WO2019198424A1 - Composition de silicone thermodurcissable et produit durci associé - Google Patents

Composition de silicone thermodurcissable et produit durci associé Download PDF

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Publication number
WO2019198424A1
WO2019198424A1 PCT/JP2019/010935 JP2019010935W WO2019198424A1 WO 2019198424 A1 WO2019198424 A1 WO 2019198424A1 JP 2019010935 W JP2019010935 W JP 2019010935W WO 2019198424 A1 WO2019198424 A1 WO 2019198424A1
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group
total number
groups
silicone composition
component
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PCT/JP2019/010935
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Japanese (ja)
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也実 細田
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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

Definitions

  • the present invention relates to a thermally conductive silicone composition having thermoplasticity and a cured product thereof.
  • a method of directly transferring heat to a heat sink using a metal having high thermal conductivity such as aluminum, copper, brass or the like is taken in order to suppress the temperature rise of the electronic component.
  • the heat sink conducts heat generated from the electronic component, and releases the heat from the surface due to a temperature difference from the outside air.
  • the heat sink and the electronic component must be in close contact with each other without any gaps.
  • a flexible low-hardness thermal conductive sheet or thermal conductive grease is used between the electronic component and the heat sink. Is intervened.
  • the heat conductive silicone rubber sheet used conventionally has a contact thermal resistance at the interface with the electronic component, there is a limit to the heat transfer performance.
  • phase change sheet phase change sheet
  • This is a heat-dissipating material with excellent handling that can be mounted freely by applying heat to the electronic components and heat sink by preparing a sheet in advance, and the interface with the electronic components by being softened by heat.
  • the contact thermal resistance is negligible, and exhibits superior heat dissipation performance compared to conventional thermal conductive sheets.
  • Patent Document 1 JP 2000-509209 A discloses heat conduction comprising an acrylic pressure-sensitive adhesive, an ⁇ -olefin thermoplastic agent, and a thermally conductive filler. Or a thermally conductive material composed of paraffin wax and a thermally conductive filler is described.
  • Patent Document 2 describes a heat conductive composition comprising a thermoplastic resin, a wax, and a heat conductive filler.
  • Patent Document 3 describes a composition comprising a thermoplastic silicone resin, a wax-like modified silicone resin, and a thermally conductive filler.
  • compositions contain organic substances such as wax and wax modified with silicone in addition to silicone, there is a disadvantage that the composition is inferior in flame retardancy and heat resistance as compared with a single silicone product.
  • Patent Document 4 describes a heat dissipating member composed of a thermoplastic silicone resin and a heat conductive filler.
  • the heat dissipating member provided a molded product as a sheet and was mounted on an electronic component or a heat sink.
  • Patent Document 4 has good workability when assembled to a large part, but has the disadvantage of poor workability when used for a small electronic part.
  • the present invention has been made in view of the above circumstances, and is a silicone composition having thermal conductivity excellent in flame retardancy and heat resistance, crosslinked by hydrosilylation reaction, solid at room temperature, and softened at high temperature Or it aims at providing the hardened
  • the present invention includes the following (A) component and (B) component that have been intensively studied to solve the above-mentioned problems and specified the phenyl group content, and (C) a thermally conductive filler and (D) a hydrosilylation catalyst. It has been found that a cured product obtained by curing a thermally conductive silicone composition is solid at room temperature and is significantly softened or liquefied at a high temperature, thus achieving the present invention.
  • the present invention provides a thermally conductive silicone composition containing the following components (A) to (D) and a cured product of the composition.
  • (A) Organopolysiloxane represented by the average composition formula (1) and having a kinematic viscosity of 500 to 1,000,000 mm 2 / s at 25 ° C .: 100 parts by mass (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e (1)
  • R 1 is independently of each other a phenyl group, an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a hydrogen atom, provided that the total number of R 1 is 50-80% of a phenyl group, 10-20% of the total number of R 1 is a hydrogen atom, 0-20% of the total
  • a linear organopolysiloxane having at least two alkenyl groups having 2 to 6 carbon atoms in one molecule, and 40 to 70% of the total number of organic groups bonded to silicon atoms is phenyl groups.
  • An amount in which the ratio of the number of SiH groups in component (A) to the total number of alkenyl groups in component (A) and component (B) is 0.5 to 2,
  • the thermally conductive silicone composition of the present invention can provide a thermoplastic cured product, which is a solid (soft rubber) at room temperature and softens or liquefies at a high temperature (for example, 100 ° C.).
  • the thermally conductive silicone composition of the present invention can be in the form of grease and can be easily applied to small electronic components and heat sinks.
  • the heat conductive silicone composition of the present invention can be cured by being interposed between the heat generating member and the cooling member. Moreover, after apply
  • a component is a main component of this composition and is represented by the following average composition formula (1).
  • the organopolysiloxane has a kinematic viscosity at 25 ° C. of 500 to 1,000,000 mm 2 / s. Preferably, it has 1,000 to 10,000 mm 2 / s. If the kinematic viscosity is less than the lower limit, sufficient hardness at room temperature of the resulting crosslinked product may not be obtained. On the other hand, when the value exceeds the upper limit, handling workability decreases.
  • the kinematic viscosity is a value measured at 25 ° C. using an Ubbelohde Ostwald viscometer.
  • R 1 represents a phenyl group, an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a hydrogen atom.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
  • the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • the thermally conductive silicone composition of the present invention is characterized in that the component (A) has specific amounts of phenyl groups and SiH groups. That is, in the above formula, the phenyl group content is 50 to 80% of the total number of R 1 , preferably 50 to 70%. When the phenyl group amount is less than the lower limit, sufficient hardness cannot be obtained at room temperature. Exceeding the upper limit is not preferable because the mechanical strength of the resulting cured product is lowered. Further, in the above formula, the ratio of the number of hydrogen atoms in the total number of R 1 is 10 to 20%, preferably 10 to 15%. When the amount of SiH groups is less than the lower limit, the obtained cured product cannot obtain sufficient hardness at room temperature.
  • the component (A) may have an alkenyl group, and the content of the alkenyl group is 0 to 20%, preferably 0 to 15%, of the total number of R 1 .
  • the content of the alkenyl group exceeds the above upper limit, the resulting crosslinked product is not sufficiently softened at high temperature, which is not preferable.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • they are a methyl group and an ethyl group.
  • c is less than the above lower limit, the obtained cured product cannot obtain sufficient hardness at room temperature.
  • cured material obtained will become inadequate.
  • e is a number indicating the ratio of units represented by the general formula: R 2 O 1/2 and is a number satisfying 0 ⁇ e ⁇ 0.1. This is because if e exceeds the above upper limit, sufficient hardness at room temperature of the resulting crosslinked product cannot be obtained.
  • the sum of a, b, c, and d is 1.
  • the component (B) is a linear organopolysiloxane having at least two alkenyl groups having 2 to 6 carbon atoms in one molecule. 40 to 70% of the total number of organic groups bonded to the silicon atom of the siloxane is a phenyl group.
  • the composition is cured by hydrosilylation of the alkenyl group in component (B) with the SiH group in component (A).
  • the component (B) is preferably represented by the following general formula (2).
  • R 3 s independently of one another are a phenyl group, an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
  • alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
  • cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
  • alkenyl group examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • the phenyl group content is 40 to 70%, preferably 50 to 70%.
  • the ratio of the phenyl group in (B) component exceeds the said upper limit, the mechanical strength of the obtained hardened
  • at least two of R 3 are alkenyl groups. If the number of alkenyl groups is less than 1, the component (B) is not taken into the crosslinking reaction and a cured product cannot be formed, or the cured product may not have sufficient hardness at room temperature.
  • m is an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably 1 to 20. If m exceeds the above upper limit, the resulting cured product may not have sufficient hardness at room temperature.
  • the amount of component (B) is such that the ratio of the number of SiH groups in component (A) to the total number of alkenyl groups in component (A) and component (B) is 0.5-2.
  • the amount is preferably 0.5 to 1.5.
  • the amount of component (B) is less than the above lower limit, the resulting cured product may be insufficiently softened at high temperatures. Moreover, when it exceeds the above upper limit, there is a possibility that sufficient hardness at room temperature of the obtained cured product cannot be obtained.
  • the thermally conductive filler is a thermally conductive filler and imparts thermal conductivity to the composition.
  • the thermally conductive filler is preferably made of at least one material selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, and carbon allotropes.
  • metals metal oxides, metal hydroxides, metal nitrides, metal carbides, and carbon allotropes.
  • metals aluminum, silver, copper, metal silicon, alumina, zinc oxide, magnesium oxide, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, carbon nanotube, graphene, and the like can be given.
  • the shape of the thermally conductive filler may be any of spherical shape, indefinite shape, and needle shape, and is not particularly limited.
  • the heat conductive filler is preferably a combination of a large particle size component and a small particle size component.
  • the large particle size component means an average particle size of 10 to 120 ⁇ m, preferably 15 to 75 ⁇ m. If the average particle size of the large particle size component is less than the lower limit, the viscosity of the resulting composition may be too high. Above the above upper limit, the resulting composition may be non-uniform.
  • the small particle size component may be a filler having an average particle size of 0.01 to 10 ⁇ m, preferably 0.1 to 4 ⁇ m. There exists a possibility that the viscosity of the composition obtained may become too high that the average particle diameter of a small particle size component is less than the said minimum. Above the above upper limit, the resulting composition may be non-uniform.
  • the average particle diameter in this invention can be calculated
  • the compounding amount of the component (C) is 100 to 3500 parts by mass, preferably 500 to 3000 parts by mass with respect to 100 parts by mass of the component (A).
  • amount of component (C) is less than the above lower limit, the thermal conductivity is poor. Above the upper limit, the extensibility is poor.
  • Component (D) is a hydrosilylation catalyst and promotes a hydrosilylation reaction between the SiH group in component (A) and the alkenyl group in components (A) and (B).
  • the hydrosilylation catalyst may be a conventionally known catalyst, and examples thereof include platinum-based, palladium-based, and rhodium-based catalysts. Of these, platinum or platinum compounds that are relatively easily available are preferred. More specifically, for example, platinum alone, platinum black, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum coordination compounds and the like can be mentioned.
  • a platinum-type catalyst may be used individually by 1 type or in combination of 2 or more types.
  • the content of the component (D) is not particularly limited as long as it is a catalytic amount.
  • the catalytic amount is an amount sufficient to promote the hydrosilylation reaction.
  • the amount is 0.1 to 500 ppm, more preferably 1.0 to 100 ppm in terms of mass unit in terms of the amount of metal atoms of the catalyst with respect to the total mass of the present composition. If the amount of component (D) is less than the above lower limit, the effect as a catalyst may not be obtained. On the other hand, if the value exceeds the upper limit, the catalytic effect does not increase and is uneconomical.
  • the thermally conductive silicone composition of the present invention further comprises (E) at least one silyl group represented by the following general formula (3) in one molecule, and a viscosity at 25 ° C. of 0.01 to 30 Pa ⁇ s. It can contain the organopolysiloxane which has.
  • the component (E) functions as a wetter.
  • a component may be used individually by 1 type, or may use 2 or more types together.
  • R 4 are each independently an unsubstituted or substituted monovalent hydrocarbon group
  • R 5 are each independently an alkyl group, an alkoxyalkyl group, an alkenyl group or an acyl group
  • f Is 0, 1 or 2.
  • the component (E) has a viscosity at 25 ° C. of 0.01 to 30 Pa ⁇ s, and preferably 0.01 to 10 Pa ⁇ s. If the viscosity is less than the above lower limit, oil bleed is likely to occur from the silicone composition, and it tends to sag, which is not preferable. On the other hand, if it exceeds the above upper limit, the fluidity of the resulting silicone composition becomes extremely poor, and the coating workability may be deteriorated. In the present invention, the viscosity is a value measured by a rotational viscometer.
  • component (E) examples include organopolysiloxanes represented by the following general formula. (Wherein R 4 is each independently an unsubstituted or substituted monovalent hydrocarbon group, R 5 is independently an alkyl group, an alkoxyalkyl group, an alkenyl group or an acyl group, and n is an integer of 2 to 100) And f is 0, 1 or 2.)
  • R 4 s independently of each other, are unsubstituted or substituted monovalent hydrocarbon groups having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • Examples thereof include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogenated alkyl group.
  • the linear alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, and a decyl group.
  • Examples of the branched alkyl group include isopropyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group and the like.
  • Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.
  • Examples of the alkenyl group include a vinyl group and an allyl group.
  • Examples of the aryl group include a phenyl group and a tolyl group.
  • Examples of the aralkyl group include 2-phenylethyl group and 2-methyl-2-phenylethyl group.
  • halogenated alkyl group examples include 3,3,3-trifluoropropyl group, 2- (nonafluorobutyl) ethyl group, 2- (heptadecafluorooctyl) ethyl group, and the like.
  • R 4 a methyl group and a phenyl group are preferable.
  • R 5 s independently of one another are an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
  • the number of carbon atoms is preferably 1-8.
  • the alkyl group include linear alkyl groups, branched-chain alkyl groups, and include cyclic alkyl groups, in particular include the groups exemplified in R 4.
  • Examples of the alkoxyalkyl group include a methoxyethyl group and a methoxypropyl group.
  • Examples of the alkenyl group include the groups exemplified for R 4 .
  • the acyl group include an acetyl group and an octanoyl group.
  • R 5 is preferably an alkyl group, particularly preferably a methyl group or an ethyl group.
  • n is 2 to 100, preferably 5 to 50.
  • f is 0, 1 or 2, preferably 0.
  • the content of the component (E) is preferably 0.1 to 80 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the component (A). If it exceeds the above upper limit, the cured product may not have sufficient hardness at room temperature.
  • the silicone composition of the present invention may further contain (F) an organopolysiloxane in which the phenyl group in the silicon atom-bonded organic group is less than 40 mol%.
  • the organopolysiloxane has at least two alkenyl groups bonded to silicon atoms in one molecule and has a kinematic viscosity at 25 ° C. of 10 to 10,000 mm 2 / s.
  • the component (F) forms a crosslinked structure by hydrosilylation with a silicon atom-bonded hydrogen atom in the silicone composition.
  • a component may be used individually by 1 type, or may use 2 or more types together.
  • Component (F) may be linear or branched, and two or more organopolysiloxanes having different viscosities may be used in combination.
  • the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, and a 1-hexenyl group, and a vinyl group is preferable from the viewpoint of ease of synthesis and cost.
  • the alkenyl group bonded to the silicon atom may be present at any end of the molecular chain of the organopolysiloxane, but is preferably present at least at the end.
  • Examples of the organic group other than the alkenyl group bonded to the silicon atom include a substituted or unsubstituted monovalent hydrocarbon group.
  • Examples of the monovalent hydrocarbon group 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, a 2-phenylethyl group, and a 2-phenylpropyl group.
  • an aralkyl group such as a group.
  • the component (F) preferably has a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s, more preferably 100 to 50,000 mm 2 / s. If this is less than the above lower limit, the storage stability of the silicone composition may deteriorate. On the other hand, if it exceeds the upper limit, the extensibility of the resulting silicone composition may be deteriorated.
  • the content of the component (F) is preferably 0.1 to 50 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the component (A).
  • the amount of the component (F) exceeds the above upper limit, the cured product may be insufficiently softened at a high temperature.
  • the silicone composition of the present invention can further contain (G) a linear organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule.
  • the organohydrogenpolysiloxane is crosslinked by hydrosilylation reaction of alkenyl groups in the composition to form a network structure.
  • a component may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the organic group bonded to the silicon atom of the linear organohydrogenpolysiloxane include a substituted or unsubstituted monovalent hydrocarbon group.
  • Examples of the monovalent hydrocarbon group 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, a 2-phenylethyl group, and a 2-phenylpropylene group.
  • a monovalent hydrocarbon group in which a hydrogen atom bonded to a carbon atom of the hydrocarbon group is substituted with a halogen atom or a glycidoxy group for example, a chloromethyl group, 3,3,3-trialkyl group
  • a halogen atom or a glycidoxy group for example, a chloromethyl group, 3,3,3-trialkyl group
  • the amount of component (G) is such that the ratio of the total number of SiH groups to the total number of alkenyl groups in the silicone composition is 0.5 to 2, preferably 0.5 to 1.5. It is. This is because the cured product obtained when the content of the component (G) is less than the lower limit of the above range may not have sufficient hardness at room temperature. On the other hand, when the above upper limit is exceeded, the cured product is not preferable because softening at high temperatures may be insufficient.
  • the present invention is a silicone composition
  • a silicone composition comprising the above components (A) to (D) and optional components (E) to (G).
  • (H) a reaction control agent and (I) an adhesion promoter may be contained as optional components.
  • reaction control agent suppresses the progress of the hydrosilylation reaction at room temperature and prolongs shelf life and pot life.
  • Known reaction control agents can be used, such as ethynylhexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl- Alkyne alcohols such as 3-butyn-2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7- Examples include tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and benzotriazole.
  • reaction control agents may be used alone or in combination of two or more.
  • the amount of the reaction control agent is not limited as long as the effects of the present invention are not impaired, but for example, it is preferably 1 to 5000 ppm with respect to the total mass of the silicone composition.
  • the adhesion promoter further improves the adhesion to the substrate in contact with the curing process.
  • the adhesion promoter include trialkoxysiloxane group (for example, trimethoxysiloxy group, triethoxysiloxy group) or trialkoxysilylalkyl group (for example, trimethoxysilylethyl group, triethoxysilylethyl group) and hydrosilyl group.
  • an organosilane having an alkenyl group for example, vinyl group, allyl group
  • trialkoxysiloxane group or trialkoxysilyl An organosilane having an alkyl group and a methacryloxyalkyl group (for example, 3-methacryloxypropyl group), or an organosiloxane oligomer having a linear structure, a branched structure or a cyclic structure having about 4 to 20 silicon atoms;
  • a xysiloxy group or trialkoxysilylalkyl group and an epoxy-bonded alkyl group for example, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group), or a linear,
  • the silicone composition of the present invention includes, as other optional components, polyorganosiloxanes other than the components (A) to (I); silica, glass, alumina, zinc oxide, etc.
  • An inorganic filler such as polymethacrylate resin; a heat-resistant agent, a dye, a pigment, a phosphor, a flame retardant, and a solvent.
  • the silicone composition of the present invention is preferably in the form of a grease. Being grease-like, it can be easily applied to small electronic components or heat sinks.
  • the viscosity of the silicone composition at 25 ° C. is not particularly limited, but is preferably in the range of 10 to 500 Pa ⁇ s, particularly preferably in the range of 10 to 300 Pa ⁇ s.
  • the viscosity is less than the above lower limit, the handleability of the composition is deteriorated.
  • it exceeds the said upper limit when a composition is dispense-applied etc., it becomes easy to chew foam, and it is not preferable.
  • the viscosity of the silicone composition can be measured, for example, with a spiral viscometer.
  • the silicone composition preferably has a thermal conductivity of at least 1.0 W / mK or more, and particularly preferably 2.0 W / mK or more. If the thermal conductivity is less than the above lower limit, the desired heat dissipation performance cannot be obtained, which is not preferable.
  • the method for producing the silicone composition may be in accordance with a conventional method for producing a silicone composition, and is not particularly limited.
  • the above-mentioned components (A) to (I) and other necessary components are trimix, twin mix, planetary mixer (all registered trademark of mixer manufactured by Inoue Seisakusho Co., Ltd.), ultra mixer (Mizuho Industry Co., Ltd.) It can be manufactured by a method of mixing with a mixer such as a registered trademark of a mixer manufactured by Hibisu Dispersix (registered trademark of a mixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
  • a cured product can be obtained by crosslinking the silicone composition by a hydrosilylation reaction.
  • the curing conditions of the composition are not particularly limited, and may be according to the curing conditions of a conventional addition reaction curable silicone composition.
  • the cured product is solid at room temperature, for example, 25 ° C., more specifically, soft rubber, and is characterized by being softened or liquefied at a high temperature, for example, 100 ° C.
  • the cured product preferably has an Asker C hardness of 5 or more at 25 ° C.
  • cured material is a soft rubber-like thing which has fluidity
  • the viscosity in the present invention means a value of storage elastic modulus (E ′) measured by dynamic viscoelasticity measurement (DMA) described in JIS K7244-4.
  • Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
  • the amount of Ph groups is the number ratio of phenyl groups to the total number of hydrogen atoms and substituents bonded to silicon atoms.
  • the amount of SiH groups is the number ratio of SiH groups to the total number of hydrogen atoms and substituents bonded to silicon atoms.
  • the kinematic viscosity is a value measured at 25 ° C. using an Ubbelohde Ostwald viscometer.
  • Component (B) Organopolysiloxane represented by the following formula B-1: Organotrisiloxane represented by the following formula Ph group content: 67%
  • component C-1 Spherical aluminum oxide with an average particle size of 1.0 ⁇ m
  • C-2 Spherical aluminum oxide with an average particle size of 10 ⁇ m
  • C-3 Spherical aluminum oxide with an average particle size of 45 ⁇ m
  • C-4 Average particle size of 70 ⁇ m
  • D-1 F-1 solution of platinum-divinyltetramethyldisiloxane complex (containing 1% by mass as platinum atom)
  • F-1 is an organopolysiloxane of the following component (F) is there)
  • Component F-1 Organopolysiloxane represented by the following formula (kinematic viscosity at 25 ° C. 700 mm 2 / s) (Ph base amount: 30%)
  • Examples 1 to 7, Comparative Examples 1 to 4 The above components were mixed in the amounts shown in Table 1 or 2 according to the following method to obtain a silicone composition. That is, the components (A), (B), (C), (E), and (F) are added to a 5-liter gate mixer (Inoue Seisakusho Co., Ltd., trade name: 5-liter planetary mixer). The mixture was degassed and heated at 150 ° C. for 1 hour. Then, it cools until it becomes normal temperature (25 degreeC), (H) component is added, it mixes at room temperature (25 degreeC) so that it may become uniform, (D) component is added continuously, and room temperature will become uniform. (25 ° C).
  • a 5-liter gate mixer Inoue Seisakusho Co., Ltd., trade name: 5-liter planetary mixer.
  • the mixture was degassed and heated at 150 ° C. for 1 hour. Then, it cools until it becomes normal temperature (25 degreeC), (H) component is added, it mixes at room temperature (25 degreeC) so that
  • the cured product having a thickness of 2 mm was punched out so as to have a strip shape of 1.0 cm ⁇ 3.0 cm.
  • the molded cured product conforms to the dynamic viscoelasticity measurement (DMA) described in JIS K7244-4, and the modulus from 25 ° C. to 100 ° C. using a viscoelasticity measuring device DMA 7100 manufactured by Hitachi High-Tech Science Co., Ltd. Changes were measured.
  • Tables 1 and 2 show the modulus (MPa) at 25 ° C and the modulus (MPa) at 100 ° C.
  • cured material obtained from the composition of Example 6 and 7 had fluidity
  • the cured product obtained by curing the compositions of Comparative Examples 1 and 2 containing the organopolysiloxane (A-3) having a small amount of phenyl groups is sufficient at room temperature (25 ° C.). Hardness cannot be obtained.
  • a cured product obtained by curing the compositions of Comparative Examples 3 and 4 containing an organopolysiloxane (A-4) having an SiH content below the lower limit can also obtain a sufficient hardness at room temperature (25 ° C.). Absent.
  • the obtained cured product has a high viscosity at 100 ° C. and does not have fluidity.
  • the cured products made of the silicone compositions of Examples 1 to 7 are solids (soft rubber) having an Asker C hardness of 5 or more at room temperature (25 ° C.). Further, as can be seen from the value of the modulus at 25 ° C. and the value of the modulus at 100 ° C., the cured products of Examples 1 to 5 were softened at a high temperature (100 ° C.). Moreover, the hardened
  • the thermally conductive silicone composition of the present invention can provide a cured product having thermoplasticity by heat curing. Moreover, since the heat conductive silicone composition of this invention has a grease form, it can also be hardened by interposing this composition between a heat generating member and a cooling member. Furthermore, it can be combined with the other member by once applying and curing to either one of the heat generating member or the cooling member and then softening with heat. Therefore, the thermally conductive silicone composition of the present invention can be easily applied to electronic components and heat sinks, and can be suitably used even in small electronic components.

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Abstract

La présente invention est conçue dans les situations précitées, et aborde le problème de la fourniture d'une composition de silicone qui présente une excellente ininflammabilité et une excellente résistance à la chaleur, ainsi qu'une conductivité thermique, et qui peut être réticulée par l'intermédiaire d'une réaction d'hydrosilylation pour obtenir un article durci qui a une forme solide à température ambiante et qui est ramolli ou liquéfié à une température élevée. La présente invention aborde également le problème de la fourniture d'une composition de silicone thermoconductrice qui peut être facilement appliquée à un petit composant électronique et à un dissipateur thermique. La solution selon l'invention porte sur une composition de silicone thermoconductrice contenant les composants suivants (A) à (D) : (A) un organopolysiloxane représenté par la formule de composition moyenne (1) et ayant une viscosité cinématique de 500 à 1 000 000 mm2/s à 25 °C, dans une quantité de 100 parties en masse :(R1 3SiO1/2)a(R1 2SiO2/2)b(R1SiO3/2)c(SiO4/2)d(R2O1/2)e (1) (les R1 représentant indépendamment un groupe phényle, un groupe alkyle ou cycloalkyle possédant 1 à 6 atomes de carbone, un groupe alcényle possédant 2 à 6 atomes de carbone, ou un atome d'hydrogène, 50 à 80 % du nombre total de R1 étant des groupes phényle, 10 à 20 % du nombre total de R1 étant des atomes d'hydrogène, et 0 à 20 % du nombre total de R1 étant des groupes alcényle; R2 représente un atome d'hydrogène ou un groupe alkyle possédant 1 à 6 atomes de carbone; et a, b, c, d et e sont des nombres numériques satisfaisant aux exigences représentées par les formules suivantes : 0 ≤ a ≤ 0.2, 0.2 ≤ b ≤ 0.7, 0.2 ≤ c ≤ 0.6, 0 ≤ d ≤ 0.2, 0 ≤ e ≤ 0.1, et a+b+c+d = 1; (B) un organopolysiloxane linéaire qui possède au moins deux groupes alcényle ayant chacun 2 à 6 atomes de carbone par molécule, 40 à 70 % du nombre total de groupes organiques se liant chacun à un atome de silicium sont des groupes phényle, dans une quantité telle que le rapport du nombre de groupes SiH dans le composant (A) au nombre total de groupes alcényle dans les composants (A) et (B) peut passer de 0,5 à 2; (C) une charge thermoconductrice dans une quantité de 100 à 3500 parties en masse; et (D) un catalyseur d'hydrosilylation. L'invention concerne également un article durci obtenu par durcissement de la composition de silicone thermoconductrice.
PCT/JP2019/010935 2018-04-09 2019-03-15 Composition de silicone thermodurcissable et produit durci associé WO2019198424A1 (fr)

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WO2023189699A1 (fr) * 2022-03-31 2023-10-05 株式会社タイカ Composition de silicone thermoconductrice
WO2023243707A1 (fr) * 2022-06-17 2023-12-21 積水化学工業株式会社 Composition de silicone, élément de dissipation de chaleur et dispositif électronique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011102272A1 (fr) * 2010-02-19 2011-08-25 東レ株式会社 Silicone durci contenant un luminophore, son procédé de fabrication, composition de silicone contenant un luminophore, précurseur de la composition, produits moulés en forme de feuille, boîtier pour del, dispositif électroluminescent et procédé de fabrication de substrat monté sur del
JP2013122037A (ja) * 2011-11-10 2013-06-20 Sekisui Chem Co Ltd 光半導体装置用硬化性組成物及び光半導体装置
JP2015065330A (ja) * 2013-09-25 2015-04-09 信越化学工業株式会社 放熱シート、高放熱性シート状硬化物、及び放熱シートの使用方法
JP2015171767A (ja) * 2014-03-11 2015-10-01 信越化学工業株式会社 金属張複合積層基板及び半導体装置
JP2018056595A (ja) * 2015-08-17 2018-04-05 積水化学工業株式会社 半導体装置及び半導体素子保護用材料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4862032B2 (ja) * 2008-12-05 2012-01-25 信越化学工業株式会社 高屈折率を有する硬化物を与える付加硬化型シリコーン組成物、及び該組成物からなる光学素子封止材
JP2013100464A (ja) * 2011-10-13 2013-05-23 Shin-Etsu Chemical Co Ltd 導電性シリコーン組成物及びその製造方法
JP6485262B2 (ja) * 2015-07-16 2019-03-20 信越化学工業株式会社 剥離紙又は剥離フィルム用シリコーン組成物、剥離紙及び剥離フィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011102272A1 (fr) * 2010-02-19 2011-08-25 東レ株式会社 Silicone durci contenant un luminophore, son procédé de fabrication, composition de silicone contenant un luminophore, précurseur de la composition, produits moulés en forme de feuille, boîtier pour del, dispositif électroluminescent et procédé de fabrication de substrat monté sur del
JP2013122037A (ja) * 2011-11-10 2013-06-20 Sekisui Chem Co Ltd 光半導体装置用硬化性組成物及び光半導体装置
JP2015065330A (ja) * 2013-09-25 2015-04-09 信越化学工業株式会社 放熱シート、高放熱性シート状硬化物、及び放熱シートの使用方法
JP2015171767A (ja) * 2014-03-11 2015-10-01 信越化学工業株式会社 金属張複合積層基板及び半導体装置
JP2018056595A (ja) * 2015-08-17 2018-04-05 積水化学工業株式会社 半導体装置及び半導体素子保護用材料

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