WO2024024503A1 - Composition de silicone de type à durcissement par addition à deux composants thermoconductrice, produit durci et feuille - Google Patents

Composition de silicone de type à durcissement par addition à deux composants thermoconductrice, produit durci et feuille Download PDF

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WO2024024503A1
WO2024024503A1 PCT/JP2023/025649 JP2023025649W WO2024024503A1 WO 2024024503 A1 WO2024024503 A1 WO 2024024503A1 JP 2023025649 W JP2023025649 W JP 2023025649W WO 2024024503 A1 WO2024024503 A1 WO 2024024503A1
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group
component
thermally conductive
liquid
silicone composition
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勇志 多畑
充弘 岩田
淳一 塚田
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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
    • 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
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon

Definitions

  • the present invention relates to a thermally conductive silicone composition.
  • the present invention relates to a thermally conductive two-component addition-curing silicone composition that can be used under high temperature and high humidity conditions without corroding metal wiring.
  • heat-generating electronic components generate heat during use and their performance deteriorates due to this, and various heat dissipation techniques are used as a means to solve this problem.
  • heat is radiated by disposing a cooling member (such as a heat sink) near a heat generating part, bringing the two into close contact with each other, and efficiently removing heat from the cooling member.
  • a cooling member such as a heat sink
  • air with poor thermal conductivity is present, resulting in a decrease in thermal conductivity and the temperature of the heat generating member cannot be lowered sufficiently.
  • Patent Documents 1 to 13 Japanese Patent No. 2938428, No. 2938429, No. 3580366, No. 3952184, No. 4572243, No. 4656340, No. 4913874, No. 4917380, No. 4933094, No. 5283346 Publication, Japanese Patent No. 5233325, Japanese Patent No. 5553006, Japanese Patent No. 5447337).
  • metal wiring such as copper wire is used for reactor coils, and the surface is generally plated with nickel or tin or coated with insulation.
  • metal wiring corrodes under high temperature and humidity conditions due to cationic impurities in the heat dissipating material.
  • Japanese Patent No. 5577553 reports a heat dissipating compound composition containing a benzotriazole derivative as an example of a metal deactivator
  • Japanese Patent No. 6523261 reports an adhesive composition for a heat dissipating adhesive tape containing a benzotriazole compound.
  • the base oil is limited to hydrocarbon-based synthetic oils, ether-based synthetic oils, and ester-based synthetic oils, and in Japanese Patent No.
  • JP-A-2004-168920 a thermally conductive silicone elastomer containing a phenol compound and/or a benzotriazole compound is disclosed, and in Japanese Patent No. 6,614,362, a thermally conductive silicone composition containing a benzotriazole derivative is disclosed. It is shown.
  • JP-A No. 2004-168920 aims to prevent the deterioration of curability during storage, and JP-A No. 6614362 aims to prevent the hardness of the cured product when exposed to high temperatures for a long time without reducing the initial hardening speed.
  • Corrosion is expected to be suppressed when a benzotriazole compound is blended in a thermally conductive silicone composition containing a large amount of filler containing ionic impurities that cause corrosion of copper and copper alloys.
  • a benzotriazole compound is blended, there is a problem in that the curing rate is reduced in an addition curing system using a platinum catalyst.
  • curing cannot be accelerated by heating, so there is a problem in that it is difficult to obtain a material with a desired hardness.
  • an object of the present invention is to provide a thermally conductive two-component addition-curing silicone composition that can suppress corrosion of metal wiring made of copper and copper alloy.
  • a first liquid containing an alkenyl group-containing organopolysiloxane, a thermally conductive filler, and a hydrosilylation reaction catalyst, and an alkenyl group-containing organopolysiloxane A thermally conductive two-component addition-curing silicone composition consisting of a second component containing a siloxane, an organohydrogenpolysiloxane, a thermally conductive filler, and a benzotriazole derivative contacts metals under high temperature and high humidity conditions. It was discovered that corrosion of wiring can be suppressed, and the present invention was completed.
  • the present invention provides the following thermally conductive two-component addition-curing silicone composition, cured product, and sheet.
  • Platinum group catalyst a first liquid containing an amount of platinum group metal in an amount of 0.1 to 500 ppm in terms of mass, based on the entire composition including the first liquid and the second liquid; (A) an organopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule; (B) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule; (C) Thermal conductive filler: 300 to 15,000 parts by mass based on the total of 100 parts by mass of components (A) and (B) in the first and second liquids, and (D) the following general formula ( 1) (In the formula, R 1 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 2 is a hydrogen atom or a monovalent organic group.) Benzotriazole derivative represented by: Consists of a second liquid containing an amount of 10 to 500 ppm of the total composition of the first liquid
  • R 2 is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or the following formula (2)
  • R 3 is a monovalent hydrocarbon group having 1 to 15 carbon atoms, or -(CH 2 ) a -Si(OR 4 ) 3
  • R 4 is an alkyl group having 1 to 4 carbon atoms, or -SiR 5 3 (R 5 is an alkyl group having 1 to 4 carbon atoms), and a is an integer of 1 to 6.
  • * indicates a bond.
  • the thermally conductive two-component addition-curing silicone composition according to any one of [1] to [3].
  • the thermally conductive two-component addition-curing silicone composition of the present invention is suitable as a heat dissipation material suitable for locations where metal wiring such as copper is used.
  • Component (A) of the composition of the present invention is a component that becomes the main ingredient (base polymer) of the composition.
  • Component (A) is an organopolysiloxane represented by the following average composition formula (6) and having at least two alkenyl groups bonded to a silicon atom (hereinafter referred to as "silicon atom bonded alkenyl group") in one molecule.
  • the silicon-bonded alkenyl group has at least 2 in one molecule, preferably 2 to 50, and more preferably 2 to 20.
  • These silicon-bonded alkenyl groups may be bonded to a silicon atom at the end of the molecular chain, a non-terminal silicon atom (i.e., other than the end of the molecular chain), or a combination thereof.
  • You can. (In the formula, R 10 is independently an alkenyl group, R 11 is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and g is 0.0001 to 0.2 , h is a number that satisfies 1.7 to 2.2, and g+h satisfies 1.9 to 2.4.)
  • alkenyl group examples include those having 2 to 6 carbon atoms, such as vinyl group, allyl group, isopropenyl group, 1-butenyl group, 1-pentenyl group, and 1-hexenyl group. Among these, alkenyl groups having 2 to 4 carbon atoms are preferred, and vinyl groups are particularly preferred.
  • the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond which is the remaining organic group bonded to the silicon atom, includes those having 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms. ⁇ 6.
  • alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group; phenyl group, Aryl groups such as 1-naphthyl group, 2-naphthyl group, and tolyl group; Aralkyl groups such as benzyl group and 2-phenylethyl group; Some or all of the hydrogen atoms of these groups are fluorine, chlorine, bromine, etc. Examples include chloromethyl group, 3,3,3-trifluoropropyl group, etc. substituted with a halogen atom; Propyl group is preferred.
  • g is a number from 0.0001 to 0.2, preferably from 0.0005 to 0.1.
  • h is a number from 1.7 to 2.2, preferably from 1.9 to 2.0.
  • g+h is a number satisfying 1.90 to 2.40, preferably 1.95 to 2.05.
  • the kinematic viscosity of component (A) at 25° C. as measured by an Ostwald meter is preferably in the range of 10 to 100,000 mm 2 /s, more preferably 100 to 50,000 mm 2 /s.
  • the resulting cured product will have better strength, fluidity, and workability.
  • R 12 is independently an unsubstituted or substituted monovalent hydrocarbon group, provided that at least two of R 12 are alkenyl groups, and i is a number from 10 to 2,000.
  • the unsubstituted or substituted monovalent hydrocarbon group represented by R 12 is the above-mentioned R 10 (alkenyl group) and R 11 (unsubstituted or substituted without an aliphatic unsaturated bond). (monovalent hydrocarbon group), and the number of carbon atoms, specific examples, etc. are also the same. However, at least 2, preferably 2 to 50, more preferably 2 to 20 R 12 are alkenyl groups. If the number of alkenyl groups is too small, the resulting cured thermally conductive silicone product may have a crosslinking density so low that it may not be cured.
  • i is preferably a number from 40 to 1,200, more preferably from 50 to 600. If the number of i is too small, the resulting thermally conductive silicone composition will have a low viscosity, resulting in poor handling and workability, and the resulting cured product will become brittle. If the number of i is too large, the resulting thermally conductive silicone composition will have a high viscosity and will be difficult to handle.
  • organopolysiloxane represented by the above formula (7) include dimethylpolysiloxane with dimethylvinylsiloxy groups endblocked at both ends of the molecular chain, dimethylsiloxane/methylvinylsiloxane copolymer endblocked with trimethylsiloxy groups at both ends of the molecular chain, and Dimethylsiloxane/methylvinylsiloxane copolymer with trimethylsiloxy group at one chain end and dimethylvinylsiloxy group at one end, dimethylsiloxane/methylvinylsiloxane copolymer with dimethylvinylsiloxy group at both molecular chain ends, dimethylvinylsiloxane at both molecular chain ends Examples include group-blocked dimethylsiloxane/diphenylsiloxane copolymers.
  • the organopolysiloxane (A) component may be used alone or in combination of two or more.
  • the amount of component (A) in the entire composition including the first liquid and the second liquid is preferably 0.5 to 20.0% by mass, and preferably 0.8 to 10.0% by mass. is more preferable.
  • the blending amount of component (A) in the first liquid is preferably 0.05 to 20.0% by mass, more preferably 0.8 to 15.0% by mass, and particularly preferably 1.0 to 10.0% by mass. .
  • the blending amount of component (A) in the second liquid is preferably 0.05 to 20.0% by mass, more preferably 0.8 to 15.0% by mass, and particularly preferably 1.0 to 10.0% by mass. .
  • the ratio of component (A) in the first liquid to component (A) in the second liquid is preferably 100:100 to 100:50, more preferably 100:95 to 100:55, and 100:90 to 100: 60 is particularly preferred.
  • the above-mentioned organopolysiloxane having an alkenyl group is known per se, and is produced by a conventionally known method.
  • Component (B) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (hereinafter also referred to as "silicon-bonded hydrogen atoms") in one molecule.
  • the number of silicon-bonded hydrogen atoms in one molecule of this organohydrogenpolysiloxane is preferably 2 to 100, more preferably 2 to 50, particularly preferably 2 to 20. If the number of silicon-bonded hydrogen atoms is too small, the crosslinking density of the resulting thermally conductive cured silicone product will be too low and will not be cured.
  • the resulting cured thermally conductive silicone product will have too high a crosslinking density, impairing its flexibility, and may also cause voids due to dehydrogenation during storage and curing.
  • the hydrogen atom bonded to the silicon atom may be located at the end of the molecular chain, in the middle of the molecular chain, or both.
  • Examples of the component (B) include those represented by the following average compositional formula (8). (In the formula, R 13 is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, j is 0.7 to 2.2, and k is 0.001 to 0.5. , and j+k is a number satisfying 0.8 to 2.5.)
  • R 13 is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and preferably has 1 to 12 carbon atoms, more preferably 1 carbon number. ⁇ 6. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group; phenyl group, Aryl groups such as 1-naphthyl group, 2-naphthyl group, and tolyl group; Aralkyl groups such as benzyl group and 2-phenylethyl group; Some or all of the hydrogen atoms of these groups are fluorine, chlorine, bromine, etc.
  • Examples include chloromethyl group, 3,3,3-trifluoropropyl group, etc. substituted with a halogen atom. Among these, from the viewpoint of ease of synthesis, methyl group, phenyl group, and 3,3,3-trifluoropropyl group are preferred.
  • j is a number from 0.7 to 2.2, preferably from 1.0 to 2.1.
  • k is a number from 0.001 to 0.5, preferably from 0.005 to 0.1.
  • j+k is a number that satisfies 0.8 to 2.5, preferably a number that satisfies 1.0 to 2.3, and more preferably a number that satisfies 1.5 to 2.2. .
  • the number of silicon atoms in one molecule of the organohydrogenpolysiloxane (B) component is usually 10 to 1,000, but it depends on the handling efficiency of the composition and the resulting cured product.
  • the number is preferably from 20 to 500, more preferably from 20 to 100, in terms of good characteristics. If the degree of polymerization is too low, the resulting thermally conductive silicone composition will have a low viscosity, resulting in poor handling and workability, and the resulting cured product will become brittle. If the degree of polymerization is too large, the resulting thermally conductive silicone composition will have a high viscosity, resulting in poor handling and workability.
  • the molecular structure of the organohydrogenpolysiloxane as component (B) is not particularly limited as long as it satisfies the above requirements.
  • the viscosity of the organohydrogenpolysiloxane as component (B) is preferably 1 to 10,000 mPa ⁇ s, more preferably 3 to 2,000 mPa ⁇ s, particularly preferably 10 to 1,000 mPa ⁇ s, and the viscosity at room temperature ( It is desirable that it is liquid at 25°C.
  • the viscosity is a value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). Note that the rotor, rotation speed, and rotation time are appropriately selected according to the viscosity based on a conventional method.
  • organohydrogenpolysiloxane represented by the above formula (8) examples include methylhydrogensiloxane/dimethylsiloxane cyclic copolymer, methylhydrogenpolysiloxane with dimethylhydrogensiloxy groups endblocked at both molecular chain ends, Methylhydrogen/dimethylsiloxane copolymer with dimethyl hydrogen siloxy group endblocked at both ends of the molecular chain, methylhydrogen/diphenylsiloxane copolymer endblocked with dimethylhydrogensiloxy group at both ends of the molecular chain, methylhydrogen endblocked with dimethylhydrogensiloxy group at both end of the molecular chain ⁇ Dimethylsiloxane/diphenylsiloxane copolymer, methylhydrogenpolysiloxane blocked with trimethylsiloxy groups at both ends of the molecular chain, dimethylsiloxane/methylhydrogensiloxane copo
  • Copolymer (CH 3 ) (CF 3 C 2 H 4 ) HSiO 1/2 units and (CH 3 ) (CF 3 C 2 H 4 ) SiO units and (CH 3 ) 2 SiO units and CH 3 SiO 3/
  • Examples include copolymers consisting of (CH 3 ) 3 SiO 1/2 units, (CH 3 ) 2 SiO units, (CH 3 )HSiO units, and SiO 4/2 units.
  • the organohydrogenpolysiloxane of component (B) may be used alone or in combination of two or more.
  • this organohydrogenpolysiloxane is synthesized by a conventionally known method.
  • the amount of the organohydrogenpolysiloxane (B) component is determined based on the silicon atom bond in the (B) component per alkenyl group in the (A) component in the entire composition of the first and second fluids.
  • the amount is such that the number of hydrogen atoms (SiH groups) is 0.1 to 5.0, preferably 0.2 to 2.0, and more preferably 0.5 to 1.5. If the amount is too small, the effect of improving storage stability may be insufficient, and if the amount is too large, the physical properties of the resulting thermally conductive cured silicone product may become unstable.
  • component (B) is used in the second liquid and is not contained in the first liquid.
  • component (B) is used in the first liquid, the first liquid increases in viscosity and hardens over time under room temperature conditions, making it impossible to maintain the viscosity at the time of manufacture.
  • Component (C) is a thermally conductive filler, specifically aluminum hydroxide, magnesium hydroxide, aluminum oxide, crystalline silica, zinc oxide, magnesium oxide, titanium oxide, beryllium oxide, aluminum nitride, Examples include boron nitride, metallic silicon, silicon nitride, silicon carbide, gold, silver, copper, iron, nickel, aluminum, stainless steel, gallium, indium, graphite, carbon fiber, diamond, etc., but are not particularly limited.
  • the thermally conductive filler of component (C) preferably has a thermal conductivity in the range of 1 to 1000 W/m ⁇ K, more preferably has a lower limit of thermal conductivity of 10 W/m ⁇ K or more, and particularly preferably has a thermal conductivity of 1 to 1000 W/m ⁇ K.
  • the thermally conductive filler has a lower limit of rate of 15 W/m ⁇ K or more. The higher the thermal conductivity, the better, but technically the upper limit of the thermal conductivity of a heat conductive filler that can be handled is 1,000 W/m ⁇ K. If the thermal conductivity of the filler is less than 1 W/m ⁇ K, the thermal conductivity of the thermally conductive silicone composition itself will be low.
  • Such thermally conductive fillers may be one type or a mixture of two or more types.
  • the average particle diameter of component (C) as measured by laser diffraction is preferably in the range of 0.1 to 100 ⁇ m, more preferably in the range of 0.1 to 80 ⁇ m.
  • the particles of component (C) may have any shape, but are preferably crushed particles, rounded particles, spherical particles, or polyhedral particles. As long as the effects of the present invention are not impaired, component (C) may be used alone or in combination of two or more types having different average particle diameters. If the average particle size is less than 0.1 ⁇ m, the resulting composition may not become grease-like and have poor extensibility; if it is larger than 100 ⁇ m, the thermal resistance of the composition may increase and performance may deteriorate. This is because there is.
  • the thermal conductivity of the composition If it is more than 15,000 parts by mass, the viscosity of the composition will increase and the extensibility will be poor, so the blending amount is in the range of 300 to 15,000 parts by mass, preferably 400 parts by mass. 14,500 parts by weight, more preferably 500 to 14,000 parts by weight.
  • component (C) is used in both the first and second liquids, and the ratio of component (C) used in the first and second liquids is based on the mixture of the first and second liquids. There is no particular limitation as long as the proportions are used so as to have substantially the same mass ratio.
  • Component (D) of the composition of the present invention is represented by the following general formula (1) (In the formula, R 1 is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 2 is a hydrogen atom or a monovalent organic group.) It is a benzotriazole derivative represented by
  • R 1 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, Alkyl groups such as butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group; Aryl group such as phenyl group, some or all of the hydrogen atoms of these groups are fluorine or chlorine , a chloromethyl group, a 3,3,3-trifluoropropyl group, a cyanoethyl group, etc. substituted with a halogen atom such as bromine, a cyano group, etc. From the viewpoint of synthesis, R 1 is preferably a hydrogen atom or a methyl group.
  • R 2 is a hydrogen atom or a monovalent organic group, and examples of the organic group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and neopentyl group. , hexyl group, cyclohexyl group; Aryl group such as phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group; Carbon number of aralkyl group such as benzyl group, 2-phenylethyl group, etc.
  • Examples include 1 to 10 monovalent hydrocarbon groups, and groups represented by the following formulas.
  • R 3 is a monovalent hydrocarbon group having 1 to 15 carbon atoms, or -(CH 2 ) a -Si(OR 4 ) 3
  • R 4 is an alkyl group having 1 to 4 carbon atoms, or -SiR 5 3 (R 5 is an alkyl group having 1 to 4 carbon atoms), and a is an integer of 1 to 6.
  • * indicates a bond.
  • the monovalent hydrocarbon group for R 3 includes 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 benzyl group, and a 2-phenylethyl group.
  • Examples include aralkyl groups such as groups.
  • Examples of the alkyl group for R 4 and R 5 include those having 1 to 4 carbon atoms, particularly 1 to 3 carbon atoms, such as a methyl group, ethyl group, and propyl group.
  • n is a number from 1 to 6, and R 14 is an alkyl group having 1 to 3 carbon atoms, or each alkyl group is a trialkylsilyl group having 1 to 3 carbon atoms.
  • the blending amount of component (D) is in the range of 10 to 500 ppm, preferably 15 to 400 ppm, more preferably 20 to 300 ppm, based on the total composition including the first and second liquids. If the amount of component (D) is less than 10 ppm, corrosion of the object cannot be sufficiently inhibited, and if it is more than 500 ppm, a large amount of platinum catalyst must be added, which is uneconomical.
  • component (D) is used in the second liquid and is not contained in the first liquid.
  • component (E) is deactivated and the curability of the composition is significantly reduced. After mixing the first and second liquids, curing at room temperature for 24 hours However, a cured product cannot be obtained.
  • Component (E) of the composition of the present invention is a platinum group metal catalyst, and is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the silicon-bonded hydrogen atom in component (B).
  • a platinum group metal catalyst for example, chloroplatinic acid, alcohol-modified chloroplatinic acid, or coordination compounds of chloroplatinic acid and olefins, aldehydes, vinylsiloxanes, or acetylene compounds; tetrakis(triphenylphosphine)palladium, chlorotris(triphenylphosphine) ) Rhodium or the like is used, preferably a platinum catalyst, and most preferably a coordination compound of chloroplatinic acid and vinylsiloxane.
  • the amount of component (E) may be a catalytic amount, but it is usually an amount of 0.1 to 500 ppm in terms of mass of platinum group metal based on the entire composition including the first liquid and the second liquid, The amount is preferably 1 to 100 ppm. It is preferable that the amount of component (E) is within this range since appropriate curability can be obtained.
  • component (E) is used in the first liquid and is not contained in the second liquid.
  • a silane coupling agent can be used in the composition of the present invention, if necessary. By blending a silane coupling agent, the effect of lowering the viscosity of the first liquid and the second liquid can be obtained.
  • the silane coupling agent include vinyl silane coupling agents, epoxy silane coupling agents, acrylic silane coupling agents, and long-chain alkyl silane coupling agents, which may be used singly or in combination. can be used in appropriate combinations.
  • Examples include hexyltrimethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane, decylmethyldimethoxysilane, decyldimethylmethoxysilane, decyltriethoxysilane, 7-octenyltrimethoxysilane, phenyltrimethoxysilane, etc. Particularly suitable is decyltrimethoxysilane.
  • composition of the present invention may optionally contain the following general formula (3).
  • R 6 is independently an unsubstituted or substituted monovalent hydrocarbon group
  • R 7 is independently an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
  • b is a number from 5 to 100.
  • c is a number from 1 to 3.
  • An organopolysiloxane (F) containing at least one hydrolyzable silyl group represented by the following in one molecule can be used.
  • component (F) By blending component (F), the effect of lowering the viscosity of the resulting silicone composition can be obtained.
  • R 6 is independently an unsubstituted or substituted monovalent hydrocarbon group having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and specifically Examples include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group; phenyl group chloromethyl group, 3,3,3-trifluoropropyl group in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, cyano group, etc. , cyanoethyl group, etc.
  • R 6 is preferably a methyl group, a phenyl group,
  • R 7 is independently an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
  • the alkyl group include the same linear alkyl group, branched alkyl group, and cyclic alkyl group as exemplified for R 7 .
  • the alkoxyalkyl group include a methoxyethyl group and a methoxypropyl group, and those having 2 to 10 carbon atoms are preferred.
  • Examples of the alkenyl group include vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, and 1-hexenyl, and those having 1 to 8 carbon atoms are preferred.
  • acyl group examples include an acetyl group and an octanoyl group, and those having 2 to 10 carbon atoms are preferred.
  • R 7 is preferably an alkyl group, particularly preferably a methyl group or an ethyl group.
  • b is a number from 5 to 100, preferably from 8 to 50, and c is a number from 1 to 3, preferably 3.
  • organopolysiloxane as component (F) include the following. (In the formula, Me is a methyl group. The same applies hereinafter.)
  • the viscosity of the organopolysiloxane (F) component at 25° C. is usually 0.01 to 30 Pa ⁇ s, preferably 0.1 to 10 Pa ⁇ s. If the viscosity is lower than 0.01 Pa ⁇ s, there is a possibility that oil bleed of component (F) is likely to occur from the silicone composition. If the viscosity is higher than 30 Pa ⁇ s, the resulting silicone composition will have significantly poor fluidity, and there is a risk that the coating workability will deteriorate.
  • component (F) when component (F) is used, it is preferable to form a heat-treated mixture together with the above-mentioned component (C) or components (A) to (C) at a temperature of 70° C. or higher. A more preferred temperature is 80 to 180°C.
  • the above-mentioned (C) component when using the (F) component, can also be treated with the (F) component in advance.
  • the surface treatment method for component (C) using component (F) includes a spraying method using a fluid nozzle, a stirring method with shear force, a dry method using a ball mill or mixer, and a wet method using an aqueous or organic solvent system. law may be adopted. Stirring is carried out to an extent that does not cause destruction of the thermally conductive filler.
  • the temperature within the system or the drying temperature after treatment in the dry method is appropriately determined depending on the type of surface treatment agent and within a range where the surface treatment agent does not volatilize or decompose, and is, for example, 80 to 180°C.
  • the blending amount is preferably 0.1 to 10.0 parts by mass, and preferably 0.3 to 8.0 parts by mass, per 100 parts by mass of component (C). More preferred. If the amount is less than 0.1 part by mass, the effect of lowering the viscosity will be small, and if it is more than 8.0 parts by mass, the effect corresponding to the amount blended will not be achieved.
  • the (F) component when using the (F) component, it can be used for both the first liquid and the second liquid, or it can be used for either one, and the ratio of the (F) component used for the first liquid and the second liquid is Although not particularly limited, the same amount can be used for the first liquid and the second liquid, for example.
  • the composition of the present invention may contain an inorganic ion scavenger (G) in the first liquid.
  • the inorganic ion trapping agent can suppress the aging deterioration of component (E) by trapping sodium ions contained in component (C), and can also be used together with component (D) by trapping copper ions. , can enhance the corrosion inhibition effect of copper and copper alloys.
  • the inorganic ion scavenger is not particularly limited, but is preferably a composite of one or more selected from hydrotalcite compounds and/or inorganic cation exchangers.
  • inorganic ion trapping agent As the inorganic ion trapping agent, commercially available products such as IXE-100, IXE-600, IXEPLAS-A1, and IXEPLAS-A2 (manufactured by Toagosei Co., Ltd.) can be used.
  • the amount of the inorganic ion scavenger is usually in the range of 10 to 10,000 ppm, preferably 100 to 5,000 ppm, more preferably 200 to 1. ,000ppm. If the amount of the inorganic ion scavenger added is 10 ppm or less, it may not be possible to suppress the aging deterioration of component (E), and if it exceeds 10,000 ppm, appropriate curability may not be obtained.
  • composition of the present invention may also contain the following general formula (4) as needed.
  • R 8 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond, and d is a number of 5 to 2,000.
  • R 8 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond
  • R 9 is a phenyl group
  • e and f are each a number of 1 to 20.
  • Phenylpolysiloxane (I) represented by can be used.
  • these components (H) and (I) exist in the composition as oil without affecting the crosslinked structure, they gradually flow out of the composition.
  • the component (D) By containing the component (D) in this bleed oil, the component (D) efficiently reaches the surface of the object and forms a film, thereby providing a corrosion inhibiting effect.
  • the amount of components (H) and (I) to be blended is usually in the range of 0.1 to 100 parts by mass, with the total amount of components (H) and (I) being 0.1 to 100 parts by mass per 100 parts by mass of component (A). is 1 to 80 parts by weight, more preferably 5 to 60 parts by weight. If the blending amount of components (H) and (I) is less than 0.1 part by mass, the outflow of component (D) will be suppressed and the resulting corrosion inhibiting effect will be small; if it is more than 100 parts by mass, Since there is too much bleed oil, the viscosity of the composition increases over time, and the cured product may become brittle.
  • additives known per se can be blended into the composition of the present invention as long as they do not impair the purpose of the present invention. .
  • reaction control agents for adjusting curing speed and storage stability specifically acetylene alcohols such as triallylisocyanate alkyl maleate, ethynyldecylmethyl carbinol, ethynylcyclohexanol, and silanes and siloxane modified products thereof.
  • hydroperoxide, tetramethylethylenediamine, ferrous oxide, ferric oxide, etc. as a coloring agent, singly or in combination, and fumed silica as a thixotropic agent, etc. can be blended.
  • the amount of each of these compounds is preferably 0.01 to 100,000 ppm in terms of mass per the composition of the present invention.
  • a known mixer such as a static mixer, a planetary mixer, or a paddle mixer can be used as a mixing device for preparing the first liquid and the second liquid.
  • the curing conditions for the composition of the present invention are not particularly limited and may be the same as those for known addition reaction-curing silicone compositions. good. Note that the curing conditions in the case of heating can be 40 to 180° C. for 1 to 120 minutes.
  • Component A-1 dimethylpolysiloxane with dimethylvinylsiloxy groups endblocked at both molecular chain ends (kinematic viscosity 600 mm 2 /s, amount of Vi group per 100 g 0.015 mol, i in general formula (7) is 180)
  • A-2 Dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both molecular chain ends (kinematic viscosity 400 mm 2 /s, amount of Vi group per 100 g 0.0185 mol, i in general formula (7) is 146)
  • Component B-1 Trimethylsiloxy group-blocked methylhydrogen dimethylpolysiloxane represented by formula (15) (Si-H amount 0.00128 mol/g)
  • B-2 Dimethylhydrogensiloxy group-blocked dimethylpolysiloxane represented by formula (16) (Si-H amount 0.00130 mol/g)
  • Component C-1 Molten spherical aluminum
  • a sheet-like cured product was prepared according to the procedure described in "Hardness” below, and the hardness was measured using a Shore OO hardness meter specified in ASTM D 2240-05. As a result, the measured value was 30. If the value became 0 within seconds, it was judged as “fail”. If the hardness was determined to be “fail”, hardness and copper corrosion tests were not evaluated.
  • Viscosity The viscosity of each of the first and second liquids in each example was measured at 25° C. using a spiral viscometer: Malcolm viscometer (type PC-10AA, rotation speed 10 rpm).
  • Thermal conductivity of each of the first and second liquids in each example was measured at 25°C using a hot disk method thermophysical property measuring device TPS 2500 S (manufactured by Kyoto Electronics Industry Co., Ltd.) (ISO 22007 -2 compliant hot disk method).
  • the first and second liquids of each example were mixed at room temperature (25°C) using a static mixer MXA6.3-21 (manufactured by Noritake Co., Ltd.) so that they were uniform at a 1:1 mass ratio. After discharging, the mixture was sufficiently degassed under vacuum, poured into a mold having a thickness of 6 mm after curing, and cured at 25° C. for 24 hours to obtain a sheet-like cured product. The hardness (hardness) of the obtained cured product was measured using a Shore OO hardness meter specified in ASTM D 2240-05, and the value 30 seconds after the start of measurement was adopted.
  • the composition was discharged onto a copper plate to a thickness of 2 mm and allowed to stand for 24 hours in a 25°C environment to cure the composition, thereby obtaining a test piece having a cured product on the copper plate. Thereafter, the test piece was stored in a high temperature and high humidity tank at 85° C./85% RH, and aged for 1000 hours. After 1000 hours had elapsed, the test piece was taken out, and the presence or absence of corrosion was determined by observing the change in color tone of the surface of the copper plate in the area in contact with the cured product.
  • compositions of Examples 1 to 7 of the present invention showed no discoloration due to corrosion of the copper plate after 1000 hours of storage at 85°C/85% RH, whereas the compositions of Comparative Examples 1, 2, 3, Compositions Nos. 8 and 9 showed discoloration in the copper plate corrosion test. It can be seen from Comparative Examples 1, 2, 8, and 9 that it is preferable to contain component (D). Moreover, from Comparative Example 3, it can be seen that when the amount of component (D) is too small, the effect of inhibiting corrosion of the copper plate is small. Comparative Examples 4 and 7 show that if the amount of component (D) is too large or the amount of component (E) is too small, component (E) will be deactivated and the silicone composition will not cure at room temperature.
  • Comparative Examples 5 and 6 show that it is not preferable to add the component (D) to the first liquid containing the component (E), and that the component (D) should be added to the second liquid. Therefore, according to the present invention, a thermally conductive silicone composition and a cured product thereof that can be used under high temperature and high humidity conditions without corroding metal wiring can be obtained.
  • the thermally conductive cured silicone material that can suppress the corrosion of copper plates under high temperature and high humidity conditions obtained by the present invention can suppress the corrosion of the copper wires for a long period of time when used in contact with the copper wires of the reactor coil. Therefore, it is expected to improve reliability in heat dissipation and protection applications for electronic components such as power devices, transistors, thyristors, and CPUs (central processing units).

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Abstract

L'invention concerne une composition de silicone de type à durcissement par addition à deux composants thermoconductrice qui peut supprimer la corrosion de câblages métalliques formés de cuivre et d'un alliage de cuivre.　Cette composition de silicone de type à durcissement par addition à deux composants thermoconductrice comprend : un premier liquide contenant (A) un organopolysiloxane ayant au moins deux groupes alcényle liés à des atomes de silicium, (C) une charge thermoconductrice, et (E) un catalyseur de groupe platine pour une réaction d'hydrosilylation ; et un second liquide contenant (A) l'organopolysiloxane ayant au moins deux groupes alcényle liés à des atomes de silicium, (B) un organohydrogénopolysiloxane ayant au moins deux atomes d'hydrogène liés à des atomes de silicium, (C) la charge thermoconductrice, et (D) un dérivé de benzotriazole représenté par la formule générale (1) (dans la formule, chaque R1 représente indépendamment un atome d'hydrogène ou un groupe hydrocarboné monovalent substitué ou non substitué ayant de 1 à 6 atomes de carbone, et R2 représente un atome d'hydrogène ou un groupe organique monovalent).
PCT/JP2023/025649 2022-07-26 2023-07-12 Composition de silicone de type à durcissement par addition à deux composants thermoconductrice, produit durci et feuille WO2024024503A1 (fr)

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WO2018079309A1 (fr) * 2016-10-26 2018-05-03 信越化学工業株式会社 Composition de silicone thermoconductrice
JP2019031601A (ja) * 2017-08-07 2019-02-28 信越化学工業株式会社 付加硬化型シリコーン組成物及びシリコーンゴム硬化物
JP2020041024A (ja) * 2018-09-07 2020-03-19 信越化学工業株式会社 熱伝導性シリコーン組成物
JP2020063380A (ja) * 2018-10-18 2020-04-23 信越化学工業株式会社 熱伝導性シリコーン組成物
JP2021187877A (ja) * 2020-05-26 2021-12-13 信越化学工業株式会社 二液付加硬化型シリコーンゴム組成物
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JPS63234013A (ja) * 1987-03-23 1988-09-29 Tatsuta Electric Wire & Cable Co Ltd 半導体封止用樹脂組成物
JPH02242854A (ja) * 1989-03-16 1990-09-27 Shin Etsu Chem Co Ltd 硬化性シリコーンゴム組成物
JP2002235184A (ja) * 2001-02-06 2002-08-23 Mitsubishi Cable Ind Ltd 銅または銅合金の防錆処理方法
JP2006056986A (ja) * 2004-08-19 2006-03-02 Shin Etsu Chem Co Ltd 二液硬化型シリコーン組成物
JP2011012251A (ja) * 2009-06-02 2011-01-20 Sumitomo Metal Ind Ltd 鋼管ねじ継手の防錆に適した光硬化性組成物
JP2014177612A (ja) * 2013-02-14 2014-09-25 Nitto Denko Corp 粘着剤組成物、粘着剤層、粘着シート、光学部材、及びタッチパネル
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JP2019031601A (ja) * 2017-08-07 2019-02-28 信越化学工業株式会社 付加硬化型シリコーン組成物及びシリコーンゴム硬化物
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JP2020063380A (ja) * 2018-10-18 2020-04-23 信越化学工業株式会社 熱伝導性シリコーン組成物
JP2021187877A (ja) * 2020-05-26 2021-12-13 信越化学工業株式会社 二液付加硬化型シリコーンゴム組成物
JP2022185620A (ja) * 2021-06-03 2022-12-15 信越化学工業株式会社 熱伝導性シリコーン組成物及びその硬化物

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