WO2018230189A1 - Thermally-conductive silicone composition - Google Patents
Thermally-conductive silicone composition Download PDFInfo
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- WO2018230189A1 WO2018230189A1 PCT/JP2018/017750 JP2018017750W WO2018230189A1 WO 2018230189 A1 WO2018230189 A1 WO 2018230189A1 JP 2018017750 W JP2018017750 W JP 2018017750W WO 2018230189 A1 WO2018230189 A1 WO 2018230189A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
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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
- C08K5/00—Use of organic ingredients
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
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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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
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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
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the present invention relates to a thermally conductive silicone composition in which the hardness after curing does not increase and the initial curing rate does not decrease even when exposed to a high temperature for a long time.
- Electronic parts such as LSIs and IC chips are widely known to generate heat during use and performance degradation associated therewith, and various heat dissipation techniques are used as means for solving this.
- a heat sink or other cooling application member is placed near the heat generating part, and by bringing them into close contact with each other, efficient heat transfer to the cooling member is promoted to cool the heat generation, thereby efficiently dissipating the heat from the heat generating part. It is known to do. At this time, if there is a gap between the heat generating member and the cooling member, heat transfer becomes inefficient due to the presence of air having low heat conductivity, and the temperature of the heat generating member cannot be sufficiently lowered.
- a heat-dissipating material, a heat-dissipating sheet or a heat-dissipating grease having a good thermal conductivity and following the surface of the member is used for the purpose of preventing the air from interposing between the heat-generating member and the cooling member ( Japanese Patent No. 2938428, Japanese Patent No. 2938429, Japanese Patent No. 3952184: Patent Documents 1 to 3).
- the heat dissipating grease exhibits a high performance from the viewpoint of thermal resistance because it can be used with a reduced thickness when mounted.
- thermal grease Some types are used after being cured between heat and heat.
- the heat-cured heat-dissipating grease is further heated when the element is in operation, so that the hardness may increase during use. If the hardness increases, there is a concern that the material becomes inflexible and cannot follow the “sleigh” during operation. When the follow-up cannot be performed, a gap is generated between the member and the heat-dissipating grease, so that the heat-dissipating characteristics are deteriorated.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermally conductive silicone composition in which the increase in hardness during high-temperature aging after curing is small and at the same time, the decrease in the curing rate is suppressed.
- E hydrogenated organohydrogenpolysiloxane
- F platinum compounds
- G triazole compounds
- isocyanate compounds each containing a specific ratio
- the present invention provides the following thermally conductive silicone composition.
- (A) Organopolysiloxane having at least two alkenyl groups in one molecule and a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s
- (B) The following general formula (1) (In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, and a is a positive number having 5 to 100.)
- One-terminal trifunctional hydrolyzable methylpolysiloxane represented by: (A) 10 to 150 parts by mass with respect to 100 parts by mass of component (C) Thermally conductive filling having a thermal conductivity of 10 W / m ⁇ ° C.
- reaction control agent selected from acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds and organic chloro compounds: an amount of 0.1 to 5% by mass based on component (A) [1 ]-The heat conductive silicone composition in any one of [5].
- the thermally conductive silicone composition of the present invention can suppress the increase in hardness during high-temperature aging of the cured product and suppress the decrease in the curing rate by blending specific amounts of triazole compound and isocyanate compound, respectively. it can.
- the organopolysiloxane of component (A) constituting the present invention has at least 2, preferably 2 to 10, more preferably 2 to 5, alkenyl groups directly bonded to silicon atoms in one molecule.
- the chain may be branched or branched, and a mixture of two or more different viscosities may be used.
- alkenyl group examples include those having 2 to 6 carbon atoms such as a vinyl group, an allyl group, a 1-butenyl group, and a 1-hexenyl group, but a vinyl group is preferable from the viewpoint of ease of synthesis and cost.
- the remaining organic group bonded to the silicon atom is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond.
- alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and dodecyl group, aryl groups such as phenyl group, aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group, etc.
- aryl groups such as phenyl group
- aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group
- halogen-substituted hydrocarbon groups such as chloromethyl group and 3,3,3-trifluoropropyl group.
- a methyl group is preferred from the viewpoint of ease of synthesis and cost.
- the alkenyl group bonded to the silicon atom may be present at either the terminal or the middle of the molecular chain of the organopolysiloxane, but is preferably present at least at the terminal.
- the kinematic viscosity of the component (A) measured at 25 ° C. with an Ostwald meter is in the range of 10 to 100,000 mm 2 / s, preferably in the range of 100 to 50,000 mm 2 / s, and more preferably in the range of 100 to 1,000 mm 2 / s is preferable. If the kinematic viscosity is less than 10 mm 2 / s, the oil bleed of the composition will be severe and the reliability will be poor, and if it exceeds 100,000 mm 2 / s, the viscosity of the composition will increase and the extensibility will be poor. .
- component (A) for example, dimethylpolysiloxane blocked with a dimethylvinylsiloxy group blocked at both ends of the molecular chain, and one end of the molecular chain blocked with a dimethylvinylsiloxy group and the other end of the molecular chain blocked with a trimethylsiloxy group Siloxane / methylvinylpolysiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked Examples thereof include, but are not limited to, a dimethylsiloxane / methylvinylsiloxane copolymer, and two or more of these may be used in combination.
- the component (B) has the following general formula (1) (Wherein R 1 is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group, and a is a positive number of 5 to 100.) Is a one-terminal trifunctional hydrolyzable methylpolysiloxane.
- the oil bleed of the composition becomes so bad that the reliability becomes worse. If it is large, the wettability is not sufficient, so it is a positive number of 5 to 100, preferably in the range of 10 to 60.
- this one-terminal trifunctional hydrolyzable methylpolysiloxane is less than 10 parts by mass with respect to 100 parts by mass of component (A), sufficient wettability cannot be exhibited, and if more than 150 parts by mass, oil bleed Is in the range of 10 to 150 parts by mass, preferably 20 to 140 parts by mass.
- the component (C) is a thermally conductive filler having a thermal conductivity of 10 W / m ⁇ ° C. or higher.
- the thermally conductive filler of component (C) those having a thermal conductivity of 10 W / m ⁇ ° C. or higher, preferably 15 W / m ⁇ ° C. or higher are used. This is because if the thermal conductivity of the filler is less than 10 W / m ⁇ ° C., the thermal conductivity of the thermally conductive silicone composition itself becomes small.
- Such heat conductive fillers include aluminum powder, copper powder, silver powder, iron powder, nickel powder, gold powder, tin powder, metal silicon powder, aluminum nitride powder, boron nitride powder, alumina powder, diamond powder, carbon powder. Indium powder, gallium powder, zinc oxide powder, etc., any filler may be used as long as it is 10 W / m ⁇ ° C. or more, and one or a mixture of two or more may be used.
- the average particle size of the component (C) is preferably in the range of 0.1 to 100 ⁇ m, more preferably in the range of 0.1 to 90 ⁇ m, and still more preferably in the range of 0.1 to 20 ⁇ m. If the average particle size is less than 0.1 ⁇ m, the resulting composition may not be in the form of grease and may have poor extensibility. If the average particle size is greater than 100 ⁇ m, the thermal resistance of the heat dissipating grease will increase and the performance will deteriorate. This is because there are cases. In the present invention, the average particle diameter can be measured by Nikkiso Co., Ltd. Microtrac MT330OEX, and is a volume-based volume average diameter.
- the shape of the component (C) may be indefinite, spherical, or any shape.
- the amount of the (C) component is less than 500 parts by mass with respect to 100 parts by mass of the total of the (A) component and the (B) component, the thermal conductivity of the composition becomes low and 3,000 parts by mass. If it is more, the viscosity of the composition increases and the extensibility becomes poor. Therefore, it is in the range of 500 to 3,000 parts by mass, preferably in the range of 500 to 2,800 parts by mass, more preferably 500 A range of ⁇ 2,500 parts by mass is preferable.
- the organohydrogenpolysiloxane of component (D) has at least two, preferably 2 to 50, hydrogen atoms (Si—H groups) directly linked to silicon atoms in order to reticulate the composition by crosslinking. More preferably, it is necessary to have 2 to 30.
- the Si—H group may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both.
- the remaining organic group other than the Si—H group bonded to the silicon atom is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond.
- an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a dodecyl group, an aryl group such as a phenyl group, a 2-phenylethyl group, or a 2-phenylpropyl group
- halogen-substituted hydrocarbon groups such as aralkyl group, chloromethyl group, 3,3,3-trifluoropropyl group, etc., and 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4- Examples include epoxy-substituted hydrocarbon groups such as glycidoxybutyl groups.
- Such an organohydrogenpolysiloxane having a Si—H group may be linear, branched or cyclic, or a mixture thereof.
- the number of silicon atoms in the organohydrogenpolysiloxane is preferably 10 to 250, particularly 10 to 200.
- This organohydrogenpolysiloxane may be used alone or in combination of two or more.
- Examples of the component (D) include a copolymer comprising (CH 3 ) 2 HSiO 1/2 units and (CH 3 ) 2 SiO units, (CH 3 ) 2 HSiO 1/2 units and (CH 3 ) 3 SiO.
- a copolymer comprising 1/2 units and (CH 3 ) 2 SiO units a copolymer comprising (CH 3 ) 3 SiO 1/2 units, (CH 3 ) 2 SiO units and (CH 3 ) HSiO units
- a copolymer comprising units and (CH 3 ) HSiO units a copolymer comprising (CH 3 ) 2 HSiO 1/2 units, (CH 3 ) 2 SiO units and (CH 3 ) HSiO units, (CH 3 ) 3 SiO
- the blending amount of the component (D) is such that the composition cannot be reticulated sufficiently if the ⁇ number of Si—H groups in the component (D) ⁇ / ⁇ number of alkenyl groups in the component (A) ⁇ is less than 0.5. Is pumped out, and if it is larger than 1.5, the crosslinking density becomes too high and peels off during the reliability test, so the range is 0.5 to 1.5, preferably 0.7. A range of ⁇ 1.3 is good.
- the catalyst selected from platinum and platinum compounds as the component (E) is a component for promoting the addition reaction between the alkenyl group in the component (A) and the Si—H group in the component (D).
- Examples of the component (E) include platinum alone, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum coordination compounds, and the like.
- the amount of component (E) is less than 0.1 ppm as platinum atoms with respect to the mass of component (A), and there is no effect as a catalyst. Therefore, it is in the range of 0.1 to 500 ppm, preferably 0.1 to 400 ppm.
- the (F) component triazole compound, together with the component (G) described later, is added to the composition at a specific blending amount to suppress a decrease in the curing rate of the thermally conductive silicone composition, and after curing.
- the increase in hardness during high temperature aging can be suppressed.
- Examples of the (F) component triazole-based compound include 1,2,3-triazole, 1,2,4-triazole, and derivatives thereof.
- the derivatives of 1,2,3-triazole include benzotriazole, 4-hydroxy-1,2,3-triazole, 1,2,3-triazole-4-aldehyde, 4-cyano-1,2 , 3-triazole and the like.
- Examples of the 1,2,4-triazole derivatives include 5-amino-3-methyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole and the like.
- preferred are benzotriazole, 1,2,3-triazole, and 1,2,4-triazole, and most preferred is benzotriazole. These may be used alone or in combination of two or more.
- the compounding amount of component (F) is 2 to 1,000 mol, preferably 2 to 800 mol, more preferably 2 to 500 mol, per 1 mol of platinum atom in component (E). If the blending amount is less than 2 mol, the increase in hardness cannot be sufficiently suppressed, and if it is more than 1,000 mol, the curing rate becomes slow.
- Examples of the isocyanate compound as component (G) include alkyl isocyanate compounds such as methyl isocyanate, butyl isocyanate and octyl isocyanate, aryl isocyanate compounds such as phenyl isocyanate and tolyl isocyanate, and further, for example, the following general formula (2) And an isocyanate silane compound containing an isocyanate group and a silyl group, as shown in FIG. (Wherein R 2 represents an alkyl group or a trialkylsilyl group, and b represents an integer of 1 to 6)
- the alkyl group represented by R 2 is preferably one having 1 to 4 carbon atoms, particularly a methyl group or ethyl group, and the alkyl group of the trialkylsilyl group is also one having 1 to 4 carbon atoms, particularly a methyl group or ethyl group.
- the alkyl group represented by R 2 is preferably one having 1 to 4 carbon atoms, particularly a methyl group or ethyl group
- the alkyl group of the trialkylsilyl group is also one having 1 to 4 carbon atoms, particularly a methyl group or ethyl group.
- a trimethylsilyl group and a triethylsilyl group are preferable.
- octyl isocyanate 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyltris (trimethylsiloxy) silane are most preferred. These may be used alone or in combination of two or more.
- the amount of component (G) is 0.1 to 10 moles, preferably 0.5 to 5 moles, and more preferably 0.5 to 2 moles per mole of component (F). If the blending amount is less than 0.1 mol, the curing rate decreases, and if it exceeds 10 mol, the hardness increase after aging cannot be sufficiently suppressed.
- a reaction control agent in the thermally conductive silicone composition of the present invention, can be further blended as the component (H) for the purpose of suppressing the catalytic activity of the component (E).
- the reaction control agent of component (H) suppresses the progress of the hydrosilylation reaction at room temperature and extends shelf life and pot life.
- Known reaction control agents can be used, and acetylene compounds, various nitrogen compounds, organic phosphorus compounds, oxime compounds, organic chloro compounds, and the like can be used.
- the blending amount of the component (H) is less than 0.1% by mass relative to the component (A), sufficient shelf life and pot life may not be obtained. Since the speed may decrease, the range of 0.1 to 5% by mass is preferable, and the range of 0.1 to 4% by mass is particularly preferable. These may be used by diluting with a solvent such as toluene in order to improve dispersibility in the heat conductive silicone composition.
- an antioxidant or the like may be added to the thermally conductive silicone composition of the present invention as necessary in order to prevent deterioration.
- the components (A) to (H) are trimix, twin mix, planetary mixer (all are registered trademarks of a mixer manufactured by Inoue Seisakusho Co., Ltd.), ultra mixer It can be produced by mixing with a mixer such as (registered trademark of Mizuho Kogyo Co., Ltd.), Hibis Disper Mix (registered trademark of Special Kikai Kogyo Co., Ltd.).
- the absolute viscosity at 25 ° C. of the obtained heat conductive silicone composition measured with a rotational viscometer is preferably 5 to 2,000 Pa ⁇ s, particularly 10 to 900 Pa ⁇ s.
- the obtained heat conductive silicone composition can be made into a cured product by heating at 80 to 180 ° C., particularly 90 to 170 ° C. for 30 to 150 minutes, particularly 30 to 140 minutes.
- the thermally conductive silicone composition of the present invention can suppress a decrease in curing rate, and the cured product of the composition can suppress an increase in hardness during high-temperature aging. It can use suitably as a use of the heat conductive material to a cooling member.
- the heat conductive silicone composition was applied in a thickness of 2 mm between two parallel plates having a diameter of 2.5 cm. After the temperature of the coated plate was increased from 25 ° C. at 5 ° C./min, a program was created to maintain the temperature at 150 ° C. for 90 minutes, and the storage elastic modulus G ′ and loss elastic modulus G ′′ were measured. . The time when the value of the storage elastic modulus G ′ exceeded the loss elastic modulus G ′′ was defined as the crossover time, and was used as an index of the curing rate. The measurement was carried out using a viscoelasticity measuring device (Type ARES-G2 manufactured by TA Instruments).
- the thermally conductive silicone composition was poured into a 6 cm ⁇ 6 cm ⁇ 6 mm mold and heated at 150 ° C. for 90 minutes to prepare a sheet-like sample. About what superposed
- thermo resistance measurement A heat conductive silicone composition is sandwiched between a 15 mm ⁇ 15 mm ⁇ 1 mmt Si chip and a 15 mm ⁇ 15 mm ⁇ 1 mmt Ni plate so as to have a thickness of 80 ⁇ m, compressed at 0.7 MPa for 15 minutes, and then loaded. The sample was placed in an oven at 150 ° C. for 90 minutes with heat applied, and the thermally conductive silicone composition was heated and cured to prepare a test piece for measuring thermal resistance. Further, after that, a heat cycle test (-55 ° C. to 125 ° C.) was carried out for 500 cycles, and changes in thermal resistance were observed. In addition, this thermal resistance measurement was performed by nanoflash (the Niche company make, LFA447).
- the following components were prepared in order to prepare the thermally conductive silicone composition of the present invention.
- Component A-1 Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity at 25 ° C. of 600 mm 2 / s
- Component (C) The following aluminum powder or alumina powder and zinc oxide powder were mixed for 15 minutes at room temperature using a 5-liter planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) at the mass mixing ratio shown in Table 1 below. 1 or C-2 was obtained.
- Aluminum powder with an average particle size of 10 ⁇ m (thermal conductivity: 236 W / m ⁇ ° C.)
- G Component G-1: 3-isocyanatopropyltriethoxysilane
- G-2 3-isocyanatopropyltrimethoxysilane
- G-3 3-isocyanatopropyltris (trimethylsiloxy) silane
- the components (A) to (H) were mixed as follows to obtain thermally conductive silicone compositions of Examples 1 to 6 and Comparative Examples 1 to 6. That is, take the component (A) into a 5 liter planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), add the components (B) and (C) in the amounts shown in Tables 2 and 3, and mix at 170 ° C. for 1 hour. did. The mixture was cooled to room temperature, and then the components (D), (E), (F), (G), and (H) were added in the blending amounts shown in Tables 2 and 3 and mixed to be uniform.
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Abstract
This thermally-conductive silicone composition exhibits, after being cured, a small increase in hardness when being aged at a high temperature, and also any decrease in curing speed is constrained, wherein the composition contains (A) an organopolysiloxane having at least two alkenyl groups per molecule, and having a kinematic viscosity of 10-100,000 mm2/s at 25ºC, (B) a hydrolyzable methyl polysiloxane having three functional groups at one terminal thereof, (C) a thermally-conductive filler having a thermal conductivity of 10 W/m·ºC or higher, (D) an organohydrogenpolysiloxane having hydrogen atoms bonded directly to at least two silicon atoms per molecule, (E) a catalyst selected from the group consisting of platinum and platinum compounds, (F) a specific amount of a triazole compound, and (G) a specific amount of an isocyanate compound.
Description
本発明は、高温に長時間さらされた場合にも硬化後の硬度が上昇せず、かつ初期の硬化速度が低下しない熱伝導性シリコーン組成物に関する。
The present invention relates to a thermally conductive silicone composition in which the hardness after curing does not increase and the initial curing rate does not decrease even when exposed to a high temperature for a long time.
ＬＳＩやＩＣチップ等の電子部品は使用中の発熱及びそれに伴う性能の低下が広く知られており、これを解決するための手段として様々な放熱技術が用いられている。例えば、発熱部の付近にヒートシンクなどの冷却用途の部材を配置し、両者を密接させることで冷却部材へと効率的な伝熱を促して発熱を冷却することにより発熱部の放熱を効率的に行うことが知られている。その際、発熱部材と冷却部材との間に隙間があると、熱伝導性の低い空気が介在することにより伝熱が効率的でなくなるために発熱部材の温度が十分に下がらなくなってしまう。このような現象を防止するために発熱部材と冷却部材の間の空気の介在を防ぐ目的として、熱伝導率がよく部材の表面に追随性のある放熱材料、放熱シートや放熱グリースが用いられる（特許第２９３８４２８号公報、特許第２９３８４２９号公報、特許第３９５２１８４号公報：特許文献１～３）。その中でも放熱グリースは実装時の厚みを薄くして使用することができるために熱抵抗の観点から高い性能を発揮する。
Electronic parts such as LSIs and IC chips are widely known to generate heat during use and performance degradation associated therewith, and various heat dissipation techniques are used as means for solving this. For example, a heat sink or other cooling application member is placed near the heat generating part, and by bringing them into close contact with each other, efficient heat transfer to the cooling member is promoted to cool the heat generation, thereby efficiently dissipating the heat from the heat generating part. It is known to do. At this time, if there is a gap between the heat generating member and the cooling member, heat transfer becomes inefficient due to the presence of air having low heat conductivity, and the temperature of the heat generating member cannot be sufficiently lowered. In order to prevent such a phenomenon, a heat-dissipating material, a heat-dissipating sheet or a heat-dissipating grease having a good thermal conductivity and following the surface of the member is used for the purpose of preventing the air from interposing between the heat-generating member and the cooling member ( Japanese Patent No. 2938428, Japanese Patent No. 2938429, Japanese Patent No. 3952184: Patent Documents 1 to 3). Among them, the heat dissipating grease exhibits a high performance from the viewpoint of thermal resistance because it can be used with a reduced thickness when mounted.
放熱グリースの中には部材間に挟まれたのちに、加熱硬化して使用するようなタイプもある。加熱硬化された放熱グリースは素子稼働時にさらに加熱されるため、使用中に硬度が上昇してしまう場合がある。硬度が上昇すると、材料に柔軟性がなくなってしまい、稼働時の“そり”に追従できなくなってしまう点が懸念される。追従できなくなると、部材と放熱グリースの間に空隙が発生してしまうため放熱特性が悪化する。
Some types of thermal grease are used after being cured between heat and heat. The heat-cured heat-dissipating grease is further heated when the element is in operation, so that the hardness may increase during use. If the hardness increases, there is a concern that the material becomes inflexible and cannot follow the “sleigh” during operation. When the follow-up cannot be performed, a gap is generated between the member and the heat-dissipating grease, so that the heat-dissipating characteristics are deteriorated.
一方で、シリコーンゴムにトリアゾール系化合物を配合すると、圧縮永久歪が小さくなることが知られている。圧縮永久歪が小さくなるということは、高温エージング時の硬度の上昇も抑制されることが期待できる。しかし、トリアゾール系化合物のみを配合した場合、加熱時の硬化速度が低下してしまうという課題があった。放熱グリースの硬化速度が低下すると、材料の硬化前に微量のガスが発生し、加熱により膨張、その後に硬化することによって材料中にボイド（空隙）が発生してしまい、放熱性能が低下してしまうという課題があった。
On the other hand, it is known that when a triazole compound is added to silicone rubber, the compression set is reduced. A reduction in compression set can be expected to suppress an increase in hardness during high temperature aging. However, when only a triazole-based compound is blended, there is a problem that the curing rate during heating is reduced. If the curing rate of the heat dissipation grease decreases, a small amount of gas is generated before the material is cured, expands due to heating, and then cures, creating voids in the material, resulting in decreased heat dissipation performance. There was a problem of ending up.
本発明は、上記事情に鑑みなされたもので、硬化後の高温エージング時の硬度上昇が小さく、同時に硬化速度の低下を抑制した熱伝導性シリコーン組成物を提供することを目的とする。
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermally conductive silicone composition in which the increase in hardness during high-temperature aging after curing is small and at the same time, the decrease in the curing rate is suppressed.
本発明者らは、上記目的を達成するために鋭意検討した結果、
（Ａ）１分子中に少なくとも２個のアルケニル基を有する、２５℃の動粘度が１０～１００，０００ｍｍ2／ｓのオルガノポリシロキサン
（Ｂ）下記一般式（１）
（式中、Ｒ1は炭素数１～６のアルキル基であり、ａは５～１００の正数である。）
で表される片末端３官能の加水分解性メチルポリシロキサン
（Ｃ）１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材
（Ｄ）１分子中に少なくとも２個のケイ素原子に直結した水素原子を含有するオルガノハイドロジェンポリシロキサン
（Ｅ）白金及び白金化合物からなる群より選択される触媒
（Ｆ）トリアゾール系化合物
（Ｇ）イソシアネート系化合物
をそれぞれ特定割合で含有する熱伝導性シリコーン組成物（シリコーングリース組成物）が、硬化後の高温エージング時の硬度上昇が小さく、同時に硬化速度の低下が抑制されることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors
(A) Organopolysiloxane having at least two alkenyl groups in one molecule and a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s (B) The following general formula (1)
(In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, and a is a positive number having 5 to 100.)
One-terminal trifunctional hydrolyzable methylpolysiloxane (C) represented by the following formula: Thermally conductive filler having a thermal conductivity of 10 W / m · ° C. or higher (D) Directly linked to at least two silicon atoms in one molecule Conductive hydrogen composition containing hydrogenated organohydrogenpolysiloxane (E) platinum and a catalyst selected from the group consisting of platinum compounds (F) triazole compounds (G) isocyanate compounds each containing a specific ratio The product (silicone grease composition) was found to have a small increase in hardness during high-temperature aging after curing, and at the same time, a decrease in the curing rate was suppressed, and the present invention was made.
（Ａ）１分子中に少なくとも２個のアルケニル基を有する、２５℃の動粘度が１０～１００，０００ｍｍ2／ｓのオルガノポリシロキサン
（Ｂ）下記一般式（１）
（式中、Ｒ1は炭素数１～６のアルキル基であり、ａは５～１００の正数である。）
で表される片末端３官能の加水分解性メチルポリシロキサン
（Ｃ）１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材
（Ｄ）１分子中に少なくとも２個のケイ素原子に直結した水素原子を含有するオルガノハイドロジェンポリシロキサン
（Ｅ）白金及び白金化合物からなる群より選択される触媒
（Ｆ）トリアゾール系化合物
（Ｇ）イソシアネート系化合物
をそれぞれ特定割合で含有する熱伝導性シリコーン組成物（シリコーングリース組成物）が、硬化後の高温エージング時の硬度上昇が小さく、同時に硬化速度の低下が抑制されることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors
(A) Organopolysiloxane having at least two alkenyl groups in one molecule and a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s (B) The following general formula (1)
(In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, and a is a positive number having 5 to 100.)
One-terminal trifunctional hydrolyzable methylpolysiloxane (C) represented by the following formula: Thermally conductive filler having a thermal conductivity of 10 W / m · ° C. or higher (D) Directly linked to at least two silicon atoms in one molecule Conductive hydrogen composition containing hydrogenated organohydrogenpolysiloxane (E) platinum and a catalyst selected from the group consisting of platinum compounds (F) triazole compounds (G) isocyanate compounds each containing a specific ratio The product (silicone grease composition) was found to have a small increase in hardness during high-temperature aging after curing, and at the same time, a decrease in the curing rate was suppressed, and the present invention was made.
従って、本発明は、下記の熱伝導性シリコーン組成物を提供する。
〔１〕
（Ａ）１分子中に少なくとも２個のアルケニル基を有する、２５℃の動粘度が１０～１００，０００ｍｍ2／ｓのオルガノポリシロキサン
（Ｂ）下記一般式（１）
（式中、Ｒ1は炭素数１～６のアルキル基であり、ａは５～１００の正数である。）
で表される片末端３官能の加水分解性メチルポリシロキサン：（Ａ）成分１００質量部に対して１０～１５０質量部
（Ｃ）１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材：（Ａ）成分と（Ｂ）成分の合計１００質量部に対して５００～３，０００質量部
（Ｄ）１分子中に少なくとも２個のケイ素原子に直結した水素原子を含有するオルガノハイドロジェンポリシロキサン：｛（Ｄ）成分のＳｉ－Ｈ基の個数｝／｛（Ａ）成分のアルケニル基の個数｝が０．５～１．５になる量
（Ｅ）白金及び白金化合物からなる群より選択される触媒：白金原子として（Ａ）成分の質量に対して０．１～５００ｐｐｍとなる量
（Ｆ）トリアゾール系化合物：（Ｅ）成分の白金原子１モルに対して２～１，０００モル
（Ｇ）イソシアネート系化合物：（Ｆ）成分のトリアゾール系化合物１モルに対して０．１～１０モル
を含有する熱伝導性シリコーン組成物。
〔２〕
（Ｆ）成分が、１，２，３－トリアゾール、１，２，４－トリアゾール及びこれらの誘導体から選ばれるものである〔１〕に記載の熱伝導性シリコーン組成物。
〔３〕
（Ｆ）成分が、ベンゾトリアゾールである〔２〕に記載の熱伝導性シリコーン組成物。
〔４〕
（Ｇ）成分が、アルキルイソシアネート系化合物、アリールイソシアネート系化合物及びイソシアネートシラン系化合物から選ばれるものである〔１〕～〔３〕のいずれかに記載の熱伝導性シリコーン組成物。
〔５〕
（Ｇ）成分が、下記式（２）
（式中、Ｒ2はアルキル基又はトリアルキルシリル基であり、ｂは１～６の整数である。）
で示される化合物である〔４〕に記載の熱伝導性シリコーン組成物。
〔６〕
更に、（Ｈ）アセチレン化合物、窒素化合物、有機りん化合物、オキシム化合物及び有機クロロ化合物より選択される反応制御剤：（Ａ）成分に対して０．１～５質量％となる量
を含む〔１〕～〔５〕のいずれかに記載の熱伝導性シリコーン組成物。 Accordingly, the present invention provides the following thermally conductive silicone composition.
[1]
(A) Organopolysiloxane having at least two alkenyl groups in one molecule and a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s (B) The following general formula (1)
(In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, and a is a positive number having 5 to 100.)
One-terminal trifunctional hydrolyzable methylpolysiloxane represented by: (A) 10 to 150 parts by mass with respect to 100 parts by mass of component (C) Thermally conductive filling having a thermal conductivity of 10 W / m · ° C. or more Material: 500 to 3,000 parts by mass with respect to a total of 100 parts by mass of component (A) and component (B) (D) Organohydrogen containing hydrogen atoms directly bonded to at least two silicon atoms in one molecule Polysiloxane: {Equivalent number of Si-H groups in component (D)} / {Number of alkenyl groups in component (A)} is 0.5 to 1.5 (E) From the group consisting of platinum and platinum compounds Catalyst selected: An amount of 0.1 to 500 ppm as platinum atom based on the mass of component (A) (F) Triazole compound: 2 to 1,000 mol per mol of platinum atom of component (E) (G) Isocyanate compound: ( ) Heat conductive silicone composition containing 0.1 to 10 mol relative to triazole compound 1 mole of component.
[2]
The heat conductive silicone composition according to [1], wherein the component (F) is selected from 1,2,3-triazole, 1,2,4-triazole and derivatives thereof.
[3]
(F) The heat conductive silicone composition as described in [2] whose component is benzotriazole.
[4]
The thermally conductive silicone composition according to any one of [1] to [3], wherein the component (G) is selected from alkyl isocyanate compounds, aryl isocyanate compounds and isocyanate silane compounds.
[5]
The component (G) is represented by the following formula (2)
(Wherein R 2 represents an alkyl group or a trialkylsilyl group, and b represents an integer of 1 to 6)
[4] The heat conductive silicone composition according to [4].
[6]
Furthermore, (H) a reaction control agent selected from acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds and organic chloro compounds: an amount of 0.1 to 5% by mass based on component (A) [1 ]-The heat conductive silicone composition in any one of [5].
〔１〕
（Ａ）１分子中に少なくとも２個のアルケニル基を有する、２５℃の動粘度が１０～１００，０００ｍｍ2／ｓのオルガノポリシロキサン
（Ｂ）下記一般式（１）
（式中、Ｒ1は炭素数１～６のアルキル基であり、ａは５～１００の正数である。）
で表される片末端３官能の加水分解性メチルポリシロキサン：（Ａ）成分１００質量部に対して１０～１５０質量部
（Ｃ）１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材：（Ａ）成分と（Ｂ）成分の合計１００質量部に対して５００～３，０００質量部
（Ｄ）１分子中に少なくとも２個のケイ素原子に直結した水素原子を含有するオルガノハイドロジェンポリシロキサン：｛（Ｄ）成分のＳｉ－Ｈ基の個数｝／｛（Ａ）成分のアルケニル基の個数｝が０．５～１．５になる量
（Ｅ）白金及び白金化合物からなる群より選択される触媒：白金原子として（Ａ）成分の質量に対して０．１～５００ｐｐｍとなる量
（Ｆ）トリアゾール系化合物：（Ｅ）成分の白金原子１モルに対して２～１，０００モル
（Ｇ）イソシアネート系化合物：（Ｆ）成分のトリアゾール系化合物１モルに対して０．１～１０モル
を含有する熱伝導性シリコーン組成物。
〔２〕
（Ｆ）成分が、１，２，３－トリアゾール、１，２，４－トリアゾール及びこれらの誘導体から選ばれるものである〔１〕に記載の熱伝導性シリコーン組成物。
〔３〕
（Ｆ）成分が、ベンゾトリアゾールである〔２〕に記載の熱伝導性シリコーン組成物。
〔４〕
（Ｇ）成分が、アルキルイソシアネート系化合物、アリールイソシアネート系化合物及びイソシアネートシラン系化合物から選ばれるものである〔１〕～〔３〕のいずれかに記載の熱伝導性シリコーン組成物。
〔５〕
（Ｇ）成分が、下記式（２）
で示される化合物である〔４〕に記載の熱伝導性シリコーン組成物。
〔６〕
更に、（Ｈ）アセチレン化合物、窒素化合物、有機りん化合物、オキシム化合物及び有機クロロ化合物より選択される反応制御剤：（Ａ）成分に対して０．１～５質量％となる量
を含む〔１〕～〔５〕のいずれかに記載の熱伝導性シリコーン組成物。 Accordingly, the present invention provides the following thermally conductive silicone composition.
[1]
(A) Organopolysiloxane having at least two alkenyl groups in one molecule and a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s (B) The following general formula (1)
(In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, and a is a positive number having 5 to 100.)
One-terminal trifunctional hydrolyzable methylpolysiloxane represented by: (A) 10 to 150 parts by mass with respect to 100 parts by mass of component (C) Thermally conductive filling having a thermal conductivity of 10 W / m · ° C. or more Material: 500 to 3,000 parts by mass with respect to a total of 100 parts by mass of component (A) and component (B) (D) Organohydrogen containing hydrogen atoms directly bonded to at least two silicon atoms in one molecule Polysiloxane: {Equivalent number of Si-H groups in component (D)} / {Number of alkenyl groups in component (A)} is 0.5 to 1.5 (E) From the group consisting of platinum and platinum compounds Catalyst selected: An amount of 0.1 to 500 ppm as platinum atom based on the mass of component (A) (F) Triazole compound: 2 to 1,000 mol per mol of platinum atom of component (E) (G) Isocyanate compound: ( ) Heat conductive silicone composition containing 0.1 to 10 mol relative to triazole compound 1 mole of component.
[2]
The heat conductive silicone composition according to [1], wherein the component (F) is selected from 1,2,3-triazole, 1,2,4-triazole and derivatives thereof.
[3]
(F) The heat conductive silicone composition as described in [2] whose component is benzotriazole.
[4]
The thermally conductive silicone composition according to any one of [1] to [3], wherein the component (G) is selected from alkyl isocyanate compounds, aryl isocyanate compounds and isocyanate silane compounds.
[5]
The component (G) is represented by the following formula (2)
[4] The heat conductive silicone composition according to [4].
[6]
Furthermore, (H) a reaction control agent selected from acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds and organic chloro compounds: an amount of 0.1 to 5% by mass based on component (A) [1 ]-The heat conductive silicone composition in any one of [5].
本発明の熱伝導性シリコーン組成物は、トリアゾール系化合物とイソシアネート系化合物をそれぞれ特定量配合することにより、硬化物の高温エージング時の硬度上昇を抑制し、かつ硬化速度の低下を抑制することができる。
The thermally conductive silicone composition of the present invention can suppress the increase in hardness during high-temperature aging of the cured product and suppress the decrease in the curing rate by blending specific amounts of triazole compound and isocyanate compound, respectively. it can.
［（Ａ）成分］
本発明を構成する（Ａ）成分のオルガノポリシロキサンは、ケイ素原子に直結したアルケニル基を１分子中に少なくとも２個、好ましくは２～１０個、より好ましくは２～５個有するもので、直鎖状でも分岐状でもよく、またこれら２種以上の異なる粘度の混合物でもよい。 [(A) component]
The organopolysiloxane of component (A) constituting the present invention has at least 2, preferably 2 to 10, more preferably 2 to 5, alkenyl groups directly bonded to silicon atoms in one molecule. The chain may be branched or branched, and a mixture of two or more different viscosities may be used.
本発明を構成する（Ａ）成分のオルガノポリシロキサンは、ケイ素原子に直結したアルケニル基を１分子中に少なくとも２個、好ましくは２～１０個、より好ましくは２～５個有するもので、直鎖状でも分岐状でもよく、またこれら２種以上の異なる粘度の混合物でもよい。 [(A) component]
The organopolysiloxane of component (A) constituting the present invention has at least 2, preferably 2 to 10, more preferably 2 to 5, alkenyl groups directly bonded to silicon atoms in one molecule. The chain may be branched or branched, and a mixture of two or more different viscosities may be used.
アルケニル基としては、ビニル基、アリル基、１－ブテニル基、１－ヘキセニル基等の炭素数２～６のものが例示されるが、合成のし易さ、コストの面からビニル基が好ましい。
ケイ素原子に結合する残余の有機基としては、非置換又は置換の炭素数１～１２、特に炭素数１～６の脂肪族不飽和結合を含まない一価炭化水素基であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ドデシル基等のアルキル基、フェニル基等のアリール基、２－フェニルエチル基、２－フェニルプロピル基等のアラルキル基などが例示され、更にクロロメチル基、３，３，３－トリフルオロプロピル基等のハロゲン置換炭化水素基なども例として挙げられる。これらのうち、合成のし易さ、コストの面からメチル基が好ましい。
ケイ素原子に結合するアルケニル基は、オルガノポリシロキサンの分子鎖の末端、途中のいずれに存在してもよいが、少なくとも末端に存在することが好ましい。 Examples of the alkenyl group include those having 2 to 6 carbon atoms such as a vinyl group, an allyl group, a 1-butenyl group, and a 1-hexenyl group, but a vinyl group is preferable from the viewpoint of ease of synthesis and cost.
The remaining organic group bonded to the silicon atom is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and dodecyl group, aryl groups such as phenyl group, aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group, etc. Examples thereof include halogen-substituted hydrocarbon groups such as chloromethyl group and 3,3,3-trifluoropropyl group. Of these, a methyl group is preferred from the viewpoint of ease of synthesis and cost.
The alkenyl group bonded to the silicon atom may be present at either the terminal or the middle of the molecular chain of the organopolysiloxane, but is preferably present at least at the terminal.
ケイ素原子に結合する残余の有機基としては、非置換又は置換の炭素数１～１２、特に炭素数１～６の脂肪族不飽和結合を含まない一価炭化水素基であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ドデシル基等のアルキル基、フェニル基等のアリール基、２－フェニルエチル基、２－フェニルプロピル基等のアラルキル基などが例示され、更にクロロメチル基、３，３，３－トリフルオロプロピル基等のハロゲン置換炭化水素基なども例として挙げられる。これらのうち、合成のし易さ、コストの面からメチル基が好ましい。
ケイ素原子に結合するアルケニル基は、オルガノポリシロキサンの分子鎖の末端、途中のいずれに存在してもよいが、少なくとも末端に存在することが好ましい。 Examples of the alkenyl group include those having 2 to 6 carbon atoms such as a vinyl group, an allyl group, a 1-butenyl group, and a 1-hexenyl group, but a vinyl group is preferable from the viewpoint of ease of synthesis and cost.
The remaining organic group bonded to the silicon atom is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and dodecyl group, aryl groups such as phenyl group, aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group, etc. Examples thereof include halogen-substituted hydrocarbon groups such as chloromethyl group and 3,3,3-trifluoropropyl group. Of these, a methyl group is preferred from the viewpoint of ease of synthesis and cost.
The alkenyl group bonded to the silicon atom may be present at either the terminal or the middle of the molecular chain of the organopolysiloxane, but is preferably present at least at the terminal.
（Ａ）成分のオストワルド計により測定した２５℃における動粘度は、１０～１００，０００ｍｍ2／ｓの範囲であり、好ましくは１００～５０，０００ｍｍ2／ｓの範囲であり、更に好ましくは１００～１，０００ｍｍ2／ｓがよい。動粘度が１０ｍｍ2／ｓ未満であると組成物のオイルブリードがひどくなり信頼性が悪くなるし、１００，０００ｍｍ2／ｓを超えると組成物の粘度が上昇し、伸展性の乏しいものになる。
The kinematic viscosity of the component (A) measured at 25 ° C. with an Ostwald meter is in the range of 10 to 100,000 mm 2 / s, preferably in the range of 100 to 50,000 mm 2 / s, and more preferably in the range of 100 to 1,000 mm 2 / s is preferable. If the kinematic viscosity is less than 10 mm 2 / s, the oil bleed of the composition will be severe and the reliability will be poor, and if it exceeds 100,000 mm 2 / s, the viscosity of the composition will increase and the extensibility will be poor. .
（Ａ）成分としては、例えば、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、分子鎖片末端がジメチルビニルシロキシ基で封鎖され分子鎖の他方の末端がトリメチルシロキシ基で封鎖されたジメチルポリシロキサン・メチルビニルポリシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体などが挙げられるが、これらに限定されるものではなく、またこれらのうち２種類以上を混合して用いてもよい。
As the component (A), for example, dimethylpolysiloxane blocked with a dimethylvinylsiloxy group blocked at both ends of the molecular chain, and one end of the molecular chain blocked with a dimethylvinylsiloxy group and the other end of the molecular chain blocked with a trimethylsiloxy group Siloxane / methylvinylpolysiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked Examples thereof include, but are not limited to, a dimethylsiloxane / methylvinylsiloxane copolymer, and two or more of these may be used in combination.
［（Ｂ）成分］
（Ｂ）成分は、下記一般式（１）
（式中、Ｒ1は炭素数１～６のメチル基、エチル基、プロピル基、ブチル基、ヘキシル基等のアルキル基であり、ａは５～１００の正数である。）
で表される片末端３官能の加水分解性メチルポリシロキサンである。 [Component (B)]
The component (B) has the following general formula (1)
(Wherein R 1 is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group, and a is a positive number of 5 to 100.)
Is a one-terminal trifunctional hydrolyzable methylpolysiloxane.
（Ｂ）成分は、下記一般式（１）
で表される片末端３官能の加水分解性メチルポリシロキサンである。 [Component (B)]
The component (B) has the following general formula (1)
Is a one-terminal trifunctional hydrolyzable methylpolysiloxane.
（Ｂ）成分の一般式（１）で表される片末端３官能の加水分解性メチルポリシロキサンのａは、５より小さいと組成物のオイルブリードがひどくなり信頼性が悪くなるし、１００より大きいと濡れ性が十分でないため、５～１００の正数であり、好ましくは１０～６０の正数の範囲がよい。
If (a) of the one-terminal trifunctional hydrolyzable methylpolysiloxane represented by the general formula (1) of the component (B) is less than 5, the oil bleed of the composition becomes so bad that the reliability becomes worse. If it is large, the wettability is not sufficient, so it is a positive number of 5 to 100, preferably in the range of 10 to 60.
この片末端３官能の加水分解性メチルポリシロキサンの添加量は、（Ａ）成分１００質量部に対して１０質量部より少ないと十分な濡れ性を発揮できないし、１５０質量部より多いとオイルブリードが激しくなり信頼性が悪くなるため、１０～１５０質量部であり、好ましくは２０～１４０質量部の範囲がよい。
If the addition amount of this one-terminal trifunctional hydrolyzable methylpolysiloxane is less than 10 parts by mass with respect to 100 parts by mass of component (A), sufficient wettability cannot be exhibited, and if more than 150 parts by mass, oil bleed Is in the range of 10 to 150 parts by mass, preferably 20 to 140 parts by mass.
［（Ｃ）成分］
（Ｃ）成分は、１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材である。
（Ｃ）成分の熱伝導性充填材としては、熱伝導率が１０Ｗ／ｍ・℃以上、好ましくは１５Ｗ／ｍ・℃以上のものが使用される。充填材のもつ熱伝導率が１０Ｗ／ｍ・℃より小さいと、熱伝導性シリコーン組成物の熱伝導率そのものが小さくなるためである。かかる熱伝導性充填材としては、アルミニウム粉末、銅粉末、銀粉末、鉄粉末、ニッケル粉末、金粉末、錫粉末、金属ケイ素粉末、窒化アルミニウム粉末、窒化ホウ素粉末、アルミナ粉末、ダイヤモンド粉末、カーボン粉末、インジウム粉末、ガリウム粉末、酸化亜鉛粉末などが挙げられるが、１０Ｗ／ｍ・℃以上を有する充填材であれば如何なる充填材でもよく、１種類あるいは２種類以上を混ぜ合わせたものでもよい。 [Component (C)]
The component (C) is a thermally conductive filler having a thermal conductivity of 10 W / m · ° C. or higher.
As the thermally conductive filler of component (C), those having a thermal conductivity of 10 W / m · ° C. or higher, preferably 15 W / m · ° C. or higher are used. This is because if the thermal conductivity of the filler is less than 10 W / m · ° C., the thermal conductivity of the thermally conductive silicone composition itself becomes small. Such heat conductive fillers include aluminum powder, copper powder, silver powder, iron powder, nickel powder, gold powder, tin powder, metal silicon powder, aluminum nitride powder, boron nitride powder, alumina powder, diamond powder, carbon powder. Indium powder, gallium powder, zinc oxide powder, etc., any filler may be used as long as it is 10 W / m · ° C. or more, and one or a mixture of two or more may be used.
（Ｃ）成分は、１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材である。
（Ｃ）成分の熱伝導性充填材としては、熱伝導率が１０Ｗ／ｍ・℃以上、好ましくは１５Ｗ／ｍ・℃以上のものが使用される。充填材のもつ熱伝導率が１０Ｗ／ｍ・℃より小さいと、熱伝導性シリコーン組成物の熱伝導率そのものが小さくなるためである。かかる熱伝導性充填材としては、アルミニウム粉末、銅粉末、銀粉末、鉄粉末、ニッケル粉末、金粉末、錫粉末、金属ケイ素粉末、窒化アルミニウム粉末、窒化ホウ素粉末、アルミナ粉末、ダイヤモンド粉末、カーボン粉末、インジウム粉末、ガリウム粉末、酸化亜鉛粉末などが挙げられるが、１０Ｗ／ｍ・℃以上を有する充填材であれば如何なる充填材でもよく、１種類あるいは２種類以上を混ぜ合わせたものでもよい。 [Component (C)]
The component (C) is a thermally conductive filler having a thermal conductivity of 10 W / m · ° C. or higher.
As the thermally conductive filler of component (C), those having a thermal conductivity of 10 W / m · ° C. or higher, preferably 15 W / m · ° C. or higher are used. This is because if the thermal conductivity of the filler is less than 10 W / m · ° C., the thermal conductivity of the thermally conductive silicone composition itself becomes small. Such heat conductive fillers include aluminum powder, copper powder, silver powder, iron powder, nickel powder, gold powder, tin powder, metal silicon powder, aluminum nitride powder, boron nitride powder, alumina powder, diamond powder, carbon powder. Indium powder, gallium powder, zinc oxide powder, etc., any filler may be used as long as it is 10 W / m · ° C. or more, and one or a mixture of two or more may be used.
（Ｃ）成分の平均粒径は０．１～１００μｍの範囲が好ましく、より好ましくは０．１～９０μｍの範囲であり、更に好ましくは０．１～２０μｍの範囲がよい。該平均粒径が０．１μｍより小さいと得られる組成物がグリース状にならず伸展性に乏しいものになる場合があり、１００μｍより大きいと放熱グリースの熱抵抗が大きくなってしまい性能が低下する場合があるためである。なお、本発明において、平均粒径は日機装（株）製マイクロトラックＭＴ３３０ＯＥＸにより測定でき、体積基準の体積平均径である。
（Ｃ）成分の形状は、不定形でも球形でも如何なる形状でもよい。 The average particle size of the component (C) is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.1 to 90 μm, and still more preferably in the range of 0.1 to 20 μm. If the average particle size is less than 0.1 μm, the resulting composition may not be in the form of grease and may have poor extensibility. If the average particle size is greater than 100 μm, the thermal resistance of the heat dissipating grease will increase and the performance will deteriorate. This is because there are cases. In the present invention, the average particle diameter can be measured by Nikkiso Co., Ltd. Microtrac MT330OEX, and is a volume-based volume average diameter.
The shape of the component (C) may be indefinite, spherical, or any shape.
（Ｃ）成分の形状は、不定形でも球形でも如何なる形状でもよい。 The average particle size of the component (C) is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.1 to 90 μm, and still more preferably in the range of 0.1 to 20 μm. If the average particle size is less than 0.1 μm, the resulting composition may not be in the form of grease and may have poor extensibility. If the average particle size is greater than 100 μm, the thermal resistance of the heat dissipating grease will increase and the performance will deteriorate. This is because there are cases. In the present invention, the average particle diameter can be measured by Nikkiso Co., Ltd. Microtrac MT330OEX, and is a volume-based volume average diameter.
The shape of the component (C) may be indefinite, spherical, or any shape.
（Ｃ）成分の充填量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して５００質量部より少ないと組成物の熱伝導率が低くなってしまうし、３，０００質量部より多いと組成物の粘度が上昇し、伸展性の乏しいものになるため、５００～３，０００質量部の範囲であり、好ましくは５００～２，８００質量部の範囲がよく、より好ましくは５００～２，５００質量部の範囲がよい。
When the amount of the (C) component is less than 500 parts by mass with respect to 100 parts by mass of the total of the (A) component and the (B) component, the thermal conductivity of the composition becomes low and 3,000 parts by mass. If it is more, the viscosity of the composition increases and the extensibility becomes poor. Therefore, it is in the range of 500 to 3,000 parts by mass, preferably in the range of 500 to 2,800 parts by mass, more preferably 500 A range of ˜2,500 parts by mass is preferable.
［（Ｄ）成分］
（Ｄ）成分のオルガノハイドロジェンポリシロキサンは、架橋により組成を網状化するためにケイ素原子に直結した水素原子（Ｓｉ－Ｈ基）を１分子中に少なくとも２個、好ましくは２～５０個、より好ましくは２～３０個有することが必要である。なお、このＳｉ－Ｈ基は、分子鎖末端、分子鎖の途中のいずれに位置していてもよく、両方に位置するものであってもよい。 [(D) component]
The organohydrogenpolysiloxane of component (D) has at least two, preferably 2 to 50, hydrogen atoms (Si—H groups) directly linked to silicon atoms in order to reticulate the composition by crosslinking. More preferably, it is necessary to have 2 to 30. The Si—H group may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both.
（Ｄ）成分のオルガノハイドロジェンポリシロキサンは、架橋により組成を網状化するためにケイ素原子に直結した水素原子（Ｓｉ－Ｈ基）を１分子中に少なくとも２個、好ましくは２～５０個、より好ましくは２～３０個有することが必要である。なお、このＳｉ－Ｈ基は、分子鎖末端、分子鎖の途中のいずれに位置していてもよく、両方に位置するものであってもよい。 [(D) component]
The organohydrogenpolysiloxane of component (D) has at least two, preferably 2 to 50, hydrogen atoms (Si—H groups) directly linked to silicon atoms in order to reticulate the composition by crosslinking. More preferably, it is necessary to have 2 to 30. The Si—H group may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both.
ケイ素原子に結合するＳｉ－Ｈ基以外の残余の有機基としては、非置換又は置換の炭素数１～１２、特に炭素数１～６の脂肪族不飽和結合を含まない一価炭化水素基であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ドデシル基等のアルキル基、フェニル基等のアリール基、２－フェニルエチル基、２－フェニルプロピル基等のアラルキル基、クロロメチル基、３，３，３－トリフルオロプロピル基等のハロゲン置換炭化水素基などが挙げられ、また２－グリシドキシエチル基、３－グリシドキシプロピル基、４－グリシドキシブチル基等のエポキシ置換炭化水素基なども例として挙げられる。
The remaining organic group other than the Si—H group bonded to the silicon atom is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a dodecyl group, an aryl group such as a phenyl group, a 2-phenylethyl group, or a 2-phenylpropyl group And halogen-substituted hydrocarbon groups such as aralkyl group, chloromethyl group, 3,3,3-trifluoropropyl group, etc., and 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4- Examples include epoxy-substituted hydrocarbon groups such as glycidoxybutyl groups.
かかるＳｉ－Ｈ基を有するオルガノハイドロジェンポリシロキサンは、直鎖状、分岐状及び環状のいずれであってもよく、またこれらの混合物であってもよい。なお、オルガノハイドロジェンポリシロキサン中のケイ素原子数は、１０～２５０個、特に１０～２００個であることが好ましい。
このオルガノハイドロジェンポリシロキサンは、１種単独で用いても、２種以上を組み合わせて用いてもよい。 Such an organohydrogenpolysiloxane having a Si—H group may be linear, branched or cyclic, or a mixture thereof. The number of silicon atoms in the organohydrogenpolysiloxane is preferably 10 to 250, particularly 10 to 200.
This organohydrogenpolysiloxane may be used alone or in combination of two or more.
このオルガノハイドロジェンポリシロキサンは、１種単独で用いても、２種以上を組み合わせて用いてもよい。 Such an organohydrogenpolysiloxane having a Si—H group may be linear, branched or cyclic, or a mixture thereof. The number of silicon atoms in the organohydrogenpolysiloxane is preferably 10 to 250, particularly 10 to 200.
This organohydrogenpolysiloxane may be used alone or in combination of two or more.
（Ｄ）成分としては、例えば、（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）2ＳｉＯ単位からなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）3ＳｉＯ1/2単位と（ＣＨ3）2ＳｉＯ単位からなる共重合体、（ＣＨ3）3ＳｉＯ1/2単位と（ＣＨ3）2ＳｉＯ単位と（ＣＨ3）ＨＳｉＯ単位からなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）3ＳｉＯ1/2単位と（ＣＨ3）2ＳｉＯ単位と（ＣＨ3）ＨＳｉＯ単位からなる共重合体、（ＣＨ3）3ＳｉＯ1/2単位と（ＣＨ3）ＨＳｉＯ単位からなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）2ＳｉＯ単位と（ＣＨ3）ＨＳｉＯ単位からなる共重合体、（ＣＨ3）3ＳｉＯ1/2単位と（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）ＨＳｉＯ単位からなる共重合体、（ＣＨ3）ＨＳｉＯ単位からなる環状共重合体、（ＣＨ3）ＨＳｉＯ単位と（ＣＨ3）2ＳｉＯ単位からなる環状共重合体などが挙げられるが、これらに限定されるものではない。
Examples of the component (D) include a copolymer comprising (CH 3 ) 2 HSiO 1/2 units and (CH 3 ) 2 SiO units, (CH 3 ) 2 HSiO 1/2 units and (CH 3 ) 3 SiO. A copolymer comprising 1/2 units and (CH 3 ) 2 SiO units, a copolymer comprising (CH 3 ) 3 SiO 1/2 units, (CH 3 ) 2 SiO units and (CH 3 ) HSiO units, A copolymer comprising (CH 3 ) 2 HSiO 1/2 units, (CH 3 ) 3 SiO 1/2 units, (CH 3 ) 2 SiO units and (CH 3 ) HSiO units, (CH 3 ) 3 SiO 1/2 A copolymer comprising units and (CH 3 ) HSiO units, a copolymer comprising (CH 3 ) 2 HSiO 1/2 units, (CH 3 ) 2 SiO units and (CH 3 ) HSiO units, (CH 3 ) 3 A copolymer comprising SiO 1/2 units, (CH 3 ) 2 HSiO 1/2 units and (CH 3 ) HSiO units, (CH 3 ) Examples thereof include, but are not limited to, cyclic copolymers composed of HSiO units, cyclic copolymers composed of (CH 3 ) HSiO units and (CH 3 ) 2 SiO units.
（Ｄ）成分の配合量は、｛（Ｄ）成分のＳｉ－Ｈ基の個数｝／｛（Ａ）成分のアルケニル基の個数｝が０．５より小さいと十分に組成を網状化できないためグリースがポンプアウトしてしまうし、１．５より大きいと架橋密度が高くなりすぎてしまい信頼性試験中に剥離してしまうため、０．５～１．５の範囲であり、好ましくは０．７～１．３の範囲がよい。
The blending amount of the component (D) is such that the composition cannot be reticulated sufficiently if the {number of Si—H groups in the component (D)} / {number of alkenyl groups in the component (A)} is less than 0.5. Is pumped out, and if it is larger than 1.5, the crosslinking density becomes too high and peels off during the reliability test, so the range is 0.5 to 1.5, preferably 0.7. A range of ~ 1.3 is good.
［（Ｅ）成分］
（Ｅ）成分の白金及び白金化合物から選択される触媒は、（Ａ）成分中のアルケニル基と（Ｄ）成分中のＳｉ－Ｈ基との間の付加反応の促進成分である。この（Ｅ）成分は、例えば、白金の単体、塩化白金酸、白金－オレフィン錯体、白金－アルコール錯体、白金配位化合物などが挙げられる。 [(E) component]
The catalyst selected from platinum and platinum compounds as the component (E) is a component for promoting the addition reaction between the alkenyl group in the component (A) and the Si—H group in the component (D). Examples of the component (E) include platinum alone, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum coordination compounds, and the like.
（Ｅ）成分の白金及び白金化合物から選択される触媒は、（Ａ）成分中のアルケニル基と（Ｄ）成分中のＳｉ－Ｈ基との間の付加反応の促進成分である。この（Ｅ）成分は、例えば、白金の単体、塩化白金酸、白金－オレフィン錯体、白金－アルコール錯体、白金配位化合物などが挙げられる。 [(E) component]
The catalyst selected from platinum and platinum compounds as the component (E) is a component for promoting the addition reaction between the alkenyl group in the component (A) and the Si—H group in the component (D). Examples of the component (E) include platinum alone, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum coordination compounds, and the like.
（Ｅ）成分の配合量は、（Ａ）成分の質量に対し、白金原子として０．１ｐｐｍより少ないと触媒としての効果がなく、５００ｐｐｍを超えても効果が増大することがなく、不経済であるので、０．１～５００ｐｐｍの範囲であり、好ましくは０．１～４００ｐｐｍである。
The amount of component (E) is less than 0.1 ppm as platinum atoms with respect to the mass of component (A), and there is no effect as a catalyst. Therefore, it is in the range of 0.1 to 500 ppm, preferably 0.1 to 400 ppm.
［（Ｆ）成分］
（Ｆ）成分のトリアゾール系化合物は、後述する（Ｇ）成分と共に、組成物中に特定の配合量で添加することによって熱伝導性シリコーン組成物の硬化速度の低下を抑制すると共に、硬化後の高温エージング時の硬度上昇を抑制することができる。 [(F) component]
The (F) component triazole compound, together with the component (G) described later, is added to the composition at a specific blending amount to suppress a decrease in the curing rate of the thermally conductive silicone composition, and after curing. The increase in hardness during high temperature aging can be suppressed.
（Ｆ）成分のトリアゾール系化合物は、後述する（Ｇ）成分と共に、組成物中に特定の配合量で添加することによって熱伝導性シリコーン組成物の硬化速度の低下を抑制すると共に、硬化後の高温エージング時の硬度上昇を抑制することができる。 [(F) component]
The (F) component triazole compound, together with the component (G) described later, is added to the composition at a specific blending amount to suppress a decrease in the curing rate of the thermally conductive silicone composition, and after curing. The increase in hardness during high temperature aging can be suppressed.
（Ｆ）成分のトリアゾール系化合物としては、例えば、１，２，３－トリアゾール、１，２，４－トリアゾール及びこれらの誘導体が挙げられる。具体的に、１，２，３－トリアゾールの誘導体としては、ベンゾトリアゾール、４－ヒドロキシ－１，２，３－トリアゾール、１，２，３－トリアゾール－４－アルデヒド、４－シアノ－１，２，３－トリアゾールなどが挙げられる。１，２，４－トリアゾールの誘導体としては、５－アミノ－３－メチル－１，２，４－トリアゾール、３－メルカプト－１，２，４－トリアゾールなどが挙げられる。これらのうち好適なものは、ベンゾトリアゾール、１，２，３－トリアゾール、１，２，４－トリアゾールであり、最も好適なものはベンゾトリアゾールである。これらは１種単独で使用しても、２種以上を併用してもよい。
Examples of the (F) component triazole-based compound include 1,2,3-triazole, 1,2,4-triazole, and derivatives thereof. Specifically, the derivatives of 1,2,3-triazole include benzotriazole, 4-hydroxy-1,2,3-triazole, 1,2,3-triazole-4-aldehyde, 4-cyano-1,2 , 3-triazole and the like. Examples of the 1,2,4-triazole derivatives include 5-amino-3-methyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole and the like. Among these, preferred are benzotriazole, 1,2,3-triazole, and 1,2,4-triazole, and most preferred is benzotriazole. These may be used alone or in combination of two or more.
この成分（Ｆ）の配合量は、（Ｅ）成分の白金原子１モルに対し、２～１，０００モルであり、好ましくは２～８００モル、より好ましくは２～５００モルである。配合量が２モルより少ないと十分に硬度上昇を抑制することができず、１，０００モルより多いと、硬化速度が遅くなってしまう。
The compounding amount of component (F) is 2 to 1,000 mol, preferably 2 to 800 mol, more preferably 2 to 500 mol, per 1 mol of platinum atom in component (E). If the blending amount is less than 2 mol, the increase in hardness cannot be sufficiently suppressed, and if it is more than 1,000 mol, the curing rate becomes slow.
［（Ｇ）成分］
（Ｇ）成分のイソシアネート系化合物は、前記（Ｆ）成分と共に、組成物中に特定の配合量で併用添加することによって熱伝導性シリコーン組成物の硬化速度の低下を抑制すると共に、硬化後の高温エージング時の硬度上昇を抑制することができる。 [(G) component]
The isocyanate-based compound of component (G), together with the component (F), suppresses a decrease in the curing rate of the thermally conductive silicone composition by being added to the composition at a specific blending amount, and after curing. The increase in hardness during high temperature aging can be suppressed.
（Ｇ）成分のイソシアネート系化合物は、前記（Ｆ）成分と共に、組成物中に特定の配合量で併用添加することによって熱伝導性シリコーン組成物の硬化速度の低下を抑制すると共に、硬化後の高温エージング時の硬度上昇を抑制することができる。 [(G) component]
The isocyanate-based compound of component (G), together with the component (F), suppresses a decrease in the curing rate of the thermally conductive silicone composition by being added to the composition at a specific blending amount, and after curing. The increase in hardness during high temperature aging can be suppressed.
（Ｇ）成分のイソシアネート系化合物としては、例えば、メチルイソシアネート、ブチルイソシアネート、オクチルイソシアネート等のアルキルイソシアネート系化合物、フェニルイソシアネート、トリルイソシアネート等のアリールイソシアネート系化合物、更に、例えば、下記一般式（２）で示されるような、イソシアネート基及びシリル基を含有するイソシアネートシラン系化合物などが挙げられる。
（式中、Ｒ2はアルキル基又はトリアルキルシリル基であり、ｂは１～６の整数である。）
Examples of the isocyanate compound as component (G) include alkyl isocyanate compounds such as methyl isocyanate, butyl isocyanate and octyl isocyanate, aryl isocyanate compounds such as phenyl isocyanate and tolyl isocyanate, and further, for example, the following general formula (2) And an isocyanate silane compound containing an isocyanate group and a silyl group, as shown in FIG.
(Wherein R 2 represents an alkyl group or a trialkylsilyl group, and b represents an integer of 1 to 6)
この場合、Ｒ2のアルキル基としては、炭素数１～４のもの、特にメチル基、エチル基が好ましく、トリアルキルシリル基のアルキル基も炭素数１～４のもの、特にメチル基、エチル基が好ましく、トリメチルシリル基、トリエチルシリル基が好ましい。
In this case, the alkyl group represented by R 2 is preferably one having 1 to 4 carbon atoms, particularly a methyl group or ethyl group, and the alkyl group of the trialkylsilyl group is also one having 1 to 4 carbon atoms, particularly a methyl group or ethyl group. Are preferable, and a trimethylsilyl group and a triethylsilyl group are preferable.
これらのうち、最も好適なものはオクチルイソシアネート、３－イソシアネートプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、３－イソシアネートプロピルトリス（トリメチルシロキシ）シランである。これらは１種単独でも２種以上を併用してもよい。
Of these, octyl isocyanate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyltris (trimethylsiloxy) silane are most preferred. These may be used alone or in combination of two or more.
この（Ｇ）成分の配合量は、（Ｆ）成分１モルに対し、０．１～１０モルであり、好ましくは０．５～５モル、より好ましくは０．５～２モルである。配合量が０．１モルより少ないと硬化速度が低下してしまうし、１０モルより多いとエージング後の硬度上昇を十分に抑制することができなくなる。
The amount of component (G) is 0.1 to 10 moles, preferably 0.5 to 5 moles, and more preferably 0.5 to 2 moles per mole of component (F). If the blending amount is less than 0.1 mol, the curing rate decreases, and if it exceeds 10 mol, the hardness increase after aging cannot be sufficiently suppressed.
［（Ｈ）成分］
本発明の熱伝導性シリコーン組成物には、更に（Ｈ）成分として、（Ｅ）成分の触媒活性を抑制する目的で反応制御剤を配合することができる。（Ｈ）成分の反応制御剤は、室温でのヒドロシリル化反応の進行を抑え、シェルフライフ、ポットライフを延長させるものである。反応制御剤としては公知のものを使用することができ、アセチレン化合物、各種窒素化合物、有機りん化合物、オキシム化合物、有機クロロ化合物等が利用できる。 [(H) component]
In the thermally conductive silicone composition of the present invention, a reaction control agent can be further blended as the component (H) for the purpose of suppressing the catalytic activity of the component (E). The reaction control agent of component (H) suppresses the progress of the hydrosilylation reaction at room temperature and extends shelf life and pot life. Known reaction control agents can be used, and acetylene compounds, various nitrogen compounds, organic phosphorus compounds, oxime compounds, organic chloro compounds, and the like can be used.
本発明の熱伝導性シリコーン組成物には、更に（Ｈ）成分として、（Ｅ）成分の触媒活性を抑制する目的で反応制御剤を配合することができる。（Ｈ）成分の反応制御剤は、室温でのヒドロシリル化反応の進行を抑え、シェルフライフ、ポットライフを延長させるものである。反応制御剤としては公知のものを使用することができ、アセチレン化合物、各種窒素化合物、有機りん化合物、オキシム化合物、有機クロロ化合物等が利用できる。 [(H) component]
In the thermally conductive silicone composition of the present invention, a reaction control agent can be further blended as the component (H) for the purpose of suppressing the catalytic activity of the component (E). The reaction control agent of component (H) suppresses the progress of the hydrosilylation reaction at room temperature and extends shelf life and pot life. Known reaction control agents can be used, and acetylene compounds, various nitrogen compounds, organic phosphorus compounds, oxime compounds, organic chloro compounds, and the like can be used.
（Ｈ）成分を配合する場合の配合量は、（Ａ）成分に対して０．１質量％より小さいと十分なシェルフライフ、ポットライフが得られない場合があり、５質量％より大きいと硬化速度が低下する場合があるため、０．１～５質量％の範囲が好ましく、特には０．１～４質量％の範囲が好ましい。これらは熱伝導性シリコーン組成物への分散性を良くするためにトルエン等の溶剤で希釈して使用してもよい。
When the blending amount of the component (H) is less than 0.1% by mass relative to the component (A), sufficient shelf life and pot life may not be obtained. Since the speed may decrease, the range of 0.1 to 5% by mass is preferable, and the range of 0.1 to 4% by mass is particularly preferable. These may be used by diluting with a solvent such as toluene in order to improve dispersibility in the heat conductive silicone composition.
また、本発明の熱伝導性シリコーン組成物には、上記した（Ａ）～（Ｈ）成分以外に必要に応じて、劣化を防ぐために酸化防止剤等を入れてもよい。
In addition to the components (A) to (H) described above, an antioxidant or the like may be added to the thermally conductive silicone composition of the present invention as necessary in order to prevent deterioration.
本発明の熱伝導性シリコーン組成物を製造するには、（Ａ）～（Ｈ）成分をトリミックス、ツウィンミックス、プラネタリミキサー（いずれも（株）井上製作所製混合機の登録商標）、ウルトラミキサー（みずほ工業（株）製混合機の登録商標）、ハイビスディスパーミックス（特殊機化工業（株）製混合機の登録商標）等の混合機にて混合することにより製造することができる。
In order to produce the heat conductive silicone composition of the present invention, the components (A) to (H) are trimix, twin mix, planetary mixer (all are registered trademarks of a mixer manufactured by Inoue Seisakusho Co., Ltd.), ultra mixer It can be produced by mixing with a mixer such as (registered trademark of Mizuho Kogyo Co., Ltd.), Hibis Disper Mix (registered trademark of Special Kikai Kogyo Co., Ltd.).
得られた熱伝導性シリコーン組成物の回転粘度計により測定した２５℃における絶対粘度は、５～２，０００Ｐａ・ｓ、特に１０～９００Ｐａ・ｓであることが好ましい。
The absolute viscosity at 25 ° C. of the obtained heat conductive silicone composition measured with a rotational viscometer is preferably 5 to 2,000 Pa · s, particularly 10 to 900 Pa · s.
また、得られた熱伝導性シリコーン組成物は、８０～１８０℃、特に９０～１７０℃にて３０～１５０分間、特に３０～１４０分間加熱することにより硬化物とすることができる。
The obtained heat conductive silicone composition can be made into a cured product by heating at 80 to 180 ° C., particularly 90 to 170 ° C. for 30 to 150 minutes, particularly 30 to 140 minutes.
本発明の熱伝導性シリコーン組成物は、硬化速度の低下を抑制することができ、該組成物の硬化物は、高温エージング時の硬度上昇を抑制することができることから、半導体チップなど発熱素子の冷却部材への熱伝導材料の用途として好適に使用することができる。
The thermally conductive silicone composition of the present invention can suppress a decrease in curing rate, and the cured product of the composition can suppress an increase in hardness during high-temperature aging. It can use suitably as a use of the heat conductive material to a cooling member.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
本発明の効果に関する試験は次のように行った。
The test regarding the effect of the present invention was performed as follows.
〔粘度〕
熱伝導性シリコーン組成物の絶対粘度は、マルコム粘度計（タイプＰＣ－１ＴＬ；（株）マルコム製）を用いて２５℃で測定した。 〔viscosity〕
The absolute viscosity of the thermally conductive silicone composition was measured at 25 ° C. using a Malcolm viscometer (type PC-1TL; manufactured by Malcolm).
熱伝導性シリコーン組成物の絶対粘度は、マルコム粘度計（タイプＰＣ－１ＴＬ；（株）マルコム製）を用いて２５℃で測定した。 〔viscosity〕
The absolute viscosity of the thermally conductive silicone composition was measured at 25 ° C. using a Malcolm viscometer (type PC-1TL; manufactured by Malcolm).
〔熱伝導率〕
各組成物を３ｃｍ厚の型に流し込み、キッチン用ラップをかぶせて京都電子工業（株）製のＭｏｄｅｌ ＱＴＭ－５００で２５℃において測定した。 〔Thermal conductivity〕
Each composition was poured into a 3 cm thick mold, covered with a kitchen wrap, and measured at 25 ° C. with Model QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd.
各組成物を３ｃｍ厚の型に流し込み、キッチン用ラップをかぶせて京都電子工業（株）製のＭｏｄｅｌ ＱＴＭ－５００で２５℃において測定した。 〔Thermal conductivity〕
Each composition was poured into a 3 cm thick mold, covered with a kitchen wrap, and measured at 25 ° C. with Model QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd.
〔硬化速度評価〕
直径２．５ｃｍの２枚のパラレルプレートの間に、熱伝導性シリコーン組成物を厚み２ｍｍで塗布した。塗布したプレートを２５℃から５℃／分にて昇温後、１５０℃において９０分間温度を維持するようにプログラムを作成し、貯蔵弾性率Ｇ'及び損失弾性率Ｇ''の測定を行った。貯蔵弾性率Ｇ'の値が、損失弾性率Ｇ''を上回った時点をクロスオーバータイムとし、硬化速度の指標とした。測定は、粘弾性測定装置（ティー・エイ・インスツルメント社製、タイプＡＲＥＳ－Ｇ２）を用いて行った。 [Evaluation of curing speed]
The heat conductive silicone composition was applied in a thickness of 2 mm between two parallel plates having a diameter of 2.5 cm. After the temperature of the coated plate was increased from 25 ° C. at 5 ° C./min, a program was created to maintain the temperature at 150 ° C. for 90 minutes, and the storage elastic modulus G ′ and loss elastic modulus G ″ were measured. . The time when the value of the storage elastic modulus G ′ exceeded the loss elastic modulus G ″ was defined as the crossover time, and was used as an index of the curing rate. The measurement was carried out using a viscoelasticity measuring device (Type ARES-G2 manufactured by TA Instruments).
直径２．５ｃｍの２枚のパラレルプレートの間に、熱伝導性シリコーン組成物を厚み２ｍｍで塗布した。塗布したプレートを２５℃から５℃／分にて昇温後、１５０℃において９０分間温度を維持するようにプログラムを作成し、貯蔵弾性率Ｇ'及び損失弾性率Ｇ''の測定を行った。貯蔵弾性率Ｇ'の値が、損失弾性率Ｇ''を上回った時点をクロスオーバータイムとし、硬化速度の指標とした。測定は、粘弾性測定装置（ティー・エイ・インスツルメント社製、タイプＡＲＥＳ－Ｇ２）を用いて行った。 [Evaluation of curing speed]
The heat conductive silicone composition was applied in a thickness of 2 mm between two parallel plates having a diameter of 2.5 cm. After the temperature of the coated plate was increased from 25 ° C. at 5 ° C./min, a program was created to maintain the temperature at 150 ° C. for 90 minutes, and the storage elastic modulus G ′ and loss elastic modulus G ″ were measured. . The time when the value of the storage elastic modulus G ′ exceeded the loss elastic modulus G ″ was defined as the crossover time, and was used as an index of the curing rate. The measurement was carried out using a viscoelasticity measuring device (Type ARES-G2 manufactured by TA Instruments).
〔硬度上昇評価〕
熱伝導性シリコーン組成物を６ｃｍ×６ｃｍ×６ｍｍの型枠に流し込み、１５０℃において９０分間加熱することによりシート状のサンプルを作製した。これらを２枚重ね合わせたものについてアスカーＣ硬度計を用いて硬度を測定し、初期硬度とした。その後１２５℃にて５００時間エージングを行い、硬度を測定した。 [Evaluation of hardness increase]
The thermally conductive silicone composition was poured into a 6 cm × 6 cm × 6 mm mold and heated at 150 ° C. for 90 minutes to prepare a sheet-like sample. About what superposed | stacked two of these, hardness was measured using the Asker C hardness meter and it was set as initial stage hardness. Thereafter, aging was performed at 125 ° C. for 500 hours, and the hardness was measured.
熱伝導性シリコーン組成物を６ｃｍ×６ｃｍ×６ｍｍの型枠に流し込み、１５０℃において９０分間加熱することによりシート状のサンプルを作製した。これらを２枚重ね合わせたものについてアスカーＣ硬度計を用いて硬度を測定し、初期硬度とした。その後１２５℃にて５００時間エージングを行い、硬度を測定した。 [Evaluation of hardness increase]
The thermally conductive silicone composition was poured into a 6 cm × 6 cm × 6 mm mold and heated at 150 ° C. for 90 minutes to prepare a sheet-like sample. About what superposed | stacked two of these, hardness was measured using the Asker C hardness meter and it was set as initial stage hardness. Thereafter, aging was performed at 125 ° C. for 500 hours, and the hardness was measured.
〔熱抵抗測定〕
１５ｍｍ×１５ｍｍ×１ｍｍｔのＳｉチップと１５ｍｍ×１５ｍｍ×１ｍｍｔのＮｉプレートの間に、熱伝導性シリコーン組成物を厚さ８０μｍとなるように挟み込み、０．７ＭＰａにて１５分間圧縮させた後、荷重をかけたまま１５０℃のオーブンに９０分間装入して熱伝導性シリコーン組成物を加熱硬化させ、熱抵抗測定用の試験片を作製した。さらにその後ヒートサイクル試験（－５５℃⇔１２５℃）を５００サイクル実施して熱抵抗の変化を観察した。なお、この熱抵抗測定はナノフラッシュ（ニッチェ社製、ＬＦＡ４４７）によって行った。 (Thermal resistance measurement)
A heat conductive silicone composition is sandwiched between a 15 mm × 15 mm × 1 mmt Si chip and a 15 mm × 15 mm × 1 mmt Ni plate so as to have a thickness of 80 μm, compressed at 0.7 MPa for 15 minutes, and then loaded. The sample was placed in an oven at 150 ° C. for 90 minutes with heat applied, and the thermally conductive silicone composition was heated and cured to prepare a test piece for measuring thermal resistance. Further, after that, a heat cycle test (-55 ° C. to 125 ° C.) was carried out for 500 cycles, and changes in thermal resistance were observed. In addition, this thermal resistance measurement was performed by nanoflash (the Niche company make, LFA447).
１５ｍｍ×１５ｍｍ×１ｍｍｔのＳｉチップと１５ｍｍ×１５ｍｍ×１ｍｍｔのＮｉプレートの間に、熱伝導性シリコーン組成物を厚さ８０μｍとなるように挟み込み、０．７ＭＰａにて１５分間圧縮させた後、荷重をかけたまま１５０℃のオーブンに９０分間装入して熱伝導性シリコーン組成物を加熱硬化させ、熱抵抗測定用の試験片を作製した。さらにその後ヒートサイクル試験（－５５℃⇔１２５℃）を５００サイクル実施して熱抵抗の変化を観察した。なお、この熱抵抗測定はナノフラッシュ（ニッチェ社製、ＬＦＡ４４７）によって行った。 (Thermal resistance measurement)
A heat conductive silicone composition is sandwiched between a 15 mm × 15 mm × 1 mmt Si chip and a 15 mm × 15 mm × 1 mmt Ni plate so as to have a thickness of 80 μm, compressed at 0.7 MPa for 15 minutes, and then loaded. The sample was placed in an oven at 150 ° C. for 90 minutes with heat applied, and the thermally conductive silicone composition was heated and cured to prepare a test piece for measuring thermal resistance. Further, after that, a heat cycle test (-55 ° C. to 125 ° C.) was carried out for 500 cycles, and changes in thermal resistance were observed. In addition, this thermal resistance measurement was performed by nanoflash (the Niche company make, LFA447).
本発明の熱伝導性シリコーン組成物を調製するために以下の各成分を用意した。
The following components were prepared in order to prepare the thermally conductive silicone composition of the present invention.
（Ａ）成分
Ａ－１：両末端がジメチルビニルシリル基で封鎖され、２５℃における動粘度が６００ ｍｍ2／ｓのジメチルポリシロキサン (A) Component A-1: Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity at 25 ° C. of 600 mm 2 / s
Ａ－１：両末端がジメチルビニルシリル基で封鎖され、２５℃における動粘度が６００ ｍｍ2／ｓのジメチルポリシロキサン (A) Component A-1: Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity at 25 ° C. of 600 mm 2 / s
（Ｂ）成分
Ｂ－１：下記式で示される片末端トリアルコキシシリル基封鎖ジメチルポリシロキサン
(B) Component B-1: One-terminal trialkoxysilyl group-blocked dimethylpolysiloxane represented by the following formula
Ｂ－１：下記式で示される片末端トリアルコキシシリル基封鎖ジメチルポリシロキサン
（Ｃ）成分
下記のアルミニウム粉末又はアルミナ粉末と酸化亜鉛粉末を５リットルプラネタリーミキサー（（株）井上製作所製）を用いて下記表１の質量混合比で室温にて１５分間混合し、Ｃ－１又はＣ－２を得た。
平均粒径１０μｍのアルミニウム粉末（熱伝導率：２３６Ｗ／ｍ・℃）
平均粒径６μｍのアルミナ粉末（熱伝導率：２７Ｗ／ｍ・℃）
平均粒径０．６μｍの酸化亜鉛粉末（熱伝導率：２５Ｗ／ｍ・℃）
Component (C) The following aluminum powder or alumina powder and zinc oxide powder were mixed for 15 minutes at room temperature using a 5-liter planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) at the mass mixing ratio shown in Table 1 below. 1 or C-2 was obtained.
Aluminum powder with an average particle size of 10 μm (thermal conductivity: 236 W / m · ° C.)
Alumina powder with an average particle size of 6 μm (thermal conductivity: 27 W / m · ° C)
Zinc oxide powder with an average particle size of 0.6 μm (thermal conductivity: 25 W / m · ° C)
下記のアルミニウム粉末又はアルミナ粉末と酸化亜鉛粉末を５リットルプラネタリーミキサー（（株）井上製作所製）を用いて下記表１の質量混合比で室温にて１５分間混合し、Ｃ－１又はＣ－２を得た。
平均粒径１０μｍのアルミニウム粉末（熱伝導率：２３６Ｗ／ｍ・℃）
平均粒径６μｍのアルミナ粉末（熱伝導率：２７Ｗ／ｍ・℃）
平均粒径０．６μｍの酸化亜鉛粉末（熱伝導率：２５Ｗ／ｍ・℃）
Aluminum powder with an average particle size of 10 μm (thermal conductivity: 236 W / m · ° C.)
Alumina powder with an average particle size of 6 μm (thermal conductivity: 27 W / m · ° C)
Zinc oxide powder with an average particle size of 0.6 μm (thermal conductivity: 25 W / m · ° C)
（Ｄ）成分
下記式で表されるオルガノハイドロジェンポリシロキサン
Ｄ－１：
Ｄ－２：
Component (D) Organohydrogenpolysiloxane D-1 represented by the following formula:
D-2:
下記式で表されるオルガノハイドロジェンポリシロキサン
Ｄ－１：
（Ｅ）成分
Ｅ－１：白金－ジビニルテトラメチルジシロキサン錯体のＡ－１溶液、白金原子として１質量％含有 (E) Component E-1: A-1 solution of platinum-divinyltetramethyldisiloxane complex, containing 1% by mass as platinum atoms
Ｅ－１：白金－ジビニルテトラメチルジシロキサン錯体のＡ－１溶液、白金原子として１質量％含有 (E) Component E-1: A-1 solution of platinum-divinyltetramethyldisiloxane complex, containing 1% by mass as platinum atoms
（Ｆ）成分
Ｆ－１：ベンゾトリアゾール (F) Component F-1: Benzotriazole
Ｆ－１：ベンゾトリアゾール (F) Component F-1: Benzotriazole
（Ｇ）成分
Ｇ－１：３－イソシアネートプロピルトリエトキシシラン
Ｇ－２：３－イソシアネートプロピルトリメトキシシラン
Ｇ－３：３－イソシアネートプロピルトリス（トリメチルシロキシ）シラン (G) Component G-1: 3-isocyanatopropyltriethoxysilane G-2: 3-isocyanatopropyltrimethoxysilane G-3: 3-isocyanatopropyltris (trimethylsiloxy) silane
Ｇ－１：３－イソシアネートプロピルトリエトキシシラン
Ｇ－２：３－イソシアネートプロピルトリメトキシシラン
Ｇ－３：３－イソシアネートプロピルトリス（トリメチルシロキシ）シラン (G) Component G-1: 3-isocyanatopropyltriethoxysilane G-2: 3-isocyanatopropyltrimethoxysilane G-3: 3-isocyanatopropyltris (trimethylsiloxy) silane
（Ｈ）成分
Ｈ－１：１－エチニル－１－シクロヘキサノール (H) Component H-1: 1-ethynyl-1-cyclohexanol
Ｈ－１：１－エチニル－１－シクロヘキサノール (H) Component H-1: 1-ethynyl-1-cyclohexanol
（Ａ）～（Ｈ）成分を以下のように混合して実施例１～６及び比較例１～６の熱伝導性シリコーン組成物を得た。
即ち、５リットルプラネタリーミキサー（（株）井上製作所製）に（Ａ）成分を取り、表２、表３に示す配合量で（Ｂ）、（Ｃ）成分を加え、１７０℃で１時間混合した。常温になるまで冷却し、次に（Ｄ）、（Ｅ）、（Ｆ）、（Ｇ）、（Ｈ）成分を表２、表３に示す配合量で加えて均一になるように混合した。 The components (A) to (H) were mixed as follows to obtain thermally conductive silicone compositions of Examples 1 to 6 and Comparative Examples 1 to 6.
That is, take the component (A) into a 5 liter planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), add the components (B) and (C) in the amounts shown in Tables 2 and 3, and mix at 170 ° C. for 1 hour. did. The mixture was cooled to room temperature, and then the components (D), (E), (F), (G), and (H) were added in the blending amounts shown in Tables 2 and 3 and mixed to be uniform.
即ち、５リットルプラネタリーミキサー（（株）井上製作所製）に（Ａ）成分を取り、表２、表３に示す配合量で（Ｂ）、（Ｃ）成分を加え、１７０℃で１時間混合した。常温になるまで冷却し、次に（Ｄ）、（Ｅ）、（Ｆ）、（Ｇ）、（Ｈ）成分を表２、表３に示す配合量で加えて均一になるように混合した。 The components (A) to (H) were mixed as follows to obtain thermally conductive silicone compositions of Examples 1 to 6 and Comparative Examples 1 to 6.
That is, take the component (A) into a 5 liter planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), add the components (B) and (C) in the amounts shown in Tables 2 and 3, and mix at 170 ° C. for 1 hour. did. The mixture was cooled to room temperature, and then the components (D), (E), (F), (G), and (H) were added in the blending amounts shown in Tables 2 and 3 and mixed to be uniform.
Claims (6)
- （Ａ）１分子中に少なくとも２個のアルケニル基を有する、２５℃の動粘度が１０～１００，０００ｍｍ2／ｓのオルガノポリシロキサン
（Ｂ）下記一般式（１）
（式中、Ｒ1は炭素数１～６のアルキル基であり、ａは５～１００の正数である。）
で表される片末端３官能の加水分解性メチルポリシロキサン：（Ａ）成分１００質量部に対して１０～１５０質量部
（Ｃ）１０Ｗ／ｍ・℃以上の熱伝導率を有する熱伝導性充填材：（Ａ）成分と（Ｂ）成分の合計１００質量部に対して５００～３，０００質量部
（Ｄ）１分子中に少なくとも２個のケイ素原子に直結した水素原子を含有するオルガノハイドロジェンポリシロキサン：｛（Ｄ）成分のＳｉ－Ｈ基の個数｝／｛（Ａ）成分のアルケニル基の個数｝が０．５～１．５になる量
（Ｅ）白金及び白金化合物からなる群より選択される触媒：白金原子として（Ａ）成分の質量に対して０．１～５００ｐｐｍとなる量
（Ｆ）トリアゾール系化合物：（Ｅ）成分の白金原子１モルに対して２～１，０００モル
（Ｇ）イソシアネート系化合物：（Ｆ）成分のトリアゾール系化合物１モルに対して０．１～１０モル
を含有する熱伝導性シリコーン組成物。 (A) Organopolysiloxane having at least two alkenyl groups in one molecule and a kinematic viscosity at 25 ° C. of 10 to 100,000 mm 2 / s (B) The following general formula (1)
(In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, and a is a positive number having 5 to 100.)
One-terminal trifunctional hydrolyzable methylpolysiloxane represented by: (A) 10 to 150 parts by mass with respect to 100 parts by mass of component (C) Thermally conductive filling having a thermal conductivity of 10 W / m · ° C. or more Material: 500 to 3,000 parts by mass with respect to a total of 100 parts by mass of component (A) and component (B) (D) Organohydrogen containing hydrogen atoms directly bonded to at least two silicon atoms in one molecule Polysiloxane: {Equivalent number of Si-H groups in component (D)} / {Number of alkenyl groups in component (A)} is 0.5 to 1.5 (E) From the group consisting of platinum and platinum compounds Catalyst selected: An amount of 0.1 to 500 ppm as platinum atom based on the mass of component (A) (F) Triazole compound: 2 to 1,000 mol per mol of platinum atom of component (E) (G) Isocyanate compound: ( ) Heat conductive silicone composition containing 0.1 to 10 mol relative to triazole compound 1 mole of component. - （Ｆ）成分が、１，２，３－トリアゾール、１，２，４－トリアゾール及びこれらの誘導体から選ばれるものである請求項１に記載の熱伝導性シリコーン組成物。 The heat conductive silicone composition according to claim 1, wherein the component (F) is selected from 1,2,3-triazole, 1,2,4-triazole and derivatives thereof.
- （Ｆ）成分が、ベンゾトリアゾールである請求項２に記載の熱伝導性シリコーン組成物。 The heat conductive silicone composition according to claim 2, wherein the component (F) is benzotriazole.
- （Ｇ）成分が、アルキルイソシアネート系化合物、アリールイソシアネート系化合物及びイソシアネートシラン系化合物から選ばれるものである請求項１～３のいずれか１項に記載の熱伝導性シリコーン組成物。 The thermally conductive silicone composition according to any one of claims 1 to 3, wherein the component (G) is selected from alkyl isocyanate compounds, aryl isocyanate compounds and isocyanate silane compounds.
- （Ｇ）成分が、下記式（２）
で示される化合物である請求項４に記載の熱伝導性シリコーン組成物。 The component (G) is represented by the following formula (2)
The heat conductive silicone composition of Claim 4 which is a compound shown by these. - 更に、（Ｈ）アセチレン化合物、窒素化合物、有機りん化合物、オキシム化合物及び有機クロロ化合物より選択される反応制御剤：（Ａ）成分に対して０．１～５質量％となる量
を含む請求項１～５のいずれか１項に記載の熱伝導性シリコーン組成物。 Furthermore, (H) a reaction control agent selected from acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds and organic chloro compounds: an amount of 0.1 to 5% by mass based on component (A) 6. The thermally conductive silicone composition according to any one of 1 to 5.
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| JP2017117347A JP6943028B2 (en) | 2017-06-15 | 2017-06-15 | Thermally conductive silicone composition |
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| WO2020149335A1 (en) * | 2019-01-17 | 2020-07-23 | バンドー化学株式会社 | Heat-conductive sheet |
| WO2021235214A1 (en) * | 2020-05-22 | 2021-11-25 | 信越化学工業株式会社 | Highly thermally-conductive silicone composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004168920A (en) * | 2002-11-21 | 2004-06-17 | Dow Corning Toray Silicone Co Ltd | Thermally conductive silicone elastomer composition |
| JP2017031364A (en) * | 2015-08-05 | 2017-02-09 | 信越化学工業株式会社 | Addition curable silicone rubber composition |
| WO2018079309A1 (en) * | 2016-10-26 | 2018-05-03 | 信越化学工業株式会社 | Thermally-conductive silicone composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004168920A (en) * | 2002-11-21 | 2004-06-17 | Dow Corning Toray Silicone Co Ltd | Thermally conductive silicone elastomer composition |
| JP2017031364A (en) * | 2015-08-05 | 2017-02-09 | 信越化学工業株式会社 | Addition curable silicone rubber composition |
| WO2018079309A1 (en) * | 2016-10-26 | 2018-05-03 | 信越化学工業株式会社 | Thermally-conductive silicone composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020149335A1 (en) * | 2019-01-17 | 2020-07-23 | バンドー化学株式会社 | Heat-conductive sheet |
| JP6754917B1 (en) * | 2019-01-17 | 2020-09-16 | バンドー化学株式会社 | Thermal conductivity sheet |
| WO2021235214A1 (en) * | 2020-05-22 | 2021-11-25 | 信越化学工業株式会社 | Highly thermally-conductive silicone composition |
| JPWO2021235214A1 (en) * | 2020-05-22 | 2021-11-25 | ||
| JP7371249B2 (en) | 2020-05-22 | 2023-10-30 | 信越化学工業株式会社 | High thermal conductivity silicone composition |
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| JP6943028B2 (en) | 2021-09-29 |
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