸化アルミニウムを用いた場合でも、加熱減量４．０％を境にして、得られる熱伝導性シリコーンゴムの高温安定性が急激に悪化し、密着不良や硬化物の破壊が発生することが確認された。 As shown in Table 1, by using a thermally conductive filler with a loss on heating of less than 4.0% by mass, poor adhesion and curing of the thermally conductive silicone rubber cured product after the high temperature holding test to the container (beaker) It has been found that the destruction (cracking) of objects is extremely effectively suppressed. In particular, as is clear from the comparison between Example 1 and Comparative Example 4, even when similar aluminum hydroxide is used, the high temperature stability of the resulting heat conductive silicone rubber is limited to a heating loss of 4.0%. It was confirmed that the property deteriorated rapidly, resulting in poor adhesion and destruction of the cured product.
本発明の熱伝導性シリコーンゴム組成物は、基材への密着性に優れ、硬化に伴うクラックの発生を抑制することができるので、電気・電子部品の放熱接着剤、例えば、トランジスター、ＩＣ、メモリー素子等の電子部品を登載したプリント回路基板、ハイブリッドＩＣのポッティング材や接着剤、半導体素子の接着剤、及びエンジンマウントの接着・シール剤として好適である。 The heat conductive silicone rubber composition of the present invention is excellent in adhesion to the substrate and can suppress the occurrence of cracks due to curing, so that a heat-dissipating adhesive for electrical and electronic parts, such as transistors, ICs, It is suitable as a printed circuit board on which electronic parts such as a memory element are mounted, a potting material or adhesive for a hybrid IC, an adhesive for a semiconductor element, and an adhesive / sealant for an engine mount.
Claims (10)
を含む、熱伝導性シリコーン組成物。 (A) A thermally conductive silicone comprising a thermally conductive filler of aluminum hydroxide or magnesium oxide, wherein the mass change by thermogravimetric analysis (TGA) before and after holding at 250 ° C. for 30 minutes is less than 4.0% by mass Composition.
（Ｃ）一分子中に少なくとも２個のケイ素原子結合水素原子を有し、ケイ素原子結合アルケニル基、水酸基及びアルコキシを有しないオルガノポリシロキサン、及び
（Ｄ）ヒドロシリル化反応用触媒
を更に含む、請求項１に記載の熱伝導性シリコーン組成物。 (B) an organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule;
(C) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and having no silicon-bonded alkenyl group, hydroxyl group and alkoxy, and (D) a catalyst for hydrosilylation reaction. Item 2. The thermally conductive silicone composition according to item 1.
を更に含む、請求項１から５のいずれか一項に記載の熱伝導性シリコーン組成物。 (E) The heat conductive silicone composition according to any one of claims 1 to 5, further comprising an adhesion-imparting agent.
を更に含む、請求項１から７のいずれか一項に記載の熱伝導性シリコーン組成物。 (F) The thermally conductive silicone composition according to any one of claims 1 to 7, further comprising a thermally conductive filler other than the component (A).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012274714A JP6339761B2 (en) | 2012-12-17 | 2012-12-17 | Thermally conductive silicone composition and thermally conductive member |
| PCT/JP2013/084177 WO2014098204A1 (en) | 2012-12-17 | 2013-12-13 | Thermally conductive silicone composition and thermally conductive member |
| TW102146748A TW201428057A (en) | 2012-12-17 | 2013-12-17 | Thermally conductive silicone composition and thermally conductive member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012274714A JP6339761B2 (en) | 2012-12-17 | 2012-12-17 | Thermally conductive silicone composition and thermally conductive member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014118484A true JP2014118484A (en) | 2014-06-30 |
| JP6339761B2 JP6339761B2 (en) | 2018-06-06 |
Family
ID=49917213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012274714A Active JP6339761B2 (en) | 2012-12-17 | 2012-12-17 | Thermally conductive silicone composition and thermally conductive member |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6339761B2 (en) |
| TW (1) | TW201428057A (en) |
| WO (1) | WO2014098204A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018182222A1 (en) * | 2017-03-31 | 2018-10-04 | 주식회사 케이씨씨 | Heat-dissipating gel-type silicone rubber composition |
| WO2020084860A1 (en) * | 2018-10-26 | 2020-04-30 | 信越化学工業株式会社 | Thermally conductive silicone composition and cured product thereof |
| WO2021112070A1 (en) * | 2019-12-02 | 2021-06-10 | 信越化学工業株式会社 | Wafer processing temporary adhesive, wafer laminate, thin wafer manufacturing method |
| WO2022049816A1 (en) * | 2020-09-03 | 2022-03-10 | 富士高分子工業株式会社 | Heat conductive silicone composition and method for producing same |
| WO2022049817A1 (en) * | 2020-09-03 | 2022-03-10 | 富士高分子工業株式会社 | Thermally conductive silicone composition and method for producing same |
| WO2022071707A1 (en) * | 2020-09-29 | 2022-04-07 | 주식회사 엘지에너지솔루션 | Curable composition and two-liquid-type curable composition |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106158790B (en) * | 2015-04-10 | 2018-11-16 | 台达电子工业股份有限公司 | power module and its thermal interface structure |
| EP3737727B1 (en) * | 2018-01-11 | 2022-03-09 | Dow Silicones Corporation | Method for applying thermally conductive composition on electronic components |
| JP7088215B2 (en) * | 2018-01-17 | 2022-06-21 | 信越化学工業株式会社 | Thermally conductive thin-film cured product, its manufacturing method, and thermally conductive member |
| JP2023522541A (en) * | 2020-03-16 | 2023-05-31 | ダウ シリコーンズ コーポレーション | Thermally conductive silicone composition |
| WO2023030167A1 (en) * | 2021-08-30 | 2023-03-09 | Dow Silicones Corporation | Thermally conductive silicone rubber composition |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140456A (en) * | 1991-11-20 | 1993-06-08 | Shin Etsu Chem Co Ltd | Production of heat-conductive silicone rubber composition |
| JPH05239358A (en) * | 1992-03-02 | 1993-09-17 | Toshiba Silicone Co Ltd | Thermally conductive silicone rubber composition |
| JPH06293861A (en) * | 1993-03-23 | 1994-10-21 | Toshiba Silicone Co Ltd | Heat conductive silicone rubber composition |
| JPH0940871A (en) * | 1995-07-27 | 1997-02-10 | Shin Etsu Chem Co Ltd | Silicone rubber composition for high-voltage electric insulator |
| JP2002072728A (en) * | 2000-08-30 | 2002-03-12 | Dow Corning Toray Silicone Co Ltd | Thermally conductive liquid silicone rubber composition for fixing roll and fixing roll coated with fluororesin |
| JP2011025676A (en) * | 2009-06-29 | 2011-02-10 | Shin-Etsu Chemical Co Ltd | Heat-conductive silicone rubber composite sheet |
| JP2011098566A (en) * | 2009-10-08 | 2011-05-19 | Shin-Etsu Chemical Co Ltd | Thermal conductive silicone rubber composite sheet |
| JP2011153252A (en) * | 2010-01-28 | 2011-08-11 | Dow Corning Toray Co Ltd | Heat-conductive silicone rubber composition |
| JP2013124257A (en) * | 2011-12-13 | 2013-06-24 | Shin-Etsu Chemical Co Ltd | Thermally conductive silicone composition and cured product of the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157569A (en) | 1984-12-28 | 1986-07-17 | Shin Etsu Polymer Co Ltd | Thermally conductive adhesive composition |
| JPS63251466A (en) | 1987-04-06 | 1988-10-18 | Shin Etsu Chem Co Ltd | Thermally conductive liquid silicone rubber composition |
| JP2704732B2 (en) | 1988-08-01 | 1998-01-26 | 東レ・ダウコーニング・シリコーン株式会社 | Curable liquid organopolysiloxane composition |
| JP2691823B2 (en) | 1991-01-24 | 1997-12-17 | 信越化学工業株式会社 | Curable silicone composition and cured product thereof |
-
2012
- 2012-12-17 JP JP2012274714A patent/JP6339761B2/en active Active
-
2013
- 2013-12-13 WO PCT/JP2013/084177 patent/WO2014098204A1/en active Application Filing
- 2013-12-17 TW TW102146748A patent/TW201428057A/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140456A (en) * | 1991-11-20 | 1993-06-08 | Shin Etsu Chem Co Ltd | Production of heat-conductive silicone rubber composition |
| JPH05239358A (en) * | 1992-03-02 | 1993-09-17 | Toshiba Silicone Co Ltd | Thermally conductive silicone rubber composition |
| JPH06293861A (en) * | 1993-03-23 | 1994-10-21 | Toshiba Silicone Co Ltd | Heat conductive silicone rubber composition |
| JPH0940871A (en) * | 1995-07-27 | 1997-02-10 | Shin Etsu Chem Co Ltd | Silicone rubber composition for high-voltage electric insulator |
| JP2002072728A (en) * | 2000-08-30 | 2002-03-12 | Dow Corning Toray Silicone Co Ltd | Thermally conductive liquid silicone rubber composition for fixing roll and fixing roll coated with fluororesin |
| JP2011025676A (en) * | 2009-06-29 | 2011-02-10 | Shin-Etsu Chemical Co Ltd | Heat-conductive silicone rubber composite sheet |
| JP2011098566A (en) * | 2009-10-08 | 2011-05-19 | Shin-Etsu Chemical Co Ltd | Thermal conductive silicone rubber composite sheet |
| JP2011153252A (en) * | 2010-01-28 | 2011-08-11 | Dow Corning Toray Co Ltd | Heat-conductive silicone rubber composition |
| JP2013124257A (en) * | 2011-12-13 | 2013-06-24 | Shin-Etsu Chemical Co Ltd | Thermally conductive silicone composition and cured product of the same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018182222A1 (en) * | 2017-03-31 | 2018-10-04 | 주식회사 케이씨씨 | Heat-dissipating gel-type silicone rubber composition |
| WO2020084860A1 (en) * | 2018-10-26 | 2020-04-30 | 信越化学工業株式会社 | Thermally conductive silicone composition and cured product thereof |
| WO2021112070A1 (en) * | 2019-12-02 | 2021-06-10 | 信越化学工業株式会社 | Wafer processing temporary adhesive, wafer laminate, thin wafer manufacturing method |
| JPWO2021112070A1 (en) * | 2019-12-02 | 2021-06-10 | ||
| WO2022049816A1 (en) * | 2020-09-03 | 2022-03-10 | 富士高分子工業株式会社 | Heat conductive silicone composition and method for producing same |
| WO2022049817A1 (en) * | 2020-09-03 | 2022-03-10 | 富士高分子工業株式会社 | Thermally conductive silicone composition and method for producing same |
| JP7055255B1 (en) * | 2020-09-03 | 2022-04-15 | 富士高分子工業株式会社 | Method for Producing Thermally Conductive Silicone Composition |
| JP7055254B1 (en) * | 2020-09-03 | 2022-04-15 | 富士高分子工業株式会社 | Method for Producing Thermally Conductive Silicone Composition |
| WO2022071707A1 (en) * | 2020-09-29 | 2022-04-07 | 주식회사 엘지에너지솔루션 | Curable composition and two-liquid-type curable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014098204A1 (en) | 2014-06-26 |
| TW201428057A (en) | 2014-07-16 |
| JP6339761B2 (en) | 2018-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6339761B2 (en) | Thermally conductive silicone composition and thermally conductive member | |
| JP5534837B2 (en) | Thermally conductive silicone rubber composition | |
| TWI755437B (en) | One-liquid curable thermal conductive silicone grease composition and electric/electronic article | |
| JP6610429B2 (en) | Thermally conductive silicone composition, cured product thereof and method for producing the same | |
| JP6705919B2 (en) | Gel type thermal interface material | |
| JP5372388B2 (en) | Thermally conductive silicone grease composition | |
| KR102477726B1 (en) | Silicone composition containing filler | |
| JP6654593B2 (en) | Silicone resin composition for die bonding and cured product | |
| KR20110017864A (en) | Thermally conductive silicone composition and electronic device | |
| JP2010059237A (en) | Thermally conductive silicone composition and semiconductor device | |
| JP6791815B2 (en) | Thermally conductive silicone resin composition | |
| CN112867765B (en) | Heat-conductive silicone composition and cured product thereof | |
| KR102479137B1 (en) | thermally conductive composition | |
| TWI798283B (en) | Addition hardening polysiloxane composition, cured product, optical element | |
| JP2009235279A (en) | Heat-conductive molding and manufacturing method therefor | |
| TW202200711A (en) | Thermally conductive silicone composition and cured product of same | |
| JP3758176B2 (en) | Thermally conductive silicone rubber and composition thereof | |
| JP2004083905A (en) | Thermally conductive filler, thermally conductive silicone elastomer composition and semiconductor device | |
| JP5648290B2 (en) | Electronic device and manufacturing method thereof | |
| JP6656509B1 (en) | Method for producing conductive filler, conductive addition-curable silicone composition, and semiconductor device | |
| JP2018027997A (en) | Thermally conductive silicone resin composition and method for curing the same | |
| TW202313855A (en) | Thermal conductive silicone composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20151111 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20151218 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170117 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170309 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170905 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180508 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180511 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6339761 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S802 | Written request for registration of partial abandonment of right |
Free format text: JAPANESE INTERMEDIATE CODE: R311802 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |