WO2015155948A1 - 熱伝導性シリコーン組成物および電気・電子機器 - Google Patents
熱伝導性シリコーン組成物および電気・電子機器 Download PDFInfo
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- WO2015155948A1 WO2015155948A1 PCT/JP2015/001762 JP2015001762W WO2015155948A1 WO 2015155948 A1 WO2015155948 A1 WO 2015155948A1 JP 2015001762 W JP2015001762 W JP 2015001762W WO 2015155948 A1 WO2015155948 A1 WO 2015155948A1
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- thermally conductive
- conductive silicone
- silicone composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 135
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 133
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- 239000011231 conductive filler Substances 0.000 claims abstract description 18
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- 239000002184 metal Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
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- 230000018044 dehydration Effects 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 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 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- YNKIIBQOKMXIGH-UHFFFAOYSA-N propan-2-yl 3-oxohexaneperoxoate;titanium Chemical compound [Ti].CCCC(=O)CC(=O)OOC(C)C.CCCC(=O)CC(=O)OOC(C)C YNKIIBQOKMXIGH-UHFFFAOYSA-N 0.000 description 1
- HWFKKBUUAKXIJF-UHFFFAOYSA-N propan-2-yl 3-oxopentaneperoxoate;titanium Chemical compound [Ti].CCC(=O)CC(=O)OOC(C)C.CCC(=O)CC(=O)OOC(C)C HWFKKBUUAKXIJF-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant 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
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 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
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910021355 zirconium silicide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/42—Fillings or auxiliary members in containers or encapsulations selected or arranged to facilitate heating or cooling
-
- 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
-
- 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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a thermally conductive silicone comprising an organopolysiloxane having a specific alkoxysilyl-containing group and a thermally conductive filler capable of suppressing thermal conductivity, heat resistance, and thickening in an uncured state. It relates to a composition.
- the present invention also relates to an electric / electronic device including a member (including a grease or a cured product) made of the heat conductive silicone composition.
- thermally conductive silicone grease compositions comprising thermally conductive fillers such as aluminum oxide powder and zinc oxide powder are used (see Patent Documents 1 to 3).
- thermally conductive silicone grease composition has a problem in that the heat conductive filler cannot be highly filled, and the heat dissipation characteristics are insufficient.
- thermally conductive silicone grease composition with a thermally conductive filler, organopolysiloxane, a thermally conductive filler, and an organohydro having at least three silicon-bonded hydrogen atoms in one molecule are used.
- a thermally conductive silicone grease composition made of genpolysiloxane has been proposed (see Patent Document 4).
- a heat conductive silicone grease composition has a problem that it has heat resistance, that is, it exhibits fluidity by heating when it is applied thickly or applied to a vertical surface.
- thermoly conductive silicone grease composition containing an organopolysiloxane in which an alkoxysilyl group is bonded to a molecular chain terminal or the like via a silalkylene bond (see Patent Document 5).
- a heat conductive silicone grease composition is excellent in suppression of oil bleed and heat resistance, but may cause problems such as thickening and gelation over time, and further improvement has been desired.
- a curable organopolysiloxane composition containing an alkoxysilyl-containing group represented by (6) is proposed (Patent Document 6), and it is proposed that an aluminum oxide powder or the like may be optionally contained.
- Patent Document 6 A curable organopolysiloxane composition containing an alkoxysilyl-containing group represented by (6) is proposed (Patent Document 6), and it is proposed that an aluminum oxide powder or the like may be optionally contained.
- Patent Document 6 A curable organopolysiloxane composition containing an alkoxysilyl-containing group represented by (6)
- an aluminum oxide powder or the like may be optionally contained.
- JP 50-105573 A JP-A 51-55870 JP-A 61-157487 JP-A-4-20296 JP 2009-179714
- a Japanese Patent Laid-Open No. 2006-348119 A Japanese Patent Laid-Open No. 2006-348119
- the present invention has been made to solve the above-mentioned problems, is excellent in heat resistance and thermal conductivity, is suppressed in thickening in an uncured state, is a thermally conductive silicone composition excellent in handling workability, An object of the present invention is to provide an electric / electronic device using the same as a member.
- the present inventors have (A) (a1) a general formula of at least one silicon atom bond in one molecule: Wherein R 1 is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, R 2 is an alkyl group, R 3 is the same or different alkylene group, a Is an integer from 0 to 2, and p is an integer from 1 to 50), or an organopolysiloxane having an alkoxysilyl-containing group represented by: (a1) and (a2) at least 2 in one molecule Mixture with organopolysiloxane having an alkenyl group and no alkoxysilyl-containing group (in the mixture, the content of component (a1) is 10 to 100% by mass (however, not including 100% by mass) .)
- the inventors have found that the above problems can be solved by a thermally conductive silicone composition comprising 100 parts by mass and (B) 400 to 3,500 parts by mass of a thermally conductive filler, and have reached
- the object of the present invention is “[1] (A) (a1) The general formula of at least one silicon atom bond in one molecule: Wherein R 1 is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, R 2 is an alkyl group, R 3 is the same or different alkylene group, a Is an integer from 0 to 2, and p is an integer from 1 to 50), or an organopolysiloxane having an alkoxysilyl-containing group represented by: (a1) and (a2) at least 2 in one molecule Mixture with organopolysiloxane having an alkenyl group and no alkoxysilyl-containing group (in the mixture, the content of component (a1) is 10 to 100% by mass (however, not including 100% by mass) .) ⁇ A thermally conductive silicone composition comprising 100 parts by mass and (B) 400 to 3,500 parts by mass of a thermally conductive filler.
- the alkoxysilyl-containing group in the component (A) has the formula: The heat conductive silicone composition according to [1], wherein the heat conductive silicone composition is a group represented by the formula: [3] The thermally conductive silicone composition according to [1] or [2], wherein the average particle size of the component (B) is 0.01 to 100 ⁇ m. [4] The thermally conductive silicone composition according to any one of [1] to [3], wherein the component (B) is a metal powder, a metal oxide powder, a metal nitride powder, or a carbon powder.
- the thermally conductive silicone composition according to any one of [1] to [4], wherein the component (B) is silver powder, aluminum powder, aluminum oxide powder, zinc oxide powder, aluminum nitride powder, or graphite.
- the component (B) is (B1) a plate-like boron nitride powder having an average particle size of 0.1 to 30 ⁇ m, and (B2) a granular boron nitride powder having an average particle size of 0.1 to 50 ⁇ m.
- An electric / electronic device comprising a member made of the heat conductive silicone composition according to any one of [1] to [6]. Is achieved.
- the object of the present invention can also be achieved by an electric / electronic device provided with a member made of the above heat conductive silicone composition.
- the present invention provides a heat conductive silicone composition having excellent heat resistance and heat conductivity, suppressing thickening in an uncured state, and having excellent handling workability, and an electric / electronic device using the same as a member. be able to.
- the thermally conductive silicone composition of the present invention comprises (A) 100 parts by mass of a specific alkoxysilyl group organopolysiloxane or a mixture containing the same in one molecule, and (B) 400 to 3,500 parts by mass of a thermally conductive filler.
- a non-curable (grease-like) thermally conductive silicone grease composition which is a curable thermally conductive silicone composition that cures to form a gel or cured product. May be.
- the composition will be described. *
- Component (A) has the general formula (a1): at least one silicon atom bond in one molecule: Wherein R 1 is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, R 2 is an alkyl group, R 3 is the same or different alkylene group, a Is an integer from 0 to 2, and p is an integer from 1 to 50), or an organopolysiloxane having an alkoxysilyl-containing group represented by: (a1) and (a2) at least 2 in one molecule Mixture with organopolysiloxane having an alkenyl group and no alkoxysilyl-containing group (in the mixture, the content of component (a1) is 10 to 100% by mass (however, not including 100% by mass) .) ⁇ . Accordingly, the component (a1) alone or a mixture with the component (a2) may be used, but the component (a1) needs to be contained in an amount of 10% by mass or more.
- Component (a1) is the main component of the present composition, suppresses thickening in an uncured state, and has an alkoxysilyl group in the molecule, and therefore functions as a surface treatment agent for component (B). For this reason, even when the component (B) is highly filled so as to be 400 to 3,500 parts by mass with respect to the entire component (A) (100 parts by mass), the viscosity of the resulting composition is increased. It is suppressed and handling workability is not impaired. *
- the component (a1) is an organopolysiloxane having an alkoxysilyl-containing group represented by the above general formula bonded to at least one silicon atom in one molecule.
- R 1 is an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, preferably a methyl group.
- R 2 is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, and is methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl Group, octyl group, nonyl group, decyl group, octadecyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; phenyl group, tolyl group, xylyl group, naphthyl group and other aryl groups; benzyl group, phenethyl group Aralkyl groups such as phenylpropyl group; halogenated alkyl groups such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc.
- R 3 in the above formula is the same or different divalent organic group, and is an alkylene group such as an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group or an octylene group; an ethyleneoxyethylene group ,
- An alkyleneoxyalkylene group such as a propyleneoxyethylene group and a propyleneoxypropylene group is exemplified, preferably an alkylene group, and particularly preferably an ethylene group.
- p is an integer of 1 to 50, preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
- a is an integer of 0 to 2, and preferably 0.
- alkoxysilyl-containing group for example, as an alkoxysilyl-containing group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: A group represented by the formula: The group represented by these is illustrated.
- the component (a1) is optional and may have an average of 0.5 or more alkenyl groups, and particularly has an alkenyl group when the thermally conductive silicone composition is cured by a hydrosilylation reaction.
- alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferable.
- the organic group bonded to the other silicon atom in the component (a1) the same aliphatic unsaturated bond as the above R 1 such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a halogenated alkyl group
- a monovalent hydrocarbon group having no hydrogen atom, and an alkyl group and an aryl group are preferable, and a methyl group and a phenyl group are particularly preferable.
- the thermally conductive silicone composition of the present invention when curable, it preferably has an average of at least 0.5 and less than 20 alkenyl groups in one molecule.
- the bonding position of the alkenyl group is not limited and may be either the molecular chain end or the molecular chain side chain.
- the component (a1) has at least one alkoxysilyl-containing group in one molecule, but is highly filled with the component (B), and realizes excellent handling workability by suppressing thickening in an uncured state.
- the upper limit of the number of alkoxysilyl-containing groups in one molecule is not particularly limited, but is preferably 20 or less. This is because even if the number of alkoxysilyl-containing groups in one molecule exceeds 20, suppression of increase in viscosity and significant improvement in handling workability when highly charged with a heat conductive filler cannot be expected.
- the bonding position of the alkoxysilyl-containing group is not limited, and may be either a molecular chain end or a molecular chain side chain.
- the molecular structure of the component (a1) is not particularly limited, and examples thereof include linear, partially branched linear, branched, network, and dendritic.
- the component (a1) may be a mixture of organopolysiloxanes having such a molecular structure.
- the component (a1) is preferably a linear organopolysiloxane that bonds the alkoxysilyl-containing group to silicon atoms at both ends of the molecular chain and the side chains of the molecular chain.
- the viscosity at 25 ° C. of the component (a1) is not particularly limited, but is preferably 20 mPa ⁇ s or more, and particularly preferably in the range of 100 to 1,000,000 mPa ⁇ s. This is because when the viscosity is lowered, the physical properties, particularly flexibility and elongation, of the resulting cured product are significantly reduced.
- X is an alkoxysilyl-containing group exemplified above
- n ′ and n ′′ are each an integer of 1 or more
- n ′ ′′ is a number of 0 or more.
- b, d, and e are positive numbers
- c is a number of 0 or more.
- Such component (a1) has an alkenyl group-containing organopolysiloxane and a general formula for the alkenyl group: Can be prepared by hydrosilylation reaction in the presence of a catalyst for hydrosilylation reaction.
- R 1 , R 2 , R 3 , p, and a are the same as described above.
- the component (a2) is an arbitrary component, and is an organopolysiloxane having at least two alkenyl groups in one molecule and not having the alkoxysilyl-containing group.
- the component (a2) includes an alkenyl group-containing organopolysiloxane and the above general formula:
- the alkoxysilyl-containing siloxane represented by the formula (1) may be added separately from the reactant.
- alkenyl group in component (a2) examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is preferable.
- the bonding position of the alkenyl group is not particularly limited, and examples thereof include molecular chain ends or molecular chain side chains.
- the organic group bonded to the silicon atom other than the alkenyl group in the component (a2) the same alkyl group, cycloalkyl group, aryl group, aralkyl group, halogenated alkyl group and the like as those described above for R 2 And monovalent hydrocarbon groups having no group unsaturated bond are exemplified, preferably an alkyl group and an aryl group, and particularly preferably a methyl group and a phenyl group.
- the molecular structure of the component (a2) is not particularly limited, and examples include linear, partially branched linear, branched, cyclic, network, and dendritic.
- the component (a2) may be a mixture of two or more having these molecular structures.
- the molecular structure of the component (a2) is preferably linear.
- the viscosity at 25 ° C. of the component (a2) is not particularly limited, and is preferably in the range of 20 to 1,000,000 mPa ⁇ s, for example, particularly in the range of 100 to 100,000 mPa ⁇ s. Preferably there is. This is because when the viscosity at 25 ° C. is less than the lower limit of the above range, the physical properties of the resulting composition may be lowered. On the other hand, when the upper limit of the above range is exceeded, the resulting composition has a high viscosity. This is because the handling workability may be significantly deteriorated.
- Examples of the component (a2) include: a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both molecular chain terminals, a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer with both molecular chain terminals, Dimethylvinylsiloxy group-blocked dimethylpolysiloxane with both ends of molecular chain, dimethylvinylsiloxy group-blocked methylphenylpolysiloxane with both ends of molecular chain, dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, both ends of molecular chain Examples thereof include dimethylphenylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer and molecular chain both
- the component (a2) is an optional component, its blending amount is arbitrary, but when used in combination with the component (a1), the content of the component (a2) is the same as the component (a1) and the component (a2). In the mixture with the component, within the range of 0 to 90% by mass (excluding 0% by mass), that is, the content of the component (a1) is 10 to 100% by mass (however, not including 100% by mass) )). *
- Component (A) is the main component of the thermally conductive silicone composition of the present invention, and contains component (a1) having the above alkoxysilyl-containing group, and thus effectively suppresses thickening of the composition in an uncured state.
- component (B) since it has an alkoxysilyl group in the molecule, it also functions as a surface treatment agent for the component (B). For this reason, even when the component (B) is highly filled so as to be 400 to 3,500 parts by mass with respect to the entire component (A) (100 parts by mass), the viscosity of the resulting composition is increased. And a composition having excellent thermal conductivity at a viscosity at 25 ° C.
- the component (A) may have a part or all of a curable functional group, such as hydrosilylation reaction curable organopolysiloxane; dealcohol condensation reaction, dehydration condensation reaction, dehydrogenation.
- a curable functional group such as hydrosilylation reaction curable organopolysiloxane; dealcohol condensation reaction, dehydration condensation reaction, dehydrogenation.
- condensation reaction such as condensation reaction, deoxime condensation reaction, deacetic acid condensation reaction, deacetone condensation reaction
- a high energy ray-curable organopolysiloxane that undergoes a curing reaction by a high energy ray (for example, ultraviolet rays or the like) such as a radical reaction or a cationic polymerization reaction of an epoxy group or a vinyl ether group.
- a high energy ray for example, ultraviolet rays or the like
- the component (A) has a curable functional group such as an alkenyl group, it can be used as a non-curable silicone grease composition unless a curing catalyst or a crosslinking agent is blended. . Even when (a3) an organopolysiloxane having at least two silicon-bonded hydrogen atoms is contained in one molecule described later, a non-curable silicone grease composition can be obtained by using no curing catalyst. Can be used. *
- thermally conductive silicone composition of the present invention is a curable composition
- it is not particularly limited in the curing system, but hydrosilylation reaction; dealcohol condensation reaction, dehydration condensation reaction, dehydrogenation condensation reaction, dehydrogenation reaction, and the like. It is preferable to cure by a condensation reaction such as an oxime condensation reaction, a deacetic acid condensation reaction, and a deacetone condensation reaction.
- the thermally conductive silicone composition of the present invention may further contain (a3) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
- organopolysiloxane having silicon-bonded hydrogen atoms at both ends of the molecular chain and in the molecular chain oil bleed from this composition (including non-cured grease-like composition) is effectively suppressed. There are cases where it is possible.
- component (a3) is an organopolysiloxane having two alkenyl groups in one molecule in the presence of a hydrosilylation reaction catalyst. It is a crosslinking agent.
- the organic group bonded to the silicon atom in component (a3) is a monovalent hydrocarbon having no aliphatic unsaturated bond such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogenated alkyl group. Examples of the group include an alkyl group and an aryl group, and a methyl group and a phenyl group are particularly preferable.
- the molecular structure of the component (a3) is not particularly limited, and examples thereof include linear, partially branched linear, branched, cyclic, network, and dendritic, and are preferably linear.
- the viscosity of component (a3) at 25 ° C. is not particularly limited but is preferably in the range of 1 to 10,000 mPa ⁇ s. *
- Examples of such component (a3) include molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane copolymer, molecular chain both ends dimethylhydrogen.
- Examples include a siloxy group-capped methylhydrogensiloxane / dimethylsiloxane copolymer, a dimethylhydrogensiloxy group-capped dimethylpolysiloxane having molecular ends at both ends, and a mixture of two or more of these organopolysiloxanes.
- the content of component (a3) is such that the silicon atom-bonded hydrogen atom in this component is one alkenyl group in component (a1) and component (a2). Is an amount within the range of 0.3 to 20. This is because if the content of the component (a3) is less than the lower limit of the above range, the resulting composition will not sufficiently cure, whereas if the upper limit of the above range is exceeded, the resulting composition will be This is because hydrogen gas may be generated during the curing process, and the heat resistance of the obtained cured product may be significantly reduced.
- the above condition can be achieved by blending component (a3) in a range of 0.5 to 50 parts by mass with respect to 100 parts by mass of the sum of component (a1) and component (a2). *
- a component is a heat conductive filler for providing thermal conductivity to this composition.
- Such (B) component was selected from the group consisting of pure metal, alloy, metal oxide, metal hydroxide, metal nitride, metal carbide, metal silicide, carbon, soft magnetic alloy and ferrite, At least one kind of powder and / or fiber is preferable, and metal powder, metal oxide powder, metal nitride powder, or carbon powder is preferable.
- these powders and / or fibers those treated with various surface treating agents known as coupling agents may be used.
- the surface treatment agent for treating the powder and / or fiber of the component (B) include surfactants, silane coupling agents, aluminum coupling agents, and silicone surface treatment agents.
- the component (D) and / or (B) described later is an organopolysiloxane having a silanol group at both ends of a molecular chain having a viscosity of 20 to 100 mPa ⁇ s at 25 ° C., particularly preferably both ends of the molecular chain.
- Pure metals include bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron and metallic silicon.
- Examples of the alloy include alloys made of two or more metals selected from the group consisting of bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, aluminum, iron, and metallic silicon.
- Examples of the metal oxide include alumina, zinc oxide, silicon oxide, magnesium oxide, beryllium oxide, chromium oxide, and titanium oxide.
- Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, barium hydroxide, and calcium hydroxide.
- Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride.
- Examples of the metal carbide include silicon carbide, boron carbide, and titanium carbide.
- Metal silicides include magnesium silicide, titanium silicide, zirconium silicide, tantalum silicide, niobium silicide, chromium silicide, tungsten silicide and molybdenum silicide.
- Examples of carbon include diamond, graphite, fullerene, carbon nanotube, graphene, activated carbon, and amorphous carbon black.
- soft magnetic alloys include Fe-Si alloys, Fe-Al alloys, Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Ni alloys, Fe-Ni-Co alloys, Fe-Ni-Mo alloys, Fe -Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy and Fe-Si-Co-B alloy.
- the ferrite include Mn—Zn ferrite, Mn—Mg—Zn ferrite, Mg—Cu—Zn ferrite, Ni—Zn ferrite, Ni—Cu—Zn ferrite and Cu—Zn ferrite.
- the component (B) is at least one powder and / or fiber selected from these.
- the component (B) is preferably silver powder, aluminum powder, aluminum oxide powder, zinc oxide powder, aluminum nitride powder or graphite.
- the composition is preferably a metal oxide powder or a metal nitride powder, particularly an aluminum oxide powder, a zinc oxide powder, or an aluminum nitride powder. Preferably there is.
- the shape of (B) 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 and indefinite shape.
- the average particle size of the component (B) is not particularly limited, but is preferably in the range of 0.01 to 100 ⁇ m, and more preferably in the range of 0.01 to 50 ⁇ m.
- the component (B) having a large particle size and the component (B) having a small particle size can be used in combination.
- the different thermally conductive fillers may be the same or different.
- Component (B) includes (B1) a plate-like boron nitride powder having an average particle size of 0.1 to 30 ⁇ m, (B2) a granular boron nitride powder having an average particle size of 0.1 to 50 ⁇ m, and (B3 ) Spherical and / or crushed aluminum oxide powder having an average particle size of 0.01 to 50 ⁇ m, or (B4) Spherical and / or crushed graphite having an average particle size of 0.01 to 50 ⁇ m, or 2 of these A mixture of two or more types is particularly preferred.
- the content of component (B) is in the range of 400 to 3,500 parts by mass, preferably in the range of 400 to 3,000 parts by mass, with respect to 100 parts by mass of component (A). This is because if the content of the component (B) is less than the lower limit of the above range, the thermal conductivity of the resulting composition will be insufficient, whereas if it exceeds the upper limit of the above range, the viscosity of the resulting composition will be This is because it becomes extremely high and the handling workability is lowered.
- the heat conductive silicone composition of the present invention has a viscosity at 25 ° C. of 1500 mPa ⁇ s or less, preferably 1000 mPa ⁇ s or less, more preferably within the range of the content of the component (B). A composition having excellent thermal conductivity at 500 mPa ⁇ s or less can be obtained, and it is extremely excellent in handling workability as both a grease material and a curable material.
- the thermally conductive silicone composition of the present invention comprises the components (A) and (B), and is preferably a non-curable thermally conductive silicone grease composition.
- the heat conductive silicone composition may be used.
- the thermally conductive silicone composition of the present invention contains (C) a curing catalyst, and depending on the curing reaction system of component (A), a hydrosilylation reaction catalyst; a condensation reaction catalyst One or two or more kinds selected from radical polymerization initiators such as organic acid peroxides and azo compounds; and photosensitizers can be used.
- a hydrosilylation reaction catalyst or condensation reaction-curable organopolysiloxane, which includes a hydrosilylation reaction catalyst or a condensation reaction catalyst. It is preferable. Further, it may be a curing system including both a hydrosilylation reaction catalyst and a condensation reaction catalyst.
- the catalyst for hydrosilylation reaction is a component for curing the present composition containing the hydrosilylation reaction-curable organopolysiloxane.
- Such components include platinum black, platinum-supported activated carbon, platinum-supported silica fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum olefin complex, platinum vinylsiloxane complex, and other platinum-based catalysts; Palladium-based catalysts such as phenylphosphine) palladium; rhodium-based catalysts are exemplified.
- the component (C) is preferably a platinum-based hydrosilylation reaction catalyst.
- the amount used is a catalyst amount and can be appropriately selected according to the desired curing conditions, but is generally in the range of about 1 to 1000 ppm with respect to the curable organopolysiloxane.
- the condensation reaction catalyst is a component for curing the present composition containing the condensation reaction curable organopolysiloxane.
- the curability of the present composition at room temperature to 50 ° C. or less and the adhesion to various substrates can be improved. There are cases where it is possible.
- condensation reaction catalysts include, for example, tin compounds such as dimethyltin dineodecanoate and stannous octoate; tetra (isopropoxy) titanium, tetra (n-butoxy) titanium, tetra (t-butoxy) titanium, Examples include titanium compounds such as di (isopropoxy) bis (ethylacetoacetate) titanium, di (isopropoxy) bis (methylacetoacetate) titanium, and di (isopropoxy) bis (acetylacetonate) titanium.
- tin compounds such as dimethyltin dineodecanoate and stannous octoate
- titanium compounds such as di (isopropoxy) bis (ethylacetoacetate) titanium, di (isopropoxy) bis (methylacetoacetate) titanium, and di (isopropoxy) bis (acetylacetonate) titanium.
- the amount of the catalyst used is a catalyst amount and can be appropriately selected according to the desired curing conditions, but is in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the curable organopolysiloxane in the entire composition. It is common.
- composition according to the present invention contains 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol as an optional component for improving storage stability and handling workability.
- the content of these curing inhibitors should be appropriately selected according to the curing conditions of the present composition. For example, 0.001 to 5 parts by mass with respect to 100 parts by mass in total of the organopolysiloxane having reactive functional groups. It is preferable to be within the range. In addition, when hardening this composition at room temperature, it is preferable not to contain.
- the heat conductive silicone composition concerning this invention may contain the (D) silica type filler as other arbitrary components.
- the component (D) include fumed silica, fused silica, precipitated silica, and fillers obtained by surface-treating these surfaces with organosilicon compounds such as organoalkoxysilane, organochlorosilane, and organosilazane. It is done.
- the component (B) and / or the component (D) is an organopolysiloxane having a silanol group at both ends of a molecular chain having a viscosity at 25 ° C. of 20 to 100 mPa ⁇ s, particularly preferably at both ends of the molecular chain.
- the content of the component (D) is not particularly limited, but is preferably in the range of 1 to 100 parts by weight, and more preferably in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the component (A). In particular, it is preferably in the range of 1 to 20 parts by mass.
- the present composition may contain (E) a coupling agent as other optional components.
- a coupling agent examples include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N- (2-aminoethyl).
- silane coupling agents such as silane
- titanium coupling agents such as tetrabutyl titanate and tetraisopropyl titanate.
- the content of the component (E) is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the component (A). It is preferable to be within the range.
- pigments such as carbon black and bengara; other dyes, fluorescent dyes, heat-resistant additives, flame retardants, You may contain a plasticizer and an adhesion imparting agent.
- the method for preparing this composition is not particularly limited. For example, the method of mixing the component (A) and the component (B) at the same time; after mixing the component (A), the component (B), and the component (E) (A3) A component is added and mixed; after (A) component, (B) component, and (D) component are mixed, the method of mixing (a3) component to this is mentioned.
- a curing catalyst as component (C) and optionally a curing inhibitor may be added after the mixing step.
- the component (A) when mixing the component (A) and the component (B), it is preferable to mix them by heating. It is preferable to heat and mix at a temperature of 0 to 200 ° C.
- the component (A) is an organopolysiloxane having an alkoxysilyl-containing group, and in order to accelerate the surface treatment of the component (B), acetic acid, phosphoric acid, in addition to the above heating mixing or in addition to the above heating mixing
- a catalytic amount of an acidic substance such as trialkylamine, quaternary ammonium salts, ammonia gas, or ammonium carbonate may be added.
- the heat conductive silicone composition of the present invention is a heat transfer material that is interposed at the interface between a heat boundary surface of a heat generating electronic component and a heat radiating member such as a heat sink or a circuit board for cooling of the electric / electronic component by heat conduction. It is useful as a (thermally conductive member).
- an electronic circuit board such as a printed board; a diode (LED), an organic electric field element (organic EL) ), IC chips packaged with optical semiconductor elements such as laser diodes and LED arrays; CPUs used in electronic devices such as personal computers, digital video disks, mobile phones, smartphones; LSI chips such as driver ICs and memories Is exemplified.
- heat removal heat dissipation
- Thermally conductive members made of silicone compositions can be used for power semiconductor applications such as engine control, power train systems, and air conditioner control in transportation equipment. Excellent workability and excellent heat resistance and thermal conductivity can be realized even when used in a harsh environment by being incorporated in an in-vehicle electronic component such as an electronic control unit (ECU).
- ECU electronice control unit
- thermally conductive silicone composition of the present invention can be used as a non-curable thermally conductive silicone grease composition or a curable thermally conductive silicone composition applied to these substrates.
- the present invention is not limited by these.
- the adhesiveness of the protective agent composition for electrical / electronic parts according to the present invention was evaluated by the following method.
- the viscosity of the thermally conductive silicone composition was measured using a rheometer (AR550) manufactured by TA Instruments. The geometry used a 20 mm diameter plate. The viscosity was a value of Shearrate 1 (1 / s). Moreover, the thing with remarkable viscosity increase in the mixing process was evaluated as a viscosity "x”.
- Thermal conductivity Using a resin material thermal resistance measuring device manufactured by Hitachi, Ltd., the thermal resistance at 50 ° C. of a thermally conductive silicone grease composition having an area of 1 cm ⁇ 1 cm, a thickness of 200 ⁇ m and a thickness of 500 ⁇ m was measured. The thermal conductivity was determined.
- each component used is as follows.
- the viscosity is a value measured with a rotational viscometer at 25 ° C.
- A1-1) Both-end modified polysiloxane: Dimethylpolysiloxane having the above alkoxysilyl-containing groups at both ends of the molecular chain (viscosity 400 mPa ⁇ s) (a1-2)
- Example 1 After premixing the organopolysiloxane having an alkoxysilyl-containing group, the Vi-terminated siloxane, and the thermally conductive filler as the component (B) for 30 minutes at room temperature in the parts shown in Table 1, The mixture was heated and mixed at 150 ° C. for 60 minutes under reduced pressure. Thereafter, it is cooled to room temperature, and if necessary, (a3) SiH siloxane and (C) Pt complex are added to form a grease-like thermally conductive silicone composition (Examples 1, 2, 4, 5) or curability. A thermally conductive silicone composition (Example 3) was obtained. *
- thermally conductive silicone compositions of the present invention shown in Examples 1 to 4 are entirely contained even when various thermal conductive fillers are contained about 10 times (mass unit) with respect to the silicone material as the main component.
- the viscosity was suppressed to 1000 mPa ⁇ s or less, and high thermal conductivity could be realized.
- the heat conductive silicone compositions shown in Comparative Examples 1 and 2 when the same amount and the same kind of heat conductive filler were blended, the viscosity increased remarkably and the handling workability was insufficient.
- Example 5 which mix
- the heat conductive silicone composition of this application was able to implement
- Comparative Example 3 using the same type of thermally conductive filler the viscosity increased remarkably, and a practically thermally conductive grease could not be prepared.
- the heat conductive silicone composition is excellent in heat resistance and heat conductivity, and has low viscosity and excellent handling workability. Therefore, a highly integrated CPU, LSI chip, IC chip packaged with an optical semiconductor element, etc.
- the performance and reliability can be improved by using as a heat dissipation component.
- it is also useful as a heat dissipation component for power devices such as motor control used in high temperature conditions, motor control for transport aircraft, power generation systems, or space transport systems, which has been in increasing demand in recent years.
- General-purpose inverter control such as engine control, power train system, air-conditioner control, in-vehicle electronic parts such as electronic control unit (ECU), servo motor control, motor control such as machine tool / elevator, electric vehicle, hybrid car, or rail transportation It is useful as a heat dissipating part for machine motor control, generator systems such as solar, wind, and fuel cell power generation, and space transportation systems used in outer space.
- ECU electronice control unit
- servo motor control motor control
- motor control such as machine tool / elevator, electric vehicle, hybrid car, or rail transportation It is useful as a heat dissipating part for machine motor control, generator systems such as solar, wind, and fuel cell power generation, and space transportation systems used in outer space.
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Abstract
Description
、前記R1と同様のアルキル基、シクロアルキル基、アリール基、アラルキル基、ハロゲン化アルキル基等の脂肪族不飽和結合を有さない一価炭化水素基が例示され、好ましくは、アルキル基、アリール基であり、特に好ましくは、メチル基、フェニル基である。特に、本発明の熱伝導性シリコーン組成物が硬化性の場合、一分子中に少なくとも平均0.5個以上、20個未満のアルケニル基を有することが好ましい。このアルケニル基の結合位置は限定されず、分子鎖末端、分子鎖側鎖のいずれであってもよい。
適である。これらの粉体及び/又はファイバーとして、カップリング剤として知られている各種表面処理剤により処理されているものを用いてもよい。(B)成分の粉体及び/又はファイバーを処理するための表面処理剤としては、界面活性剤、シランカップリング剤、アルミニウム系カップリング剤及びシリコーン系表面処理剤などが挙げられる。特に、後述する(D)成分及び/又は(B)成分を、25℃における粘度が20~100mPa・sの分子鎖両末端にシラノール基を有するオルガノポリシロキサン、特に好適には、分子鎖両末端にシラノール基を有し、分子中に当該末端シラノール基以外の反応性官能基を有しないジメチルポリシロキサンにより表面処理することにより、比較的低温かつ短時間で硬化させた場合の初期接着性に優れ、硬化後は、特に接着耐久性に優れ及び高い接着強度を実現でき、かつ、1液型の硬化性組成物とした場合、十分な使用可能時間(保存期間および取り扱い作業時間)を確保できる場合がある。
0~200℃の温度で加熱混合することが好ましい。特に、(A)成分はアルコキシシリル含有基を有するオルガノポリシロキサンであり、(B)成分の表面処理を促進するため、上記の加熱混合と同時にあるいは上記の加熱混合のほかに、酢酸、リン酸などの酸性物質や、トリアルキルアミン、4級アンモニウム塩類、アンモニアガス、炭酸アンモニウムなどの塩基性物質を触媒量添加してもよい。
Claims (10)
- (A) (a1)一分子中に、少なくとも1個のケイ素原子結合の一般式:
- (B)成分の平均粒子径が0.01~100μmである、請求項1または請求項2記載の熱伝導性シリコーン組成物。
- (B)成分が、金属系粉末、金属酸化物系粉末、金属窒化物系粉末、または炭素粉末である、請求項1~3のいずれか記載の熱伝導性シリコーン組成物。
- (B)成分が、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、窒化アルミニウム粉末またはグラファイトである、請求項1~4のいずれか記載の熱伝導性シリコーン組成物。
- (B)成分が、(B1)平均粒径が0.1~30μmである板状の窒化ホウ素粉末、(B2)平均粒径が0.1~50μmである顆粒状の窒化ホウ素粉末、(B3)平均粒径が0.01~50μmである球状及び/若しくは破砕状の酸化アルミニウム粉末、又は(B4)平均粒径が0.01~50μmであるグラファイト、或いはこれらの2種類以上の混合物である、請求項1~5のいずれか記載の熱伝導性シリコーン組成物。
- 熱伝導性シリコーングリース組成物である、請求項1~6のいずれか記載の熱伝導性シリコーン組成物。
- 硬化性熱伝導性シリコーン組成物である、請求項1~6のいずれか記載の熱伝導性シリコーン組成物。
- 請求項1~6のいずれか記載の熱伝導性シリコーン組成物からなる部材を備えた電気・電子機器。
- 請求項1~6のいずれか記載の熱伝導性シリコーン組成物からなる電気・電子機器用の放熱部材。
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US15/302,555 US10150902B2 (en) | 2014-04-09 | 2015-03-26 | Thermally conductive silicone composition and electrical/electronic apparatus |
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JP2016512584A JP6468660B2 (ja) | 2014-04-09 | 2015-03-26 | 熱伝導性シリコーン組成物および電気・電子機器 |
CN201580030470.5A CN106414613B (zh) | 2014-04-09 | 2015-03-26 | 导热有机硅组合物和电气电子设备 |
KR1020167031212A KR102348372B1 (ko) | 2014-04-09 | 2015-03-26 | 열전도성 실리콘 조성물 및 전기·전자 기기 |
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EP3141583B1 (en) | 2021-03-10 |
EP3141583A4 (en) | 2018-02-28 |
CN106414613A (zh) | 2017-02-15 |
US10150902B2 (en) | 2018-12-11 |
TW201542695A (zh) | 2015-11-16 |
CN106414613B (zh) | 2019-12-27 |
TWI656175B (zh) | 2019-04-11 |
KR102348372B1 (ko) | 2022-01-11 |
KR20160143783A (ko) | 2016-12-14 |
JPWO2015155948A1 (ja) | 2017-04-13 |
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