WO2024224832A1 - 熱伝導性シリコーン樹脂組成物 - Google Patents

熱伝導性シリコーン樹脂組成物 Download PDF

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WO2024224832A1
WO2024224832A1 PCT/JP2024/008950 JP2024008950W WO2024224832A1 WO 2024224832 A1 WO2024224832 A1 WO 2024224832A1 JP 2024008950 W JP2024008950 W JP 2024008950W WO 2024224832 A1 WO2024224832 A1 WO 2024224832A1
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thermally conductive
resin composition
silicone resin
mass
conductive silicone
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French (fr)
Japanese (ja)
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片石拓海
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Fuji Polymer Industries Co Ltd
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Fuji Polymer Industries Co Ltd
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    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
    • 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
    • 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

Definitions

  • the present invention relates to a thermally conductive silicone resin composition that is suitable for placement between a heat generating part of an electric or electronic component and a heat sink.
  • thermally conductive grease is used to improve the adhesion between the heat sink and the heat source, such as a semiconductor. As devices become smaller, more powerful, and more highly integrated, thermally conductive grease is required to have high thermal conductivity as well as drop resistance.
  • JP 2018-104714 A proposes a composition containing a thermally conductive filler, a polyorganosiloxane resin containing at least one polysiloxane having one curable functional group in the molecule, and a siloxane compound having an alkoxysilyl group and a linear siloxane structure.
  • JP 2016-044213 A proposes a thermally conductive silicone composition containing liquid silicone, a thermally conductive filler, and hydrophobic spherical silica microparticles, and having improved heat dissipation.
  • JP 2004-131540 A proposes a resin sheet in which a thermally conductive filler is blended with an ⁇ -olefin copolymer containing two or more ⁇ -olefins having 2 to 12 carbon atoms.
  • JP 2004-143195 A proposes a resin sheet in which a surface-treated thermally conductive filler is blended with an ⁇ -olefin copolymer containing two or more ⁇ -olefins having 2 to 12 carbon atoms.
  • Patent Publication No. 7047199 the inventors proposed a thermally conductive grease that combines an ethylene- ⁇ -olefin copolymer with a thermally conductive filler.
  • the present invention provides a thermally conductive silicone resin composition
  • a matrix resin component (A) and thermally conductive inorganic particles (B) The matrix resin component (A) contains, relative to 100 parts by mass of the matrix resin component (A), 70 to 99 parts by mass of liquid dimethylpolysiloxane (A1), A mixed oil (A2) of polydecene and an ethylene-propylene copolymer is contained in an amount of 1 to 30 parts by mass,
  • the liquid dimethylpolysiloxane (A1) has a kinetic viscosity at 40° C. of 50 to 10,000 mm 2 /s
  • the mixed oil (A2) has a kinetic viscosity at 40° C. of 1 to 1,000 mm 2 /s
  • the thermally conductive silicone resin composition contains 400 to 3,000 parts by mass of the thermally conductive inorganic particles (B) per 100 parts by mass of the matrix resin component (A).
  • FIG. 1A and 1B are explanatory diagrams showing a method for measuring the thermal conductivity of a sample in one embodiment of the present invention.
  • 2A to 2D are schematic explanatory views illustrating a drop test used in one embodiment of the present invention.
  • FIG. 3 is a scanning electron microscope (SEM) photograph (magnification: 5000 times) of amorphous alumina (B1) (D50 (median diameter) is 0.3 ⁇ m) used in one embodiment of the present invention.
  • FIG. 4 is an SEM photograph (magnification: 2000 times) of amorphous alumina (B1) (D50 (median diameter) is 2.3 ⁇ m) used in one embodiment of the present invention.
  • FIG. 5 is an SEM photograph (magnification 2000 times) of amorphous aluminum nitride (B2) (D50 (median diameter) is 15 ⁇ m) used in one embodiment of the present invention.
  • FIG. 6 is an SEM photograph (magnification: 100 times) of spherical alumina (B3) (D50 (median diameter) is 105 ⁇ m) used in one embodiment of the present invention.
  • thermally conductive silicone grease of the above-mentioned prior art had the problem of dripping when clamped vertically.
  • greases have been reported that use ethylene-propylene copolymers to improve drop resistance, but these have the problem of being more viscous than those that use silicone.
  • silicone greases that use a mixture of silicone and ethylene-propylene copolymers to improve drop resistance and have a relatively low viscosity have been reported, but a grease with even better ejection properties was desired.
  • the present invention provides a thermally conductive silicone resin composition that has high thermal conductivity, is relatively resistant to dripping, and has good ejection properties.
  • the present invention provides a thermally conductive silicone resin composition
  • a matrix resin component (A) and thermally conductive inorganic particles (B) The matrix resin component (A) contains, relative to 100 parts by mass of the matrix resin component (A), 70 to 99 parts by mass of liquid dimethylpolysiloxane (A1), A mixed oil (A2) of polydecene and an ethylene-propylene copolymer is contained in an amount of 1 to 30 parts by mass,
  • the liquid dimethylpolysiloxane (A1) has a kinetic viscosity at 40° C. of 50 to 10,000 mm 2 /s
  • the mixed oil (A2) has a kinetic viscosity at 40° C. of 1 to 1,000 mm 2 /s
  • the thermally conductive silicone resin composition contains 400 to 3,000 parts by mass of the thermally conductive inorganic particles (B) per 100 parts by mass of the matrix resin component (A).
  • the present invention by adopting the above-mentioned configuration, can provide a thermally conductive silicone resin composition that has high thermal conductivity, is relatively resistant to dripping, and has good dischargeability. That is, by providing a thermally conductive silicone resin composition that contains a liquid dimethylpolysiloxane (A1) of a specific viscosity as the matrix resin component (A) and a mixed oil (A2) of polydecene and an ethylene-propylene copolymer, and contains 400 to 3,000 parts by mass of the thermally conductive inorganic particles (B) per 100 parts by mass of the matrix resin component (A), it is possible to provide a thermally conductive silicone resin composition that has high thermal conductivity, is relatively resistant to dripping, and has good dischargeability.
  • A1 liquid dimethylpolysiloxane
  • A2 a mixed oil
  • B thermally conductive inorganic particles
  • the thermally conductive silicone resin composition of the present invention contains a matrix resin component (A) and thermally conductive inorganic particles (B).
  • the matrix resin component (A) contains 70 to 99 parts by mass of liquid dimethylpolysiloxane (A1) and 1 to 30 parts by mass of a mixed oil of polydecene and an ethylene-propylene copolymer (A2) per 100 parts by mass of the matrix resin component (A).
  • liquid dimethylpolysiloxane (A1) has a kinetic viscosity at 40° C. of 50 to 10,000 mm 2 /s, preferably 60 to 9,000 mm 2 /s, and more preferably 70 to 8,000 mm 2 /s.
  • a thermally conductive silicone resin composition that has high thermal conductivity, is relatively resistant to dripping, and has good dischargeability.
  • liquid dimethylpolysiloxane (A1) is 70 to 99 parts by mass, preferably 71 to 98 parts by mass, and more preferably 72 to 98 parts by mass, per 100 parts by mass of matrix resin component (A).
  • the kinematic viscosity of the mixed oil (A2) of polydecene and ethylene-propylene copolymer at 40°C is 1 to 1,000 mm 2 /s, preferably 5 to 900 mm 2 /s, and more preferably 10 to 800 mm 2 /s.
  • the mixed oil (A2) of polydecene and ethylene-propylene copolymer is a hydrocarbon-based synthetic oil that does not contain a polar group, and is commercially available from Mitsui Chemicals under the trade name "Lucant" HC-10.
  • This mixed oil (A2) has a specific gravity of 0.83 (density is 0.83 g/cm 3 ), and by containing this, there is an advantage in that the specific gravity of the thermally conductive silicone resin composition is lightened.
  • a mixed oil (A2) it is possible to obtain a thermally conductive silicone resin composition having high thermal conductivity, relatively less dripping, and good dischargeability.
  • the content of the mixed oil (A2) is 1 to 30 parts by mass, preferably 2 to 29 parts by mass, and more preferably 3 to 28 parts by mass, per 100 parts by mass of the matrix resin component (A).
  • the mixed oil (A2) preferably contains 30 to 99 mass% polydecene and 1 to 70 mass% ethylene-propylene copolymer, more preferably 35 to 95 mass% polydecene and 5 to 65 mass% ethylene-propylene copolymer, and even more preferably 40 to 90 mass% polydecene and 10 to 60 mass% ethylene-propylene copolymer, relative to 100 mass% mixed oil (A2).
  • the thermally conductive inorganic particles (B) preferably include thermally conductive inorganic particles (B1) having a median particle size (D50) of 0.01 to 10 ⁇ m, thermally conductive inorganic particles (B2) having a median particle size (D50) of more than 10 ⁇ m and not more than 80 ⁇ m, and thermally conductive inorganic particles (B3) having a median particle size (D50) of more than 80 ⁇ m and not more than 150 ⁇ m.
  • thermally conductive inorganic particles (B) By using thermally conductive inorganic particles (B) having such a configuration, the thermally conductive inorganic particles (B) can be packed in a state close to closest packing in the thermally conductive silicone resin composition, and as a result, the thermal conductivity of the thermally conductive silicone resin composition can be increased.
  • the median particle size is the D50 (median diameter) of the cumulative particle size distribution based on volume measured by a laser diffraction light scattering method.
  • An example of this measuring device is the LA-950S2 laser diffraction/scattering type particle size distribution measuring device manufactured by Horiba, Ltd.
  • the thermally conductive inorganic particles (B1) are preferably amorphous alumina. This is because alumina is inexpensive.
  • the thermally conductive inorganic particles (B2) are preferably at least one inorganic particle selected from the group consisting of alumina, zinc oxide, magnesium oxide, aluminum nitride, boron nitride, aluminum hydroxide, and silicon carbide.
  • the shape of the thermally conductive inorganic particles (B2) is preferably amorphous.
  • the thermally conductive inorganic particles (B3) are preferably spherical alumina.
  • the thermally conductive inorganic particles (B3) it is preferable to use a combination of so-called submicron particles (B1-1) having a D50 (median diameter) of 0.01 ⁇ m or more and less than 1 ⁇ m, small particles (B1-2) having a D50 (median diameter) of 1 ⁇ m or more and 10 ⁇ m or less, and large particles (B3) having a D50 of more than 80 ⁇ m and 150 ⁇ m or less.
  • submicron particles (B1-1) having a D50 (median diameter) of 0.01 ⁇ m or more and less than 1 ⁇ m
  • small particles (B1-2) having a D50 (median diameter) of 1 ⁇ m or more and 10 ⁇ m or less
  • large particles (B3) having a D50 of more than 80 ⁇ m and 150 ⁇ m or less.
  • thermally conductive inorganic particles (B) of such a configuration the thermally conductive inorganic particles (B) can be closely packed in the thermally conductive silicone resin composition, and as a result, the thermal conductivity of the thermally conductive silicone resin composition can be increased.
  • amorphous alumina is manufactured by pulverization or crushing, and commercially available products can be used. These thermally conductive inorganic particles (B1), (B2) and (B3) have high thermal conductivity.
  • the mass ratio of the thermally conductive inorganic particles (B1), (B2), and (B3) is preferably (B2) ⁇ (B1) ⁇ (B3).
  • the thermally conductive inorganic particles (B) preferably contain 100 to 1,000 parts by mass of the thermally conductive inorganic particles (B1) relative to 100 parts by mass of the matrix resin component (A), more preferably 150 to 1,000 parts by mass, and even more preferably 300 to 850 parts by mass.
  • the thermally conductive inorganic particles (B) preferably contain 100 to 500 parts by mass of the thermally conductive inorganic particles (B2) relative to 100 parts by mass of the matrix resin component (A), more preferably 150 to 500 parts by mass, and even more preferably 200 to 450 parts by mass.
  • the thermally conductive inorganic particles (B) preferably contain 300 to 1,400 parts by mass of the thermally conductive inorganic particles (B3) relative to 100 parts by mass of the matrix resin component (A), more preferably 300 to 1,300 parts by mass, and even more preferably 500 to 1,200 parts by mass. This makes it possible to obtain a thermally conductive silicone resin composition that has high thermal conductivity, is relatively resistant to dripping, and has good dischargeability.
  • the thermally conductive inorganic particles (B) preferably contain 100 to 1,000 parts by mass of the thermally conductive inorganic particles (B1), 100 to 500 parts by mass of the thermally conductive inorganic particles (B2), and 300 to 1,400 parts by mass of the thermally conductive inorganic particles (B3) relative to 100 parts by mass of the matrix resin component (A), more preferably contain 150 to 1,000 parts by mass of the thermally conductive inorganic particles (B1), 150 to 500 parts by mass of the thermally conductive inorganic particles (B2), and 300 to 1,300 parts by mass of the thermally conductive inorganic particles (B3), and even more preferably contain 300 to 850 parts by mass of the thermally conductive inorganic particles (B1), 200 to 450 parts by mass of the thermally conductive inorganic particles (B2), and 500 to 1,200 parts by mass of the thermally conductive inorganic particles (B3).
  • the thermally conductive inorganic particles (B1) having a median particle diameter (D50) of 0.01 to 10 ⁇ m, the thermally conductive inorganic particles (B2) having a median particle diameter (D50) of more than 10 ⁇ m and not more than 80 ⁇ m, and the thermally conductive inorganic particles (B3) having a median particle diameter (D50) of more than 80 ⁇ m and not more than 150 ⁇ m may each contain two or more types of thermally conductive inorganic particles having different median particle diameters (D50).
  • thermally conductive inorganic particles (B) By using thermally conductive inorganic particles (B) having such a configuration, the thermally conductive inorganic particles (B) can be closely packed in the thermally conductive silicone resin composition, and as a result, the thermal conductivity of the thermally conductive silicone resin composition can be increased.
  • the thermally conductive inorganic particles (B1) contain two or more types of thermally conductive inorganic particles having different median particle diameters (D50).
  • the thermally conductive inorganic particles (B1) preferably include thermally conductive inorganic particles (B1-1) having a median particle diameter (D50) of 0.01 ⁇ m or more and less than 1 ⁇ m and thermally conductive inorganic particles (B1-2) having a median particle diameter (D50) of 1 ⁇ m or more and 10 ⁇ m or less, more preferably include thermally conductive inorganic particles (B1-1) having a median particle diameter (D50) of 0.05 ⁇ m or more and less than 1 ⁇ m and thermally conductive inorganic particles (B1-2) having a median particle diameter (D50) of 1 ⁇ m or more and 8 ⁇ m or less, and even more preferably include thermally conductive inorganic particles (B1-1) having a median particle diameter (D50) of 0.1 ⁇ m or more and less than 1 ⁇ m and thermally conductive inorganic particles (B1-2) having a median particle diameter (D50) of 1 ⁇ m or more and 5 ⁇ m or less
  • the thermally conductive inorganic particles (B) By using the thermally conductive inorganic particles (B) having such a configuration, the thermally conductive inorganic particles (B) can be closely packed in the thermally conductive silicone resin composition, and as a result, the thermal conductivity of the thermally conductive silicone resin composition can be increased.
  • the thermally conductive inorganic particles (B1) include the thermally conductive inorganic particles (B1-1) and the thermally conductive inorganic particles (B1-2)
  • the thermally conductive inorganic particles (B1) preferably include 50 to 400 parts by mass of the thermally conductive inorganic particles (B1-1) and 50 to 600 parts by mass of the thermally conductive inorganic particles (B1-2) relative to 100 parts by mass of the matrix resin component (A), more preferably include 50 to 400 parts by mass of the thermally conductive inorganic particles (B1-1) and 100 to 600 parts by mass of the thermally conductive inorganic particles (B1-2), and even more preferably include 100 to 350 parts by mass of the thermally conductive inorganic particles (B1-1) and 200 to 500 parts by mass of the thermally conductive inorganic particles (B1-2).
  • thermally conductive inorganic particles (B) By using thermally conductive inorganic particles (B) with this configuration, the thermally conductive inorganic particles (B) can be closely packed in the thermally conductive silicone resin composition, and as a result, the thermal conductivity of the thermally conductive silicone resin composition can be increased.
  • thermally conductive inorganic particles (B1) having a median particle size (D50) of 0.01 to 10 ⁇ m is surface-treated in advance with an alkoxysilane represented by the formula RaSi(OR') 4-a (wherein R is an unsubstituted or substituted organic group having 8 to 12 carbon atoms, R' is an alkyl group having 1 to 4 carbon atoms, and a is 0 or 1).
  • R is an unsubstituted or substituted organic group having 8 to 12 carbon atoms
  • R' is an alkyl group having 1 to 4 carbon atoms
  • a is 0 or 1
  • thermally conductive inorganic particles (B1) By surface-treating the thermally conductive inorganic particles (B1) in advance, it becomes easier to fill the thermally conductive inorganic particles (B1) into the matrix resin component (A), and it is effective in preventing the adsorption of a curing catalyst (e.g., a platinum-based catalyst) to the thermally conductive inorganic particles (B1), thereby preventing curing inhibition.
  • a curing catalyst e.g., a platinum-based catalyst
  • This is useful for storage stability.
  • small particles having a D50 (median diameter) of 10 ⁇ m or less tend to adsorb a curing catalyst, so it is preferable to surface-treat thermally conductive inorganic particles having a D50 (median diameter) of 10 ⁇ m or less.
  • the surface treatment here includes not only covalent bonding but also adsorption.
  • the surface-treated thermally conductive inorganic particles (B1) have good mixability with the matrix resin component (A). It is preferable to add 0.01 to 10 parts by mass of the alkoxysilane to 100 parts by mass of the thermally conductive inorganic particles.
  • alkoxysilane examples include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.
  • the alkoxysilanes can be used alone or in combination of two or more.
  • a surface treatment agent an alkoxysilane and a siloxane having a silanol terminal may be used in combination.
  • the content of the thermally conductive inorganic particles (B) is 400 to 3,000 parts by mass, preferably 500 to 2,900 parts by mass, and more preferably 600 to 2,800 parts by mass, per 100 parts by mass of the matrix resin component (A).
  • the thermally conductive silicone resin composition is produced by mixing the matrix resin component (A) with the thermally conductive inorganic particles (B) and, if necessary, other components.
  • the thermally conductive silicone resin composition further contains 0.1 to 8 parts by mass of an alkoxysilane represented by the formula RaSi(OR') 4-a (wherein R is an unsubstituted or substituted organic group having 8 to 12 carbon atoms, R' is an alkyl group having 1 to 4 carbon atoms, and a is 0 or 1) as a viscosity modifier.
  • R is an unsubstituted or substituted organic group having 8 to 12 carbon atoms
  • R' is an alkyl group having 1 to 4 carbon atoms
  • a is 0 or 1
  • alkoxysilane examples include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.
  • the alkoxysilanes can be used alone or in combination of two or more.
  • a surface treatment agent an alkoxysilane and a siloxane having a silanol terminal may be used in combination.
  • the thermal conductivity of the thermally conductive silicone resin composition is preferably 1.0 W/m ⁇ K or more, more preferably 1.0 to 10 W/m ⁇ K, and even more preferably 1.5 to 9 W/m ⁇ K.
  • a thermally conductive silicone resin composition is suitable as a heat sink between heat generating parts and heat dissipating parts of electronic components, etc.: a TIM (Thermal Interface Material).
  • the thermally conductive silicone resin composition preferably has an absolute viscosity at 23°C measured with a B-type viscometer at a rotation speed of 5 rpm using a T-E spindle in the range of 1,000 to 20,000 Pa ⁇ s, more preferably 1,000 to 18,000 Pa ⁇ s, and even more preferably 1,000 to 15,000 Pa ⁇ s.
  • Such a thermally conductive silicone resin composition has good ejection properties.
  • such a thermally conductive silicone resin composition has excellent workability and is easily injected (ejected) or applied between a heat generating part and a heat dissipating part.
  • the thermally conductive silicone resin composition is preferably subjected to a heat shock test in which 1.0 g of the thermally conductive silicone resin composition is placed between two plates, the two plates are compressed and sandwiched between the thermally conductive silicone resin composition so that the thickness of the layer made of the thermally conductive silicone resin composition is 1.0 mm, the plates are held in a heat shock tester so that the main surfaces of the plates are perpendicular to the ground, and the heat shock test is performed for 500 or 100 cycles, in which the heat shock test is performed at -40°C for 30 minutes, followed by heating, and then at 125°C for 30 minutes, followed by cooling to -40°C.
  • the thermally conductive silicone resin composition falls within 5 mm from the start of the test. This can increase the drop resistance and make it less likely to drip. It is even more preferable that the thermally conductive silicone resin composition falls within 5 mm from the start of the test in both the 500 and 100 cycles of the heat shock test.
  • the thermally conductive silicone resin composition is filled into a 30 mL syringe, and when discharged for 9 seconds with a discharge hole diameter of 2.5 mm and a discharge pressure of 0.5 MPa, the discharge amount is preferably 2 to 10 g, more preferably 2 to 9 g, and even more preferably 2 to 8 g. This allows the thermally conductive silicone resin composition to have high drop resistance and good dischargeability while being less likely to drip.
  • the thermally conductive silicone resin composition of the present invention can be used in the form of grease, putty, or liquid, but is preferably a thermally conductive grease.
  • the thermally conductive silicone resin composition of the present invention is a thermally conductive grease
  • the thermally conductive grease is suitable for filling a syringe and applying to a heat sink between a heat generating part and a heat dissipating part of an electronic component, etc.: a TIM (Thermal Interface Material).
  • the thermally conductive silicone resin composition of the present invention is in an uncured or non-cured state. Therefore, the thermally conductive silicone resin composition does not require a curing catalyst or a curing agent, but may be added in some cases.
  • the thermally conductive silicone resin composition of the present invention can contain components other than those mentioned above, if necessary.
  • the thermally conductive silicone resin composition may contain heat resistance improvers such as red iron oxide, titanium oxide, and cerium oxide, flame retardants, and flame retardant assistants.
  • the thermally conductive silicone resin composition may contain organic or inorganic particle pigments for the purpose of coloring and color matching. Alkoxy group-containing silicones may be added to the thermally conductive silicone resin composition as a material to be added for the purpose of filler surface treatment, etc.
  • thermally conductive silicone resin composition of the present invention can be filled into dispensers, bottles, cans, tubes, etc. to produce commercial products.
  • the present invention includes the following aspects:
  • a thermally conductive silicone resin composition comprising a matrix resin component (A) and thermally conductive inorganic particles (B),
  • the matrix resin component (A) contains, relative to 100 parts by mass of the matrix resin component (A), 70 to 99 parts by mass of liquid dimethylpolysiloxane (A1),
  • a mixed oil (A2) of polydecene and an ethylene-propylene copolymer is contained in an amount of 1 to 30 parts by mass
  • the liquid dimethylpolysiloxane (A1) has a kinetic viscosity at 40° C. of 50 to 10,000 mm 2 /s
  • the mixed oil (A2) has a kinetic viscosity at 40° C. of 1 to 1,000 mm 2 /s
  • a thermally conductive silicone resin composition comprising 400 to 3,000 parts by mass of the thermally conductive inorganic particles (B) per 100 parts by mass of the matrix resin component (A).
  • Item 6 The thermally conductive silicone resin composition according to any one of Items 1 to 5, preferably containing 30 to 99 mass% of polydecene and 1 to 70 mass% of an ethylene-propylene copolymer, more preferably containing 35 to 95 mass% of polydecene and 5 to 65 mass% of an ethylene-propylene copolymer, and even more preferably containing 40 to 90 mass% of polydecene and 10 to 60 mass% of an ethylene-propylene copolymer, relative to 100 mass% of the mixed oil (A2).
  • Item 8 The thermally conductive silicone resin composition according to any one of Items 1 to 7, wherein the alkoxysilane is at least one selected from the group consisting of octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.
  • the thermally conductive inorganic particles (B) are Thermally conductive inorganic particles (B1) having a median particle size (D50) of 0.01 to 10 ⁇ m; Thermally conductive inorganic particles (B2) having a median particle size (D50) of more than 10 ⁇ m and not more than 80 ⁇ m; Thermally conductive inorganic particles (B3) having a median particle size (D50) of more than 80 ⁇ m and not more than 150 ⁇ m Item 9.
  • the thermally conductive silicone resin composition according to any one of items 1 to 8, comprising:
  • Item 10 The thermally conductive silicone resin composition according to any one of items 1 to 9, wherein the thermally conductive inorganic particles (B1) are preferably amorphous alumina.
  • thermally conductive silicone resin composition according to any one of Items 1 to 10, wherein the thermally conductive inorganic particles (B2) are preferably at least one inorganic particle selected from the group consisting of alumina, zinc oxide, magnesium oxide, aluminum nitride, boron nitride, aluminum hydroxide, and silicon carbide, and more preferably amorphous aluminum nitride.
  • Item 14 The thermally conductive silicone resin composition according to any one of Items 9 to 13, wherein a part or all of the thermally conductive inorganic particles (B1) have been surface-treated in advance with an alkoxysilane represented by the formula RaSi(OR')4-a (wherein R is an unsubstituted or substituted organic group having 8 to 12 carbon atoms, R' is an alkyl group having 1 to 4 carbon atoms, and a is 0 or 1).
  • R alkoxysilane represented by the formula RaSi(OR')4-a (wherein R is an unsubstituted or substituted organic group having 8 to 12 carbon atoms, R' is an alkyl group having 1 to 4 carbon atoms, and a is 0 or 1).
  • Item 15 The thermally conductive silicone resin composition according to any one of items 9 to 14, wherein the alkoxysilane is one or more selected from the group consisting of octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane.
  • the thermally conductive inorganic particles (B) preferably contain 100 to 1,000 parts by mass, more preferably 150 to 1,000 parts by mass, and even more preferably 300 to 850 parts by mass of the thermally conductive inorganic particles (B1) per 100 parts by mass of the matrix resin component (A).
  • the thermally conductive inorganic particles (B) preferably contain 100 to 500 parts by mass, more preferably 150 to 500 parts by mass, and even more preferably 200 to 450 parts by mass of the thermally conductive inorganic particles (B2) per 100 parts by mass of the matrix resin component (A).
  • the thermally conductive inorganic particles (B) preferably contain 300 to 1,400 parts by mass, more preferably 300 to 1,300 parts by mass, and even more preferably 500 to 1,200 parts by mass of the thermally conductive inorganic particles (B3) per 100 parts by mass of the matrix resin component (A).
  • thermoly conductive silicone resin composition according to any one of items 9 to 18, wherein the thermally conductive inorganic particles (B1) preferably contain two or more types of thermally conductive inorganic particles having different median particle sizes (D50).
  • the thermally conductive inorganic particles (B1) are Preferably, the thermally conductive inorganic particles (B1-1) have a median particle size (D50) of 0.01 ⁇ m or more and less than 1 ⁇ m, and the thermally conductive inorganic particles (B1-2) have a median particle size (D50) of 1 ⁇ m or more and 10 ⁇ m or less, More preferably, the thermally conductive inorganic particles (B1-1) have a median particle size (D50) of 0.05 ⁇ m or more and less than 1 ⁇ m, and the thermally conductive inorganic particles (B1-2) have a median particle size (D50) of 1 ⁇ m or more and 8 ⁇ m or less, Item 20.
  • D50 median particle size
  • thermally conductive silicone resin composition according to Item 19 further preferably comprising thermally conductive inorganic particles (B1-1) having a median particle diameter (D50) of 0.1 ⁇ m or more and less than 1 ⁇ m, and thermally conductive inorganic particles (B1-2) having a median particle diameter (D50) of 1 ⁇ m or more and 5 ⁇ m or less.
  • the thermally conductive inorganic particles (B1) are mixed in an amount of 100 parts by mass of the matrix resin component (A), Preferably, the thermally conductive inorganic particles (B1-1) are contained in an amount of 50 to 400 parts by mass, and the thermally conductive inorganic particles (B1-2) are contained in an amount of 50 to 600 parts by mass, More preferably, the thermally conductive inorganic particles (B1-1) are contained in an amount of 50 to 400 parts by mass, and the thermally conductive inorganic particles (B1-2) are contained in an amount of 100 to 600 parts by mass, More preferably, the thermally conductive silicone resin composition contains 100 to 350 parts by mass of the thermally conductive inorganic particles (B1-1) and 200 to 500 parts by mass of the thermally conductive inorganic particles (B1-2).
  • Item 23 The thermally conductive silicone resin composition according to any one of items 1 to 22, wherein the thermal conductivity is preferably 1.0 W/m K or more, more preferably 1.0 to 10 W/m K, and even more preferably 1.5 to 9 W/m K.
  • Item 27 The thermally conductive silicone resin composition according to any one of items 1 to 26, which is a thermally conductive grease.
  • Item 28 The thermally conductive silicone resin composition according to any one of items 1 to 27, which is in an uncured state or a cured state.
  • thermal conductivity of the thermally conductive silicone resin composition was measured by a hot disk (ISO 22007-2: 2008 compliant). As shown in FIG. 1A, this thermal conductivity measuring device 1 sandwiches a polyimide film sensor 2 between two samples 3a and 3b, applies a constant power to the sensor 2, and generates constant heat to analyze the thermal characteristics from the temperature rise value of the sensor 2.
  • the sensor 2 has a tip 4 with a diameter of 7 mm, and as shown in FIG. 1B, has a double spiral structure of electrodes, with an applied current electrode 5 and a resistance value electrode (temperature measurement electrode) 6 arranged at the bottom.
  • the measurement sample can be obtained by rolling and molding the degassed thermally conductive liquid composition to a thickness of 7 mm or more.
  • the thermal conductivity is calculated by the following formula (Equation 1).
  • the absolute viscosity of the thermally conductive silicone resin composition was measured using a Brookfield viscometer (HBDV2T) using a TE spindle, at a rotation speed of 5 rpm and at 23° C.
  • ⁇ Drop test> The measurements were performed using the drop test shown in Figures 2A-D.
  • 1.0 g of the thermally conductive silicone resin composition 14 was applied to an aluminum plate 12 having a length of 40 mm, a width of 100 mm, and a thickness of 5 mm (FIG. 2A), and a spacer 13 was interposed between the aluminum plate and a glass plate 11 having a length of 40 mm, a width of 100 mm, and a thickness of 5 mm, and the thermally conductive silicone resin composition was compressed and sandwiched to a thickness of 1.0 mm (FIG. 2B).
  • 15 is the thermally conductive silicone resin composition compressed to a thickness of 1.0 mm.
  • FIG. 2C 16 is the test piece before the test.
  • a heat cycle test was performed in which the plate was held at -40°C for 30 minutes, heated to 125°C, held at 125°C for 30 minutes, and cooled to -40°C for 100 cycles and 500 cycles. After 100 cycles and 500 cycles, the test piece was removed and observed to see if the thermally conductive silicone resin composition 15 had fallen.
  • Reference numeral 17 denotes the test piece after the test (FIG. 2D), and 18 denotes the fall distance.
  • Evaluation criterion A The falling distance of the thermally conductive silicone resin composition was within 5 mm.
  • B The thermally conductive silicone resin composition fell a distance of more than 5 mm.
  • the thermally conductive silicone resin composition was filled into a 30 mL syringe PSY-30F manufactured by Musashi Engineering Co., Ltd., and the amount discharged was measured when the composition was discharged for 9 seconds with a discharge hole diameter of 2.5 mm and a discharge pressure of 0.5 MPa.
  • Table 1 The blending amounts are shown in Table 1.
  • Viscosity modifier (C) Decyltrimethoxysilane, specific gravity 0.90g/ cm3 2.
  • the above matrix resin component (A) was mixed with the thermally conductive inorganic particles (B) and a viscosity modifier to obtain the composition shown in Table 1 below, thereby producing a thermally conductive silicone resin composition.
  • the thermally conductive silicone resin compositions thus obtained were evaluated. The compositions and results are shown in Table 1 below.
  • Example 1 has better ejection properties than Comparative Example 2.
  • Example 2 has better ejection properties than Comparative Example 3, and does not fall even after 500 cycles of the drop test.
  • Drop resistance is also exhibited in Example 3, in which a small amount of mixed oil (A2) is blended.
  • Comparative Example 1 which does not contain the mixed oil (A2), shows poor results in the drop test.
  • Comparative Example 2 in which ethylene-propylene copolymer oil was used instead of the mixed oil (A2), the drop test results were good, but the ejection properties were poor compared to Example 1.
  • Comparative Example 3 in which the amount of oil blended in the ethylene-propylene copolymer was reduced, exhibited poor results in the drop test.
  • (7) Overall, it was confirmed that, compared with Comparative Examples 1 to 3, Examples 1 to 3 were able to provide a thermally conductive silicone resin composition that had high thermal conductivity, was relatively resistant to dripping, and had good dischargeability.
  • the thermally conductive silicone resin composition of the present invention is suitable for use between heat generating parts of electrical and electronic components and heat sinks.

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JP2000353771A (ja) * 1999-06-09 2000-12-19 Kitagawa Ind Co Ltd 熱伝導材及びその製造方法
JP2002237554A (ja) * 2001-02-07 2002-08-23 Denki Kagaku Kogyo Kk 熱伝導性樹脂成形体及びその用途
WO2006064782A1 (ja) * 2004-12-17 2006-06-22 Kabushiki Kaisha Fine Rubber Kenkyuusho 誘電性素材、アンテナ装置、携帯電話機及び電磁波遮蔽体
JP2017530220A (ja) * 2014-09-22 2017-10-12 ダウ グローバル テクノロジーズ エルエルシー 超分岐状オレフィン流体を基とする放熱グリス
CN107312493A (zh) * 2017-08-04 2017-11-03 东莞市联洲知识产权运营管理有限公司 一种led封装用有机硅导热胶粘剂及其制备方法
WO2022054330A1 (ja) * 2020-09-11 2022-03-17 富士高分子工業株式会社 熱伝導性グリース及びその製造方法
JP7047199B1 (ja) * 2021-04-08 2022-04-04 富士高分子工業株式会社 熱伝導性グリース組成物
WO2024070068A1 (ja) * 2022-09-26 2024-04-04 富士高分子工業株式会社 熱伝導性グリース組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07252130A (ja) * 1994-01-26 1995-10-03 L'oreal Sa シリコーンオイルと、エチレンホモポリマー又はコポリマーから作られたワックスとの組合わせを含む無水の化粧品又は皮膚科学的組成物
JP2000345042A (ja) * 1999-06-09 2000-12-12 Kitagawa Ind Co Ltd 熱伝導材及びその製造方法
JP2000353771A (ja) * 1999-06-09 2000-12-19 Kitagawa Ind Co Ltd 熱伝導材及びその製造方法
JP2002237554A (ja) * 2001-02-07 2002-08-23 Denki Kagaku Kogyo Kk 熱伝導性樹脂成形体及びその用途
WO2006064782A1 (ja) * 2004-12-17 2006-06-22 Kabushiki Kaisha Fine Rubber Kenkyuusho 誘電性素材、アンテナ装置、携帯電話機及び電磁波遮蔽体
JP2017530220A (ja) * 2014-09-22 2017-10-12 ダウ グローバル テクノロジーズ エルエルシー 超分岐状オレフィン流体を基とする放熱グリス
CN107312493A (zh) * 2017-08-04 2017-11-03 东莞市联洲知识产权运营管理有限公司 一种led封装用有机硅导热胶粘剂及其制备方法
WO2022054330A1 (ja) * 2020-09-11 2022-03-17 富士高分子工業株式会社 熱伝導性グリース及びその製造方法
JP7047199B1 (ja) * 2021-04-08 2022-04-04 富士高分子工業株式会社 熱伝導性グリース組成物
WO2024070068A1 (ja) * 2022-09-26 2024-04-04 富士高分子工業株式会社 熱伝導性グリース組成物

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