WO2023162323A1 - 熱伝導性組成物、熱伝導性シート及びその製造方法 - Google Patents

熱伝導性組成物、熱伝導性シート及びその製造方法 Download PDF

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WO2023162323A1
WO2023162323A1 PCT/JP2022/037639 JP2022037639W WO2023162323A1 WO 2023162323 A1 WO2023162323 A1 WO 2023162323A1 JP 2022037639 W JP2022037639 W JP 2022037639W WO 2023162323 A1 WO2023162323 A1 WO 2023162323A1
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thermally conductive
mass
parts
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average particle
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鈴村克之
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Fuji Polymer Industries Co Ltd
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Fuji Polymer Industries Co Ltd
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Priority to US18/838,118 priority Critical patent/US20250145799A1/en
Priority to CN202280091609.7A priority patent/CN118696096A/zh
Priority to KR1020247027618A priority patent/KR20240150441A/ko
Priority to EP22927614.2A priority patent/EP4477713A4/en
Priority to JP2023530708A priority patent/JP7499414B2/ja
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/247—Heating methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present invention relates to a thermally conductive composition, a thermally conductive sheet, and a method for producing the same.
  • Patent Literature 1 proposes that the viscosity of a thermally conductive silicone composition before curing be 800 Pa ⁇ s or less at 23° C. to improve compressibility, insulation, thermal conductivity, and the like.
  • Patent Literature 2 proposes improving the adhesion and conformability to electronic components by setting the average particle size of the thermally conductive filler to a specific one.
  • Patent Literature 3 proposes forming irregularities on the surface of a thermally conductive sheet to increase flexibility and improve conformability to electronic components.
  • Patent Document 4 the present applicant has proposed a thermally conductive sheet with a low steady load value by using a matrix resin with a low polymer viscosity after a cross-linking reaction.
  • the present invention provides a thermally conductive composition having a low viscosity of a compound (mixture) before curing, improving moldability, and a low steady load value of a thermally conductive sheet after curing, A thermally conductive sheet and a method for manufacturing the same are provided.
  • the thermally conductive composition of the present invention is a thermally conductive composition containing a curable polyorganosiloxane (A) and a thermally conductive inorganic filler (B), wherein 100 parts by mass of the curable polyorganosiloxane (A) 500 to 5000 parts by mass of the thermally conductive inorganic filler (B).
  • the thermally conductive inorganic filler (B) contains spherical alumina (B1) having an average particle size of 1 ⁇ m or more and less than 10 ⁇ m and crushed alumina (B2) having an average particle size of 0.01 ⁇ m or more and less than 1 ⁇ m.
  • the proportion of the spherical alumina (B1) having an average particle size of 1 ⁇ m or more and less than 10 ⁇ m is more than 0 parts by mass and 1500 parts by mass or less, and the average particle size is 0.01 ⁇ m.
  • the proportion of the crushed alumina (B2) having a particle size of less than 1 ⁇ m is more than 0 parts by mass and 1000 parts by mass or less.
  • the thermally conductive sheet of the present invention is a thermally conductive sheet obtained by forming the thermally conductive composition into a sheet and curing it.
  • the method for producing a thermally conductive sheet of the present invention includes forming a compound of the thermally conductive composition into a sheet and heat-curing it.
  • the thermally conductive composition of the present invention is a thermally conductive composition containing a curable polyorganosiloxane (A) and a thermally conductive inorganic filler (B), wherein 100 parts by mass of the curable polyorganosiloxane (A) , contains 500 to 5000 parts by mass of the thermally conductive inorganic filler (B), and the thermally conductive inorganic filler (B) includes spherical alumina (B1) having an average particle size of 1 ⁇ m or more and less than 10 ⁇ m, and an average particle size of The ratio of spherical alumina (B1) having an average particle diameter of 1 ⁇ m or more and less than 10 ⁇ m to 100 parts by mass of the curable polyorganosiloxane (A) is 0.
  • B2 crushed alumina
  • FIG. 1 is a schematic cross-sectional view showing how to use a thermally conductive sheet in one embodiment of the present invention.
  • FIG. 2 is a scanning electron microscope (SEM) photograph (magnification: 10,000) of spherical alumina (B1) according to one embodiment of the present invention.
  • FIG. 3 is a scanning electron microscope (SEM) photograph of polygonal or rounded alumina not contained in the spherical alumina (B1) of the present invention.
  • FIG. 4 is a schematic side sectional view of a compressive load measuring device used in one embodiment of the present invention.
  • 5A-B are explanatory diagrams showing a method of measuring thermal conductivity used in one embodiment of the present invention.
  • the present invention is a thermally conductive composition containing a curable polyorganosiloxane (A) and a thermally conductive inorganic filler (B).
  • the curable polyorganosiloxane (A) comprises a base polymer, a cross-linking component and a catalyst component, and is preferably an addition-curable silicone polymer.
  • the thermally conductive composition for example, the following are preferable.
  • Base polymer A straight-chain organopolysiloxane containing an average of two or more alkenyl groups per molecule and bonded to silicon atoms at both ends of the molecular chain.
  • (A2) Cross-linking component: Organohydrogenpolysiloxane containing an average of two or more silicon-bonded hydrogen atoms per molecule is added in an amount of 0.00 to 1 mol of silicon-bonded alkenyl groups in component A1. An amount of 1 mol or more and less than 3 mol.
  • (B) Thermally conductive inorganic filler (B): 500 to 5000 parts by mass, preferably 500 to 4000 parts by mass, more preferably 500 to 3000 parts by mass based on 100 parts by mass of the curable polyorganosiloxane (A) part by mass. As a result, the thermal conductivity of the thermally conductive sheet becomes 2.0 W/m ⁇ K or more, which makes it suitable as a TIM (Thermal Interface Material).
  • the thermally conductive inorganic filler (B) contains spherical alumina (B1) having an average particle size of 1 ⁇ m or more and less than 10 ⁇ m and crushed alumina (B2) having an average particle size of 0.01 ⁇ m or more and less than 1 ⁇ m, and curable polyorganosiloxane ( A)
  • the proportion of spherical alumina (B1) having an average particle size of 1 ⁇ m or more and less than 10 ⁇ m is more than 0 parts by mass and 1500 parts by mass or less with respect to 100 parts by mass.
  • the proportion of the spherical alumina (B1) is preferably more than 0 parts by mass and 1000 parts by mass or less, more preferably more than 0 parts by mass and 800 parts by mass or less with respect to 100 parts by mass of the curable polyorganosiloxane (A).
  • the viscosity of the compound (mixed raw material) before curing is low, the moldability is improved, and the thermally conductive sheet after curing has a low instantaneous and constant load value, and the thermally conductive composition.
  • a thermally conductive sheet formed from is obtained.
  • spherical alumina refers to true spherical alumina obtained by a melting method.
  • the crushed alumina (B2) having an average particle diameter of 0.01 ⁇ m or more and less than 1 ⁇ m is more than 0 parts by mass and 1000 parts by mass or less, preferably 0 parts by mass with respect to 100 parts by mass of the curable polyorganosiloxane (A). More than 800 parts by mass or less, more preferably more than 0 parts by mass and 700 parts by mass or less.
  • the thermally conductive inorganic filler (B) further contains spherical alumina (B3) having an average particle size of 10 ⁇ m or more and 150 ⁇ m or less, preferably more than 0 parts by mass and 3500 parts by mass or less, more preferably more than 0 parts by mass and 3000 parts by mass. parts or less, more preferably more than 0 parts by mass and 2000 parts by mass or less.
  • spherical alumina (B3) having an average particle size of 10 ⁇ m or more and 150 ⁇ m or less, preferably more than 0 parts by mass and 3500 parts by mass or less, more preferably more than 0 parts by mass and 3000 parts by mass. parts or less, more preferably more than 0 parts by mass and 2000 parts by mass or less.
  • the thermally conductive inorganic filler (B) further contains crushed aluminum nitride (B4) having an average particle size of 10 ⁇ m or more and 100 ⁇ m or less. It is 300 parts by mass or less, more preferably more than 0 parts by mass and 150 parts by mass or less. As a result, the viscosity of the compound (mixed raw material) before curing is further low, the moldability is improved, and the thermally conductive composition and thermally conductive sheet with low instantaneous and steady load values of the thermally conductive sheet after curing are obtained. can get.
  • thermally conductive inorganic filler other than the above may be added.
  • examples include boron nitride, zinc oxide, magnesium oxide, aluminum hydroxide, silicon carbide and silica. These may be used alone or in combination. These preferably have an average particle size of 10 to 150 ⁇ m, and may be of any shape such as crushed, spherical, rounded, or needle-like. Part by mass can be added.
  • the thermally conductive inorganic filler may be surface-treated with a silane compound, a titanate compound, an aluminate compound, or a partial hydrolyzate thereof. Thereby, deactivation of the curing catalyst and the cross-linking agent can be prevented, and the storage stability can be improved.
  • the thermally conductive composition is formed into a sheet and cured to form the thermally conductive sheet of the present invention.
  • the thermally conductive sheet has high versatility and is suitable as a TIM (Thermal Interface Material).
  • the thickness of the thermally conductive sheet is preferably in the range of 0.2-10 mm.
  • the thermally conductive silicone sheet of the present invention has an instantaneous load value of 300 N or less when a sheet with a diameter of 28.6 mm and an initial thickness of 2 mm is compressed by 50% according to the compressive load measurement method according to ASTM D575-91:2012. is preferably 1 to 270N, more preferably 1 to 250N.
  • the steady load value at 50% compression of a sheet with a diameter of 28.6 mm and an initial thickness of 2 mm is preferably 80 N or less, more preferably 1 to 80 N, according to the compression load measurement method according to ASTM D575-91:2012. Yes, more preferably 1 to 50N.
  • the curable polyorganosiloxane (A) is also called a silicone polymer, has high heat resistance, is soft, and has good properties as a material for heat-dissipating sheets.
  • Addition-curable, peroxide-curable, and condensation-type silicone polymers can be used, and among these, addition-curable silicone polymers are preferred.
  • the thermally conductive sheet of the present invention is preferably obtained by forming a sheet of a compound having the following composition containing a curable polyorganosiloxane (A) and a thermally conductive inorganic filler (B), followed by crosslinking.
  • Curable polyorganosiloxane (A) consists of a base polymer, a cross-linking component and a catalyst component.
  • Base polymer A straight-chain organopolysiloxane containing an average of two or more alkenyl groups per molecule and bonded to silicon atoms at both ends of the molecular chain.
  • (A2) Cross-linking component: Organohydrogenpolysiloxane containing an average of two or more silicon-bonded hydrogen atoms per molecule is added in an amount of 0.00 to 1 mol of silicon-bonded alkenyl groups in component A1. An amount of 1 mol or more and less than 3 mol.
  • (B) Thermally conductive inorganic filler: 500 to 5000 parts by mass, preferably 500 to 4000 parts by mass, more preferably 500 to 3000 parts by mass based on 100 parts by mass of the curable polyorganosiloxane (A) be. As a result, the thermal conductivity of the thermally conductive sheet becomes 2.0 W/m ⁇ K or more.
  • Catalyst component 0.01 to 1000 ppm in terms of metal atom weight relative to component A1. The catalyst is preferably a platinum-based catalyst.
  • the method for producing a thermally conductive sheet of the present invention includes vacuum defoaming the compound of the thermally conductive composition, rolling, sheet forming, and then heat curing.
  • the thermally conductive composition formed into a sheet shape and heat-cured becomes a thermally conductive sheet.
  • vacuum defoaming the thermally conductive composition (compound) is placed under a pressure of, for example, -0.08 to -0.1 MPa for about 5 to 10 minutes to defoam.
  • Rolling methods include roll rolling, press working, and the like, and roll rolling is preferable because continuous production is possible.
  • roll rolling as an example, the compound is sandwiched between two synthetic resin films and then rolled with rolls.
  • Heat curing conditions for the molded sheet are preferably a temperature of 90 to 120° C. and a time of 5 to 180 minutes. As used herein, curing and cross-linking are the same.
  • the base polymer is an organopolysiloxane containing two or more silicon-bonded alkenyl groups in one molecule, and the organopolysiloxane containing two or more alkenyl groups is the main ingredient in the thermally conductive composition of the present invention. be.
  • This organopolysiloxane has two or more silicon-bonded alkenyl groups having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, such as vinyl groups and allyl groups, in one molecule.
  • the viscosity of the base polymer at 25° C. is preferably 10 to 100,000 mPa ⁇ s, particularly 100 to 10,000 mPa ⁇ s, from the viewpoint of workability and curability.
  • an organopolysiloxane containing an average of two or more alkenyl groups per molecule represented by the following general formula (Chemical Formula 1) and bonded to silicon atoms at both ends of the molecular chain is used.
  • the side chains are linear organopolysiloxanes blocked with alkyl groups.
  • the base polymer preferably has a viscosity of 10 to 100,000 mPa ⁇ s at 25°C.
  • This linear organopolysiloxane may contain a small amount of branched structures (trifunctional siloxane units) in the molecular chain.
  • R 1 is the same or different unsubstituted or substituted monovalent hydrocarbon group free of aliphatic unsaturation
  • 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 preferably 1 to 6 carbon atoms.
  • the alkenyl group for R 2 preferably has 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms, specifically vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, and hexenyl. , cyclohexenyl group and the like, preferably vinyl group.
  • k is generally 0 or a positive integer that satisfies 0 ⁇ k ⁇ 10000, preferably 5 ⁇ k ⁇ 2000, more preferably an integer that satisfies 10 ⁇ k ⁇ 1200 is.
  • Component A1 organopolysiloxane has 3 or more, usually 3 to 30, silicon-bonded alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, such as vinyl groups and allyl groups, in one molecule.
  • an organopolysiloxane having about 3 to 20 groups may be used in combination with the organopolysiloxane represented by the general formula (1).
  • the molecular structure may be linear, cyclic, branched or three-dimensional network.
  • the main chain consists of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with triorganosiloxy groups. It is a linear organopolysiloxane.
  • An alkenyl group can be attached to any part of the molecule.
  • it may contain those bonded to silicon atoms at the ends of the molecular chains or non-terminals of the molecular chains (middle of the molecular chains).
  • the silicon atoms at both ends of the molecular chain represented by the following general formula (Chemical Formula 2) each have 1 to 3 alkenyl groups (provided that the alkenyl groups bonded to the silicon atoms at the ends of the molecular chain are When the total number of terminals is less than 3, a straight chain having at least one alkenyl group bonded to a silicon atom at a non-terminal (middle of the molecular chain) (for example, as a substituent in a diorganosiloxane unit) Organopolysiloxane), and as mentioned above, those having a viscosity of 10 to 100,000 mPa ⁇ s at 25° C.
  • This linear organopolysiloxane may contain a small amount of branched structures (trifunctional siloxane units) in the molecular chain.
  • R 3 are the same or different unsubstituted or substituted monovalent hydrocarbon groups, at least one of which is an alkenyl group.
  • R 4 is the same or different unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond,
  • R 5 is an alkenyl group, and 1 and m are 0 or positive integers.
  • the monovalent hydrocarbon group for R 3 preferably has 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, benzyl aralkyl groups such as phenylethyl group and phenylpropyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group; Halogen
  • the monovalent hydrocarbon group for R 4 those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms are preferable, and the same specific examples as those for R 1 above can be exemplified, but alkenyl groups are not included.
  • the alkenyl group for R 5 for example, those having 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms, are specifically exemplified by the same groups as those for R 2 in the above formula (Chemical Formula 1), preferably a vinyl group. is.
  • l and 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 cross-linking agent, and the SiH groups in this component and the alkenyl groups in the A1 component undergo an addition reaction (hydrosilylation) to form a cured product. It is.
  • 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 , Linear, cyclic, branched, or three-dimensional network structure, but the number of silicon atoms in one molecule (that is, the degree of polymerization) is 2 to 1000, especially 2 to 300. can be used.
  • the position of the silicon atom to which the hydrogen atom is bonded is not particularly limited, and may be at the terminal or non-terminal (in the middle) of the molecular chain.
  • examples of the organic group bonded to a silicon atom other than a hydrogen atom include unsubstituted or substituted monovalent hydrocarbon groups having no aliphatic unsaturated bond, similar to R 1 in the general formula (1). .
  • organohydrogenpolysiloxane of component A2 those having the following structures can be exemplified.
  • R6 is the same or different hydrogen, alkyl group, phenyl group, epoxy group, acryloyl group, methacryloyl group, 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.
  • the catalyst component of the C component is a component that accelerates the first stage curing of the present composition.
  • catalysts used for hydrosilylation reactions can be used.
  • platinum black chloroplatinic acid, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid with olefins or vinylsiloxanes, platinum-based catalysts such as platinum bisacetoacetate, palladium and platinum group metal catalysts such as platinum-based catalysts and rhodium-based catalysts.
  • the amount of component C to be blended may be any amount necessary for curing, and can be appropriately adjusted according to 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 the A1 component.
  • Thermally conductive inorganic filler (B component) The thermally conductive inorganic filler of component B is as described above.
  • Alumina is preferably ⁇ -alumina with a purity of 99.5% or higher.
  • the average particle size is D50 (median size) of cumulative particle size distribution based on volume measured by a laser diffraction light scattering method.
  • An example of such a measuring device is a laser diffraction/scattering type inorganic filler distribution measuring device LA-950S2 manufactured by Horiba, Ltd.
  • the thermally conductive inorganic filler is R a Si(OR′) 4-a (R is an unsubstituted or substituted organic group having 1 to 20 carbon atoms, R′ is an alkyl group having 1 to 4 carbon atoms, a is 0 or 1 ) or a partial hydrolyzate thereof.
  • An alkoxysilane compound represented by R a Si(OR') 4-a (R is an unsubstituted or substituted organic group having 1 to 20 carbon atoms, R' is an alkyl group having 1 to 4 carbon atoms, a is 0 or 1) (hereinafter simply referred to as "silane") is, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, Methoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane
  • the silane compounds can be used singly or in combination of two or more.
  • the above alkoxysilane compound and one-end silanol siloxane may be used in combination.
  • surface treatment includes not only covalent bonding but also adsorption and the like.
  • composition of the present invention may contain components other than those mentioned above, if necessary.
  • inorganic pigments such as red iron oxide and alkyltrialkoxysilane may be added for the purpose of surface treatment of fillers.
  • Alkoxy group-containing silicone may be added as a material added for the purpose of surface treatment of the filler.
  • FIG. 1 is a schematic cross-sectional view of a thermally conductive sheet incorporated into a heat dissipation structure 30 according to one embodiment of the present invention.
  • the thermally conductive sheet 31 b dissipates heat generated by the electronic component 33 such as a semiconductor element, is fixed to the main surface 32 a of the heat spreader 32 facing the electronic component 33 , and is positioned between the electronic component 33 and the heat spreader 32 . sandwiched. Also, the heat conductive sheet 31 a is sandwiched between the heat spreader 32 and the heat sink 35 .
  • the heat conductive sheets 31 a and 31 b constitute a heat dissipating member for dissipating heat from the electronic component 33 together with the heat spreader 32 .
  • the heat spreader 32 is formed, for example, in the shape of a square plate, and has a main surface 32a facing the electronic component 33 and side walls 32b erected along the outer circumference of the main surface 32a.
  • a heat conductive sheet 31b is provided on the main surface 32a surrounded by the side walls 32b of the heat spreader 32, 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 BGA, and is mounted on the wiring board 34 .
  • FIG. 2 is a scanning electron microscope (SEM) photograph (magnification of 10,000 times) of spherical alumina (B1) according to one embodiment of the present invention.
  • This spherical alumina is produced by a melting method and commercially available (for example, trade name "AZ2-75" manufactured by Nippon Steel Chemical & Materials Co., Ltd., average particle size 2 ⁇ m).
  • FIG. 3 is a scanning electron microscope (SEM) photograph of polygonal or rounded alumina not contained in the spherical alumina (B1) of the present invention.
  • FIG. 4 is a schematic side cross-sectional view of a compressive load measuring device used in one embodiment of the present invention.
  • This compressive load measuring device 1 comprises 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.
  • the conductive sheet sample 4 is compressed.
  • the maximum load value (instantaneous load value) of the load value when compressing 50% of the thickness of the sample and the load value (steady load value) after holding the compression for 1 minute are recorded.
  • this thermal conductivity measuring device 11 sandwiches a polyimide film sensor 12 between two thermally conductive sheet samples 13a and 13b, applies constant power to the sensor 12, heats the sensor 12 at a constant level, and heats the sensor 12. Analyze the thermal characteristics from the temperature rise value.
  • the sensor 12 has a tip 14 with a diameter of 7 mm, and as shown in FIG. 5B, has a double spiral electrode structure, and an applied current electrode 15 and a resistance value electrode (temperature measurement electrode) 16 are arranged at the bottom. It is The thermal conductivity was calculated by the following formula (Equation 1).
  • Example 1 Matrix resin component A commercially available two-liquid room temperature curing silicone polymer was used as the matrix resin component. A base polymer and a platinum-based metal catalyst are added in advance to component A of this two-component room temperature curing silicone polymer, and a base polymer and a cross-linking component are added in advance to component B.
  • the commercially available two-part room temperature vulcanizing silicone polymer used is an addition reaction silicone polymer.
  • Examples 2-5 Comparative Examples 1-6
  • Example 1 The same procedures as in Example 1 were carried out except for those shown in Tables 1 and 2.
  • the spherical alumina of Examples 2, 3, 5 and 6 had the shape shown in the photograph of FIG.
  • the rounded alumina of Comparative Examples 7 and 9 has a shape shown in the photograph of FIG. Tables 1 and 2 collectively show the above conditions and results.
  • each example has a high thermal conductivity, a low instantaneous and steady load value, a large compression relaxation, and can be clamped with a low load by compressing slowly. Since the damage to the body is small and the load value is low and soft, the conformability to the irregularities of the electronic parts is good.
  • Examples 6 and 7 are examples in which only spherical alumina with an average particle size of 1 to 10 ⁇ m and crushed alumina with an average particle size of less than 1 ⁇ m are used, and no filler with a large particle size is used. The effect of the invention was confirmed.
  • Comparative Example 8 does not contain pulverized alumina having an average particle size of less than 1 ⁇ m, and in order to match the total weight of the fillers, other fillers were added so as not to change the ratio. As a result, it did not come together well, and workability (moldability) was greatly reduced.
  • Comparative Example 9 since only round alumina particles with an average particle size of 1 to 10 ⁇ m and crushed alumina particles with an average particle size of less than 1 ⁇ m were used, the 50% compressive load values (instantaneous and constant) were high.
  • Comparative Example 10 contained only crushed alumina with an average particle size of 1 to 10 ⁇ m and crushed alumina with an average particle size of less than 1 ⁇ m, so the workability was poor and the 50% compression load value (instantaneous and constant) was high. , did not like it.
  • 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 parts such as semiconductors, LEDs, home appliances, information communication modules including optical communication equipment, and in-vehicle applications.

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PCT/JP2022/037639 2022-02-22 2022-10-07 熱伝導性組成物、熱伝導性シート及びその製造方法 Ceased WO2023162323A1 (ja)

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CN202280091609.7A CN118696096A (zh) 2022-02-22 2022-10-07 导热性组合物、导热片及其制造方法
KR1020247027618A KR20240150441A (ko) 2022-02-22 2022-10-07 열전도성 조성물, 열전도성 시트 및 그 제조 방법
EP22927614.2A EP4477713A4 (en) 2022-02-22 2022-10-07 THERMOCONDUCTIVE COMPOSITION, THERMOCONDUCTIVE SHEET AND THEIR MANUFACTURING PROCESS
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KR20240150441A (ko) 2024-10-15
EP4477713A4 (en) 2026-03-04
US20250145799A1 (en) 2025-05-08
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