Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
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  • 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
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  • 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
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  • 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
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  • C08K3/02—Elements
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  • 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
  • C08L83/04—Polysiloxanes
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
  • C09J183/04—Polysiloxanes
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/10—Arrangements for heating
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/136—Phenols containing halogens
• • 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
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond

Definitions

• the present invention relates to a thermally conductive addition-curable silicone composition and its cured product.
• a common problem with electronic component packages and power modules is heat generation during operation and the resulting deterioration in performance, and various heat dissipation technologies are used as a means to solve this problem.
• a technique of radiating heat by arranging a cooling member in the vicinity of the heat-generating part and bringing them into close contact with each other to efficiently remove the heat from the cooling member is generally used.
• heat dissipation grease that is thin and compressible and has excellent penetrability into the gap between the heat generating part and the cooling member is suitable from the viewpoint of heat dissipation performance.
• thermal grease by compressing to the desired thickness and then heating and hardening, it is difficult for the thermal grease to flow out (pumping out) due to expansion and contraction due to the thermal history of repeated heat generation and cooling of the heat generating part.
• Addition-curing thermal greases are particularly useful because they can increase the reliability of modules (eg, US Pat.
• JP-A-2002-327116 JP-A-2004-130646 JP 2009-234112 A Japanese Patent Application Laid-Open No. 2009-209230 JP 2010-095730 A JP 2008-031336 A Japanese Patent Application Laid-Open No. 2007-177001 Japanese Patent Application Laid-Open No. 2008-260798 JP 2009-209165 A JP 2016-053140 A
• an object of the present invention is to provide a thermally conductive addition-curable silicone composition with excellent heat dissipation properties.
• the present invention provides a thermally conductive addition-curable silicone composition, (A) an organopolysiloxane having at least one aliphatic unsaturated hydrocarbon group per molecule and a kinematic viscosity at 25°C of 60 to 100,000 mm 2 /s; (B) a phenolic compound: an amount of 0.01 to 10% by mass based on the total composition; (C) silver powder: an amount of 10 to 98% by mass based on the total composition; (D) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms in one molecule: an effective amount sufficient for the composition to form a cured product; (E) a platinum group metal catalyst: an effective amount;
• a thermally conductive addition-curable silicone composition is provided comprising:
• Such a thermally conductive addition-curable silicone composition is excellent in heat dissipation.
• the component (B) is preferably a phenol compound represented by the following general formula (1A).
• R 1 represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group.
• R 3 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a phenyl group, and each Xf is independently substituted with a hydrogen atom, a halogen atom or a fluorine atom having 1 to 10 carbon atoms.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 3 to 20 carbon atoms, and the carbon atoms of the ring ZZ are substituted with a nitrogen atom, an oxygen atom, or a sulfur atom.
• ka represents an integer of 0 to 2.
• kb and kd represent 1 or 2.
• kc and ke represent integers of 0 to 2.
• Such a thermally conductive addition-curable silicone composition is more excellent in heat dissipation.
• the component (B) is preferably a phenol compound represented by the following general formula (1B).
• R 1 , R 2 and R 3 are the same as above.
• Such a thermally conductive addition-curable silicone composition is more reliably excellent in heat dissipation.
• the average particle size of the component (C) is 0.01 to 300 ⁇ m.
• the resulting composition is uniform, does not have an excessively high viscosity, and has excellent extensibility.
• (F) one or more addition curing reaction inhibitors selected from the group consisting of acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds, and organic chloro compounds, in an effective amount. is preferred.
• the thermally conductive addition-curable silicone composition described above is sandwiched between two silicon plates having a diameter of 12.7 mm and heated at 125° C. for 1 hour under a pressure of 0.14 MPa.
• a test piece for thermal resistance measurement was prepared, the thermal resistance value of the thermally conductive addition-curable silicone cured product was measured using a thermal conductivity measuring device, and the thickness of the test piece was measured using a microgauge.
• the thickness of the thermally conductive addition-curable silicone cured product is calculated from the difference between the thickness of the silicone plate measured in advance and the thickness of the thermally conductive addition-curable silicone cured product.
• Thermal conductivity obtained by deriving the thermal conductivity of the cured thermally conductive addition-curable silicone product from the thermal resistance value (mm 2 K/W) of the cured thermally conductive addition-curable silicone product ( ⁇ m) is 7.0 W/m ⁇ K or more.
• Such a thermally conductive addition-curable silicone cured product has excellent heat dissipation.
• the thermally conductive addition-curable silicone composition of the present invention achieves high thermal conductivity by blending a phenolic compound and silver powder. As a result, excellent heat dissipation performance can be exhibited by mounting in an electronic component package or a power module.
• the present inventors have conducted intensive research to achieve the above objects, and as a result, identified an aliphatic unsaturated hydrocarbon group-containing organopolysiloxane, a phenolic compound, silver powder, an organohydrogenpolysiloxane, and a platinum group metal catalyst.
• the inventors have found that a thermally conductive addition-curable silicone composition with excellent heat dissipation can be obtained by blending an amount of these compounds, and have completed the present invention.
• the present invention provides a thermally conductive addition-curable silicone composition
• A an organopolysiloxane having at least one aliphatic unsaturated hydrocarbon group per molecule and a kinematic viscosity at 25°C of 60 to 100,000 mm 2 /s
• B a phenolic compound: an amount of 0.01 to 10% by mass based on the total composition
• C silver powder: an amount of 10 to 98% by mass based on the total composition
• D an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms in one molecule: an effective amount sufficient for the composition to form a cured product
• E a platinum group metal catalyst: an effective amount
• a thermally conductive addition-curable silicone composition comprising:
• thermally Conductive Addition-Cure Silicone Composition The thermally conductive addition-curable silicone composition of the present invention comprises components (A) to (E) described later, and, if necessary, component (F) and other components. It contains Each component will be described in detail below.
• Component (A) has at least 1, preferably 1 to 100, more preferably 2 to 50 aliphatic unsaturated hydrocarbon groups in one molecule, and has a kinematic viscosity at 25°C of 60 to 100,000 mm 2 /s.
• the aliphatic unsaturated hydrocarbon group is preferably a monovalent hydrocarbon group having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably an alkenyl group, having an aliphatic unsaturated bond.
• alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl groups.
• a vinyl group is particularly preferred.
• the aliphatic unsaturated hydrocarbon group may be bonded to either a silicon atom at the end of the molecular chain, a silicon atom in the middle of the molecular chain, or both.
• the organic group other than the aliphatic unsaturated hydrocarbon group, which is bonded to the silicon atom of the organopolysiloxane has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. It is a substituted or substituted monovalent hydrocarbon group.
• 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, nonyl group, decyl group;
• Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; substituted with a halogen atom, a cyano group, etc., such as a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group, and the like.
• the organopolysiloxane has a kinematic viscosity at 25° C. of 60 to 100,000 mm 2 /s, preferably 100 to 30,000 mm 2 /s. If the kinematic viscosity is less than 60 mm 2 /s, the physical properties of the thermally conductive addition-curable silicone composition are degraded, and if it exceeds 100,000 mm 2 /s, it is Extensibility is poor.
• kinematic viscosity is a value at 25°C measured with an Ubbelohde-type Ostwald viscometer (hereinafter the same).
• the molecular structure of the organopolysiloxane is not particularly limited as long as it has the properties described above. be done.
• it preferably has a linear structure in which the main chain consists of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups.
• the organopolysiloxane having a linear structure may partially have a branched structure or a cyclic structure.
• the blending amount of component (A) is preferably 1.5 to 89% by mass, more preferably 1.7 to 50% by mass, and even more preferably 2 to 20% by mass, based on the total composition. If it is 89% by mass or less, the thermal conductivity is not poor, and if it is 1.5% by mass or more, the viscosity of the composition does not increase more than necessary and workability does not deteriorate.
• the organopolysiloxane can be used singly or in combination of two or more.
• Component (B) is a phenolic compound that is added as an additive to the thermally conductive addition-curable silicone composition.
• the phenol compound is preferably a phenol compound represented by the following general formula (1A).
• 1A a phenol compound represented by the following general formula
• R 1 represents a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group.
• R 3 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or a phenyl group, and each Xf is independently substituted with a hydrogen atom, a halogen atom or a fluorine atom having 1 to 10 carbon atoms.
• Each ring ZZ independently represents an aromatic monocyclic or polycyclic ring having 3 to 20 carbon atoms, and the carbon atoms of the ring ZZ are substituted with a nitrogen atom, an oxygen atom, or a sulfur atom.
• ka represents an integer of 0 to 2.
• kb and kd represent 1 or 2.
• kc and ke represent integers of 0 to 2.
• linear, branched or cyclic (ka+2)-valent hydrocarbon group having 1 to 20 carbon atoms in Az include the following. (In the formula, broken lines indicate bonds.)
• the linear, branched, or cyclic (ka+2)-valent fluorinated hydrocarbon group of Az having 1 to 20 carbon atoms is specifically , substituted with a fluorine atom can be exemplified.
• Az preferably has 2 to 18 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 4 to 14 carbon atoms. It is also preferred that a portion of —CH 2 — constituting the hydrocarbon group is replaced with —Si(R 2 R 3 )— or —Si(R 2 R 3 )—O—.
• linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms for R 2 and R 3 include methyl, ethyl, propyl, isopropyl, n-butyl and sec-butyl. group, tert-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
• linear, branched or cyclic monovalent hydrocarbon groups of Xf which may be substituted with fluorine atoms having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n- Alkyl groups such as butyl group, sec-butyl group, tert-butyl group, cyclopropyl group and cyclobutyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group and the like can be mentioned.
• alkoxy group of Xf having 1 to 10 carbon atoms which may be substituted with a fluorine atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group. , cyclopropoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group and the like.
• aromatic monocyclic or polycyclic ring ZZ having 3 to 20 carbon atoms include the following. Ring ZZ may further have a substituent as described below.
• a phenol compound represented by the following general formula (1B) is particularly preferable as the phenol compound represented by the general formula (1A).
• R 1 , R 2 and R 3 are the same as above.
• the amount of component (B) is 0.01 to 10% by mass of the total composition, preferably 0.03 to 5% by mass, and more preferably 0.05 to 1.0% by mass. preferable. If the amount is less than 0.01% by mass, the effect of improving the heat dissipation of the thermally conductive addition-curable silicone composition is poor. It is uneconomical and uneconomical.
• Component (C) is silver powder.
• the method for producing the silver powder is not particularly limited, and examples thereof include an electrolysis method, a pulverization method, a heat treatment method, an atomization method, a reduction method and the like.
• the shape is not particularly limited and may be flake-like, spherical, granular, amorphous, dendritic, needle-like, or the like.
• the range is preferably 0.01 to 300 ⁇ m, preferably 0.1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
• the average particle diameter can be determined as a volume-based average value (or median diameter) in particle size distribution measurement by a laser beam diffraction method, for example.
• component (C) can be used alone or in combination of two or more, and the ratio is not particularly limited and is arbitrary.
• the amount of component (C) is 10 to 98% by mass, preferably 70 to 97% by mass, more preferably 80 to 95% by mass, based on the total composition. If the amount is more than 98% by mass, the viscosity of the composition may be significantly increased and the workability may be deteriorated.
• Component (D) is an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms in one molecule, i.e., silicon-bonded hydrogen atoms (SiH groups) in one molecule. It is an organohydrogenpolysiloxane having 2 or more, particularly preferably 2 to 100, more preferably 2 to 50. In the organohydrogenpolysiloxane, the SiH groups in the molecule undergo an addition reaction with the unsaturated aliphatic hydrocarbon groups of component (A) in the presence of a platinum group metal catalyst to form a crosslinked structure. I wish I had.
• the molecular structure of the organohydrogenpolysiloxane is not particularly limited as long as it has the properties described above. structure and the like. A linear structure and a cyclic structure are preferred.
• the organohydrogenpolysiloxane has a kinematic viscosity at 25° C. of preferably 1 to 1,000 mm 2 /s, more preferably 10 to 300 mm 2 /s. If the kinematic viscosity is 1 mm 2 /s or more, the physical properties of the thermally conductive addition-curable silicone composition will not deteriorate. The extensibility of the silicone composition becomes good.
• organic groups bonded to the silicon atoms of the organohydrogenpolysiloxane include unsubstituted or substituted monovalent hydrocarbon groups other than aliphatic unsaturated hydrocarbon groups.
• it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms.
• alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and dodecyl group, aryl groups such as phenyl group, aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group, these hydrogen
• halogen atoms such as fluorine, bromine, and chlorine
• cyano groups epoxy ring-containing organic groups (glycidyl groups or glycidyloxy group-substituted alkyl groups), etc., such as chloromethyl group and chloropropyl bromoethyl, trifluoropropyl, cyanoethyl, 2-glycidoxyethyl, 3-glycidoxypropyl, and 4-glycidoxybutyl groups.
• a methyl group and a trifluoropropyl group are preferred.
• the organohydrogenpolysiloxane may be used singly or in combination of two or more.
• the amount of component (D) organohydrogenpolysiloxane to be blended is an effective amount sufficient for the composition to form a cured product, preferably the total number of aliphatic unsaturated hydrocarbon groups in component (A).
• the number of SiH groups in the component (D) is 0.5 to 10, more preferably 0.7 to 7.5, more preferably 1.0 to 5.0. . If the amount of component (D) is at least the above lower limit, the addition reaction will proceed sufficiently and crosslinking will be sufficient. Moreover, if it is below the said upper limit, a crosslinked structure will not become uneven and the storage stability of a composition will not deteriorate.
• Component (E) is a platinum group metal catalyst and functions to promote the addition reaction of the above components.
• the platinum group metal catalyst conventionally known ones used for addition reactions can be used.
• platinum-based, palladium-based, and rhodium-based catalysts can be used, but platinum or platinum compounds, which are relatively easily available, are preferred. Examples thereof include simple platinum, platinum black, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, and platinum coordination compounds.
• the platinum group metal catalysts may be used singly or in combination of two or more.
• the amount of component (E) to be added should be an effective amount as a catalyst, that is, an effective amount necessary to promote the addition reaction and cure the thermally conductive addition-curable silicone composition of the present invention. It is preferably 0.1 to 500 ppm, more preferably 1 to 200 ppm, and still more preferably 10 to 100 ppm based on the mass of platinum group metal atoms, relative to the entire composition. If the amount of the catalyst is at least the above lower limit, the effect as a catalyst can be obtained, and if it is at most the above upper limit, the catalytic effect is sufficient and economical.
• thermally conductive addition-curable silicone composition of the present invention may optionally contain the following optional components.
• Component (F) is one or more addition curing reactions selected from the group consisting of acetylene compounds, nitrogen compounds, organic phosphorus compounds, oxime compounds, and organic chloro compounds that inhibit the progress of hydrosilylation reactions at room temperature. It is a regulator and can be added to prolong shelf life and pot life.
• addition curing reaction controller conventionally known addition curing reaction controllers used in addition curing silicone compositions can be used.
• acetylene compounds such as acetylene alcohols (eg, ethynylmethyldecylcarbinol, 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol), tributylamine, tetra
• nitrogen compounds such as methylethylenediamine and benzotriazole
• organic phosphorus compounds such as triphenylphosphine, oxime compounds, and organic chloro compounds.
• the amount may be an effective amount, preferably 0.05 to 10 parts by mass, more preferably 0.07 to 5 parts by mass, based on 100 parts by mass of component (A), More preferably, it is 0.1 to 2 parts by mass.
• the amount of the reaction inhibitor is 0.05 parts by mass or more, the desired sufficient shelf life and pot life can be obtained, and when the amount is 10 parts by mass or less, the curability of the silicone composition does not deteriorate.
• reaction control agent may be diluted with organo(poly)siloxane, toluene, or the like in order to improve dispersibility in the silicone composition.
• the thermally conductive addition-curable silicone composition of the present invention may contain a non-reactive organo(poly)siloxane such as methylpolysiloxane in order to adjust the strength and viscosity of the composition.
• a non-reactive organo(poly)siloxane such as methylpolysiloxane
• one or more conventionally known thermally conductive fillers other than silver may be used in combination.
• hydrolyzable organopolysiloxanes, various modified silicones, and hydrolyzable organosilanes may be blended for the purpose of improving the filling properties of the thermally conductive filler or imparting adhesiveness to the composition.
• a solvent may be added to adjust the viscosity of the composition.
• antioxidants such as 2,6-di-tert-butyl-4-methylphenol may optionally be contained in order to prevent deterioration of the thermally conductive addition-curable silicone composition.
• dyes, pigments, flame retardants, anti-settling agents, thixotropic agents, etc. can be blended as needed.
• Step of Preparing the Thermally Conductive Addition Curing Silicone Composition The method for producing the thermally conductive addition curing silicone composition of the present invention will be described.
• the method for producing the thermally conductive addition-curable silicone composition of the present invention is not particularly limited, but the above-described components (A) to (E), and optionally component (F) and other components may be used.
• component (A) to (E), and optionally component (F) and other components for example, Trimix, Twinmix, and Planetary Mixer (both registered trademarks of Inoue Seisakusho Co., Ltd. mixer), Using a mixer such as Ultra Mixer (registered trademark of mixer manufactured by Mizuho Kogyo Co., Ltd.), Hibismix (registered trademark of mixer manufactured by Primix Co., Ltd.), etc., at 25 ° C. for usually 3 minutes to 24 hours, preferably A method of mixing for 5 minutes to 12 hours, particularly preferably 10 minutes to 6 hours, can be used. Further, degassing may be performed during mixing, and mixing may be performed while heating in the range of 40 to 170°C.
• Ultra Mixer registered trademark of mixer manufactured by Mizuho Kogyo Co., Ltd.
• Hibismix registered trademark of mixer manufactured by Primix Co., Ltd.
• degassing may be performed during mixing, and mixing may be performed while heating in the range of 40 to 170°C.
• components (A) and (C) are preliminarily mixed at 70°C, and then components (B), (D) and (E) are mixed at 25°C.
• a silicone composition is preferable from the viewpoint of exhibiting good thermal conductivity.
• the optional component (F) after mixing the (A) and (C) components in advance, the (F) component is mixed, and then the (B), (D) and (E) components are preferably mixed.
• the thermally conductive addition-curable silicone composition of the present invention has a viscosity measured at 25° C. of preferably 10 to 1,000 Pa ⁇ s, more preferably 20 to 700 Pa ⁇ s, still more preferably 40 to 600 Pa ⁇ s. is s. If the viscosity is 10 Pa ⁇ s or more, it is not difficult to maintain the shape, and workability such as precipitation of the silver powder does not deteriorate. Further, if the viscosity is 1,000 Pa ⁇ s or less, workability is not deteriorated, such as discharge and coating being not difficult.
• the said viscosity can be obtained by adjusting the compounding quantity of each component mentioned above. Said viscosity can be measured, for example, at 25° C. using a Malcolm viscometer (type PC-1T).
• the cured product of the thermally conductive addition-curable silicone composition of the present invention usually has a thermal conductivity of 0.5 to 100 W/m ⁇ K. It preferably has a thermal conductivity of 7.0 W/m ⁇ K or more in order to exhibit performance.
• the curing conditions for heat-curing the thermally conductive addition-curable silicone composition of the present invention are not particularly limited, but usually 80 to 200° C., preferably 100 to 180° C., 15 minutes to 4 hours, It is preferably 30 minutes to 2 hours.
• the thermally conductive addition-curable silicone cured product of the present invention is prepared by sandwiching the thermally conductive addition-curable silicone composition described above between two silicon plates having a diameter of 12.7 mm and applying a pressure of 0.14 MPa. Heat and cure at 125 ° C. for 1 hour in the state, prepare a test piece for thermal resistance measurement, measure the thermal resistance value of the thermally conductive addition-curable silicone cured product using a thermal conductivity measurement device, , the thickness of the test piece is measured with a microgauge, and the thickness of the thermally conductive addition-curable silicone cured product is calculated from the difference from the previously measured thickness of the silicon plate.
• the thickness of the cured conductive addition-curable silicone product ( ⁇ m) ⁇ the thermal resistance value of the cured thermally conductive addition-curable silicone product (mm 2 K/W) gives the heat of the cured thermally conductive addition-curable silicone product. It is preferable that the thermal conductivity is 7.0 W/m ⁇ K or more when the conductivity is derived.
• the kinematic viscosity indicates the value at 25° C. measured by an Ubbelohde-type Ostwald viscometer.
• thermally conductive addition-curable silicone composition of the present invention were prepared.
• Component A-1 Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity at 25°C of 600 mm 2 /s
• A-2 Both ends blocked with dimethylvinylsilyl groups, 25°C
• A-3 having a kinematic viscosity of 30,000 mm 2 /s at 25° C.:
• Organopolysiloxane having a kinematic viscosity of 800 mm 2 /s at 25° C. represented by the following formula (2)
• B-1 a phenol compound represented by the following formula (3)
• B-2 a phenol compound represented by the following formula (4)
• B-3 a phenol compound represented by the following formula (5)
• B-4 a phenol compound represented by the following formula (6)
• B-5 a phenol compound represented by the following formula (7)
• Component C-1 Flake-like silver powder with an average particle size of 15 ⁇ m, a tap density of 4.0 g/mL, and a specific surface area of 0.5 m 2 /g C-2: an average particle size of 4 ⁇ m, a tap density of 2.2 g/mL , flaky silver powder having a specific surface area of 2.0 m 2 /g C-3: average particle diameter of 4 ⁇ m, tap density of 2.3 g/mL, flaky silver powder having a specific surface area of 0.9 m 2 /g C-4: average grain Flake-like silver powder C-5 with a diameter of 2 ⁇ m, a tap density of 2.4 g/mL, and a specific surface area of 0.9 m 2 /g: an average particle diameter of 3 ⁇ m, a tap density of 6.9 g/mL, and a specific surface area of 0.2 m 2 /g spherical silver powder
• E-1 A solution of a platinum-divinyltetramethyldisiloxane complex dissolved in the same dimethylpolysiloxane as A-1 above (platinum atom content: 1% by mass)
• E-2 Solution of platinum-divinyltetramethyldisiloxane complex dissolved in ethanol (platinum atom content: 3% by mass)
• thermally conductive addition-curable silicone composition obtained by the above method was measured for viscosity and thermal conductivity according to the following methods. The results are shown in Tables 1-4.
• thermal conductivity of the thermally conductive addition-curable silicone cured product was derived from the following formula.
• the thermally conductive addition-curable silicone composition of the present invention achieves high thermal conductivity by blending a phenolic compound and silver powder. As a result, excellent heat dissipation performance can be exhibited by mounting in an electronic component package or a power module.
• the present invention is not limited to the above embodiments.
• the above-described embodiment is an example, and any device having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect is the present invention. included in the technical scope of

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