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WO2025062949A1 - Composition de silicone thermoconductrice et produit durci de type feuille - Google Patents

Composition de silicone thermoconductrice et produit durci de type feuille Download PDF

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Publication number
WO2025062949A1
WO2025062949A1 PCT/JP2024/030126 JP2024030126W WO2025062949A1 WO 2025062949 A1 WO2025062949 A1 WO 2025062949A1 JP 2024030126 W JP2024030126 W JP 2024030126W WO 2025062949 A1 WO2025062949 A1 WO 2025062949A1
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thermally conductive
component
mass
sheet
group
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Japanese (ja)
Inventor
裕也 廣中
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical 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
    • C08K3/10—Metal compounds
    • C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a thermally conductive silicone composition and a sheet-like cured product of the composition.
  • heat dissipation components such as heat sinks are installed to cool the heat generated by heat-generating components such as semiconductor elements.
  • heat dissipation components such as heat sinks
  • a heat dissipation material is sandwiched between the heat-generating component and the heat dissipation component.
  • heat dissipation materials such as thermally conductive sheets, thermally conductive grease, and hardening type thermally conductive grease, and different types are used depending on the application.
  • thermally conductive sheets are easier to work with than thermally conductive grease when assembling heat dissipation devices.
  • thermally conductive sheets have difficulty conforming to the minute irregularities on the surfaces of electronic components and heat sinks.
  • the thermally conductive sheet a low-hardness thermally conductive sheet with an Asker C hardness of 15 or less.
  • Thermally conductive sheets provide high adhesion to heat dissipation components and are effective for low thermal resistance and uneven structures.
  • low-hardness thermal conductive sheets have poor recovery properties, so once they are deformed they do not return to their original shape, making them difficult to cut or reshape, and they have the disadvantage of being difficult to handle when applied and difficult to rework.
  • the hardness of the thermal conductive sheet must be increased, and low hardness is incompatible with ease of handling and reworkability.
  • Patent Document 1 discloses a heat dissipation sheet that overcomes the above problems by specifying the average polymerization ratio of an organopolysiloxane and an organohydrogenpolysiloxane that have 2 to 9 silicon-bonded alkenyl groups in the side chains, resulting in a sheet that has low hardness and excellent reworkability.
  • the present invention aims to provide a highly thermally conductive silicone sheet that has high resilience despite its low hardness and is suitable for use as a heat dissipation component in products that generate vibration.
  • the present invention provides a thermally conductive silicone composition that is characterized by containing the following components (A) to (D): (A) an organopolysiloxane having an alkenyl group bonded to a silicon atom in a molecular side chain and having 2 to 8 alkenyl groups per molecule: 100 parts by mass, (B) an organohydrogenpolysiloxane capped at both ends with hydrosilyl groups: an amount such that the number of moles of hydrosilyl groups in component (B) is 0.1 to 1.5 moles per 1.0 mole of alkenyl groups in component (A); (C) a thermally conductive filler containing the following components (C-1) to (C-3): 1,600 to 4,100 parts by mass, (C-1) Aluminum oxide having an average particle size of 0.5 to 5 ⁇ m: 270 to 1,610 parts by mass, (C-2) spherical aluminum oxide having an average particle size of 7 to 25 ⁇ m: 430 to 2,
  • the thermally conductive silicone composition of the present invention makes it possible to produce a thermally conductive sheet that has low hardness, high resilience, and high thermal conductivity.
  • the thermally conductive silicone composition preferably further contains 10 to 100 parts by mass of (E) a surface treatment agent, and the (E) component is preferably one or more selected from (E-1) an alkoxysilane and (E-2) a dimethylpolysiloxane having one end blocked with a trialkoxysilyl group.
  • the (C) component becomes uniformly dispersed in the matrix of the (A) component.
  • the present invention also provides a sheet-like cured product of the thermally conductive silicone composition of the present invention, characterized in that the hardness of the sheet-like cured product is 20 or less on the Asker C hardness scale.
  • the sheet-shaped cured product of the thermally conductive silicone composition of the present invention has low hardness, so it deforms to fit the shape of the object to be dissipated heat, and exhibits good heat dissipation properties without applying stress to the object. Furthermore, the thermally conductive cured sheet-shaped product of the present invention has excellent handleability and reworkability, and has high recovery properties, making it useful as a heat dissipation component for products that generate vibration.
  • the thermally conductive silicone composition of the present invention has high resilience even with low hardness, making it possible to manufacture a thermally conductive silicone sheet with high thermal conductivity suitable for use as a heat dissipation component in products that generate vibration.
  • the sheet-shaped cured product of the thermally conductive silicone composition of the present invention has low hardness, so it deforms to fit the shape of the object to be dissipated heat, and exhibits good heat dissipation properties without applying stress to the object. Furthermore, the thermally conductive cured sheet-shaped product of the present invention has excellent handleability and reworkability, and has high recovery properties, making it useful as a heat dissipation component for products that generate vibration.
  • thermally conductive silicone composition containing the following components (A) to (D) can be used to manufacture a thermally conductive silicone sheet that has high recovery even with low hardness by controlling the particle size of the thermally conductive material, and has high thermal conductivity and is suitable for use as a heat dissipation component in products that generate vibration, thus completing the present invention.
  • the present invention provides a thermally conductive silicone composition
  • a thermally conductive silicone composition comprising the following components (A) to (D): (A) an organopolysiloxane having an alkenyl group bonded to a silicon atom in a molecular side chain and having 2 to 8 alkenyl groups per molecule: 100 parts by mass, (B) an organohydrogenpolysiloxane capped at both ends with hydrosilyl groups: an amount such that the number of moles of hydrosilyl groups in component (B) is 0.1 to 1.5 moles per 1.0 mole of alkenyl groups in component (A); (C) a thermally conductive filler containing the following components (C-1) to (C-3): 1,600 to 4,100 parts by mass, (C-1) Aluminum oxide having an average particle size of 0.5 to 5 ⁇ m: 270 to 1,610 parts by mass, (C-2) spherical aluminum oxide having an average particle size of 7 to 25 ⁇ m: 430 to 2,010
  • the thermally conductive silicone composition of the present invention is a composition containing (A) an organopolysiloxane, (B) an organohydrogenpolysiloxane, (C) a thermally conductive filler, and (D) a platinum group metal curing catalyst. Each of these will be described in detail below.
  • the alkenyl-containing organopolysiloxane which is component (A), is an organopolysiloxane that is required to have an alkenyl group bonded to a silicon atom in the molecular side chain, and has 2 to 8 alkenyl groups in one molecule. If the number of alkenyl groups is less than 2, the thermally conductive silicone composition of the present invention may not be cured, and if the number of alkenyl groups is more than 8, the hardness of the cured product may be too hard, which is not preferable.
  • the main chain of this organopolysiloxane may be, for example, a straight chain that is basically composed of a repetition of diorganosiloxane units and has both ends of the molecular chain blocked with triorganosiloxy groups.
  • the molecular structure may include a branched structure or may be cyclic. Among them, a straight chain diorganopolysiloxane is preferable in terms of physical properties such as the mechanical strength of the cured product.
  • the (A) component an alkenyl-containing organopolysiloxane, has an alkenyl group on the side chain, so that the alkenylsiloxane reacts with the hydrosiloxane to form a uniform network structure, which allows recovery to be achieved. If the network structure is non-uniform or if the crosslinked structure is not a network structure, the recovery will be reduced.
  • the average degree of polymerization of component (A) is preferably 10 to 10,000, and particularly preferably 50 to 2,000. If the average degree of polymerization is 10 or more, the sheet will not become too hard and the compressibility will not decrease. If the average degree of polymerization is 10,000 or less, the sheet will have high strength and good recovery.
  • the average degree of polymerization can be determined as the number average degree of polymerization or number average molecular weight converted into polystyrene by GPC (gel permeation chromatography) analysis using THF (tetrahydrofuran) as a developing solvent.
  • the component (A) is preferably an organopolysiloxane represented by the following formula (1).
  • R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms
  • X is an alkenyl group having 2 to 8 carbon atoms
  • n is an integer of 0 or more
  • m is an integer of 2 to 8.
  • R is a group selected from an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, preferably 7 to 9 carbon atoms.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups
  • cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups
  • aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups
  • aralkyl groups such as benzyl, phenylethyl, phenylpropyl, and methylbenzyl groups.
  • methyl, ethyl, and phenyl groups are preferred.
  • X is an alkenyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms.
  • Examples include vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, and cyclohexenyl groups. Of these, vinyl groups and allyl groups are preferred, and vinyl groups are particularly preferred.
  • m is an integer of 2 to 8, preferably 2 to 6.
  • n is an integer of 0 or more, preferably an integer of 5 to 9,000.
  • m and n are preferably integers that satisfy 10 ⁇ m+n ⁇ 10,000, more preferably integers that satisfy 50 ⁇ m+n ⁇ 2,000, even more preferably integers that satisfy 100 ⁇ m+n ⁇ 500, and even more preferably integers that satisfy 0 ⁇ m/(m+n) ⁇ 0.05.
  • the organohydrogenpolysiloxane of component (B) is one that is end-blocked at both ends with hydrosilyl groups (Si-H groups), and preferably has both ends blocked with hydrosilyl groups and 2 to 4 hydrosilyl groups present in each molecule. If the number of hydrosilyl groups is 2 or more, the thermally conductive silicone composition of the present invention will cure reliably.
  • the average degree of polymerization of component (B) is preferably 2 to 300, and more preferably 10 to 150. If the average degree of polymerization is 2 or more, the sheet will not be too hard and the compressibility will not decrease. If the average degree of polymerization is 300 or less, the sheet will have high strength and good recovery.
  • the component (B) is preferably an organohydrogenpolysiloxane represented by the following formula (2).
  • R is independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; p is an integer of 0 or more, and q is an integer of 0 to 2.
  • R is a group selected from an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, preferably 7 to 9 carbon atoms.
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups
  • cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups
  • aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups
  • aralkyl groups such as benzyl, phenylethyl, phenylpropyl, and methylbenzyl groups.
  • methyl, ethyl, and phenyl groups are preferred.
  • p is preferably an integer of 0 or more, particularly 2 to 100
  • q is preferably an integer of 0 or more and less than 2, particularly 0 to 1.
  • p and q are integers that satisfy 0 ⁇ p+q ⁇ 101, and are preferably integers that satisfy 2 ⁇ p+q ⁇ 80, more preferably integers that satisfy 2 ⁇ p+q ⁇ 50, and even more preferably integers that satisfy 2 ⁇ p+q ⁇ 30.
  • the amount of component (B) to be blended is such that the number of moles of hydrosilyl groups in component (B) per 1.0 mole of alkenyl groups in component (A) (i.e., Si-H/Si-Vi) is 0.1 to 1.5 moles, and preferably 0.3 to 1.0 moles. If the amount of hydrosilyl groups in component (B) is less than 0.1 mole or more than 1.5 moles per mole of alkenyl groups in component (A), a sheet-like cured product with the desired low hardness cannot be obtained.
  • thermally conductive filler which is component (C), from the standpoint of the flowability of the composition and the thermal conductivity and recovery of the molded product, the thermally conductive silicone composition of the present invention contains specified amounts of two types of thermally conductive fillers, aluminum oxide and magnesium oxide.
  • the thermally conductive filler is (C-1) aluminum oxide having an average particle size of 0.5 to 5 ⁇ m; (C-2) spherical aluminum oxide having an average particle size of 7 to 25 ⁇ m; (C-3) It is characterized by the combined use of magnesium oxide having an average particle size of 40 to 90 ⁇ m.
  • the average particle diameter is the value determined as the cumulative volume average diameter D50 (median diameter) in particle size distribution measurement by laser light diffraction. Specifically, it is the value of the cumulative 50% particle diameter (D50) on a volume basis measured using a particle size distribution measuring device MT3000II manufactured by Microtrack Bell Co., Ltd.
  • ⁇ Component (C-1) Aluminum Oxide> Aluminum oxide has various crystal phases, such as ⁇ , ⁇ , ⁇ , and ⁇ , depending on the sintering temperature. ⁇ -aluminum oxide, which has the highest sintering temperature, is preferred because it is chemically stable.
  • aluminum oxide rarely has a single crystal phase, but it is better for the proportion of alpha phase to be as high as possible, and it is preferable for the alpha phase rate to be 90% or more, and preferably 95% or more.
  • Aluminum oxide can be in a spherical or crushed granular form, depending on the manufacturing method. Generally, crushed aluminum oxide has a higher alpha conversion rate, so crushed aluminum oxide is preferred, but depending on the amount of thermally conductive filler used, the fillability into silicone and thermal conductivity can be improved by using some spherical aluminum oxide. There are no particular restrictions on the granular form of the aluminum oxide in component (C-1).
  • the average particle size of component (C-1) is 0.5 to 5 ⁇ m, preferably 0.5 to 3 ⁇ m, and more preferably 1 to 2 ⁇ m. Aluminum oxide with such particle sizes can ensure a heat transfer path and significantly improve the thermal conductivity of the silicone resin cured product. If the average particle size of component (C-1) is less than 0.5 ⁇ m, the close packing of the composition decreases, the viscosity increases, and molding becomes difficult, and if crushed alumina with a particle size of more than 5 ⁇ m is used, the surface of the cured product becomes uneven, resulting in poor adhesion and increased thermal resistance.
  • Component (C-2) Spherical Aluminum Oxide>
  • the aluminum oxide used in component (C-2) is spherical aluminum oxide, and has a gelatinization rate of 90% or more, preferably 95% or more. In the case of crushed aluminum oxide, the thermal conductivity is excellent, but the restorability is reduced.
  • the average particle size of component (C-2) is 7 ⁇ m to 25 ⁇ m, preferably 7 to 20 ⁇ m, and more preferably 7 to 15 ⁇ m.
  • Spherical aluminum oxide with such a particle size has a small specific surface area, making it easy to fill into silicone and to prepare a composition. Furthermore, spherical aluminum oxide with such a particle size can ensure a heat transfer path while reducing the number of filler/resin interfaces, significantly improving the thermal conductivity and recovery of the silicone resin cured product. If the average particle size of component (C-2) is less than 7 ⁇ m or more than 25 ⁇ m, the thermal conductivity decreases.
  • Magnesium oxide> Magnesium oxide is preferred as a thermally conductive filler because it has high thermal conductivity and insulating properties. However, because it has a problem with moisture resistance, magnesium oxide with improved moisture resistance is preferred. There are no particular limitations as long as it is a substance that is generally considered to be magnesium oxide, but it is preferred to use low-activity, high-purity magnesium oxide that has been baked at high temperatures (1,800 to 2,000°C) or magnesium oxide whose surface is coated with a polymer such as resin or resin, or an inorganic substance such as aluminum oxide that has excellent moisture resistance. Magnesium oxide with excellent moisture resistance prevents the composition from exhibiting strong basicity, thereby suppressing the decomposition of silicone in the composition and preventing the silicone cured product from softening.
  • the average particle size of the above component (C-3) is 40 to 90 ⁇ m, preferably 40 to 80 ⁇ m, and more preferably 40 to 70 ⁇ m. Magnesium oxide with such a particle size ensures a heat transfer path without impeding restorability, and can significantly improve the restorability and thermal conductivity of the silicone cured product. If the average particle size of the above component (C-3) is less than 40 ⁇ m, the viscosity is likely to increase and the thermal conductivity will also decrease. If it exceeds 90 ⁇ m, the kneading equipment and molding equipment will wear out.
  • the blending amount of the component (C) including the components (C-1) to (C-3) is 1,600 to 4,100 parts by mass, preferably 1,700 to 3,900 parts by mass, and more preferably 1,800 to 3,800 parts by mass, per 100 parts by mass of the component (A).
  • the amount of the (C-1) component is 270 to 1,610 parts by mass, preferably 500 to 1,400 parts by mass, per 100 parts by mass of the (A) component
  • the amount of the (C-2) component is 430 to 2,010 parts by mass, preferably 500 to 1,800 parts by mass, per 100 parts by mass of the (A) component
  • the amount of the (C-3) component is 530 to 1,350 parts by mass, preferably 600 to 1,200 parts by mass, per 100 parts by mass of the (A) component.
  • the mass ratio of the above component (C-2) to the above component (C-1) is set to 0.7 to 3.0.
  • Component (D) is a platinum group metal catalyst that accelerates the curing of the thermally conductive silicone composition, and examples of such catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes.
  • the amount of platinum catalyst is not particularly limited and may be an effective amount as a catalyst, but is usually an amount such that the platinum metal in component (D) is 0.01 to 1,000 ppm, and preferably 0.1 to 500 ppm, by mass relative to component (A). If the amount of component (D) is too small, the resulting thermally conductive silicone rubber composition may not cure sufficiently, while using a large amount does not improve the cure rate of the resulting silicone rubber composition, which is economically disadvantageous.
  • the thermally conductive silicone composition of the present invention can contain a surface treatment agent, component (E).
  • component (E) is to hydrophobize component (C) during preparation of the composition, improve wettability with component (A), and disperse component (C) uniformly in the matrix made of component (A). It is particularly preferable that component (E) is one or more selected from components (E-1) and (E-2) shown below.
  • the component (E-1) is, for example, an alkoxysilane compound represented by the following formula (3).
  • R 3 b R 4 c Si(OR 5 ) 4-b-c (3) (In the formula, each R3 is independently an alkyl group having 6 to 15 carbon atoms, each R4 is independently a group selected from an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and each R5 is independently an alkyl group having 1 to 6 carbon atoms.
  • b is an integer of 1 to 3
  • c is an integer of 0 to 2, with the proviso that b+c is an integer of 1 to 3.
  • examples of the alkyl group represented by R3 include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, etc.
  • the number of carbon atoms of the alkyl group represented by R3 is in the range of 6 to 15, the wettability of component (A) is sufficiently improved, the handleability is good, and the low-temperature properties of the composition are excellent.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R4 include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a neopentyl group.
  • Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group.
  • Examples of the group selected from the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group.
  • alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and a phenyl group.
  • R4 include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.
  • the component (E-2) is a dimethylpolysiloxane having one molecular chain end blocked with a trialkoxysilyl group, as represented by the following formula (4).
  • R 6 is independently an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include the same alkyl groups as those exemplified for R 5 above.
  • d is an integer of 5 to 100, preferably 5 to 70, and particularly preferably 10 to 50.
  • the surface treatment agent for component (E) may be either component (E-1) or component (E-2), or both may be combined.
  • component (E) When component (E) is added, the amount is preferably 10 to 100 parts by mass, and more preferably 20 to 80 parts by mass, per 100 parts by mass of component (A). If the proportion of component (E) is 10 parts by mass or more, the wettability of component (C) can be sufficiently improved, and if it is 100 parts by mass or less, oil separation can be sufficiently suppressed.
  • the thermally conductive silicone composition of the present invention may further contain other components, such as optional components such as a heat resistance improver such as iron oxide, a viscosity modifier such as silica or a plasticizer, a colorant, or a release agent.
  • a heat resistance improver such as iron oxide
  • a viscosity modifier such as silica or a plasticizer
  • a colorant such as a colorant, or a release agent.
  • the thermally conductive silicone composition of the present invention can be prepared by mixing the above-mentioned components (A) through (D) and any other optional components using a mixing device such as a planetary mixer.
  • the sheet-like cured product of the present invention is a sheet-like cured product of the thermally conductive silicone composition of the present invention, characterized in that it has a hardness of 20 or less on the Asker C hardness scale.
  • the sheet-like cured product of the present invention has low hardness, so it deforms to fit the shape of the object to be dissipated heat, and has excellent thermal conductivity, so it exhibits good heat dissipation characteristics without applying stress to the object to be dissipated heat.Furthermore, it has excellent handleability and reworkability, and high recovery properties, making it useful as a heat dissipation component for products that generate vibration.
  • the sheet-shaped cured product of the present invention can be produced by forming the thermally conductive silicone composition of the present invention into a sheet and curing it.
  • the curing conditions for molding the composition may be the same as those for known addition reaction curing silicone rubber compositions, and although the composition will cure sufficiently at room temperature, it is preferable to cure the composition by heating. Heating conditions are preferably at 100 to 180°C, particularly 110 to 150°C, for 5 to 30 minutes, particularly 10 to 20 minutes, and addition curing can be achieved, for example, at 120°C for 10 minutes. Secondary curing (post curing) at 100 to 200°C, particularly 130 to 170°C, for 1 to 10 hours, particularly 3 to 7 hours, is also preferable.
  • the hardness of the sheet-like cured product of the present invention is 20 or less, preferably 15 or less, as measured at 25°C using an Asker C hardness tester as specified in JIS K 7312:1996.
  • the sheet-like cured product of the present invention can exhibit excellent restoring properties even with such a low hardness. Specifically, since the sheet-like cured product has high restoring properties even with a hardness of 20 or less, the contact thermal resistance is kept low and sufficient heat dissipation properties can be exhibited.
  • the thermal conductivity of the sheet-like cured product obtained from the composition of the present invention i.e., the sheet-like cured product of the present invention, measured by the hot disk method at 25° C., is preferably 2.0 W/m K or more, and more preferably 2.5 W/m K or more.
  • a thermal conductivity of 2.0 W/m K or more can also be used for heating elements that generate a large amount of heat.
  • the thermal conductivity of the sheet-shaped cured product can be adjusted to the above value.
  • Component (A-2) Vinylpolysiloxane A polysiloxane having nine side chain vinyl groups per molecule, as represented by the following formula:
  • (B-2) A methylhydrogenpolysiloxane having hydrosilyl groups on the side chains and blocked with trimethylsilyl groups, as represented by the following formula:
  • Component (E) Surface treatment agent (E-1) Trimethoxysilane with a decyl group, represented by the following formula: C 10 H 21 Si(OCH 3 ) 3
  • (E-2) A dimethylpolysiloxane having an average degree of polymerization of 30 and one end blocked with a trimethoxysilyl group, as represented by the following formula:
  • the thermal conductivity of each of the resulting sheet-like cured products was measured using a thermal conductivity meter (TPA-501, product name manufactured by Kyoto Electronics Manufacturing Co., Ltd.).
  • compositions of Examples 1 to 8 each contained a polysiloxane (A-1) with two vinyl groups in the side chain, a hydrogen polysiloxane (B-1) with hydrosilyl groups only at both ends, and components (C-1) to (C-3), with the number of moles of hydrosilyl groups in component (B-1) being within the range of 0.1 to 1.5 moles relative to the number of moles of alkenyl groups in component (A), and the ratio of component (C-2)/component (C-1) being within the range of 0.7 to 3.0.
  • the sheet-shaped cured products obtained from each of these compositions had a hardness of 20 or less, yet had excellent restorability and thermal conductivity.
  • Comparative Example 1 which used polysiloxane (A-2) with nine vinyl groups in the side chain, the restorability of the sheet-shaped cured product was reduced.
  • Comparative Example 2 which used methylhydrogenpolysiloxane (B-2) that has hydrosilyl groups only on the molecular side chains, showed a decrease in the restorability of the sheet-shaped cured product compared to Examples 1-8.
  • thermally conductive silicone composition of the present invention can produce a sheet-like cured product that has low hardness, yet exhibits high resilience and high thermal conductivity.
  • the present invention is not limited to the above-described embodiment.
  • the above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de silicone thermoconductrice comprenant les composants (A) à (D) : (A) Un organopolysiloxane qui possède des groupes alcényle liés à des atomes de silicium sur une chaîne latérale de la molécule et dans lequel le nombre de groupes alcényle par molécule est de 2 à 8. (B) Un organohydrogénopolysiloxane dans lequel les deux terminaisons sont bloquées par des groupes hydrosilyle. (C) Une charge thermoconductrice contenant les composants (C-1) à (C-3) suivants : (C-1) un oxyde d'aluminium ayant une taille moyenne de particule de 0,5 à 5 µm ; (C-2) un oxyde d'aluminium sphérique qui a une taille moyenne de particule de 7 à 25 µm, et qui est contenu en une quantité telle que le rapport en masse de (C-2) par rapport à (C-1) est de 0,7 à 3,0 ; et (C-3) un oxyde de magnésium ayant une taille moyenne de particule de 40 à 90 µm. (D) Un catalyseur de durcissement à base de métal du groupe du platine. En conséquence, la présente invention concerne une feuille de silicone thermoconductrice qui présente une capacité de restauration élevée même lorsqu'elle a une faible dureté, et qui présente une conductivité thermique élevée appropriée pour un élément de dissipation de chaleur d'un produit dans lequel une vibration est générée.
PCT/JP2024/030126 2023-09-20 2024-08-26 Composition de silicone thermoconductrice et produit durci de type feuille Pending WO2025062949A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016923A (ja) * 2009-07-09 2011-01-27 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーン組成物およびそれを用いた熱伝導性シリコーン成形物
WO2016017495A1 (fr) * 2014-07-28 2016-02-04 信越化学工業株式会社 Composition de silicone thermiquement conductrice, et article moulé en silicone thermiquement conducteur
WO2020261958A1 (fr) * 2019-06-24 2020-12-30 信越化学工業株式会社 Composition de silicone hautement thermoconductrice et produit durci correspondant
WO2021095507A1 (fr) * 2019-11-14 2021-05-20 信越化学工業株式会社 Composition de silicone thermoconductrice et feuille de silicone thermoconductrice
WO2021131681A1 (fr) * 2019-12-26 2021-07-01 信越化学工業株式会社 Composition de résine de silicone thermoconductrice

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016923A (ja) * 2009-07-09 2011-01-27 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーン組成物およびそれを用いた熱伝導性シリコーン成形物
WO2016017495A1 (fr) * 2014-07-28 2016-02-04 信越化学工業株式会社 Composition de silicone thermiquement conductrice, et article moulé en silicone thermiquement conducteur
WO2020261958A1 (fr) * 2019-06-24 2020-12-30 信越化学工業株式会社 Composition de silicone hautement thermoconductrice et produit durci correspondant
WO2021095507A1 (fr) * 2019-11-14 2021-05-20 信越化学工業株式会社 Composition de silicone thermoconductrice et feuille de silicone thermoconductrice
WO2021131681A1 (fr) * 2019-12-26 2021-07-01 信越化学工業株式会社 Composition de résine de silicone thermoconductrice

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