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WO2007106209A2 - Graisse conductrice thermiquement et procedes et dispositifs dans lesquels ladite graisse est utilisee - Google Patents

Graisse conductrice thermiquement et procedes et dispositifs dans lesquels ladite graisse est utilisee Download PDF

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Publication number
WO2007106209A2
WO2007106209A2 PCT/US2007/001070 US2007001070W WO2007106209A2 WO 2007106209 A2 WO2007106209 A2 WO 2007106209A2 US 2007001070 W US2007001070 W US 2007001070W WO 2007106209 A2 WO2007106209 A2 WO 2007106209A2
Authority
WO
WIPO (PCT)
Prior art keywords
grease
heat spreader
interface material
electronic component
filler
Prior art date
Application number
PCT/US2007/001070
Other languages
English (en)
Other versions
WO2007106209A3 (fr
Inventor
Mark Fisher
Zuchen Lin
Original Assignee
Dow Corning Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Publication of WO2007106209A2 publication Critical patent/WO2007106209A2/fr
Publication of WO2007106209A3 publication Critical patent/WO2007106209A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • 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
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/05—Metals; Alloys
    • C10M2201/053—Metals; Alloys used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • C10M2201/0613—Carbides; Hydrides; Nitrides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C10M2201/0623—Oxides; Hydroxides; Carbonates or bicarbonates used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/043—Siloxanes with specific structure containing carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/08—Solids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/14—Composite materials or sliding materials in which lubricants are integrally molded
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73253—Bump and layer connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/161—Cap
    • H01L2924/1615—Shape
    • H01L2924/16152—Cap comprising a cavity for hosting the device, e.g. U-shaped cap
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/301—Electrical effects
    • H01L2924/3011—Impedance

Definitions

  • This invention relates to a thermally conductive grease ("grease”), methods for preparation and use of the grease, and devices containing the grease. More particularly, this invention relates to a grease including a silicone matrix and a thermally conductive filler. The silicone matrix has hydrocarbonoxy-functional groups. The grease may be used as a thermal interface material ("TIM"). BACKGROUND
  • heat can be transferred from the electronic component to the heat sink by surface contact between the electronic component and the heat sink or by contact of the electronic component and heat sink with a TIM.
  • This invention relates to a grease comprising a polyorganosiloxane and a thermally conductive filler. This invention further relates to methods and devices in which the grease may be used.
  • “Bleed” means a tendency of siloxane species to migrate out of a grease onto a surface on which the grease is applied.
  • centiSt centiStokes
  • Hydrocarbon group means a monovalent radical comprising carbon atoms and hydrogen atoms. Hydrocarbon groups may be saturated or unsaturated. Hydrocarbon groups may be substituted or unsubstituted. Unsubstituted hydrocarbon groups are exemplified by, but not limited to, aliphatically unsaturated hydrocarbon groups and hydrocarbon groups free of aliphatic unsaturation. Aliphatically unsaturated hydrocarbon groups are exemplified by, but not limited to, alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl.
  • Hydrocarbon groups free of aliphatic unsaturation are exemplified by, but not limited to, alkyl groups such as methyl, ethyl, propyl, and butyl, pentyl, and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl.
  • Substituted hydrocarbon groups are hydrocarbon groups in which at least one of the hydrogen atoms has been replaced with another substituent, for example, a halogen atom, cyano group, epoxy group, amino group, or amido group.
  • W/mK means Watts per meter Kelvin.
  • This invention relates to a grease comprising: (A) 2 to 50 %, based on the weight of the grease, of a polyorganosiloxane, and
  • (B) 50 to 98 %, based on the weight of the grease, of a thermally conductive filler.
  • Ingredient (A) is a polyorganosiloxane containing, on average, at least one silicon- bonded hydrocarbonoxy-functional group per molecule.
  • the polyorganosiloxane contains, on average, at least two silicon-bonded hydrocarbonoxy- functional groups per molecule.
  • the polyorganosiloxane contains, on average, at least three silicon-bonded hydrocarbonoxy-functional groups per molecule.
  • the polyorganosiloxane contains, on average, one to six silicon-bonded hydrocarbonoxy- functional groups per molecule.
  • the polyorganosiloxane contains, on average, one to three silicon-bonded hydrocarbonoxy-functional groups per molecule.
  • Ingredient (A) may comprise a single polyorganosiloxane discussed herein or a combination comprising two or more polyorganosiloxanes discussed herein, where the polyorganosiloxanes in the combination differ in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence.
  • the hydrocarbonoxy-functional group or groups in ingredient (A) may be at a terminal position, at a pendant position, or a combination thereof. Alternatively, the hydrocarbonoxy-functional groups in ingredient (A) may be at a terminal position. When more than one hydrocarbonoxy-functional group is present, then two or three hydrocarbonoxy-functional groups may be present at the same terminal of the polyorganosiloxane.
  • Suitable polyorganosiloxanes for ingredient (A) may comprise linear, branched, cyclic, or resinous structures.
  • Linear polyorganosiloxanes suitable as ingredient (A) may have the general formula:
  • each R 1 , R 2 , R 3 , R 6 , R 7 , and R 8 is independently a hydrocarbon group or a hydrocarbonoxy-functional group; and subscript b is 5 to 500, alternatively 25 to 100; with the proviso that at least one of R 1 , R 2 , R 3 , R 6 , R 7 , and R 8 is hydrocarbonoxy-functional group.
  • each R 1 , R 2 , R 3 , R 4 , and R 5 is independently a hydrocarbon group; each R 6 , R 7 , and R 8 is independently a hydrocarbonoxy-functional group; and subscript b is 5 to 500, alternatively 25 to 100.
  • Suitable hydrocarbon groups include, but are not limited to, aliphatically unsaturated hydrocarbon groups and hydrocarbon groups free of aliphatic unsaturation.
  • Aliphatically unsaturated hydrocarbon groups are exemplified by alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl.
  • Hydrocarbon groups free of aliphatic unsaturation are exemplified by alkyl groups such as methyl, ethyl, propyl, and butyl, pentyl, and hexyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; and aryl groups such as phenyl.
  • R 1 is an alkyl group or an alkenyl group
  • R 2 , R 3 , R 4 , and R 5 are each independently an alkyl group
  • R , R 7 , and R 8 are each independently an alkoxy group
  • b is 25 to 100.
  • Suitable hydrocarbonoxy-functional groups may have the formula:
  • Suitable polyorganosiloxanes for ingredient (A) may have the formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 9 is independently a hydrocarbon group; b is 5 to
  • Suitable linear polyorganosiloxanes for ingredient (A) may comprise, for example:
  • HL 2C H C- -Si-O- Si-O- ⁇ 25 -Si- C-C- Si— f O— CH,
  • polyorganosiloxanes suitable for use as ingredient (A) such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes, are well known in the art.
  • polyorganosiloxanes suitable for use as ingredient (A) may be prepared by ring opening polymerization of cyclic polydiorganosiloxanes using a lithium catalyst to yield polyorganosiloxanes having silicon- bonded hydroxyl groups. Thereafter, the polyorganosiloxanes having silicon-bonded hydroxyl groups may be reacted with silanes having silicon-bonded hydrocarbonoxy- functional groups to prepare ingredient (A).
  • polyorganosiloxanes suitable for use as ingredient (A) may be prepared by hydrosilylation of a polyorga ⁇ osiloxane having at least one silicon bonded hydrogen atom with a hydrocarbonoxysilane having at least one silicon bonded aliphat ⁇ cally unsaturated hydrocarbon group in the presence of a platinum group metal catalyst or by hydrosilylation of a polyorganosiloxane having at least one silicon bonded aliphatically unsaturated hydrocarbon group with hydrocarbonoxysilane having at least one silicon bonded hydrogen atom in the presence of a platinum group metal catalyst.
  • polyorganosiloxanes suitable for use as ingredient (A) may be prepared by methods such as those disclosed, for example, in U.S. Patent 4,962,174.
  • the amount of ingredient (A) depends on various factors including the polyorganosiloxane selected for ingredient (A) and the thermally conductive filler selected for ingredient (B). However, the amount of ingredient (A) may be 2 to 50 %, alternatively 2 to 10 %, alternatively 2 to 5 %, and alternatively 3 to 5%, based on the weight of the grease.
  • Ingredient (B) is a thermally conductive filler.
  • the amount of ingredient (B) in the grease depends on various factors including the polyorganosiloxane selected for ingredient (A) and the thermally conductive filler selected for ingredient (B). However, the amount of ingredient (B) may be 50 to 98 % based on the weight of the grease.
  • Ingredient (B) may be both thermally conductive and electrically conductive. Alternatively, ingredient (B) may be thermally conductive and electrically insulating. Ingredient (B) may comprise a metallic filler, a ceramic filler, or a combination thereof.
  • Metallic fillers include particulates of metals and particulates of metals having layers on the surfaces of the particles. These layers may be, for example, metal nitride layers or metal oxide layers on the surfaces of the particles. Suitable metallic fillers are exemplified by particulates of metals selected from the group consisting of aluminum, copper, gold, nickel, silver, and combinations thereof, and alternatively aluminum.
  • Suitable metallic fillers are further exemplified by the particulates of metals listed above having layers on their surfaces selected from the group consisting of aluminum oxide, copper oxide, nickel oxide, silver oxide, and combinations thereof.
  • the metallic filler may comprise aluminum particles having aluminum oxide layers on their surfaces.
  • Ceramic fillers are exemplified by aluminum oxide, beryllium oxide, boron nitride, magnesium oxide, silicon carbide, tungsten carbide, zinc oxide, and combinations thereof.
  • ceramic fillers are exemplified by aluminum oxide, zinc oxide, and combinations thereof.
  • Aluminum fillers are commercially available, for example, from Toyal America, Inc. of Naperville, Illinois, U.S.A. and Valimet Inc., of Stockton, California, U.S.A.
  • Silver filler is commercially available from Metalor Technologies U.S. A. Corp. of Attleboro, Massachusetts, U.S.A.
  • Thermally conductive fillers are known in the art and commercially available, see for example, U.S. Patent 6,169,142 (col. 4, lines 7-33).
  • CB-A20S and Al-43-Me are aluminum oxide fillers of differing particle sizes commercially available from Showa- Denko, and AA-04, AA-2, and AAl 8 are aluminum oxide fillers commercially available from Sumitomo Chemical Company.
  • Zinc oxides such as zinc oxides having trademarks KADOX® and XX®, are commercially available from Zinc Corporation of America of Monaca, Pennsylvania, U.S.A.
  • the shape of the thermally conductive filler particles is not specifically restricted, however, rounded or spherical particles may prevent viscosity increase to an undesirable level upon high loading of the thermally conductive filler in the grease.
  • Ingredient (B) may be a single thermally conductive filler or a combination of two or more thermally conductive fillers that differ in at least one property such as particle shape, average particle size, particle size distribution, and type of filler. For example, it may be desirable to use a combination of ceramic fillers, such as a first aluminum oxide having a larger average particle size and a second aluminum oxide having a smaller average particle size.
  • metallic fillers such as a first aluminum having a larger average particle size and a second aluminum having a smaller average particle size.
  • metallic and ceramic fillers such as a combination of aluminum and aluminum oxide fillers; a combination of aluminum and zinc oxide fillers; or a combination of aluminum, aluminum oxide, and zinc oxide fillers.
  • Use of a first filler having a larger average particle size and a second filler having a smaller average particle size than the first filler may improve packing efficiency, may reduce viscosity, and may enhance heat transfer.
  • the average particle size of the thermally conductive filler will depend on various factors including the type of thermally conductive filler selected for ingredient (B) and the exact amount added to the grease, however, the thermally conductive filler may have an average particle size of 0.1 to 80 micrometers, alternatively 0.1 to 50 micrometers, and alternatively 0.1 to 10 micrometers.
  • the grease may optionally further comprise an additional ingredient.
  • suitable additional ingredients include (C) an antioxidant, (D) a meltable metal, (E) a pigment, (F) a spacer, (G) a vehicle, (H) a wetting agent, (I) an antifoaming agent, (J) a flame retardant, (K) a rust preventive, and a combination thereof.
  • Additional ingredient (C) is an antioxidant.
  • Ingredient (C) may be added to the grease in an amount of 0.001 % to 1 %.
  • Suitable antioxidants are known in the art and commercially available. Suitable antioxidants include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols.
  • Stabilizers include organophosphorous derivatives such as trivalent organophosphorous compound, phosphites, phosphonates, and a combination thereof; thiosynergists such as organosulfur compounds including sulfides, dialkyldithiocarbamate, dithiodipropionates, and a combination thereof; and sterically hindered amines such as tetramethyl-piperidine derivatives. Suitable antioxidants and stabilizers are disclosed in Zweifel, Hans, "Effect of Stabilization of
  • Suitable phenolic antioxidants are known in the art and include vitamin E and IRGANOX® 1010 from Ciba Specialty Chemicals, U.S.A. IRGANOX® 1010 comprises pentaerythriol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate).
  • Additional ingredient (D) is a meltable metal.
  • Ingredient (D) may comprise Ga, In, Sn, or an alloy thereof.
  • the meltable metal may optionally further comprise Ag, Bi, Cd, Cu, Pb, Zn, or a combination thereof.
  • suitable meltable metals include Ga, In-Bi-Sn alloys, Sn-In-Zn alloys, Sn-In-Ag alloys, Sn-Ag-Bi alloys, Sn-Bi-Cu-Ag alloys, Sn-Ag-Cu- Sb alloys, Sn-Ag-Cu alloys, Sn-Ag alloys, Sn-Ag-Cu-Zn alloys, and combinations thereof.
  • the meltable metal may have a melting point of up to 250 0 C, alternatively up to 225 0 C.
  • the meltable metal may have a melting point of at least 50 0 C, alternatively at least 150 0 C.
  • the meltable metal may be a eutectic alloy, a non-eutectic alloy, or a pure metal. Meltable metals are commercially available.
  • the meltable metal may comprise 1 % to 20 % of the weight of the grease.
  • the meltable metal may be added in addition to, or instead of, a portion of ingredient (B).
  • Additional ingredient (E) is a pigment.
  • suitable pigments include Stan- Tone 50SP01 Green (which is commercially available from PolyOne).
  • Additional ingredient (F) is a spacer. Spacers may comprise organic particles, inorganic particles, or a combination thereof. Spacers may be thermally conductive, electrically conductive, or both. Spacers may have a particle size of 25 micrometers to 250 micrometers. Spacers may comprise monodisperse beads. The amount of ingredient (F) depends on various factors including the distribution of particles, pressure to be applied during placement, and temperature during placement. The grease may contain up to 15 %, alternatively up to 5 % of ingredient (F) added in addition to, or instead of, a portion of ingredient (B).
  • Additional ingredient (G) is a vehicle such as a solvent or diluent. Ingredient (G) may be added during preparation of the grease, for example, to aid mixing and delivery. All or a portion of ingredient (G) may additionally be removed after the grease is prepared.
  • Additional ingredient (H) is a wetting agent. Suitable wetting agents include the anionic, cationic, and nonionic surfactants known in the art to act as wetting agents. Anionic wetting agents are exemplified by TERGITOL® No. 7, cationic wetting agents are exemplified by TRITON® X-100, and nonionic wetting agents are exemplified by TERGITOL® NR 27.
  • the grease described above may be made by mixing all ingredients at ambient or elevated temperature using any convenient mixing equipment, such as a centrifugal mixer (such as a mixer commercially available from Hauschild) or a Baker-Perkins mixer.
  • a centrifugal mixer such as a mixer commercially available from Hauschild
  • a Baker-Perkins mixer such as a mixer commercially available from Hauschild
  • the grease described above may be used as a thermal interface material (TIM).
  • TIM thermal interface material
  • the grease may be interposed along a thermal path between a heat source and a heat spreader.
  • the grease may be interposed between a first heat spreader and a second heat spreader.
  • the grease may be interposed by any convenient means, such as wet-dispensing, screen printing, stencil printing, or solvent casting the grease.
  • the heat source may comprise an electronic component such as a semiconductor, a transistor, an integrated circuit, or a discrete device.
  • the heat spreader may comprise a thermally conductive plate, a thermally conductive cover, a fan, a circulating coolant system, a heat sink, or a combination thereof.
  • the grease may be used in direct contact with the electronic component and the heat spreader
  • the grease may be applied either to the electronic component and thereafter the heat spreader, or the grease may be applied to the heat spreader and thereafter to the electronic component.
  • the grease may be used in direct contact with a first heat spreader and a second heat spreader (TIM2).
  • the grease may be applied either to the first heat spreader and thereafter the second heat spreader, or the grease may be applied to the second heat spreader and thereafter to the first heat spreader.
  • This invention further relates to a device comprising: a) an electronic component, b) a thermal interface material, and c) a heat spreader; where the thermal interface material is interposed between the electronic component and the heat spreader along a thermal path extending from a surface of the electronic component to a surface of the heat spreader, where the thermal interface material comprises the grease described above.
  • This invention further relates to a device comprising: a) an electronic component, b) a first thermal interface material, c) a first heat spreader, d) a second thermal interface material, and e) a second heat spreader; where the first interface material is interposed between the electronic component and the heat spreader along a thermal path extending from a surface of the electronic component to a surface of the second heat spreader, the second thermal interface material is interposed along the thermal path between the first heat spreader and the second heat spreader, and at least one of the first thermal interface material and the second thermal interface material comprises the grease described above.
  • FIG. 1 shows a device 100 according to this invention.
  • the device 100 comprises an electronic component (shown as an integrated circuit (IC) chip) 103 mounted to a substrate 104 through a die attach adhesive 109.
  • the substrate 104 has solder balls 105 attached thereto through pads 110.
  • a first thermal interface material (TIMl) 106 is interposed between the IC chip 103 and a metal cover 107.
  • the metal cover 107 acts as a first heat spreader.
  • a second thermal interface material (TIM2) 102 is interposed between the metal cover 107 and a heat sink (second heat spreader) 101. Heat moves along a thermal path represented by arrows 108 when the device is operated.
  • Viscosity is measured at 25 0 C unless otherwise indicated. Samples of grease are prepared using the following ingredients.
  • Polyorganosiloxane 1 has a viscosity of 35 cSt and the following average formula.
  • Polyorganosiloxane 2 is a combination of 50 % Polyorganosiloxane 1, 25 % polyorganosiloxane of formula (i), and 25 % polyorganosiloxane of formula (ii), where formulae (i) and (ii) are as follows.
  • Formula (i) is a combination of 50 % Polyorganosiloxane 1, 25 % polyorganosiloxane of formula (i), and 25 % polyorganosiloxane of formula (ii), where formulae (i) and (ii) are as follows.
  • Filler Al(I) is aluminum having average particle size 2.5 micrometers.
  • Filler Al(2) is aluminum having average particle size 3.5 micrometers.
  • Filler Al 2 Os(I) is aluminum oxide having average particle size 9.5 micrometers.
  • Filler ZnO(I) is zinc oxide having average particle size 0.1 micrometer.
  • Filler ZnO(I) is commercially available as KADOX® 911 from Zinc Corporation of America.
  • Filler ZnO(2) is zinc oxide having average particle size 0.9 micrometers.
  • Filler ZnO(2) is commercially available as XX® 503R from Zinc Corporation of America.
  • Grease sample 1 is prepared by mixing the ingredients in Table 1 with a Hauschild mixer. Grease sample 1 has a viscosity of 4253 poise at 0.5 s ⁇ l shear rate under a steady rate sweep experiment on an AR2000 stress rheometer.
  • Grease sample 2 is prepared by mixing the ingredients in the amounts in Table 2 with a Baker-Perkins mixer. Grease sample 2 has a viscosity of 7545 poise at 0.5 s "1 shear rate under a steady rate sweep experiment on an AR2000 stress rheometer. Table 2
  • Grease sample 3 is prepared by mixing the ingredients in the amounts in Table 4. Table 4
  • Grease sample 4 is prepared by mixing the ingredients in the amounts in Table 5. Table 5
  • the grease is suitable for use as a TIM in various electronic devices.
  • the grease preferably does not react significantly, or increase significantly in viscosity, over time when used as a TIM in an electronic device.
  • ingredient (A) in the grease may reduce or eliminate Bleed when the grease is used as a TIM, even when the grease is free of silica, and it is thought that the use ingredient (A) in the grease may reduce or eliminate the need for a separate treating agent for the thermally conductive filler in the grease.
  • Figure 1 is a schematic representation of a cross section of an electronic device including the grease of this invention.
  • TIM2 102 second interface material

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  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Combustion & Propulsion (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne une graisse comprenant : (A) de 2 à 50 % en poids, par rapport au poids de la graisse, d'un polyorganosiloxane ayant en moyenne, par molécule, au moins un groupement fonctionnel hydrocarbonoxy lié par un silicium ; et (B) de 50 à 98 % en poids, par rapport au poids de la graisse, d'au moins une charge conductrice thermiquement. La graisse peut être utilisée en tant que matériau d'interface thermique pour dissiper la chaleur issue de dispositifs électroniques.
PCT/US2007/001070 2006-02-23 2007-01-16 Graisse conductrice thermiquement et procedes et dispositifs dans lesquels ladite graisse est utilisee WO2007106209A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8334592B2 (en) 2007-09-11 2012-12-18 Dow Corning Corporation Thermal interface material, electronic device containing the thermal interface material, and methods for their preparation and use
US8618211B2 (en) 2009-03-16 2013-12-31 Dow Corning Corporation Thermally conductive grease and methods and devices in which said grease is used
EP2455339A4 (fr) * 2009-07-14 2015-06-10 Sakai Chemical Industry Co Particules d'oxyde de magnésium, leur procédé de fabrication, charge à dissipation de chaleur, composition de résine, graisse à dissipation de chaleur, et composition de revêtement à dissipation de chaleur
CN109072051A (zh) * 2016-03-08 2018-12-21 霍尼韦尔国际公司 相变材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103408937B (zh) * 2013-07-30 2015-06-03 深圳德邦界面材料有限公司 一种粘性或非粘性的导热界面材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004041938A1 (fr) * 2002-11-08 2004-05-21 Dow Corning Toray Silicone Co., Ltd. Composition de silicone a conductivite thermique
WO2005047378A2 (fr) * 2003-11-05 2005-05-26 Dow Corning Corporation Graisse thermoconductrice et procede et dispositif dans lesquels ladite graisse est utilisee

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004041938A1 (fr) * 2002-11-08 2004-05-21 Dow Corning Toray Silicone Co., Ltd. Composition de silicone a conductivite thermique
WO2005047378A2 (fr) * 2003-11-05 2005-05-26 Dow Corning Corporation Graisse thermoconductrice et procede et dispositif dans lesquels ladite graisse est utilisee

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8334592B2 (en) 2007-09-11 2012-12-18 Dow Corning Corporation Thermal interface material, electronic device containing the thermal interface material, and methods for their preparation and use
US8618211B2 (en) 2009-03-16 2013-12-31 Dow Corning Corporation Thermally conductive grease and methods and devices in which said grease is used
EP2455339A4 (fr) * 2009-07-14 2015-06-10 Sakai Chemical Industry Co Particules d'oxyde de magnésium, leur procédé de fabrication, charge à dissipation de chaleur, composition de résine, graisse à dissipation de chaleur, et composition de revêtement à dissipation de chaleur
CN109072051A (zh) * 2016-03-08 2018-12-21 霍尼韦尔国际公司 相变材料
CN109072051B (zh) * 2016-03-08 2023-12-26 霍尼韦尔国际公司 相变材料

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TW200740986A (en) 2007-11-01

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