WO2020004442A1 - Composition de silicone thermoconductrice et feuille thermoconductrice - Google Patents

Composition de silicone thermoconductrice et feuille thermoconductrice Download PDF

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Publication number
WO2020004442A1
WO2020004442A1 PCT/JP2019/025311 JP2019025311W WO2020004442A1 WO 2020004442 A1 WO2020004442 A1 WO 2020004442A1 JP 2019025311 W JP2019025311 W JP 2019025311W WO 2020004442 A1 WO2020004442 A1 WO 2020004442A1
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group
thermally conductive
silicone
silicone composition
component
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PCT/JP2019/025311
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Japanese (ja)
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山田　邦弘
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信越化学工業株式会社
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Priority to JP2020527566A priority Critical patent/JP7060097B2/ja
Publication of WO2020004442A1 publication Critical patent/WO2020004442A1/fr

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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon

Definitions

  • the present invention relates to a silicone composition having high heat conductivity and excellent heat dissipation.
  • JP-A-56-28264 discloses a liquid organosilicone carrier, silica fiber, and dendritic zinc oxide.
  • a thixotropic thermal conductive material comprising at least one selected from flaky aluminum nitride and flaky boron nitride is disclosed.
  • Japanese Patent Application Laid-Open No. 2-153959 discloses a silicone grease composition comprising a specific organopolysiloxane mixed with a spherical hexagonal aluminum nitride powder having a certain particle size range.
  • Patent Document 7 discloses a thermally conductive silicone grease obtained by combining a fine particle size aluminum nitride powder and a coarse particle size aluminum nitride powder.
  • Patent Document 8 discloses a thermally conductive grease composition using aluminum nitride powder surface-treated with organosilane, which is a combination of aluminum powder and zinc oxide powder. It has been disclosed.
  • Patent Document 9 discloses a thermally conductive silicone composition using diamond, zinc oxide, and a dispersant for a silicone resin.
  • JP-A-2000-63873 Patent Document 10
  • JP-A-2008-222776 Patent Document 11
  • a heat conductive grease composition obtained by mixing metallic aluminum powder with a base oil such as silicone oil. Is disclosed. However, any of the heat conductive materials and heat conductive greases has become insufficient to generate heat of integrated circuit elements such as recent CPUs.
  • the present invention has been made in view of the above circumstances, and has as its object to provide a thermally conductive silicone composition and a thermally conductive sheet having high thermal conductivity and excellent heat dissipation.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, by using two or more liquid silicone mixtures incompatible with each other as a base oil, the thermal conductivity of the thermally conductive silicone composition has been dramatically improved.
  • the inventors have found that the present invention is improved, and have accomplished the present invention.
  • a thermally conductive silicone composition comprising (A) a liquid silicone and (B) a thermally conductive filler, wherein the component (A) is a mixture of at least two types of liquid silicones, at least two of which are mutually exclusive.
  • a thermally conductive silicone composition characterized by being incompatible.
  • the component (A) has the following average composition formula (I) R 1 a SiO (4-a) / 2 (I) (Wherein, R 1 is independently of each other an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and 1.8 ⁇ a ⁇ 2.2.) 2.
  • the thermally conductive silicone composition according to 1 which contains an organopolysiloxane having a kinematic viscosity at 25 ° C. of 10 to 500,000 mm 2 / s.
  • Component (A) is a liquid silicone mixture containing (A-1) an alkyl-modified silicone having an alkyl group having 7 to 18 carbon atoms and a liquid silicone incompatible with (A-1).
  • the component (A) is represented by the following general formula (II): (A-4-2) (In the formula, R 2 is an alkyl group having 1 to 6 carbon atoms, R 3 is independently an alkyl group having 1 to 6 carbon atoms, and b is an integer of 5 to 120.) 6.
  • a heat conductive silicone composition and a heat conductive sheet having high heat conductivity and excellent heat dissipation properties can be provided.
  • Component (A) is a mixture of at least two or more liquid silicones, at least two of which are incompatible with each other.
  • a kinematic viscosity at 25 ° C. a liquid silicone mixture is preferably 10 ⁇ 500,000mm 2 / s, more preferably 30 ⁇ 10,000mm 2 / s.
  • silicone composition When the kinematic viscosity of the liquid silicone mixture is lower than the above lower limit, oil bleed may easily occur. On the other hand, if it is larger than the above upper limit, the extensibility of the thermally conductive silicone composition (hereinafter sometimes simply referred to as silicone composition) may be poor.
  • the kinematic viscosity is a value measured at 25 ° C. with an Ostwald viscometer.
  • the component (A) are shown below, but unless otherwise specified, the kinematic viscosity of each of the exemplary components is also preferably in the same range as in the case of the liquid silicone (A).
  • the molecular structure of the liquid silicone constituting the liquid silicone mixture of the component (A) is not particularly limited, and may be any of linear, branched, and cyclic.
  • the liquid silicone constituting the liquid silicone mixture of the component (A) includes the following average composition formula (I) R 1 a SiO (4-a) / 2 (I) (Wherein, R 1 is independently of each other an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and 1.8 ⁇ a ⁇ 2.2.)
  • the liquid organopolysiloxane represented by these is illustrated.
  • R 1 is independently of each other an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18, preferably 1 to 14 carbon atoms.
  • the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; cyclopentyl, cyclohexyl Alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as 2-phenylethyl group and 2-methyl-2-phenylethyl group; A group obtained by substituting a part or all of the hydrogen atoms of a group with a halogen atom such as fluorine, bromine or chlorine, a cyano group or the like, for example,
  • a is in the range of 1.8 to 2.2, preferably in the range of 1.9 to 2.1.
  • the obtained silicone composition can have a good viscosity.
  • Examples of the liquid silicone represented by the above formula (I) include the following (A-1) to (A-3). Further, (A-4): a liquid silicone having incompatibility with the liquid silicone of (A-1) to (A-3) can be mentioned.
  • the component (A) is a mixture of at least two or more silicones, and at least two of them are not limited as long as they are incompatible with each other. Specifically, it is preferable to select and combine two or more groups from the groups (A-1), (A-2), (A-3) and (A-4). If selected from two or more groups, three or more groups may be used, and two or more types may be used from each group.
  • the two or more liquid silicones are preferably contained in the (A) liquid silicone mixture in an amount of at least 10% by mass, more preferably 20 to 100% by mass, for each group, from the viewpoint of improving thermal conductivity.
  • the definition of incompatibility means that two layers of oil are mixed in a glass bottle or the like and then separated when left to stand. Specifically, the mixing may be performed in the same volume.
  • the component (A-1) is an organopolysiloxane represented by the following average composition formula (III).
  • R 4 c SiO (4-c) / 2 (III) (Wherein, R 4 is independently of each other an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18, preferably 1 to 14 carbon atoms, including an aryl group and a fluorine-containing group. (At least 5 mol% of R 4 is an alkyl group having 7 to 14 carbon atoms. C is 1.8 to 2.2.)
  • R 4 is independently an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 14 carbon atoms, an aryl group and a fluorine-containing group. Is not included. Further, at least 5 mol%, preferably 20 to 100 mol% of R 4 is an alkyl group having 7 to 14 carbon atoms. Examples of the alkyl group having 7 to 14 carbon atoms include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. The remaining group is preferably a methyl group from the viewpoint of economy.
  • c is from 1.8 to 2.2, preferably from 1.9 to 2.1. When c is within the above range, the obtained silicone composition can have good viscosity with excellent usability.
  • organopolysiloxane represented by the above average composition formula (III) a linear organopolysiloxane represented by the following formula (IV) is preferable.
  • bonding order of each siloxane unit shown in parentheses is not limited to the following. The same applies hereinafter.
  • R 5 is an alkyl group having 7 to 14 carbon atoms
  • R 6 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
  • X 1 is 0 to 200
  • X 2 is 1 to 100. Is an integer.
  • R 5 is an alkyl group having 7 to 14 carbon atoms, preferably 10 to 14 carbon atoms, and examples thereof include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group.
  • R 6 is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group.
  • X 1 is an integer of 0 to 200, preferably 0 to 100, more preferably 1 to 50, and X 2 is an integer of 1 to 100, preferably 5 to 50.
  • the component (A-2) is an organopolysiloxane represented by the following average composition formula (V).
  • R 7 d SiO (4-d) / 2 (V) (Wherein, R 7 is independently an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and does not include an alkyl group having 7 or more carbon atoms and a fluorine-containing group. (At least 5 mol% of 7 is an aryl group. D is 1.8 to 2.2.)
  • R 7 is independently an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18, preferably 1 to 14 carbon atoms, and does not include an alkyl group having 7 or more carbon atoms and a fluorine-containing group. . At least 5 mol%, preferably 20 to 100 mol% of R 7 is an aryl group, such as a phenyl group or a tolyl group. The remaining group is preferably a methyl group from an economic viewpoint.
  • d is 1.8 to 2.2, preferably 1.9 to 2.1. When d is within the above range, the obtained silicone composition can have good viscosity with excellent usability.
  • organopolysiloxane represented by the above average composition formula (V) a linear organopolysiloxane represented by the following formula (VI) is preferable.
  • R 7 is an aryl group having 6 to 10 carbon atoms
  • R 8 is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms.
  • Y 1 is an integer of 0 to 200
  • Y 2 is Is an integer of 1 to 100.
  • R 7 is an aryl group having 6 to 10 carbon atoms, preferably a phenyl group.
  • R 8 is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group.
  • Y 1 is an integer of 0 to 200, preferably 0 to 100, more preferably 1 to 50, and Y 2 is an integer of 1 to 100, preferably 5 to 50.
  • the component (A-3) is an organopolysiloxane represented by the following average composition formula (VII).
  • R 8 e SiO (4-e) / 2 (VII) (Wherein, R 8, independently of one another, an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, .R 8 not containing alkyl and aryl group having 7 or more carbon atoms Are fluorine-containing groups, and e is from 1.8 to 2.2.
  • R 7 is independently an unsubstituted or substituted, saturated or unsaturated monovalent hydrocarbon group having 1 to 18, preferably 1 to 14 carbon atoms, and does not include an alkyl group and an aryl group having 7 or more carbon atoms. Further, at least 5 mol%, preferably 20 to 80 mol% of R 8 is a fluorine-containing group. Examples of the fluorine-containing group include a 3,3,3-trifluoropropyl group, a 2- (perfluorobutyl) ethyl group, and a 2- (perfluorooctyl) ethyl group. The remaining group is preferably a methyl group from an economic viewpoint.
  • e is 1.8 to 2.2, preferably 1.9 to 2.1. When e is within the above range, the obtained silicone composition can have good viscosity with excellent usability.
  • organopolysiloxane represented by the above average composition formula (VII) a linear organopolysiloxane represented by the following formula (VIII) is preferable.
  • R 9 is a fluorine-containing group
  • R 10 is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms.
  • Z 1 is an integer of 0 to 200, and Z 2 is 1 to 100 It is an integer.
  • R 9 is a fluorine-containing group, preferably a 3,3,3-trifluoropropyl group.
  • R 10 is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms. Particularly preferred is a methyl group.
  • Z 1 is an integer of 0 to 200, preferably 0 to 100, more preferably 0 to 50, and Z 2 is an integer of 1 to 100, preferably 5 to 50.
  • Examples of the liquid silicone (A-4) incompatible with each of the components (A-1) to (A-3) include (A-4-1) and (A-4-2).
  • A-4-1) is a dimethylpolysiloxane having no alkyl group, aryl group or fluorine-containing group having 7 or more carbon atoms.
  • an organopolysiloxane having a linear structure in which the main chain is composed of repeating diorganosiloxane units and both ends of the molecular chain are blocked with a trimethylsilyl group is preferable.
  • [(A-4-2)] Represented by the following general formula (II) (Wherein R 2 is an alkyl group having 1 to 6 carbon atoms, R 3 is independently an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms, and b is It is an integer of 5 to 120.) Hydrolyzable group-containing organopolysiloxane.
  • the hydrolyzable group-containing organopolysiloxane represented by the above formula (II) assists in filling the silicone composition with the thermally conductive filler at a high level. Further, when the silicone composition contains the organopolysiloxane, the surface of the thermally conductive filler is covered with the organopolysiloxane, and the aggregation of the thermally conductive filler is less likely to occur. Since this effect is maintained even at a high temperature, the heat resistance of the silicone composition is improved. Further, the surface of the thermally conductive filler can be subjected to a hydrophobic treatment with the organopolysiloxane.
  • R 2 is an alkyl group having 1 to 6 carbon atoms, for example, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Especially, a methyl group and an ethyl group are preferable.
  • R 3 are independently of each other an unsubstituted or substituted saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • Examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, an alkyl group such as a dodecyl group, a tetradecyl group, a hexadecyl group and an octadecyl group, a cyclopentyl group, and a cyclohexyl group.
  • Cycloalkyl group such as a group, alkenyl group such as a vinyl group and an allyl group, aryl group such as a phenyl group and a tolyl group, aralkyl group such as a 2-phenylethyl group and a 2-methyl-2-phenylethyl group, or In which some or all of the hydrogen atoms of the above groups have been substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc., for example, 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl Group, 2- (perfluorooctyl) ethyl group, p-chlorophenyl group and the like. Among them, a methyl group is particularly preferable.
  • b is an integer of 5 to 120, preferably 10 to 90.
  • hydrolyzable group-containing organopolysiloxane (A-4-2) When the hydrolyzable group-containing organopolysiloxane (A-4-2) is contained, its amount is preferably from 10 to 90% by mass, preferably from 20 to 80% by mass, based on the total mass of the liquid silicone mixture (A). % Is more preferred.
  • the thermal conductive filler preferably has a thermal conductivity of 10 W / (m ⁇ K) or more. When the thermal conductivity is less than 10 W / (m ⁇ K), the thermal conductivity of the thermally conductive silicone composition itself becomes small.
  • the upper limit of the thermal conductivity varies depending on the material used for the thermally conductive filler, but there is no particular upper limit.
  • Examples of the thermally conductive filler having a thermal conductivity of 10 W / (m ⁇ K) or more include aluminum powder, copper powder, silver powder, nickel powder, gold powder, aluminum oxide (alumina) powder, zinc oxide powder, and oxide powder. Examples include powders and granular materials such as magnesium powder, aluminum nitride powder, boron nitride powder, silicon nitride powder, diamond powder, and carbon powder, and these can be used alone or in combination of two or more.
  • the shape may be irregular, spherical or any shape, but preferably has an average particle size of 0.1 to 100 ⁇ m, more preferably 0 to 100 ⁇ m. 0.5 to 50 ⁇ m.
  • the average particle size is less than 0.1 ⁇ m, the obtained silicone composition may not have good usability and good viscosity, and may have poor extensibility. May be poor.
  • the average particle diameter is a volume-based cumulative average diameter (D 50 ) measured by Microtrack (laser diffraction confusion method).
  • the amount of component (B) is preferably from 300 to 5,000 parts by mass, more preferably from 500 to 3,000 parts by mass, per 100 parts by mass of component (A). If the amount of the component (B) is less than 300 parts by mass relative to 100 parts by mass of the component (A), the necessary thermal conductivity may not be obtained.
  • the composition may not have good usability and good viscosity, and may have poor extensibility.
  • the silicone composition of the present invention can be a curable silicone composition.
  • description will be made separately for [I] an addition reaction-curable heat-conductive silicone composition, [II] a condensation reaction-curable heat-conductive silicone composition, and [III] an organic peroxide-curable heat-conductive silicone composition. .
  • the component (A-1) in one molecule of the liquid silicone mixture (A) An organopolysiloxane having an alkenyl group bonded to at least two silicon atoms, (AI-2) an organopolysiloxane having an average of two or more hydrogen atoms bonded to silicon atoms in one molecule, and a platinum group It further contains a metal-based curing catalyst.
  • the components (AI-1) and (AI-2) may overlap with the component (A) or may not be incompatible with each other. However, as the liquid silicone mixture (A), The two are selected to be incompatible with each other.
  • the organopolysiloxane having at least two alkenyl groups bonded to at least two silicon atoms in one molecule is represented by the above average composition formula (I) and is preferably at least two in one molecule.
  • the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 1-hexenyl group and the like, and a vinyl group is preferable in terms of ease of synthesis and cost.
  • the alkenyl group bonded to the silicon atom may be present at the terminal or midway of the molecular chain of the organopolysiloxane, but is preferably present at least at the terminal.
  • Examples of the group other than the alkenyl group include those exemplified above for R 1 , but an alkyl group and an aryl group are preferable, and a methyl group and a phenyl group are more preferable.
  • the amount of the organopolysiloxane is 10 to 10% based on the total mass of the liquid silicone mixture (A).
  • the amount is preferably 90% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass.
  • the remaining organic groups bonded to silicon atoms other than hydrogen atoms bonded to silicon atoms include: , An alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a dodecyl group; an aryl group such as a phenyl group; an aralkyl group such as a 2-phenylethyl group and a 2-phenylpropyl group; Examples thereof include a monovalent hydrocarbon group having no aliphatic unsaturated bond of from 1 to 12, preferably 1 to 8, and a methyl group and a phenyl group are preferable.
  • the molecular structure of the (AI-2) organohydrogenpolysiloxane is not limited, and examples thereof include linear, branched, partially branched linear, cyclic, and dendritic (dendrimer).
  • the organopolysiloxane may be, for example, a homopolymer having these molecular structures, a copolymer having these molecular structures, or a mixture thereof.
  • organohydrogenpolysiloxanes include, for example, dimethylpolysiloxane having dimethylhydrogensiloxy groups at both ends of molecular chains, dimethylsiloxane / methylhydrogensiloxane copolymer having trimethylsiloxy groups at both ends, and dimethylhydrogen at both ends of molecular chains.
  • kinematic viscosity at 25 ° C. of (A-I-2) organohydrogenpolysiloxane is in the range of 1 ⁇ 100,000mm 2 / s, more preferably in the range of 1 ⁇ 5,000mm 2 / s .
  • (AI-2) an organohydrogenpolysiloxane is contained, its compounding amount is an amount necessary for curing, and specifically, alkenyl bonded to a silicon atom in the component (AI-1).
  • the amount of hydrogen atoms bonded to silicon atoms is preferably in the range of 0.1 to 10 mol, more preferably 0.1 to 5 mol, per 1 mol of the group. Is more preferable, and the amount is more preferably in the range of 0.1 to 3 mol. If the amount of this component is less than the lower limit of the above range, the resulting curable silicone composition may not be sufficiently cured, while if it exceeds the upper limit of the above range, the obtained cured silicone product becomes very hard and may cause many cracks on the surface.
  • platinum group metal-based curing catalyst examples include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, and a carbonyl complex of platinum. They can be used in appropriate combination.
  • the blending amount is an amount necessary for curing the present composition in the curable silicone composition, and specifically, based on the component (AI-1).
  • the amount of the platinum metal is preferably in the range of 0.01 to 1,000 ppm by mass, more preferably 0.1 to 500 ppm. If the amount of this component is less than the lower limit of the above range, the resulting curable silicone composition may not be sufficiently cured. The cure rate of the composition tends to not significantly improve.
  • the curable silicone composition contains 2-methyl-3-butyn-2-ol and 2-phenyl-3-butyn-2-ol in order to control the curing rate of the present composition and improve handling efficiency.
  • Acetylene compounds such as all and 1-ethynyl-1-cyclohexanol; ene-yne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; It is preferable to add a curing reaction inhibitor such as a hydrazine compound, a phosphine compound, or a mercaptan compound.
  • the blending amount is not limited, but is preferably 0.0001 to 1.0 part by mass with respect to 100 parts by mass of the component (AI-1).
  • (A-II-1) a Si—OH group is used as a component of the liquid silicone mixture (A).
  • (A-II-2) a silane or siloxane oligomer having a hydrolyzable group bonded to at least three silicon atoms in one molecule, and if necessary, a curing catalyst for a condensation reaction.
  • the components (A-II-1) and (A-II-2) may not be incompatible with the above component (A), but as the liquid silicone mixture (A), the two components are mutually compatible. It is chosen to be incompatible.
  • the hydrolyzable group bonded to the silicon atom examples include an alkoxy group, an alkoxyalkoxy group, an acyloxy group, a ketoxime group, an alkenoxy group, an amino group, an aminoxy group, and an amide group.
  • the silicon atom of the silane or siloxane oligomer may be, for example, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a halogenated group.
  • An alkyl group may be bonded.
  • silane or siloxane oligomer examples include tetraethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, methyltris (methylethylketoxime) silane, vinyltriacetoxysilane, and ethyl orthosilicate.
  • (A-II-1) contains an organopolysiloxane, it is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and further preferably from 30 to 70% by mass, based on the total mass of the liquid silicone mixture (A). preferable.
  • the compounding amount is an amount necessary for curing the present composition, and specifically, 100 parts by mass of the (A-II-1) component.
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.
  • the curing catalyst for the condensation reaction is an optional component, and is not essential when, for example, a silane having a hydrolyzable group such as an aminoxy group, an amino group, or a ketoxime group is used.
  • a condensation reaction catalyst include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; and organic titanium such as diisopropoxybis (acetylacetate) titanium and diisopropoxybis (ethylacetoacetate) titanium.
  • Chelate compounds organic aluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); organic zirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; dibutyltin dioctoate, dibutyltin dilaurate; Organic tin compounds such as butyltin-2-ethylhexoate; organic compounds such as tin naphthenate, tin oleate, tin butylate, cobalt naphthenate and zinc stearate Metal salts of rubonic acid; amine compounds such as hexylamine and dodecylamine phosphate, and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acid salts of alkali metals such as potassium acetate; dimethylhydroxylamine, diethylhydroxylamine
  • the blending amount is optional and may be any amount necessary for curing the present composition. Specifically, 100 parts by mass of the component (A-II-1) On the other hand, the amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.
  • this catalyst is essential, if the amount of the catalyst is less than the lower limit of the above range, the resulting curable silicone composition may not be sufficiently cured, while the amount exceeds the upper limit of the above range. In such a case, the storage stability of the obtained curable silicone composition may be reduced.
  • Organic peroxide-curable heat-conductive silicone composition When the organic peroxide-curable heat-conductive silicone composition is used, (A-I-1) It contains an organopolysiloxane having an alkenyl group bonded to at least two silicon atoms in one molecule, and further contains an organic peroxide.
  • the component (AI-1) may overlap with the component (A) or may not be incompatible. However, as the liquid silicone mixture (A), two types are incompatible with each other. Is chosen to be
  • organic peroxide examples include benzoyl peroxide, di (p-methylbenzoyl) peroxide, di (o-methylbenzoyl) peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis ( t-butylperoxy) hexane, di-t-butyl peroxide, t-butylperoxybenzoate and the like.
  • the compounding amount of the organic peroxide is an amount necessary for curing the present composition, and specifically, 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (AI-1). .
  • the method of curing is not limited, and examples thereof include a method in which the composition is molded and then left at room temperature, and a method in which the composition is molded and heated to 50 to 200 ° C.
  • the properties of the silicone cured product thus obtained are not limited, and examples thereof include a gel, a low-hardness rubber, and a high-hardness rubber.
  • the obtained cured silicone material can be sufficiently adhered to a member as a heat dissipation material.
  • the method for producing the silicone composition of the present invention is not particularly limited.
  • the components (A) and (B), and other components as required may be mixed with a trimix, a twin-mix, a planetary mixer (all of which are manufactured by Inoue Seisakusho Co., Ltd., a registered trademark), an ultra mixer ( It can be manufactured by mixing for 30 minutes to 4 hours with a mixer such as a mixer manufactured by Mizuho Industry Co., Ltd., a registered trademark) and Hibis Dispermix (mixer manufactured by Tokushu Kika Kogyo Co., Ltd.). it can. If necessary, mixing may be performed while heating at a temperature in the range of 50 to 200 ° C., preferably 50 to 150 ° C.
  • the absolute viscosity of the silicone composition of the present invention measured at 25 ° C. is preferably from 10 to 600 Pa ⁇ s, more preferably from 50 to 500 Pa ⁇ s, still more preferably from 50 to 400 Pa ⁇ s, and preferably from 50 to 350 Pa ⁇ s. Particularly preferred.
  • the silicone composition can have more excellent viscosity in use and workability. If the absolute viscosity is higher than the above upper limit, workability may be deteriorated. If the absolute viscosity is smaller than the above lower limit, the composition may flow out after being applied on various base materials, and the effect of displacement resistance may not be exhibited.
  • the absolute viscosity can be obtained by adjusting each component at the above-mentioned amount. The absolute viscosity is measured using, for example, Model No. PC-1TL (10 rpm) manufactured by Malcolm Co., Ltd.
  • the silicone composition of the present invention preferably has a high thermal conductivity of 3.0 W / (m ⁇ K) or more at 25 ° C.
  • the upper limit of the thermal conductivity is not particularly limited, it can be generally less than 10 W / (m ⁇ K), particularly less than 8 W / (m ⁇ K).
  • the thermal conductivity can be measured using a thermal conductivity meter, for example, TPA-501 manufactured by Kyoto Electronics Industry Co., Ltd.
  • the silicone composition of the present invention can be used as a paste.
  • the manner in which the silicone composition of the present invention is used as a paste is not particularly limited, and may be used in the same manner as a conventional heat-dissipating (thermally conductive) silicone paste.
  • the paste includes what is conventionally called grease.
  • the silicone composition is sandwiched between an electric / electronic component such as an LSI or other heat generating member and a cooling member or a heat radiating member, and heat from the heat generating member is transmitted to the cooling member or the heat radiating member. It can be suitably used in a mode in which heat is radiated.
  • the silicone composition of the present invention has a low viscosity, a high thermal conductivity, and extremely excellent misalignment resistance, so that it is suitably used as a heat-radiating (thermal conductive) paste for high-quality semiconductor devices. can do.
  • the silicone composition of the present invention can also be used as a sheet molding.
  • the curable silicone composition may be cured by a known method.
  • the mode of use is not particularly limited.
  • the silicone composition is sandwiched between an electric / electronic component such as an LSI and other heat generating members, and a cooling member or a heat radiating member, and heat from the heat generating member is transferred. It can be suitably used in a mode in which heat is transferred to a cooling member or a heat radiating member to release heat.
  • (A-3) Liquid silicone having a kinematic viscosity of 1,000 mm 2 / s represented by the following general formula (Z 2 is an integer that satisfies the above viscosity.)
  • (A-4-2) Liquid silicone having a kinematic viscosity of 35 mm 2 / s represented by the following general formula.
  • (A-4-1) and (A-4-2) are not included in any of (A-1) to (A-3), and (A-1), (A-2), and (A-3) ), (A-4-1) and (A-4-2) are incompatible with each other.
  • Component (B) (B-1) Aluminum oxide (alumina powder): average particle size 1.0 ⁇ m (B-2) Aluminum oxide (alumina powder): average particle size 40 ⁇ m
  • the average particle size of the thermally conductive filler of the component (B) is a volume-based cumulative average particle size (D 50 ) measured using a Microtrac MT3300EX, a particle size analyzer manufactured by Nikkiso Co., Ltd.
  • Examples 1 to 8, Comparative Examples 1 to 4 The above components (A) and (B) were charged into a 5 liter planetary mixer (registered trademark, manufactured by Inoue Seisakusho Co., Ltd.) according to the compositions and blending amounts shown in Tables 1 and 2, and added at 150 ° C. After stirring for an hour, a silicone composition was produced. The viscosity and thermal conductivity of each silicone composition obtained by the above method were measured according to the following methods. The results are shown in Tables 1 and 2.
  • Example 5 Except for changing “(A-1) 30 g and (A-2) 30 g” and “(A-4-1) 60 g”, the same operation as in Example 9 was carried out.
  • (A-4-1), (AI-1) and (AI-2) are liquid silicones having compatibility with each other.
  • the thermal conductivity of the heat conductive sheet was measured.
  • the thermal conductivity was measured at 25 ° C. by stacking five 2 mm sheets and similarly using TPA-501 manufactured by Kyoto Electronics Industry Co., Ltd.

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Abstract

L'invention concerne une composition de silicone thermoconductrice contenant (A) une silicone liquide et (B) une charge thermoconductrice, le composant (A) étant un mélange de silicone d'au moins deux types de substances, et au moins deux des substances étant incompatibles l'une avec l'autre.
PCT/JP2019/025311 2018-06-28 2019-06-26 Composition de silicone thermoconductrice et feuille thermoconductrice WO2020004442A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7082724B1 (ja) * 2021-02-15 2022-06-08 富士高分子工業株式会社 熱伝導性シリコーン組成物
WO2022172547A1 (fr) * 2021-02-15 2022-08-18 富士高分子工業株式会社 Composition de silicone thermoconductrice

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1149958A (ja) * 1997-08-06 1999-02-23 Shin Etsu Chem Co Ltd 熱伝導性シリコーン組成物
JP2007277387A (ja) * 2006-04-06 2007-10-25 Shin Etsu Chem Co Ltd 熱伝導性シリコーングリース組成物
JP2012107152A (ja) * 2010-11-19 2012-06-07 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーングリース組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1149958A (ja) * 1997-08-06 1999-02-23 Shin Etsu Chem Co Ltd 熱伝導性シリコーン組成物
JP2007277387A (ja) * 2006-04-06 2007-10-25 Shin Etsu Chem Co Ltd 熱伝導性シリコーングリース組成物
JP2012107152A (ja) * 2010-11-19 2012-06-07 Shin-Etsu Chemical Co Ltd 熱伝導性シリコーングリース組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7082724B1 (ja) * 2021-02-15 2022-06-08 富士高分子工業株式会社 熱伝導性シリコーン組成物
WO2022172547A1 (fr) * 2021-02-15 2022-08-18 富士高分子工業株式会社 Composition de silicone thermoconductrice

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