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WO2023188491A1 - Composition de silicone thermoconductrice, feuille de silicone thermoconductrice et procédé de fabrication de ladite feuille - Google Patents

Composition de silicone thermoconductrice, feuille de silicone thermoconductrice et procédé de fabrication de ladite feuille Download PDF

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Publication number
WO2023188491A1
WO2023188491A1 PCT/JP2022/039700 JP2022039700W WO2023188491A1 WO 2023188491 A1 WO2023188491 A1 WO 2023188491A1 JP 2022039700 W JP2022039700 W JP 2022039700W WO 2023188491 A1 WO2023188491 A1 WO 2023188491A1
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thermally conductive
conductive silicone
particles
sheet
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Japanese (ja)
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中島雄司
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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • 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
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating

Definitions

  • the present invention relates to a thermally conductive silicone composition with low compressive stress, a thermally conductive silicone sheet, and a method for manufacturing the same.
  • Patent Documents 1 and 2 propose thermally conductive sheets whose thermally conductive particles are mainly composed of aluminum hydroxide particles having different particle sizes.
  • Patent Document 3 proposes that aluminum hydroxide particles be surface-treated with titanate to form a thermally conductive material.
  • Patent Documents 1 and 2 do not contain crushed alumina particles and contain a large amount of aluminum hydroxide particles relative to the total amount of thermally conductive particles, resulting in high compressive stress and electronic components during mounting. There was a problem that the load on the system was large. Further, since Patent Document 3 surface-treats aluminum hydroxide particles with titanate, there is a problem in heat resistance, and further improvement has been required.
  • the present invention provides a thermally conductive silicone composition, a thermally conductive silicone sheet, and A manufacturing method thereof is provided.
  • the thermally conductive silicone composition of the present invention is a thermally conductive silicone composition containing a silicone matrix polymer (A), thermally conductive particles (B), and a silane coupling agent (C),
  • the silicone matrix polymer (A) is an addition-curing dimethylpolysiloxane
  • the thermally conductive particles (B) include aluminum hydroxide particles (B1), spherical alumina particles (B2), and crushed alumina particles (B3), and include particles that have not been surface-treated in advance, When the thermally conductive silicone composition is 100 vol.%, the thermally conductive particles (B) are 20 vol.% or more and 80 vol.% or less,
  • the silane coupling agent (C) is R 1 n Si(OR 2 ) 4-n (wherein R 1 is an alkyl group having 3 to 16 carbon atoms, R 2 is an alkyl group having 1 or 2 carbon atoms, and n is It is a compound represented by 1 to 3), and from the BET specific surface area
  • the thermally conductive silicone sheet of the present invention is characterized in that the aforementioned thermally conductive silicone composition is formed into a sheet and cured.
  • the method for producing a thermally conductive silicone sheet of the present invention is characterized by forming a compound of the thermally conductive silicone composition into a sheet and curing it by heating.
  • the thermally conductive silicone composition of the present invention includes a silicone matrix polymer (A), thermally conductive particles (B), and a silane coupling agent (C), and the silicone matrix polymer (A) is an addition-curing dimethyl
  • the thermally conductive particles (B) are polysiloxane, and the thermally conductive particles (B) include aluminum hydroxide particles (B1), spherical alumina particles (B2), and crushed alumina particles (B3), and the thermally conductive silicone composition is When the volume is 100 vol.%, the thermally conductive particles (B) have a volume of 20 vol.% or more and 80 vol.% or less, so that the compressive stress is low, the load on electronic components during mounting is low, and the heat resistance is high.
  • a highly reliable thermally conductive silicone composition, a thermally conductive silicone sheet, and a method for manufacturing the same can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a method of using a thermally conductive silicone sheet in an embodiment of the present invention.
  • FIG. 2 is a scanning electron microscope (SEM) photograph (magnification: 600 times) of bulk aluminum hydroxide particles (B1) according to an embodiment of the present invention.
  • FIG. 3 is a scanning electron microscope (SEM) photograph (10,000x magnification) of spherical alumina (B2) according to an embodiment of the present invention.
  • FIG. 4 is a scanning electron microscope (SEM) photograph of polygonal or rounded alumina, which is not included in the spherical alumina (B2) of the present invention.
  • FIG. 1 is a schematic cross-sectional view showing a method of using a thermally conductive silicone sheet in an embodiment of the present invention.
  • FIG. 2 is a scanning electron microscope (SEM) photograph (magnification: 600 times) of bulk aluminum hydroxide particles (B1) according to an embodiment of the present invention.
  • FIG. 3
  • FIG. 5 is a scanning electron microscope (SEM) photograph (magnification: 6,000 times) of crushed alumina (B3) according to an embodiment of the present invention.
  • FIG. 6 is a schematic side sectional view of a compressive load measuring device used in an embodiment of the present invention.
  • FIGS. 7A and 7B are explanatory diagrams showing a method for measuring thermal conductivity used in an embodiment of the present invention.
  • the thermally conductive silicone composition of the present invention includes a silicone matrix polymer (A), thermally conductive particles (B), and a silane coupling agent (C), and the silicone matrix polymer (A) is an addition-curing dimethyl polyester. It is siloxane.
  • the following are preferable examples of the thermally conductive silicone composition.
  • (A2) Crosslinking component: Organohydrogenpolysiloxane containing an average of two or more hydrogen atoms bonded to silicon atoms in one molecule is 3 mol per mol of silicon-bonded alkenyl group in component A1. amount less than.
  • (B) Thermal conductive particles: Contains aluminum hydroxide particles (B1), spherical alumina particles (B2), and crushed alumina particles (B3), and when the thermally conductive silicone composition is 100 vol.%, The content of the conductive particles (B) is 20 vol.% or more and 80 vol.% or less. The amount of the thermally conductive particles added is preferably 30 to 80 vol.%, more preferably 40 to 80 vol.%, and still more preferably 45 to 75 vol.%.
  • the thermal conductivity can be increased, and it is suitable as a heat radiator: TIM (Thermal Interface Material) between a heat generating part and a heat radiating part of an electronic component or the like.
  • the thermally conductive particles include particles that have not been previously surface treated, and preferably all of the thermally conductive particles have not been previously surface treated.
  • a commercially available silicone matrix polymer (A) can be used.
  • This commercial product is usually divided into Part A and Part B, one containing the component (A1) and the catalyst component (D), and the other containing the crosslinking component (A2) and a curing reaction inhibitor. There is.
  • the average particle diameter of the aluminum hydroxide particles (B1) is preferably 10 ⁇ m or more and 110 ⁇ m or less, more preferably 15 to 100 ⁇ m, and even more preferably 20 to 90 ⁇ m. Further, the amount of aluminum hydroxide particles (B1) added is preferably 20 vol.% or more and 80 vol.% or less, more preferably 30 to 75 vol.%, when the total volume of the thermally conductive particles is 100 vol.%. , more preferably 40 to 70 vol.%. It is preferable that the aluminum hydroxide particles have a block shape.
  • the average particle diameter of the spherical alumina particles (B2) is preferably 1 ⁇ m or more and 110 ⁇ m or less, more preferably 2 to 100 ⁇ m.
  • the spherical alumina particles (B2) may have an average particle diameter of 1 to 30 ⁇ m, and a plurality of spherical alumina particles (B2) having an average particle diameter of more than 30 ⁇ m and 110 ⁇ m or less may be used in combination.
  • "spherical alumina” refers to truly spherical alumina obtained by a melting method.
  • the average particle diameter of the crushed alumina particles (B3) is preferably 10 ⁇ m or less, more preferably 0.01 to 10 ⁇ m, and even more preferably 0.1 to 8 ⁇ m.
  • the total amount of the spherical alumina particles (B2) and the crushed alumina particles (B3) is preferably 20 vol.% or more and 80 vol.% or less, more preferably 30 to 80 vol.%, when the total volume of the thermally conductive particles is 100 vol.%.
  • the content is 70 vol.%, more preferably 40 to 60 vol.%.
  • the amounts of the spherical alumina particles (B2) and the crushed alumina particles (B3) are such that B2 ⁇ B3. This makes the compound suitable for processing, and allows for both high thermal conductivity and low load.
  • the thermally conductive silicone sheet of the present invention is obtained by molding the thermally conductive silicone composition into a sheet and curing it. If it is a sheet, it is suitable as a heat radiator: TIM (Thermal Interface Material) between a heat generating part and a heat radiating part of an electronic component or the like.
  • TIM Thermal Interface Material
  • the thermally conductive silicone sheet preferably has an instantaneous load value of 900 N or less, more preferably 880 N or less when compressed by 50% of a sheet with a diameter of 28.6 mm and an initial thickness of 1 mm. As a result, compressive stress is low (lower load), and the load on electronic components during mounting can be reduced.
  • the thermal conductivity of the thermally conductive silicone sheet is preferably 2 W/mK or more, more preferably 2.1 W/mK or more, and even more preferably 2.2 W/mK or more.
  • the upper limit is preferably 20 W/mK or less.
  • the heat resistance of the thermally conductive silicone sheet is preferably such that the amount of change after 100 hours from the initial Shore hardness of 00 is within ⁇ 10, more preferably within ⁇ 8, and even more preferably within ⁇ 8 when aged in air at 100 ° C. is within ⁇ 6.
  • the method for producing a thermally conductive silicone sheet of the present invention preferably includes the following steps.
  • (1) Manufacturing process of thermally conductive silicone composition Addition-curing dimethylpolysiloxane (for example, commercially available agents A and B), thermally conductive particles (B) (aluminum hydroxide particles (B1), spherical alumina particles) (B2), crushed alumina particles (B3)) and the silane coupling agent (C) are each weighed in predetermined amounts and mixed to form a compound (mixed raw material).
  • Some of the thermally conductive particles used in the present invention may be pretreated by being mixed with a silane coupling agent in advance. The reason for using thermally conductive particles (B) that have not been surface-treated in advance is to reduce costs.
  • the method of mixing the thermally conductive particles (B) that have not been surface-treated and the silane coupling agent (C) during compounding is generally called an integral blend method.
  • the present invention employs this method. Note that the present invention does not include titanate pretreated products. Titanate pretreated products have low heat resistance and are not preferred.
  • (2) Sheet forming process The compound (mixed raw materials) is formed into a sheet by roll rolling or pressing. The thickness of the thermally conductive sheet is preferably in the range of 0.2 to 10 mm.
  • Heat-curing step The heat-curing conditions for the sheet are preferably a temperature of 70 to 250°C and a time of 1 to 15 minutes.
  • the base polymer component is an organopolysiloxane containing two or more alkenyl groups bonded to a silicon atom in one molecule, and the organopolysiloxane containing two or more alkenyl groups is the main component ( base polymer component).
  • This organopolysiloxane has two or more silicon-bonded alkenyl groups having 2 to 8, particularly 2 to 6 carbon atoms, such as a vinyl group or an allyl group, in one molecule.
  • the viscosity is preferably 10 to 100,000 mPa ⁇ s at 25°C, particularly 100 to 10,000 mPa ⁇ s from the viewpoint of workability and curing properties.
  • an organopolysiloxane having an average of two or more alkenyl groups bonded to silicon atoms at both ends of the molecular chain in one molecule represented by the following general formula (Chemical Formula 1) is used.
  • the side chains are linear organopolysiloxanes capped with alkyl groups.
  • the viscosity at 25° C. is preferably 10 to 100,000 mPa ⁇ s from the viewpoint of workability, curing properties, etc.
  • this linear organopolysiloxane may contain a small amount of branched structure (trifunctional siloxane unit) in its molecular chain.
  • R 1 is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds that are the same or different from each other
  • R 2 is an alkenyl group
  • k is 0 or a positive integer.
  • the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond for R 1 preferably has 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and specifically, , methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, phenyl group aryl groups such as tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl; and some or all of the hydrogen atoms of these groups may be substituted with fluorine, bromine, chlorine, etc.
  • Examples include those substituted with a halogen atom, a cyano group, etc., such as a halogen-substituted alkyl group such as a chloromethyl group, a chloropropyl group, a bromoethyl group, and a trifluoropropyl group, and a cyanoethyl group.
  • the alkenyl group for R 2 is preferably one having 2 to 6 carbon atoms, particularly 2 to 3 carbon atoms, and specifically includes a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, and hexenyl group.
  • k is generally 0 or a positive integer satisfying 0 ⁇ k ⁇ 10000, preferably 5 ⁇ k ⁇ 2000, more preferably an integer satisfying 10 ⁇ k ⁇ 1200. It is.
  • the organopolysiloxane of component A1 has 3 or more, usually 3 to 30 alkenyl groups bonded to silicon atoms having 2 to 8 carbon atoms, especially 2 to 6 carbon atoms, such as vinyl groups and allyl groups in one molecule. , preferably an organopolysiloxane having about 3 to 20 atoms.
  • the molecular structure may be linear, cyclic, branched, or three-dimensional network.
  • the main chain is composed of repeating diorganosiloxane units, both ends of the molecular chain are blocked with triorganosiloxy groups, and the viscosity at 25°C is 10 to 100,000 mPa ⁇ s, particularly 100 to 10,000 mPa ⁇ s.
  • the alkenyl group may be bonded to any part of the molecule.
  • it may include those bonded to a silicon atom at the end of the molecular chain or at a non-terminal (in the middle of the molecular chain) of the molecular chain.
  • the following general formula (Chemical formula 2) has 1 to 3 alkenyl groups on each silicon atom at both ends of the molecular chain (however, the alkenyl group bonded to the silicon atom at the end of the molecular chain is If the total number of both ends is less than 3, it is a straight line having at least one alkenyl group bonded to a silicon atom at a non-terminus of the molecular chain (in the middle of the molecular chain) (for example, as a substituent in the diorganosiloxane unit).
  • a chain organopolysiloxane having a viscosity of 10 to 100,000 mPa ⁇ s at 25°C is desirable from the viewpoint of workability and curability.
  • this linear organopolysiloxane may contain a small amount of branched structure (trifunctional siloxane unit) in its molecular chain.
  • R 3 is the same or different unsubstituted or substituted monovalent hydrocarbon groups, and at least one of them is an alkenyl group.
  • R 4 is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds that are the same or different from each other,
  • R 5 is an alkenyl group, and l and m are 0 or a positive integer.
  • the monovalent hydrocarbon group R 3 preferably has 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group groups, aralkyl groups such as phenylethyl and phenylpropyl groups, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl and octeny
  • halogen atoms such as fluorine, bromine, and chlorine, cyano groups, etc.
  • halogen-substituted alkyl groups and cyanoethyl groups such as chloromethyl group, chloropropyl group, bromoethyl group, and trifluoropropyl group.
  • the monovalent hydrocarbon group of R 4 preferably has 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and may be exemplified by the same examples as the above-mentioned R 1 , but does not include an alkenyl group.
  • the alkenyl group for R 5 is preferably one having 2 to 6 carbon atoms, particularly 2 to 3 carbon atoms, and specifically, the same as R 2 in the above formula (Chemical formula 1) is exemplified, and preferably a vinyl group. It is.
  • l, m are generally 0 or positive integers satisfying 0 ⁇ l+m ⁇ 10000, preferably 5 ⁇ l+m ⁇ 2000, more preferably 10 ⁇ l+m ⁇ 1200, and 0 ⁇ l/(l+m ) ⁇ 0.2, preferably an integer satisfying 0.0011 ⁇ l/(l+m) ⁇ 0.1.
  • A2 component The organohydrogenpolysiloxane of the A2 component of the present invention acts as a crosslinking agent, and a cured product is formed by an addition reaction (hydrosilylation) between the SiH group in this component and the alkenyl group in the A1 component. It is something.
  • Such organohydrogenpolysiloxane may be any one having two or more silicon-bonded hydrogen atoms (i.e., SiH groups) in one molecule, and the molecular structure of this organohydrogenpolysiloxane is as follows: may have a linear, cyclic, branched, or three-dimensional network structure, but the number of silicon atoms in one molecule (i.e., degree of polymerization) is about 2 to 1000, especially about 2 to 300. can be used.
  • silicon atom to which the hydrogen atom is bonded there are no particular restrictions on the position of the silicon atom to which the hydrogen atom is bonded, and it may be at the terminal or non-terminal (in the middle) of the molecular chain.
  • organic groups bonded to silicon atoms other than hydrogen atoms include unsubstituted or substituted monovalent hydrocarbon groups that do not have an aliphatic unsaturated bond similar to R 1 in the general formula (Chemical formula 1). .
  • organohydrogenpolysiloxane of component A2 examples include those having the following structure.
  • R 6 is the same or different hydrogen, alkyl group, phenyl group, epoxy group, acryloyl group, methacryloyl group, or alkoxy group, and at least two of them are hydrogen.
  • L is an integer from 0 to 1,000, especially an integer from 0 to 300, and M is an integer from 1 to 200.
  • Thermally conductive inorganic particles (component B)
  • the thermally conductive inorganic particles of component B are as described above.
  • the alumina is preferably ⁇ -alumina with a purity of 99.5% or more.
  • the average particle diameter is determined by measuring D50 (median diameter) of the volume-based cumulative particle size distribution using a laser diffraction light scattering method.
  • An example of this measuring instrument is a laser diffraction/scattering type inorganic particle distribution measuring device LA-950S2 manufactured by Horiba, Ltd., for example.
  • the silane coupling agent (C) is R 1 n Si(OR 2 ) 4-n (wherein, R 1 is an alkyl group having 3 to 16 carbon atoms, R 2 is an alkyl group having 1 or 2 carbon atoms, and n is 1
  • R 1 is an alkyl group having 3 to 16 carbon atoms
  • R 2 is an alkyl group having 1 or 2 carbon atoms
  • n is 1
  • the alkoxysilane compounds shown in ⁇ 3 are used. This alkoxysilane compound may be a partially hydrolyzed product thereof.
  • Examples include propyltrimethoxylane, butyltrimethoxylane, pentyltrimethoxylane, hexyltrimethoxylane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxylane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane.
  • silane compounds such as silane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.
  • the silane compounds may be used alone or in combination of two or more.
  • the silane coupling agent (component C) serves as a surface treatment agent for the thermally conductive inorganic particles during compound creation or subsequent heat curing treatment.
  • Alkoxysilane and one-end silanol siloxane may be used in combination.
  • the surface treatment referred to here includes adsorption in addition to covalent bonding.
  • the catalyst component of component D is a component that accelerates curing.
  • a catalyst used in a hydrosilylation reaction can be used.
  • platinum black dichloroplatinic acid, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins or vinyl siloxanes, platinum-based catalysts such as platinum bisacetoacetate, palladium Examples include platinum group metal catalysts such as rhodium-based catalysts and rhodium-based catalysts.
  • the blending amount of component D may be any amount necessary for curing, and can be adjusted as appropriate depending on the desired curing speed and the like. It is preferable to add 0.01 to 1000 ppm in terms of metal atomic weight based on component A1.
  • composition of the present invention may contain components other than those listed above, if necessary.
  • curing reaction inhibitors include acetylene compounds such as 1-ethynyl-1-hexanol and 3-butyn-1-ol, various nitrogen compounds, organic phosphorus compounds, oxime compounds, and organic chloro compounds.
  • the amount used is preferably about 0.01 to 1 part by mass per 100 parts by mass of component (A). This is added to either the commercially available Part A or Part B.
  • an inorganic pigment such as red iron oxide may be added as a coloring agent.
  • FIG. 1 is a schematic cross-sectional view of a heat dissipating structure 30 incorporating a thermally conductive sheet according to an embodiment of the present invention.
  • Thermal conductive sheet 31b is for dissipating heat generated by electronic components 33 such as semiconductor elements, and is fixed to main surface 32a of heat spreader 32 facing electronic component 33, and is placed between electronic component 33 and heat spreader 32. Being pinched. Further, the thermally conductive sheet 31a is sandwiched between the heat spreader 32 and the heat sink 35.
  • the heat conductive sheets 31a and 31b together with the heat spreader 32 constitute a heat radiating member that radiates heat from the electronic component 33.
  • the heat spreader 32 is formed into a rectangular plate shape, for example, and has a main surface 32a facing the electronic component 33, and a side wall 32b erected along the outer periphery of the main surface 32a.
  • a heat conductive sheet 31b is provided on a main surface 32a surrounded by side walls 32b, and a heat sink 35 is provided on the other surface 32c opposite to the main surface 32a via the heat conductive sheet 31a.
  • the electronic component 33 is, for example, a semiconductor element such as a BGA, and is mounted on the wiring board 34.
  • FIG. 2 is a scanning electron microscope (SEM) photograph (magnification: 600 times) of bulk aluminum hydroxide particles (B1) according to an embodiment of the present invention.
  • These bulk aluminum hydroxide particles are produced by the Bayer method and are commercially available (for example, manufactured by Nippon Light Metal Co., Ltd., trade name "BW53", average particle size 54 ⁇ m).
  • FIG. 3 is a scanning electron microscope (SEM) photograph (10,000x magnification) of spherical alumina (B2) according to an embodiment of the present invention.
  • This spherical alumina is manufactured by a melting method and is commercially available (for example, manufactured by Nippon Steel Chemical & Materials Co., Ltd., trade name "AZ2-75", average particle size 2 ⁇ m).
  • FIG. 4 is a scanning electron microscope (SEM) photograph of polygonal or rounded alumina, which is not included in the spherical alumina (B2) of the present invention.
  • FIG. 5 is a scanning electron microscope (SEM) photograph (magnification: 6,000 times) of crushed alumina (B3) according to an embodiment of the present invention.
  • This crushed alumina is produced by the Bayer method and is commercially available (for example, manufactured by Sumitomo Chemical Co., Ltd., trade name "ALM-41-01", average particle size 1 to 2 ⁇ m).
  • FIG. 6 is a schematic side sectional view of a compressive load measuring device used in an embodiment of the present invention.
  • This compressive load measuring device 1 includes a sample stage 2 and a load cell 6.
  • a thermally conductive sheet sample 4 is sandwiched between aluminum plates 3 and 5, attached as shown in FIG. 6, and compressed by the load cell 6 to a specified thickness. do. Record the maximum load value when the thickness is compressed by 50%, and the load value after maintaining the compression for 1 minute.
  • this thermal conductivity measuring device 11 is constructed by sandwiching a polyimide film sensor 12 between two thermally conductive sheet samples 13a and 13b, and applying constant power to the sensor 12 to generate a constant amount of heat. Analyze thermal characteristics from the temperature rise value.
  • the sensor 12 has a tip 14 with a diameter of 7 mm, and has a double spiral structure of electrodes, as shown in FIG. 7B, with an applied current electrode 15 and a resistance value electrode (temperature measurement electrode) 16 arranged at the bottom. has been done.
  • the thermal conductivity was calculated using the following formula (Equation 2).
  • Silicone matrix polymer component (A1, A2) A commercially available two-part room temperature curing silicone polymer was used as the silicone matrix polymer component. A base polymer component and a platinum-based metal catalyst are added in advance to the A agent of this two-component room temperature curing silicone polymer, and a base polymer component, a crosslinking component, and a curing reaction inhibitor are added in advance to the B agent. This is an addition cure polydimethylsiloxane. Agent A is designated as A1, and agent B is designated as A2.
  • B1 Aluminum hydroxide (i) block, average particle size (D50) 43 ⁇ m, titanate pretreated product (commercial product) (ii) Massive, average particle diameter (D50) 49 ⁇ m, untreated product (commercial product), specific surface area 0.18 m 2 /g (iii) Massive, average particle diameter (D50) 75 ⁇ m, untreated product (commercial product), specific surface area 0.1 m 2 /g B2: Spherical alumina (i) average particle diameter (D50) 75 ⁇ m, untreated product (commercial product), specific surface area 0.2 m 2 /g (ii) Average particle diameter (D50) 6 ⁇ m, untreated product (commercial product), specific surface area 0.8 m 2 /g B3: Crushed alumina (i) average particle diameter (D50) 2.1 ⁇ m, untreated product (commercial product), specific surface area 1.8 m 2 /g (3) Silane coupling agent (C) Decyltrimethoxys
  • each example has a high thermal conductivity, a low steady load value, a large compression relaxation, and can be compressed slowly so that it can be clamped with a low load and has no impact on the clamping body. It was confirmed that the damage was small, the load value was low, and the sheet was soft, so it had good ability to follow the unevenness of electronic components, and the sheet was easy to handle.
  • Comparative Example 1 aluminum hydroxide particles pretreated with titanate were used, so the heat resistance was unfavorable.
  • the surface treatment coverage of the silane coupling agent on the thermally conductive particles was low, resulting in problems such as high load values, high compressive stress, and a large load on electronic components during mounting. .
  • the thermally conductive sheet of the present invention is useful as a heat radiator between a heat generating part and a heat radiating part in electronic components such as semiconductors, LEDs, and home appliances, information communication modules including optical communication equipment, and vehicle-mounted applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de silicone thermoconductrice qui contient un polymère de silicone (A), des particules thermoconductrices (B) et un agent de couplage silane (C). Les particules thermoconductrices (B) comprennent des particules d'hydroxyde d'aluminium (B1), des particules d'alumine sphériques (B2) et des particules d'alumine broyées (B3), et les particules thermoconductrices (B) représentent de 20 % en volume à 80 % en volume lorsque la composition constitue 100 % en volume. L'agent de couplage silane (C) est un composé représenté par R1 nSi(OR2)4-n (dans laquelle R1 représente un groupe alkyle ayant de 3 à 16 atomes de carbone, R2 représente un groupe alkyle ayant de 1 à 2 atomes de carbone, et n est compris entre 1 et 3). La composition de silicone thermoconductrice contient une quantité de l'agent de couplage silane qui conduit à une couverture de surface supérieure ou égale à 150 %, telle que calculée à partir de la surface spécifique BET des particules thermoconductrices (B) ainsi que de la quantité mélangée et de la surface de couverture minimale de l'agent de couplage silane. Par conséquent, l'invention concerne : une composition de silicone thermoconductrice qui présente une faible contrainte de compression, place une faible charge sur des composants électroniques pendant le montage, et est hautement fiable ; une feuille de silicone thermoconductrice ; et un procédé de fabrication de ladite feuille.
PCT/JP2022/039700 2022-03-31 2022-10-25 Composition de silicone thermoconductrice, feuille de silicone thermoconductrice et procédé de fabrication de ladite feuille Ceased WO2023188491A1 (fr)

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WO2025187352A1 (fr) * 2024-03-04 2025-09-12 信越化学工業株式会社 Tube thermorétractable en silicone thermoconductrice
WO2025204719A1 (fr) * 2024-03-29 2025-10-02 三菱マテリアル株式会社 Composition de résine thermoconductrice

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JP2011089079A (ja) * 2009-10-26 2011-05-06 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーン組成物及びその硬化物
JP2011178821A (ja) * 2010-02-26 2011-09-15 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーン組成物及びその硬化物
JP2013147600A (ja) * 2012-01-23 2013-08-01 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーン組成物及びその硬化物
JP2013189498A (ja) * 2012-03-12 2013-09-26 Dow Corning Toray Co Ltd 熱伝導性シリコーン組成物
JP2016011322A (ja) * 2014-06-27 2016-01-21 信越化学工業株式会社 熱伝導性複合シリコーンゴムシート
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Publication number Priority date Publication date Assignee Title
WO2025187352A1 (fr) * 2024-03-04 2025-09-12 信越化学工業株式会社 Tube thermorétractable en silicone thermoconductrice
WO2025204719A1 (fr) * 2024-03-29 2025-10-02 三菱マテリアル株式会社 Composition de résine thermoconductrice

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