WO2022255004A1 - Composition de silicone thermoconductrice et produit durci associé - Google Patents

Composition de silicone thermoconductrice et produit durci associé Download PDF

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Publication number
WO2022255004A1
WO2022255004A1 PCT/JP2022/018791 JP2022018791W WO2022255004A1 WO 2022255004 A1 WO2022255004 A1 WO 2022255004A1 JP 2022018791 W JP2022018791 W JP 2022018791W WO 2022255004 A1 WO2022255004 A1 WO 2022255004A1
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thermally conductive
group
conductive silicone
silicone composition
component
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PCT/JP2022/018791
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English (en)
Japanese (ja)
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俊晴 森村
靖久 石原
崇則 伊藤
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—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

Definitions

  • the present invention relates to a thermally conductive silicone composition and its cured product.
  • LSI chips such as CPUs, driver ICs, and memories used in electronic devices such as personal computers, digital video discs, and mobile phones are becoming more sophisticated, faster, smaller, and more highly integrated. Now produces heat. Since the temperature rise of the chip due to the heat causes malfunction and destruction of the chip, many heat dissipation methods and heat dissipation members used therefor have been proposed to suppress the temperature rise of the chip during operation.
  • heat sinks using metal plates with high thermal conductivity such as aluminum and copper are used in order to suppress the temperature rise of chips during operation.
  • the heat sink conducts the heat generated by the chip and dissipates the heat through the surface due to the temperature difference with the ambient air.
  • Thermally conductive sheets are easier to handle than grease, and thermally conductive sheets made of thermally conductive silicone rubber (thermally conductive silicone rubber sheets) are used in various fields.
  • an insulating composition in which at least one metal oxide selected from beryllium oxide, aluminum oxide, aluminum oxide hydrate, magnesium oxide, and zinc oxide is blended with 100 parts by mass of synthetic rubber such as silicone rubber. (Patent Document 1).
  • a method is used in which a natural cooling type or forced cooling type heat radiating component is installed near the integrated circuit element, and the heat generated in the element is transferred to the heat radiating component. If the element and the heat dissipation component are brought into direct contact with each other using this method, the heat transfer will be poor due to the unevenness of the surface. Furthermore, even if the element is attached via the heat radiation insulating sheet, the flexibility of the heat radiation insulating sheet is slightly inferior, so that stress is applied between the element and the substrate due to thermal expansion, and there is a risk of damage.
  • a sheet formed by mixing a thermally conductive material such as a metal oxide into a silicone resin in which an easily deformable silicone layer is laminated on a strong silicone resin layer.
  • Patent Document 2 Also disclosed is a thermally conductive composite sheet in which a silicone rubber layer containing a thermally conductive filler and having an Asker C hardness of 5 to 50 and a porous reinforcing material layer having pores with a diameter of 0.3 mm or more are combined.
  • Patent Document 3 Also proposed is a sheet in which the skeletal lattice surface of a flexible three-dimensional network or foam is coated with thermally conductive silicone rubber (Patent Document 4).
  • a thermally conductive composite silicone having an Asker C hardness of 5 to 50 and a thickness of 0.4 mm or less, which contains a reinforcing sheet or cloth and has adhesiveness on at least one surface.
  • a seat is disclosed (Patent Document 5).
  • a heat dissipating spacer containing an addition reaction type liquid silicone rubber and a thermally conductive insulating ceramic powder, the cured product of which has an Asker C hardness of 25 or less and a thermal resistance of 3.0° C./W or less.
  • thermally conductive silicone cured products are often required to have insulating properties, so aluminum oxide (alumina) is often used as a thermally conductive filler.
  • alumina aluminum oxide
  • amorphous alumina is more effective in improving thermal conductivity than spherical alumina.
  • silicone has a drawback that it has a poor filling property with silicone, and when the filling rate is increased, the viscosity of the material increases and the processability deteriorates.
  • Alumina has a Mohs hardness of 9, which is very hard. For this reason, a thermally conductive silicone composition using amorphous alumina with a particle size of 10 ⁇ m or more has the problem that the inner wall of the reactor and the stirring blades are scraped during production.
  • the components of the reaction vessel and stirring blades are mixed into the thermally conductive silicone composition, and the insulating properties of the thermally conductive silicone composition and the cured product using the same are lowered.
  • the stirring efficiency decreases, making it impossible to obtain a constant quality even if the product is manufactured under the same conditions.
  • thermally conductive filler with a high thermal conductivity, such as a thermally conductive filler such as aluminum nitride or boron nitride, but the cost is high, There was a problem that processing was also difficult.
  • the present invention has been made in view of the above circumstances, and aims to provide a thermally conductive silicone composition with excellent compressibility, insulation, thermal conductivity, and workability, and a cured product thereof.
  • a particular object of the present invention is to provide a thermally conductive silicone composition having a thermal conductivity of 6.5 W/m ⁇ K or more and a cured product thereof.
  • Such a thermally conductive silicone composition can be suitably used as a thermally conductive resin molding that is placed between a heat-generating component and a heat-radiating component in an electronic device and used for heat radiation.
  • the present invention provides a thermally conductive silicone composition
  • (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass
  • (B) Organohydrogenpolysiloxane having two or more hydrogen atoms directly bonded to silicon atoms: the number of moles of hydrogen atoms directly bonded to silicon atoms is 0.1 of the number of moles of alkenyl groups derived from component (A) ⁇ 5.0 times the amount
  • C a thermally conductive filler consisting of (C-1) to (C-3) below: 4,000 to 5,800 parts by mass; (C-1) spherical alumina filler having an average particle size of more than 70 ⁇ m and 135 ⁇ m or less: 1,400 to 3,000 parts by mass; (C-2) a spherical alumina filler having an average particle size of more than 8 ⁇ m and 40 ⁇ m or less: 500 to 2,300 parts by mass; (C
  • thermally conductive silicone composition provides a thermally conductive silicone composition with excellent compressibility, insulation, thermal conductivity, and workability, and a cured product thereof.
  • (F-1) an alkoxysilane compound represented by the following general formula (1), and R 1 a R 2 b Si(OR 3 ) 4-ab (1)
  • R 1 is independently an alkyl group having 6 to 15 carbon atoms
  • R 2 is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a group selected from 7 to 12 aralkyl groups
  • R 3 is independently an alkyl group having 1 to 6 carbon atoms
  • a is an integer of 1 to 3
  • b is an integer of 0 to 2
  • the proviso that a+b is an integer from 1 to 3.
  • (F-2) a dimethylpolysiloxane having one molecular chain end blocked with a trialkoxysilyl group represented by the following general formula (2);
  • R 4 is independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100.
  • Such a thermally conductive silicone composition does not induce oil separation.
  • component (G) it is preferable that 8.0 to 25.0 parts by mass of cerium oxide is contained as component (G) with respect to 100 parts by mass of component (A).
  • the hardness of the cured product of the thermally conductive silicone composition measured with an Asker C hardness tester after aging at 150° C. for 500 hours is - A score of 5 points or more and 40 points or less is preferable.
  • a cured product of such a thermally conductive silicone composition exhibits little decrease in hardness even when used at high temperatures for a long time.
  • an organopolysiloxane represented by the following general formula (3) and having a kinematic viscosity at 23° C. of 10 to 100,000 mm 2 /s (wherein R 5 is a group independently selected from an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; d is an integer of 5 to 2,000; is.) is preferably contained in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass of the component (A).
  • Such a thermally conductive silicone composition has excellent flexibility, and the resulting cured product is less prone to oil bleeding.
  • the viscosity of the thermally conductive silicone composition measured with a flow tester viscometer at 23°C is 2,000 Pa ⁇ s or less.
  • Such a thermally conductive silicone composition is excellent in moldability (workability).
  • the thermal conductivity at 23°C of the cured product of the thermally conductive silicone composition measured by the hot disk method is 6.5 W/m ⁇ K or more.
  • a cured product of such a thermally conductive silicone composition has excellent thermal conductivity.
  • the cured product of the thermally conductive silicone composition has a dielectric breakdown voltage of 10 kV/mm or more at a thickness of 1 mm.
  • a cured product of such a thermally conductive silicone composition can ensure stable insulation during use.
  • the present invention also provides a cured thermally conductive silicone product, which is a cured product of the above thermally conductive silicone composition.
  • Such a thermally conductive silicone cured product has excellent compressibility, insulation, thermal conductivity, and workability.
  • the shape of the thermally conductive silicone cured product can be a sheet.
  • Such a thermally conductive silicone cured product is excellent in handleability.
  • the thermally conductive silicone composition of the present invention comprises amorphous alumina having an average particle size of more than 0.4 ⁇ m and not more than 4 ⁇ m, spherical alumina having an average particle size of more than 8 ⁇ m and not more than 40 ⁇ m, and alumina having an average particle size of more than 70 ⁇ m.
  • a thermally conductive silicone cured product having excellent compressibility, insulation, thermal conductivity, and workability, especially having a thermal conductivity of 6.5 W / m K or more, and a heat molded into a sheet Conductive silicone moldings can be provided.
  • cerium oxide it is possible to provide a thermally conductive silicone composition in which the decrease in hardness of the cured product is suppressed when stored at high temperature.
  • amorphous alumina having an average particle size of more than 0.4 ⁇ m and not more than 4 ⁇ m and spherical alumina having an average particle size of more than 8 ⁇ m and not more than 40 ⁇ m and spherical alumina having an average particle size of more than 70 ⁇ m and not more than 135 ⁇ m in a specific compounding amount can solve the above problems. That is, by blending a large amount of spherical alumina having a small specific surface area of more than 70 ⁇ m and 135 ⁇ m or less, it is possible to effectively improve the thermal conductivity, and the silicone composition has a low viscosity and excellent workability.
  • the cured product can be provided.
  • spherical alumina and amorphous alumina having an average particle size of 40 ⁇ m or less improves the fluidity of the composition and improves workability. Furthermore, since spherical alumina is used for particles exceeding 8 ⁇ m, abrasion of the reactor and stirring blades is suppressed, and insulation is improved.
  • the shortcomings of the spherical alumina with a small particle size are compensated for by the spherical alumina with a large particle size
  • the shortcomings of the spherical alumina with a large particle size are compensated for by the spherical alumina with a small particle size and the amorphous alumina.
  • the present invention is a thermally conductive silicone composition
  • (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass
  • (B) Organohydrogenpolysiloxane having two or more hydrogen atoms directly bonded to silicon atoms: the number of moles of hydrogen atoms directly bonded to silicon atoms is 0.1 of the number of moles of alkenyl groups derived from component (A) ⁇ 5.0 times the amount
  • C a thermally conductive filler consisting of (C-1) to (C-3) below: 4,000 to 5,800 parts by mass; (C-1) spherical alumina filler having an average particle size of more than 70 ⁇ m and 135 ⁇ m or less: 1,400 to 3,000 parts by mass; (C-2) a spherical alumina filler having an average particle size of more than 8 ⁇ m and 40 ⁇ m or less: 500 to 2,300 parts by mass; (C-3) Amorphous
  • the thermally conductive silicone composition of the present invention is (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass, (B) Organohydrogenpolysiloxane having two or more hydrogen atoms directly bonded to silicon atoms: the number of moles of hydrogen atoms directly bonded to silicon atoms is 0.1 of the number of moles of alkenyl groups derived from component (A) ⁇ 5.0 times the amount, (C) a thermally conductive filler consisting of (C-1) to (C-3) below: 4,000 to 5,800 parts by mass; (C-1) spherical alumina filler having an average particle size of more than 70 ⁇ m and 135 ⁇ m or less: 1,400 to 3,000 parts by mass; (C-2) a spherical alumina filler having an average particle size of more than 8 ⁇ m and 40 ⁇ m or less: 500 to 2,300 parts by mass; (C)
  • the organopolysiloxane having two or more alkenyl groups in one molecule which is the component (A), is an organopolysiloxane having two or more silicon-bonded alkenyl groups in one molecule. It is the main ingredient of cured silicone products. Generally, the main chain basically consists of repeating diorganosiloxane units, but this may include a branched structure as part of the molecular structure, or a cyclic structure. Although it may be a solid, linear diorganopolysiloxane is preferable from the viewpoint of physical properties such as mechanical strength of the cured product.
  • Examples of functional groups other than alkenyl groups bonded to silicon atoms include monovalent hydrocarbon groups exemplified below. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.
  • these monovalent hydrocarbon groups those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred.
  • alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group, and phenyl group are preferably used.
  • the functional groups other than the alkenyl groups bonded to the silicon atoms are not limited to all being the same.
  • alkenyl group examples include those having usually about 2 to 8 carbon atoms such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group and cyclohexenyl group.
  • a lower alkenyl group such as an allyl group is preferred, and a vinyl group is particularly preferred.
  • Two or more alkenyl groups must be present in the molecule, but in order to improve the flexibility of the resulting cured product, the alkenyl group may be present bonded only to the silicon atom at the end of the molecular chain. preferable.
  • the kinematic viscosity of this organopolysiloxane at 23° C. is generally 10 to 100,000 mm 2 /s, preferably 500 to 50,000 mm 2 /s. When the kinematic viscosity is within this range, the obtained composition has good storage stability and does not deteriorate in spreadability.
  • kinematic viscosity is a value measured at 23° C. using a Canon-Fenske viscometer according to the method described in JIS Z 8803:2011.
  • the organopolysiloxane having at least two alkenyl groups in one molecule of component (A) may be used singly or in combination of two or more having different kinematic viscosities.
  • the organohydrogenpolysiloxane of component (B) is an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to silicon atoms. That is, it is an organohydrogenpolysiloxane having at least two, preferably 2 to 100, hydrogen atoms (hydrosilyl groups) directly bonded to silicon atoms in one molecule, and acts as a cross-linking agent for component (A). is an ingredient.
  • the hydrosilyl groups in the component (B) and the alkenyl groups in the component (A) are added by a hydrosilylation reaction promoted by the platinum group metal-based curing catalyst of the component (D), which will be described later, to form a crosslinked structure. gives a three-dimensional network structure with In addition, when the number of hydrosilyl groups is less than 2, it does not cure.
  • organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to silicon atoms those represented by the following average structural formula (4) are used, but are not limited thereto.
  • R 6 is independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms.
  • R 6 in one molecule are hydrogen atoms
  • e is an integer of 1 or more, preferably 10 to 200.
  • R 6 is independently a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. is. However, 2 or more, preferably 2 to 10 R 6 in one molecule are hydrogen atoms. Examples of monovalent hydrocarbon groups other than hydrogen atoms for R 6 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group and heptyl group.
  • Alkyl groups such as octyl group, nonyl group, decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group and aralkyl groups such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group.
  • monovalent hydrocarbon groups those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are particularly preferred.
  • An alkyl group having 1 to 3 carbon atoms and a phenyl group are preferably used.
  • R6 is not limited to being the same.
  • e is an integer of 1 or more, preferably an integer of 10-200.
  • the amount of component (B) to be added is such that the hydrosilyl groups derived from component (B) are 0.1 to 5.0 mol per 1 mol of alkenyl groups derived from component (A), that is, they are directly bonded to silicon atoms.
  • the amount is such that the number of moles of hydrogen atoms is 0.1 to 5.0 times the number of moles of alkenyl groups derived from component (A), preferably 0.3 to 2.0 moles, more preferably 0.3 to 2.0 times. is an amount that is 0.5 to 1.0 mol.
  • the amount of hydrosilyl groups derived from the component (B) is less than 0.1 mol per 1 mol of the alkenyl groups derived from the component (A), it will not be cured, or the strength of the cured product will be insufficient and the shape as a molded product will not be obtained. It may not be possible to hold and handle. On the other hand, if it exceeds 5.0 mol, the cured product loses flexibility and becomes brittle.
  • the thermally conductive filler which is the component (C), consists of the following components (C-1) to (C-3).
  • C-1) a spherical alumina filler having an average particle size of more than 70 ⁇ m and 135 ⁇ m or less;
  • C-2) a spherical alumina filler having an average particle size of more than 8 ⁇ m and 40 ⁇ m or less;
  • C-3) an amorphous alumina filler having an average particle size of more than 0.4 ⁇ m and 4 ⁇ m or less;
  • the average particle size is a volume-based cumulative average particle size (median diameter) value measured by a laser diffraction/scattering method using Microtrac MT3300EX, a particle size analyzer manufactured by Nikkiso Co., Ltd. is.
  • the (C-1) component spherical alumina filler can significantly improve the thermal conductivity.
  • the average particle diameter of the spherical alumina filler is more than 70 ⁇ m and 135 ⁇ m or less, preferably more than 70 ⁇ m and 120 ⁇ m or less, more preferably more than 70 ⁇ m and 100 ⁇ m or less. If the average particle diameter is 70 ⁇ m or less, the effect of improving the thermal conductivity is reduced, the viscosity of the composition is increased, and the processability is deteriorated. On the other hand, if the average particle size is larger than 135 ⁇ m, the abrasion of the reaction vessel and stirring blades becomes remarkable, and there is a concern that the insulating properties of the composition may be lowered.
  • the (C-1) component spherical alumina filler may be used singly or in combination of two or more. When two or more kinds are used in combination, each of them should satisfy the above average particle size range.
  • the spherical alumina filler of component (C-2) improves the thermal conductivity of the composition, suppresses contact between the amorphous alumina filler and the reaction vessel and stirring blades, and provides a barrier effect that suppresses wear.
  • the average particle size is more than 8 ⁇ m and 40 ⁇ m or less, preferably 10 to 40 ⁇ m. If the average particle size is 8 ⁇ m or less, the barrier effect is lowered, and the wear of the reactor and stirring blades due to the amorphous alumina filler becomes remarkable.
  • the (C-3) component amorphous alumina filler also plays a role in improving the thermal conductivity of the composition, but its main role is to adjust the viscosity of the composition, improve smoothness, and improve fillability.
  • the average particle size of the component (C-3) is more than 0.4 ⁇ m and 4 ⁇ m or less, and more preferably 0.6 to 3 ⁇ m in order to develop the properties described above.
  • the blending amount of component (C-1) is 1,400 to 3,000 parts by mass, preferably 1,600 to 2,500 parts by mass, per 100 parts by mass of component (A). If it is too small, it will be difficult to improve the thermal conductivity, and if it is too large, the wear of the reactor and stirring blades will be significant, and the insulating properties of the composition will be reduced.
  • the blending amount of component (C-2) is 500 to 2,300 parts by mass, preferably 1,000 to 1,800 parts by mass, per 100 parts by mass of component (A). If it is too small, it will be difficult to improve the thermal conductivity, and if it is too large, the fluidity of the composition will be lost and moldability will be impaired.
  • the blending amount of component (C-3) is 1,000 to 1,800 parts by mass, preferably 1,100 to 1,500 parts by mass, per 100 parts by mass of component (A). If it is too small, it will be difficult to improve the thermal conductivity, and if it is too large, the fluidity of the composition will be lost and moldability will be impaired.
  • the blending amount of component (C) (that is, the total blending amount of components (C-1) to (C-3) above) is 4,000 to 5,800 mass parts per 100 parts by mass of component (A). parts, preferably 4,500 to 5,000 parts by mass. If the amount is less than 4,000 parts by mass, the resulting composition will have poor thermal conductivity. If it exceeds 5,800 parts by mass, the fluidity of the composition is lost and moldability is impaired.
  • component (C) in the above compounding amount, the effects of the present invention described above can be achieved more advantageously and reliably.
  • the platinum group metal-based curing catalyst of the component (D) is a catalyst for promoting the addition reaction between the alkenyl group derived from the component (A) and the hydrosilyl group derived from the component (B), and is used for the hydrosilylation reaction.
  • well-known catalysts are well-known catalysts.
  • platinum including platinum black
  • rhodium, palladium, and other platinum group metal simple substances H 2 PtCl 4 ⁇ nH 2 O, H 2 PtCl 6 ⁇ nH 2 O, NaHPtCl 6 ⁇ nH 2 O , KaHPtCl6.nH2O , Na2PtCl6.nH2O , K2PtCl4.nH2O , PtCl4.nH2O , PtCl2 , Na2HPtCl4.nH2O ( wherein , n is an integer of 0 to 6, preferably 0 or 6.), platinum chloride, chloroplatinic acid and chloroplatinate, alcohol-modified chloroplatinic acid (US Pat.
  • the blending amount of component (D) is 0.1 to 2,000 ppm, preferably 50 to 1,000 ppm, based on the mass of the platinum group metal element relative to component (A). If the amount of component (D) is too small, the addition reaction will not proceed, and if it is too large, it will be economically disadvantageous.
  • Component (E) addition reaction control agent can be any of the known addition reaction inhibitors used in ordinary addition reaction curing silicone compositions. Examples thereof include acetylene compounds such as 1-ethynyl-1-hexanol, 3-butyn-1-ol and ethynylmethylidene carbinol, various nitrogen compounds, organic phosphorus compounds, oxime compounds and organic chloro compounds.
  • component (E) is blended, the amount used is desirably about 0.01 to 2.0 parts by mass, particularly about 0.1 to 1.2 parts by mass, per 100 parts by mass of component (A). If the amount of the component (E) is too small, the addition reaction may progress, resulting in poor handleability of the composition.
  • the thermally conductive filler which is component (C)
  • the thermally conductive filler which is component (C)
  • the thermally conductive filler is subjected to a hydrophobizing treatment when the composition is prepared, and wettability with the organopolysiloxane having an alkenyl group, which is component (A), is improved.
  • the surface treatment agent as component (F) can be blended.
  • the component (F) is not particularly limited, but is preferably one or more selected from the group consisting of components (F-1) and (F-2) shown below.
  • Component (F-1) is an alkoxysilane compound represented by the following general formula (1).
  • R 1 a R 2 b Si(OR 3 ) 4-ab (1) (wherein R 1 is independently an alkyl group having 6 to 15 carbon atoms, R 2 is independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a group selected from 7 to 12 aralkyl groups, R 3 is independently an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, with the proviso that a+b is an integer from 1 to 3.)
  • Examples of the alkyl group having 6 to 15 carbon atoms represented by R 1 in the general formula (1) include hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, and the like. be done.
  • the number of carbon atoms in the alkyl group represented by R 1 satisfies the range of 6 to 15, the wettability of the component (A) is sufficiently improved, the handleability is good, and the low-temperature properties of the composition are good. Become.
  • alkyl groups having 1 to 5 carbon atoms represented by R 2 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and neopentyl group. are mentioned.
  • aryl groups having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group, biphenylyl group and the like.
  • aralkyl groups having 7 to 12 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group and the like.
  • alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group, and phenyl group.
  • alkyl groups having 1 to 6 carbon atoms represented by R 3 include methyl, ethyl, propyl, butyl and hexyl groups.
  • Component (F-2) is a dimethylpolysiloxane having one molecular chain end blocked with a trialkoxysilyl group represented by the following general formula (2).
  • R 4 is independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 4 include the same alkyl groups exemplified for R 3 above.
  • c is an integer of 5-100, preferably 5-70, particularly preferably 10-50.
  • either one of the (F-1) component and the (F-2) component may be blended together.
  • the amount to be blended is preferably 0.01 to 300 parts by mass, particularly preferably 0.1 to 200 parts by mass, per 100 parts by mass of component (A).
  • the amount of component (F) is within the above range, oil separation is not induced.
  • the thermally conductive silicone composition of the present invention contains (G) cerium oxide as a thermal stabilizer for the purpose of improving heat resistance, particularly for suppressing deterioration due to softening of the cured product of the composition. good too.
  • cerium oxide When cerium oxide is blended, it is 8.0 to 25.0 parts by mass, more preferably 9.0 to 14.0 parts by mass, per 100 parts by mass of component (A). When the blending amount is within this range, even if stored at a high temperature of 150° C., no decrease in hardness is observed, which is preferable.
  • the cured product of the thermally conductive silicone composition has excellent heat resistance.
  • the hardness after aging at 150 ° C. for 500 hours is -5 points or more and +40 points or less with respect to the hardness before aging. It is preferable that there is, and it is more preferable that it is -3 points or more and +20 points or less.
  • the component (H) is a Organopolysiloxanes with viscosities of 10 to 100,000 mm 2 /s can be blended.
  • (H) component acts as a plasticizer.
  • (H) component may be used individually by 1 type, or may use 2 or more types together.
  • R 5 is a group independently selected from an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and d is an integer of 5 to 2,000. is.
  • R 5 is a group independently selected from an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms and an aralkyl group having 7 to 12 carbon atoms.
  • R 5 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group and pentyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group; Among them, alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propy
  • d is preferably an integer of 5 to 2,000, particularly preferably an integer of 10 to 1,000.
  • the kinematic viscosity of component (H) at 23° C. is preferably 10 to 100,000 mm 2 /s, particularly preferably 100 to 10,000 mm 2 /s. If the kinematic viscosity is 10 mm 2 /s or more, the cured product of the obtained composition will not cause oil bleeding. If the kinematic viscosity is within the above range, the resulting thermally conductive silicone composition will be excellent in flexibility.
  • the amount of component (H) to be added is not particularly limited as long as the desired effect is obtained. , preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass. When the amount is within this range, the thermally conductive silicone composition before curing can easily maintain good fluidity and workability, and the thermally conductive filler of component (C) is filled into the composition. is easy.
  • the thermally conductive silicone composition of the present invention may further contain other components depending on the purpose of the present invention.
  • optional components such as a heat resistance improver such as iron oxide; a viscosity modifier such as silica; a colorant; and a release agent can be blended.
  • thermally conductive silicone composition of the present invention can be prepared by uniformly mixing the components described above according to a conventional method.
  • the viscosity of the thermally conductive silicone composition of the present invention is preferably 2,000 Pa ⁇ s or less, more preferably 1,500 Pa ⁇ s or less at 23°C. Although the lower limit is not particularly limited, it can be, for example, 200 Pa ⁇ s or more. If the viscosity is within this range, moldability will not be impaired. In the present invention, this viscosity is based on measurement with a flow tester viscometer.
  • the thermally conductive silicone cured product of the present invention is obtained by curing the above-mentioned thermally conductive silicone composition of the present invention according to a conventional method.
  • the shape of the thermally conductive silicone cured product of the present invention is not particularly limited, it is preferably in the form of a sheet.
  • Curing conditions for molding the thermally conductive silicone composition may be the same as those for known addition reaction curing silicone rubber compositions. Addition curing is preferably carried out at 100 to 120° C. for 8 to 12 minutes. Such cured silicone products of the present invention are excellent in thermal conductivity.
  • the thermal conductivity of compact is 6.5 W/m ⁇ K or more, particularly 7.0 W/m ⁇ K or more at 23° C. measured by the hot disk method. It is desirable to have The higher the thermal conductivity, the better, and although the upper limit is not particularly limited, it can be, for example, 9.0 W/m ⁇ K or less.
  • the dielectric breakdown voltage of the molded body in the present invention is 10 kV/mm or more, more preferably 12 kV/mm or more, when the dielectric breakdown voltage of a 1 mm-thick molded body is measured in accordance with JIS K 6249:2003. is preferably Although the upper limit value is not particularly limited, it can be, for example, 20 kV/mm or less.
  • a compact having a dielectric breakdown voltage of 10 kV/mm or more can ensure stable insulation during use. Incidentally, such a dielectric breakdown voltage can be adjusted by adjusting the kind and purity of the filler.
  • the hardness of the molded article in the present invention is preferably 60 or less, preferably 40 or less, more preferably 30 or less, and preferably 5 or more at 23° C. measured with an Asker C hardness tester. If the hardness is within this range, it can deform so as to conform to the shape of the body to be heat dissipated, and can exhibit good heat dissipation characteristics without applying stress to the body to be heat dissipated. Such hardness can be adjusted by changing the ratio of the component (A) and the component (B) to adjust the crosslink density.
  • the viscosity of the composition was measured with a flow tester viscometer at 23°C. CFT-500EX manufactured by Shimadzu Corporation was used as a measuring device. A die hole diameter of ⁇ 2 mm, a die length of 2 mm, and a test load of 10 kg were plotted against time and stroke, and the viscosity was calculated from the slope.
  • the average particle diameter is a volume-based cumulative average particle diameter (median diameter) measured by a laser diffraction/scattering method using Microtrac MT3300EX, a particle size analyzer manufactured by Nikkiso Co., Ltd.
  • (A) Component Organopolysiloxane represented by the following formula (5). (Wherein, X is a vinyl group, and f is a number that gives the following viscosity.) (A-1) Kinematic viscosity: 600 mm 2 /s (A-2) Kinematic viscosity: 30,000 mm 2 /s
  • Component (B-1) Organohydrogenpolysiloxane represented by the following formula (6-1).
  • Component (B-2) Organohydrogenpolysiloxane represented by the following formula (6-2).
  • Component (C) spherical alumina filler and amorphous alumina filler having the following average particle diameters.
  • Component (C-1) A spherical alumina filler having an average particle size of 98.8 ⁇ m.
  • component spherical alumina filler with an average particle size of 23.4 ⁇ m.
  • Component (C-3) Component: Amorphous alumina filler having an average particle size of 1.7 ⁇ m.
  • Component (C-4) Spherical alumina filler with an average particle size of 143 ⁇ m (for comparative example).
  • Component (C-5) Spherical alumina filler with an average particle size of 3.2 ⁇ m (for comparative example).
  • (D) component 5 mass% chloroplatinic acid 2-ethylhexanol solution.
  • (E) component ethynylmethylidene carbinol.
  • Component (F) A dimethylpolysiloxane having an average degree of polymerization of 30 represented by the following formula (7) and having one end blocked with a trimethoxysilyl group.
  • (G) component cerium oxide.
  • Component (H) Dimethylpolysiloxane represented by the following formula (8).
  • Example 1 to 4 Comparative Examples 1 to 4
  • the above components (A) to (H) were used in the amounts shown in Table 1 below to prepare thermally conductive silicone compositions, which were molded and cured. Then, measure the viscosity of the thermally conductive silicone composition, the thermal conductivity, hardness, dielectric breakdown voltage of the cured thermally conductive silicone composition, and the air bubbles on the surface of the cured sheet and the embrittlement of the sheet edges according to the following methods. Observed. The results are also shown in Table 1.
  • Viscosity of thermally conductive silicone composition The viscosities of the thermally conductive silicone compositions obtained in Examples 1-4 and Comparative Examples 1-4 were measured at 23° C. using a flow tester viscometer.
  • Formability The thermally conductive silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were molded and cured into sheets of 1 mm thickness using a press molding machine at 120° C. for 10 minutes to form sheets with a thickness of 1 mm. A sheet was molded using the mold of No. 2, and the presence or absence of bubbles on the surface of the sheet and the presence or absence of embrittlement at the edge of the sheet were visually and finger-touched.
  • Thermal conductivity The thermally conductive silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were molded and cured into sheets of 6 mm thickness at 120° C. for 10 minutes using a press molding machine. The thermal conductivity of the sheet was measured with a thermal conductivity meter (trade name: TPS-2500S, manufactured by Kyoto Electronics Industry Co., Ltd.).
  • Dielectric breakdown voltage The thermally conductive silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were molded and cured into sheets of 1 mm thickness at 120° C. for 10 minutes using a press molding machine. The dielectric breakdown voltage was measured according to 6249.
  • thermally conductive silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were molded and cured into sheets of 6 mm thickness in the same manner as described above, and the sheets were stacked in two and measured with an Asker C hardness tester. .
  • Hardness after aging at 150°C for 500 hours The thermally conductive silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were molded and cured into a 6 mm thick sheet using a press molding machine at 120° C. for 10 minutes. After aging (storing) the cured silicone material in a high-temperature furnace at 150° C. for 500 hours, two sheets were stacked and measured with an Asker C hardness tester.
  • H/Vi is the amount of hydrogen atoms directly bonded to all silicon atoms in the organohydrogenpolysiloxane relative to the total amount of alkenyl groups in the organopolysiloxane having alkenyl groups.
  • Example 1 the viscosity and moldability of the thermally conductive silicone composition, the thermal conductivity of the cured thermally conductive silicone, the dielectric breakdown voltage, and the hardness were all good results. Further, when cerium oxide was added (Examples 2 to 4), even when stored at a high temperature of 150°C, no decrease in hardness due to softening deterioration was observed.
  • the present invention is not limited to the above embodiments.
  • the above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. is included in the technical scope of

Abstract

La présente invention concerne une composition de silicone thermoconductrice caractérisée en ce qu'elle comprend : (A) un organopolysiloxane qui a au moins deux groupes alcényle dans chaque molécule de celui-ci ; (B) un organohydrogénopolysiloxane qui a au moins deux atomes d'hydrogène, chacun d'entre eux étant directement lié à un atome de silicium ; (C) un matériau de charge thermoconducteur comprenant (C-1) une charge d'alumine sphérique qui a un diamètre moyen de particule de plus de 70 µm mais ne dépassant pas 135 µm, (C-2) une charge d'alumine sphérique qui a un diamètre moyen de particule de plus de 8 µm mais ne dépassant pas 40 µm, et (C-3) une charge d'alumine amorphe qui a un diamètre moyen de particule de plus de 0,4 µm mais ne dépassant pas 4 µm ; (D) un catalyseur de durcissement à base de métal du groupe du platine ; et (E) un agent de contrôle de réaction d'addition. En conséquence de cette configuration, la présente invention propose : une composition de silicone thermoconductrice qui présente d'excellentes propriétés de compressibilité, d'isolation, de conductivité thermique et d'aptitude au façonnage ; et un produit durci associé.
PCT/JP2022/018791 2021-06-01 2022-04-26 Composition de silicone thermoconductrice et produit durci associé WO2022255004A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160955A (ja) * 1997-08-14 1999-03-05 Shin Etsu Chem Co Ltd フッ素樹脂又はフッ素ラテックスコーティングシリコーンゴム定着ロール
WO2020217634A1 (fr) * 2019-04-24 2020-10-29 信越化学工業株式会社 Composition de silicone thermoconductrice, son procédé de production et produit durci à base de silicone thermoconductrice

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160955A (ja) * 1997-08-14 1999-03-05 Shin Etsu Chem Co Ltd フッ素樹脂又はフッ素ラテックスコーティングシリコーンゴム定着ロール
WO2020217634A1 (fr) * 2019-04-24 2020-10-29 信越化学工業株式会社 Composition de silicone thermoconductrice, son procédé de production et produit durci à base de silicone thermoconductrice

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