WO2004046233A1 - Thermally-conductive silicone elastomer composition - Google Patents
Thermally-conductive silicone elastomer composition Download PDFInfo
- Publication number
- WO2004046233A1 WO2004046233A1 PCT/JP2003/011457 JP0311457W WO2004046233A1 WO 2004046233 A1 WO2004046233 A1 WO 2004046233A1 JP 0311457 W JP0311457 W JP 0311457W WO 2004046233 A1 WO2004046233 A1 WO 2004046233A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- groups
- terminals
- molecular chain
- blocked
- formula
- Prior art date
Links
Classifications
-
- 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
- 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
-
- 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
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A thermally conductive silicone elastomer composition includes: (A) an organopolysiloxane containing at least two silicon-bonded alkenyl groups per molecule; (B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms per molecule; (C) a thermally-conductive filler; (D) a phenol compound and/or a benzotriazole compound; (E) a platinum catalyst; and (F) an enyne compound and/or alkyne alcohol.
Description
DESCRIPTION
THERMALLY-CONDUCTIVE SILICONE ELASTOMER COMPOSITION
Technical Field [0001] This invention relates to a thermally-conductive silicone elastomer composition. More particularly, this invention relates to a thermally-conductive silicone elastomer composition, which is characterized by a reduced tendency to the loss of curability during storage and which, when cured, forms a silicone elastomer of high thermal conductivity.
Background Art [0002] Thermally-conductive silicone rubber compositions that, when cured, form thermally-conductive silicone rubbers are known in the art. For example, Japanese Laid- Open Patent Application Publications (Kokai) H3-170581 and (Kokai) H7-133432 disclose silicone rubber compositions that contain an organopolysiloxane with at least two alkenyl groups in one molecule, an organopolysiloxane with at least two silicon-bonded hydrogen atoms, a fine silver powder, and a platinum catalyst. However, when these silicone rubber compositions are stored over a long period of time, their curability is worsened and finally is impaired to such a level that the composition becomes unsuitable for use. [0003] It is an object of this invention to provide a thermally-conductive silicone elastomer composition, which is characterized by a reduced tendency to the loss of curability during storage and which, when cured, forms a silicone elastomer of high thermal conductivity.
Disclosure of Invention [0004] This invention provides a thermally conductive silicone elastomer composition, comprising:
(A) 100 parts by weight of an organopolysiloxane containing at least two silicon- bonded alkenyl groups per molecule;
(B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms per molecule (in this component, the content of said silicon-bonded hydrogen atoms comprises 0.3 to 10 moles per 1 mole of the alkenyl groups of component (A));
(C) 50 to 5,000 parts by weight of a thermally-conductive filler;
(D) 10 to 10,000 ppm by weight of a phenol compound or a benzotriazole compound, or both;
(E) a platinum catalyst in an amount sufficient to provide metallic platinum in an amount of 10 to 10,000 ppm based on the total weight of the composition; and (F) 10 to 10,000 ppm by weight of an enyne compound or alkyne alcohol, or both.
Detailed Description of the Invention [0005] Component (A) comprises an organopolysiloxane with at least two alkenyl groups per molecule. The alkenyl groups of component (A) may include vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups and heptenyl groups. Of these, vinyl groups and hexenyl groups are preferred. The bonding positions of the alkenyl groups in component (A) include, for example, the terminals of the molecular chain or side chains of the molecular chain, or both. Organic groups that are bonded with the silicon atoms in addition to the alkenyl groups in component (A) include, for example, substituted or unsubstituted monovalent hydrocarbon groups (other than alkenyl groups) such as alkyl groups, e.g., methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups and heptyl groups; aryl groups, e.g., phenyl groups, tolyl groups, and xylyl groups; aralkyl groups, e.g., benzyl groups and phenethyl groups; 3-chloropropyl groups and 3,3,3-trifluoropropyl groups, or similar halogenated alkyl groups. The methyl groups and phenyl groups are preferred. The molecular structure of component (A) can be, for example, in a straight-chain form, a straight-chain form having some branches, and in a net-like form. The organopolysiloxane of component (A) may have a mixture of two or more of the abovementioned structures. Although there are no limitations on the viscosity of component (A), a viscosity, at 25 °C, of 50 to 500,000 mPa-s is preferred, with 100 to 50,000 mPa-s being particularly preferred. [0006] The organopolysiloxane, component (A), can include, for example, copolymers of methylvinylsiloxane and dimetliylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, methylvinylpolysiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane and methylvinylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylvinylsiloxane, and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of
the molecular chain, methylvinylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, methylphenylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of methylvinylsiloxane and dimethylsiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane and methylvinylsiloxane capped with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylvinylsiloxane, and dimethylsiloxane capped with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of diphenylsiloxane and methylvinylsiloxane capped with dimethylvinylsiloxy groups at both terminals of the molecular chain, or similar diorganopolysiloxanes; silicone resins comprised of siloxane units as indicated by the formula SiOι 2 and siloxane units as indicated by the formula SiO4/2, silicone resins comprised of siloxane units as indicated by the formula RJSiO3/2, silicone resins comprised of siloxane units as indicated by the formula R1 2SiO2/2 and siloxane units as indicated by the formula R1 SiO3/2, siloxane resins comprised of siloxane units R1 2SiO2/2, siloxane units as indicated by the formula R^iO^, and siloxane units as indicated by the formula SiO4/2, or similar silicone resins. The aforementioned organopolysiloxanes can be used in a mixtures of two or more. In the foregoing formulas, R1 designates a substituted or non-substituted monovalent hydrocarbon group, e.g., an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, or a hexyl group; an alkenyl group such as a vinyl group, allyl group, butenyl group, pentenyl group, or hexenyl group; an aryl group such as a phenyl group, tolyl group, or xylyl group; an aralkyl group such as a benzyl group or a phenethyl group; or a halogenated alkyl group such as a 3-chloropropyl group or a 3,3,3- trifluoropropyl group. At least two R1 ' s per molecule of the silicone resins should comprise alkenyl groups.
[0007] Component (B) is used as a crosslinking agent for curing the composition of the invention. Component (B) comprises an organopolysiloxane having at least two silicon-bonded hydrogen atoms per molecule. The positions of bonding of the hydrogen atoms to silicon atoms in component (B) can be, for example, the terminals of the molecular chain or side chains of the molecular chain, or both. Component (B) may further comprise silicon-bonded organic groups in addition to the silicon-bonded hydrogen atoms. These silicon bonded organic groups may be the same substituted or non-substituted
monovalent hydrocarbons as mentioned earlier, except for alkenyl groups. Methyl groups and phenyl groups are preferred. The molecular structure of component (B) may be, for example, in a straight chain form, a straight chain form having some branches, a branched chain form, or a net-like chain form. Component (B) may comprise a mixture of two or more organopolysiloxanes with different molecular structures. Although there is no limitation on the viscosity of component (B), a viscosity at 25 °C of 1 to 500,000 mPa-s is desirable, with 5 to 1000 mPa-s being preferred.
[0008] Component (B), can include, for example, a methylhydrogenpolysiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylhydrogenpolysiloxane and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane and methylhydrogensiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylhydrogensiloxane, and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, dimethylpolysiloxane blocked with dimethymydrogensiloxy groups at both terminals of the molecular chain, methylhydrogenpolysiloxane blocked with dimethy ydrogensiloxy groups at both terminals of the molecular chain, copolymers of methylhydrogenpolysiloxane and dimethylsiloxane blocked with dimethymydrogensiloxy groups at both terminals of the molecular chain, copolymers of methyphenylsiloxane and dimethylsiloxane blocked with dimethymydrogensiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylhydrogensiloxane, and dimethylsiloxane blocked with dimethylhydrogensiloxy groups at both terminals of the molecular chain, or similar diorganopolysiloxanes; silicone resins comprised of siloxane units as indicated by the formula R2 SiOι/2 and siloxane units as indicated by the formula SiO4/2, silicone resins comprised of siloxane units as indicated by the formula R SiO3/ , silicone resins comprised of siloxane units as indicated by the formula R2 2SiO2/ and siloxane units as indicated by the formula R SiO /2, siloxane resins comprised of siloxane units R2 2SiO / , siloxane units as indicated by the formula R2SiO3/ , and siloxane units as indicated by the formula SiO4/2, or similar silicone resins; as well as mixtures of two or more of the aforementioned resins. In the aforementioned formulae, R2 may comprise hydrogen atoms or a substituted or non-substituted monovalent hydrocarbons, other than alkenyl groups. The monovalent hydrocarbons that represent R2 may be the same as
specified earlier. At least two R2's per molecule of the silicone resins should be hydrogen atoms.
[0009] It is recommended that component (B) be used in the composition of the invention in an amount of 0.3 to 10 moles of the silicon-bonded hydrogen atoms per 1 mole of the alkenyl groups in component (A). If component (B) is used in an amount below the lower recommended limit of the range, the composition will have a tendency to insufficient curing. If component (B) is used in an amount exceeding the recommended upper limit, the obtained silicone elastomer will have reduced heat-resistant properties. [0010] Component (C) is a thermally conductive filler that imparts thermoconductive properties to a silicone elastomer obtained by curing the composition. Component (C) can be represented by a fine powder of gold, silver, nickel, copper, etc.; a fine powder of metal, such as gold, silver, nickel, or copper having particles electroplated or coated by vapor deposition with ceramics, glass, quartz, organic resin, or the like; metal compounds such as aluminum oxide, aluminum nitride, zinc oxide, or the like. These fillers can be used in combinations of two or more. For obtaining a silicone elastomer with high thermal conductivity of 3 W/mK or more, it is preferable to use component (C) in the form of a fine silver powder. The powder particles may have a spherical, flake-like, or a branched flake-like form. It is recommended that an average size of particles of component (C) be within the range of 1 to 100 μm, preferably 1 to 50 μm. [0011] It is recommended to use component (C) in the composition of the present invention in an amount of 50 to 5,000 parts by weight, preferably 300 to 3,000 parts by weight, for each 100 pats by weight of component (A). If component (C) is used in an amount below the lower recommended limit of the above range, it would be difficult to impart to the obtained silicone elastomer sufficient thermoconductive properties. If the amount of component (C) exceeds the upper recommended limit of the range, it will be difficult to prepare a composition with uniform properties and to handle the obtained composition.
[0012] Component (D) is a phenol-type or benzotriazole-type compound, or combination thereof, which is used in the composition for controlling changes in curing properties with the lapse of time during storage. The following are examples of the phenol-type compounds: 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di- tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-sec-butylphenol, 2- (1-methylcyclohexyl)- 4,6- dimethylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, or similar monophenol
compounds; 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4- methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4'- methylene-bis- (2,6-di-tert-butylphenol), 2,2'-methylene-bis- (6- -methylbenzyl-p-cresol), 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), or similar bisphenol compounds; 4,4'- thiobis- (6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-o-cresol), or similar thiobisphenol compounds; 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert- butylphenol), 2,2-thiobis- (4-methyl-6-tert-butylphenol), or similar hindered phenol compounds. [0013] The benzotriazole compounds can be represented by 1H- benzotriazole, 4- methyl-lH- benzotriazole, 5-methyl-lH- benzotriazole, 2- (2'-hydroxy-5'-methylphenyl)- benzotriazole, 2- (2'-hydroxy-3',5'-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'- tert-butyl-5'-methyl-phenyl)- 5-chlorobenzotriazole, 2- (2'-hydroxy-3'5 5'-di-tert-butyl- phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octyl-phenyl) benzotriazole, 2- (2'- hydroxy-3 \5'-di-tert-amylphenyl) benzotriazole, 2- [2'-hydroxy-3 '- (3",4",5",6"- tetrahydrophalimidomethyl] benzotriazole, 2,2'-methylene-bis [4-(l, 1,3,3- tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy- 3.5-bis (α, α- dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl)-2H- benzotriazole, and 2- (2H-brenzotriazol-2-yl) -4-methyl-6- (3,4,5,6- tetrahydrophalidylmethyl) phenol.
[0014] It is recommended to use component (D) in the composition in an amount that in weight units is within the range of 10 to 10,000 ppm relative to the weight of the composition. If this component is used in an amount below the lower recommended limit of the range, it will be difficult to control changes of curing properties of the composition with the lapse of time. If the content of component (D) exceeds the upper recommended limit of the range, curing of the composition will be significantly delayed. [0015] Component (E) of the composition of the invention is a platinum-type catalyst used for acceleration of curing. The platinum catalyst of component (E) can be represented by the following compounds: platinum black, platinum on an aluminum powder carrier, platinum on a silica powder carrier, platinum on a carbon powder carrier, a chloroplatinic acid, an alcoholic solution of a chloroplatinic acid, a platinum-olefin complex, and aforementioned platinum-type catalysts in the form of fine powders
dispersed in thermoplastic resins such a methacrylate resin, carbonate resin, polystyrene resin, silicone resin, etc.
[0016] It is recommended to use component (E) in the composition of the invention in such an amount that in terms of weight units the content of the metallic platinum in this composition is 0.1 to 1,000 ppm. If component (E) is used in an amount below the recommended lower limit of the range, it will be difficult to provide complete curing of the composition. If the content of component (E) exceeds the upper recommended limit, this may change the color in the obtained silicone elastomer. [0017] Component (F) is an enyne compound or alkyne alcohol, or combination thereof, used for adjusting curing properties and for improving conditions of handling of the composition. The enyne compound can be represented by 3-methyl-3-penten-l-yne and 3,5-dinιethyl-3-hexen-l-yne. The alkyne alcohol can be represented by 2-methyl-3- butyn-2-ol, 3 -dimethyl- l-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol. [0018] It is recommended to use component (E) in the composition of the invention in an amount that in weight units is within the range of l0 to l0,000 ppm relative to the weight of the composition. If this component is used in an amount below the lower recommended limit of the range, it will be more difficult to adjust the curing properties of the obtained composition and to handle the composition. If the content of component (E) exceeds the upper recommended limit of the range, curing of the composition will be significantly delayed.
[0019] The composition of the invention is prepared by uniformly mixing aforementioned components (A) through (F). However, if it is necessary to further improve adhesive properties of the obtained thermoconductive silicone elastomer, the composition may also be combined with an adhesion promoting agent, such as vinyltrimethoxysilane, vmyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3- trimethacryloxypropyltrimethoxysilane, 3-glycidoxypropyl-trimethoxysilane, or a similar alkoxysilane compound; a siloxane oligomer of the following formula:
a siloxane oligomer of the following formula:
a siloxane oligomer of the following formula:
a siloxane oligomer of the following formula:
[0020] The adhesion-imparting agent is used in the composition of the invention as an optional component. When present, it is recommended to add the adhesion-imparting agent in an amount of 20 parts by weight or less, preferably 0.5 to 10 parts by weight for each 100 parts by weight of component (A). Without the use of the adhesion-imparting agent, the obtained silicone elastomer will either have poor adhesive properties or show a tendency of changing contact resistance and spatial conductivity in time. If the adhesion- imparting agent is used in an amount that exceeds the aforementioned upper recommended limit, the silicone elastomer composition will become unstable in storage, while the silicone elastomer obtained after curing will have physical properties varying with the lapse of time. [0021] To impart to the thermoconductive silicone elastomer obtained by curing the composition of the invention appropriate hardness and strength, the composition may contain an inorganic filler as another optional component. Such a filler may be represented by fumed silica, crystalline silica, baked silica, wet-process silica, carbon black, or an inorganic filler surface-treated with an organoalkoxysilane, organochlorosilane, organodisilazane, or a similar organic silicone compound. It is recommended to add the inorganic filler in an amount of not more than 50 parts by weight for each 100 parts by weight of component (A).
[0022] Curing of the composition turns it into a silicone rubber, silicone gel, or a similar silicone elastomer. This means that the composition is suitable for use as a heat- radiation adhesive agent, heat-radiation die-bonding agent, heat-radiation paste, electromagnetic-wave shield, etc., as well as a starting material for manufacturing heat- radiating sheets and electromagnetic-wave absorbing sheets.
Examples [0023] The values of viscosities used in the examples all correspond to 25 °C. The following methods were used for measuring characteristics of the silicone elastomers obtained by curing the thermoconductive silicone elastomer composition of the invention.
Coefficient of Thermal Conductivity
[0024] The thermoconductive silicone elastomer composition was heated for 30 min. at 150 °C and formed into a 1 cm-thick sheet. A coefficient of thermal conductivity of the obtained silicone elastomer sheet was measured by a room-temperature thermal conductivity measuring system (UNITHERM MODEL 2022). Hardness
[0025] Hardness of the silicone elastomer obtained by curing the thermoconductive silicone elastomer composition of the invention for 30 min. at 150 °C was measured by means of a type- A durometer in accordance with JIS K 6253.
Example 1 [0026] A thermoconductive silicone rubber composition was prepared by uniformly mixing 99 parts by weight of a 500 mPa-s viscosity dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain (the content of vinyl groups = 0.43 wt.%), 1 part by weight of a 10 mPa-s viscosity copolymer of methylhydrogensiloxane and dimethylsiloxane block copolymer with trimethylsiloxy groups at both terminals of the molecular chain (the content of silicon-bonded hydrogen = 0.76 wt.%; wherein the silicon-bonded hydrogen was used in an amount of 0.5 mole for 1 mole of the vinyl groups in the aforementioned dimethylpolysiloxane); 900 parts by weight of flake-shaped silver microparticles with an average size of 5 μm; 1-H benzotriazole (used in an amount of 100 ppm relative to the weight of the entire composition); a particulated platinum-type catalyst obtained by finely dispersing a platinum- 1.3- divinylteramethyldisiloxane complex in a thermoplastic silicone resin with a softening point within the range of 80 to 90°C (used in such an amount that in terms of weight units the content of the metallic platinum in the catalyst is 15 ppm); and 2-phenyl-3-butyn-2-ol (used in an amount of 200 ppm relative to the weight of the entire composition). [0027] The obtained portion of the thermoconductive silicone rubber composition was divided into two parts. One part was cured by heating for 30 min. at 150 °C, and the obtained silicone rubber was tested with regard to hardness and thermal conductivity. The remaining part was stored under cold conditions, and one month later was removed from the storage, cured for 30 min. at 150 °C, and the obtained silicone rubber was tested with regard to hardness and thermal conductivity. The results are shown in Table 1.
Example 2
[0028] A thermoconductive silicone rubber composition was produced by the same method as in Example 1 with the exception that 2,6-di-tert-butyl-4-methylphenol was used instead of IH-benzotriazole. The obtained thermoconductive silicone rubber composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 1 [0029] A thermoconductive silicone rubber composition was produced by the same method as in Example 1 with the exception that IH-benzotriazole was not added. The obtained thermoconductive silicone rubber composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Table 1
Practical Example 3 [0030] A thermoconductive silicone rubber composition was prepared by uniformly mixing 90 parts by weight of a 500 mPa-s viscosity dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain (the content of vinyl groups = 0.43 wt.%), 1 part by weight of a 10 mPa-s viscosity copolymer of methylhydrogensiloxane and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain (the content of silicon-bonded hydrogen = 0.76 wt.%; wherein the silicon-bonded hydrogen was used in an amount of 0.5 mole for 1 mole of the vinyl groups in the aforementioned dimethylpolysiloxane); 9 parts by weight of 15 mPa-s viscosity dimethylpolysiloxane blocked with dimethylhydrogensiloxy groups at both terminals of the molecular chain (the content of silicon-bonded hydrogen atoms was 0.12 wt.%; wherein the aforementioned silicon-bonded hydrogen atoms were used in an amount of 0.7 mole for 1 mole of the vinyl groups in the aforementioned dimethylpolysiloxane),
900 parts by weight of spherical silver microparticles with an average size of 5 μm; 1-H benzotriazole (used in an amount of 100 ppm relative to the weight of the entire composition); a particulated platinum-type catalyst obtained by finely dispersing a platinum- 1.3 -divinylteramethyldisiloxane complex in a thermoplastic silicone resin with a softening point within the range of 80 to 90°C (used in such an amount that in terms of weight units the content of the metallic platinum in the composition is 15 ppm); and 2- phenyl-3-butyn-2-ol (used in an amount of 200 ppm relative to the weight of the entire composition).
[0031] The obtained portion of the thermoconductive silicone rubber composition was divided into two parts. One part was cured by heating for 30 min. at 150 °C, and the obtained silicone rubber was tested with regard to hardness and thermal conductivity. The remaining part was stored under cold conditions, and one month later was removed from the storage, cured for 30 min. at 150 °C, and the obtained silicone rubber was tested with regard to hardness and thermal conductivity. The results are shown in Table 2. Example 4
[0032] A thermoconductive silicone rubber composition was produced by the same method as in Example 3 with the exception that 2,6-di-tert-butyl-4-methylphenol was used instead of IH-benzotriazole. The obtained thermoconductive silicone rubber composition was evaluated in the same manner as in Example 3. The results are shown in Table 2.
Comparative Example 2 [0033] A thermoconductive silicone rubber composition was produced by the same method as in Example 3 with the exception that IH-benzotriazole was not added. The obtained thermoconductive silicone rubber composition was evaluated in the same manner as in Example 3. The results are shown in Table 2.
Table 2
Industrial Applicability [0034] The thermoconductive silicone elastomer composition of the invention is characterized by a reduced tendency to the loss of curability during storage and when cured, forms a silicone elastomer of high thermal conductivity.
Claims
1. A thermally conductive silicone elastomer composition comprising:
(A) 100 parts by weight of an organopolysiloxane containing at least two silicon- bonded alkenyl groups per molecule; (B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, wherein the content of said silicon-bonded hydrogen atoms is 0.3 to 10 moles per 1 mole of the alkenyl groups of component (A);
(C) 50 to 5,000 parts by weight of thermally-conductive filler ;
(D) 10 to 10,000 ppm by weight of a phenol compound or a benzotriazole compound, or a combination thereof;
(E) an amount of a platinum catalyst sufficient to provide metallic platinum in an amount of 10 to 10,000 ppm per total weight of the composition; and
(F) 10 to 10,000 ppm by weight of an enyne compound or alkyne alcohol, or a combination thereof.
2. The thermally-conductive silicone elastomer composition of Claim 1, wherein component (A) is selected from the group consisting of copolymers of methylvinylsiloxane and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, methylvmylpolysiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane and methylvinylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylvinylsiloxane, and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, methylvmylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, methylphenylpolysiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of methylvinylsiloxane and dimethylsiloxane blocked with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane and methylvinylsiloxane capped with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylvinylsiloxane, and dimethylsiloxane capped with dimethylvinylsiloxy groups at both terminals of the molecular chain, copolymers of diphenylsiloxane and methylvinylsiloxane capped with dimethylvinylsiloxy groups at both tenninals of the molecular chain; silicone resins comprised of siloxane units as of formula 
and siloxane units of formula SiO4/ , silicone resins comprised of siloxane units as indicated by the formula R^iO^; silicone resins comprised of siloxane units of formula R1 2SiO2/2 and siloxane units of formula R^iO^; siloxane resins comprised of siloxane units of formula R^SiO^, siloxane units of formula R'SiO^, and siloxane units of formula SiO /2; wherein, R1 is a substituted or non-substituted monovalent hydrocarbon group and at least two R s per molecule of the silicone resins are alkenyl groups; and combinations thereof.
3. The thermally-conductive silicone elastomer composition of Claim 1, wherein component (B) is selected from the group consisting of a methylhydrogenpolysiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylhydrogenpolysiloxane and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane and methylhydrogensiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylhydrogensiloxane, and dimethylsiloxane blocked with trimethylsiloxy groups at both terminals of the molecular chain, dimethylpolysiloxane blocked with dimethymydrogensiloxy groups at both terminals of the molecular chain, methylhydrogenpolysiloxane blocked with dimethylhydrogensiloxy groups at both terminals of the molecular chain, copolymers of methylhydrogenpolysiloxane and dimethylsiloxane blocked with dimethylhydrogensiloxy groups at both terminals of the molecular chain, copolymers of methyphenylsiloxane and dimethylsiloxane blocked with dimethylhydrogensiloxy groups at both terminals of the molecular chain, copolymers of methylphenylsiloxane, methylhydrogensiloxane, and dimethylsiloxane blocked with dimethylhydrogensiloxy groups at both terminals of the molecular chain; silicone resins comprised of siloxane units of formula R2 3SiOι/2 and siloxane units of formula SiO4/2, silicone resins comprised of siloxane units of formula R SiO3/2, silicone resins comprised of siloxane units of formula R 2SiO2/2 and siloxane units of formula R2SiO3/2, siloxane resins comprised of siloxane units of formula R2 2SiO2/2, siloxane units of formula R2SiO3/2, and siloxane units of formula SiO4/2; wherein, each R2 is a hydrogen atom or a substituted or non-substituted monovalent hydrocarbon, other than alkenyl groups, and at least two R2's per molecule of the silicone resin are hydrogen atoms.
4. The thermally-conductive silicone elastomer composition of Claim 1, wherein said thermally-conductive filler is a fine silver powder.
5. The thermally-conductive silicone elastomer composition of Claim 1, wherein said phenol compound is a monophenol compound, bisphenol compound, thiobisphenol compound, or a hindered phenol compound.
6. The thermally-conductive silicone elastomer composition of Claim 1, wherein said platinum catalyst of is a finely particulated catalyst dispersed in a thermoplastic resin.
7. The thermally-conductive silicone elastomer composition of Claim 1, wherein said enyne compound is selected from the group consisting of 3-methyl-3-penten-l-yn and 3,5- dimethyl-3-hexen-l-yn, and the alkyne alcohol is selected form the group consisting of 2- methyl-3-butyn-2-ol, 3-dimethyl-l-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol.
8. The thermally-conductive silicone elastomer composition of Claim 1, further comprising at least one optional component selected from the group consisting of an adhesion-imparting agent, an inorganic filler, and an inorganic filler surface-treated with an organic silicone compound.
9. A method of preparing the composition of Claim 1 comprising: unifonnly mixing (A) 100 parts by weight of an organopolysiloxane containing at least two silicon-bonded alkenyl groups per molecule;
(B) an organopolysiloxane having at least two silicon-bonded hydrogen atoms per molecule, wherein the content of said silicon-bonded hydrogen atoms is 0.3 to 10 moles per 1 mole of the alkenyl groups of component (A);
(C) 50 to 5,000 parts by weight of thermally-conductive filler ;
(D) 10 to 10,000 ppm by weight of a phenol compound or a benzotriazole compound, or a combination thereof; (E) an amount of a platinum catalyst sufficient to provide metallic platinum in an amount of 10 to 10,000 ppm per total weight of the composition; and
(F) 10 to 10,000 ppm by weight of an enyne compound or alkyne alcohol, or a combination thereof.
10. Use of the composition of claim 1 as a heat-radiation adhesive agent, heat-radiation die-bonding agent, heat-radiation paste, electromagnetic- wave shield, or a starting material for manufacturing heat-radiating sheets and electromagnetic-wave absorbing sheets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003260954A AU2003260954A1 (en) | 2002-11-21 | 2003-09-08 | Thermally-conductive silicone elastomer composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002337566A JP4676671B2 (en) | 2002-11-21 | 2002-11-21 | Thermally conductive silicone elastomer composition |
| JP2002-337566 | 2002-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004046233A1 true WO2004046233A1 (en) | 2004-06-03 |
Family
ID=32321846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2003/011457 WO2004046233A1 (en) | 2002-11-21 | 2003-09-08 | Thermally-conductive silicone elastomer composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4676671B2 (en) |
| AU (1) | AU2003260954A1 (en) |
| TW (1) | TW200416258A (en) |
| WO (1) | WO2004046233A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393547B2 (en) | 2001-04-11 | 2008-07-01 | Helix Medical, Llc | Antimicrobial elastomer composition and method for making |
| US7520897B2 (en) | 2001-04-11 | 2009-04-21 | Helix Medical, Llc | Medical devices having antimicrobial properties |
| US8317861B2 (en) | 2001-04-11 | 2012-11-27 | Helix Medical, Llc | Antimicrobial indwelling voice prosthesis |
| EP2892945B1 (en) * | 2012-09-07 | 2017-02-01 | Dow Corning Toray Co., Ltd. | Curable silicone composition and optical semiconductor device |
| CN107636078A (en) * | 2015-06-09 | 2018-01-26 | 信越化学工业株式会社 | Addition-curable silicon rubber composition and solidfied material |
| CN109486191A (en) * | 2018-09-04 | 2019-03-19 | 苏州泰吉诺新材料科技有限公司 | A kind of thermally conductive electromagnetic shielding material of the high-performance of room temperature curing and its production technology |
| US10774184B2 (en) | 2016-02-23 | 2020-09-15 | Dow Silicones Corporation | Low temperature cure silicone elastomer |
| US10844196B2 (en) | 2016-10-26 | 2020-11-24 | Shin-Etsu Chemical Co., Ltd. | Thermally-conductive silicone composition |
| US11319412B2 (en) | 2016-10-31 | 2022-05-03 | Dow Toray Co., Ltd. | Thermally conductive silicone compound |
| CN115637050A (en) * | 2021-07-20 | 2023-01-24 | 中蓝晨光化工研究设计院有限公司 | Heat-conducting siloxane composition |
| CN115746362A (en) * | 2022-09-09 | 2023-03-07 | 东莞市零度导热材料有限公司 | Wave-absorbing heat-conducting fin and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4803365B2 (en) * | 2006-02-22 | 2011-10-26 | 信越化学工業株式会社 | Thermally conductive silicone composition, thermally conductive silicone molded article and method for producing the same |
| JP5565758B2 (en) * | 2011-06-29 | 2014-08-06 | 信越化学工業株式会社 | Curable, grease-like thermally conductive silicone composition and semiconductor device |
| CN104837930B (en) * | 2012-12-07 | 2020-10-16 | 杜邦东丽特殊材料株式会社 | Curable silicone composition and optical semiconductor device |
| JP6679870B2 (en) * | 2015-10-05 | 2020-04-15 | 三菱マテリアル株式会社 | Heat dissipation sheet |
| JP6943028B2 (en) * | 2017-06-15 | 2021-09-29 | 信越化学工業株式会社 | Thermally conductive silicone composition |
| WO2019155846A1 (en) * | 2018-02-09 | 2019-08-15 | 信越化学工業株式会社 | Thermoconductive silicone composition, cured product, semiconductor device, and semiconductor device production method |
| JP2023111110A (en) * | 2022-01-31 | 2023-08-10 | 信越化学工業株式会社 | Thermally conductive addition-curable silicone composition and cured product of the same |
| JP2023122466A (en) * | 2022-02-22 | 2023-09-01 | 旭化成ワッカーシリコーン株式会社 | Heat conductive silicone composition and method for producing heat conductive cured product using the composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444944A (en) * | 1982-06-14 | 1984-04-24 | Toray Silicone Company, Ltd. | Thermally conductive silicone rubber composition |
| EP0647682A1 (en) * | 1993-10-06 | 1995-04-12 | Dow Corning Toray Silicone Company, Limited | Silver-filled electrically conductive organosiloxane compositions |
| US5530060A (en) * | 1991-06-03 | 1996-06-25 | Shin-Etsu Chemical Co., Ltd. | Silicone composition capable of yeilding a cured product having good thermal conductivity |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2868986B2 (en) * | 1993-10-06 | 1999-03-10 | 東レ・ダウコーニング・シリコーン株式会社 | Conductive silicone rubber composition |
| JP3524634B2 (en) * | 1995-05-25 | 2004-05-10 | 東レ・ダウコーニング・シリコーン株式会社 | Thermally conductive silicone rubber composition |
| JP3576639B2 (en) * | 1995-05-29 | 2004-10-13 | 東レ・ダウコーニング・シリコーン株式会社 | Thermally conductive silicone rubber composition |
| JP3597277B2 (en) * | 1995-10-17 | 2004-12-02 | 東レ・ダウコーニング・シリコーン株式会社 | Thermal conductive silicone rubber and composition thereof |
-
2002
- 2002-11-21 JP JP2002337566A patent/JP4676671B2/en not_active Expired - Fee Related
-
2003
- 2003-09-08 WO PCT/JP2003/011457 patent/WO2004046233A1/en active Application Filing
- 2003-09-08 AU AU2003260954A patent/AU2003260954A1/en not_active Abandoned
- 2003-10-13 TW TW092128292A patent/TW200416258A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444944A (en) * | 1982-06-14 | 1984-04-24 | Toray Silicone Company, Ltd. | Thermally conductive silicone rubber composition |
| US5530060A (en) * | 1991-06-03 | 1996-06-25 | Shin-Etsu Chemical Co., Ltd. | Silicone composition capable of yeilding a cured product having good thermal conductivity |
| EP0647682A1 (en) * | 1993-10-06 | 1995-04-12 | Dow Corning Toray Silicone Company, Limited | Silver-filled electrically conductive organosiloxane compositions |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393547B2 (en) | 2001-04-11 | 2008-07-01 | Helix Medical, Llc | Antimicrobial elastomer composition and method for making |
| US7520897B2 (en) | 2001-04-11 | 2009-04-21 | Helix Medical, Llc | Medical devices having antimicrobial properties |
| US8317861B2 (en) | 2001-04-11 | 2012-11-27 | Helix Medical, Llc | Antimicrobial indwelling voice prosthesis |
| EP2892945B1 (en) * | 2012-09-07 | 2017-02-01 | Dow Corning Toray Co., Ltd. | Curable silicone composition and optical semiconductor device |
| CN107636078A (en) * | 2015-06-09 | 2018-01-26 | 信越化学工业株式会社 | Addition-curable silicon rubber composition and solidfied material |
| EP3309219A4 (en) * | 2015-06-09 | 2018-12-26 | Shin-Etsu Chemical Co., Ltd. | Addition-curable silicone rubber composition and cured product |
| US10544281B2 (en) | 2015-06-09 | 2020-01-28 | Shin-Etsu Chemical Co., Ltd. | Addition-curable silicone rubber composition and cured product |
| US11203667B2 (en) | 2016-02-23 | 2021-12-21 | Dow Silicones Corporation | Low temperature cure silicone elastomer |
| US10774184B2 (en) | 2016-02-23 | 2020-09-15 | Dow Silicones Corporation | Low temperature cure silicone elastomer |
| US10844196B2 (en) | 2016-10-26 | 2020-11-24 | Shin-Etsu Chemical Co., Ltd. | Thermally-conductive silicone composition |
| US11319412B2 (en) | 2016-10-31 | 2022-05-03 | Dow Toray Co., Ltd. | Thermally conductive silicone compound |
| CN109486191A (en) * | 2018-09-04 | 2019-03-19 | 苏州泰吉诺新材料科技有限公司 | A kind of thermally conductive electromagnetic shielding material of the high-performance of room temperature curing and its production technology |
| CN115637050A (en) * | 2021-07-20 | 2023-01-24 | 中蓝晨光化工研究设计院有限公司 | Heat-conducting siloxane composition |
| CN115746362A (en) * | 2022-09-09 | 2023-03-07 | 东莞市零度导热材料有限公司 | Wave-absorbing heat-conducting fin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4676671B2 (en) | 2011-04-27 |
| TW200416258A (en) | 2004-09-01 |
| AU2003260954A1 (en) | 2004-06-15 |
| JP2004168920A (en) | 2004-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2004046233A1 (en) | Thermally-conductive silicone elastomer composition | |
| US7704607B2 (en) | Silicone rubber compositions for the sealing and encapsulation of electric and electronic parts | |
| KR101495215B1 (en) | Curable silicone composition and cured product thereof | |
| CA1290875C (en) | Curable organopolysiloxane compositions with improved adhesion | |
| JP5445415B2 (en) | Thermally conductive silicone adhesive composition and thermally conductive silicone elastomer molded article | |
| EP2892953B1 (en) | Curable silicone composition and cured product thereof | |
| US6069201A (en) | Zinc oxide-filled addition-curable silicone rubber compositions | |
| TWI734899B (en) | Silicone resin composition and hardened material for die bonding | |
| KR101468459B1 (en) | Thermocurable silicone rubber composition | |
| WO2012173167A1 (en) | Cross-linkable silicone composition and cross-linked product thereof | |
| US5283307A (en) | Organosiloxane compositions exhibiting improved bonding to substrates during curing | |
| JP3919001B2 (en) | Addition reaction curable organopolysiloxane composition | |
| JP3154208B2 (en) | Silicone rubber composition | |
| JPH08225743A (en) | Silicone gel composition | |
| JPH07150048A (en) | Electrically conductive silicone rubber composition | |
| KR20200050875A (en) | Addition-curable silicone resin composition, cured product thereof, and optical semiconductor device | |
| JP3447226B2 (en) | Addition-curable silicone rubber composition filled with zinc oxide and cured product thereof | |
| CN117413021A (en) | Thermally conductive silicone composition and cured product thereof | |
| JP3477008B2 (en) | Addition-curable silicone rubber composition filled with calcium carbonate | |
| WO2010127215A1 (en) | Highly conductive thermal interface, no pump-out thermal interface greases and method for producing them | |
| JP3447964B2 (en) | Addition-curable silicone rubber composition filled with zinc oxide | |
| JP2020029536A (en) | Silicone gel composition and silicone gel cured product | |
| JPH0482023B2 (en) | ||
| JP3550321B2 (en) | Addition-curable organopolysiloxane composition | |
| JP2023153695A (en) | Thermally conductive silicone composition and cured product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 122 | Ep: pct application non-entry in european phase |