US20130299140A1 - Insulated thermal interface material - Google Patents

Insulated thermal interface material Download PDF

Info

Publication number
US20130299140A1
US20130299140A1 US13/886,477 US201313886477A US2013299140A1 US 20130299140 A1 US20130299140 A1 US 20130299140A1 US 201313886477 A US201313886477 A US 201313886477A US 2013299140 A1 US2013299140 A1 US 2013299140A1
Authority
US
United States
Prior art keywords
group
interface material
thermal interface
filler
insulated thermal
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US13/886,477
Other languages
English (en)
Inventor
Yong-Chien Ling
Chih-Ping Wang
Jen-Yu Liu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Tsing Hua University NTHU
Original Assignee
National Tsing Hua University NTHU
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 National Tsing Hua University NTHU filed Critical National Tsing Hua University NTHU
Assigned to NATIONAL TSING HUA UNIVERSITY reassignment NATIONAL TSING HUA UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LING, YONG-CHIEN, LIU, JEN-YU, WANG, CHIH-PING
Publication of US20130299140A1 publication Critical patent/US20130299140A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F3/00—Plate-like or laminated elements; Assemblies of plate-like or laminated elements
    • 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
    • C08K3/04—Carbon
    • 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
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/14—Peroxides
    • 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
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • This invention relates to an insulated thermal interface material, especially relates to an insulated thermal interface material manufactured by dispersing graphene into a polymer to enhance its conductivity and insulation.
  • thermal dissipating element is to decrease the thickness of the elements.
  • it will cause problems because of decreasing too much thickness, such as decreasing of the strength, durability and/or electric insulating property of thermal dissipating element.
  • One of them is formation of the thermal dissipating element into multilayer structure which composed of an inner layer with great heat resistance and electric insulating property, such as aromatic polyimide, polyamide, polyamideimide or polyethylene naphthalate glycol, and an outer layer formed by thermal interface material containing thermal conductive filler with great heat and electric conductivity, such as silicon rubber.
  • the adhesion between outer and inner layers of those multilayer insulating components are unstable, meaning the duration of component is bad and peeling is inevitable as time goes by.
  • the thermal interface material such as silicon rubber
  • the abovementioned silicon rubber is obtained by curing an adhesion promoter which is composed of silicon compounds.
  • the thermal conductivity of the inner layer formed by aromatic polyimides is obviously less than that of the outer layer formed by silicon rubber, which decreases the overall thermal conductivity of the complex.
  • thermal interface material filled with conductive filler to increase the thermal conductivity such as silicon dioxide, aluminum oxide, aluminum, silicon carbide, silicon nitride, magnesium oxide, magnesium carbonate, zinc oxide and aluminum nitride which are often used as thermal conductive filler in conductive subject of the thermal interface material
  • conductive filler such as silicon dioxide, aluminum oxide, aluminum, silicon carbide, silicon nitride, magnesium oxide, magnesium carbonate, zinc oxide and aluminum nitride
  • Aluminum oxide and aluminum is amphoteric compound which is easily affected by the inner impurities.
  • the conductive subject of the thermal interface material is epoxy resin, it would have bad influence on heat resistance and permanent deformation by compression.
  • Zinc oxide is usually precipitated and sedimented when dispersing in the conductive subject of the thermal interface material because it possesses high specific gravity of 5.7, and the high hygroscopicity of zinc oxide powder is undesired.
  • Silicon carbide also has high specific gravity.
  • the refining silicon carbide powder sold on the current market tends to aggregate and sediment when dispersing in the conductive subject, such as silicon rubber, of the thermal interface material. Silicon carbide is hard to be re-dispersed and processed because it tends to agglomerate.
  • Silicon nitride and aluminum nitride is easily reacting with water resulting in worst wet fastness.
  • Magnesium oxide is optional high thermal conductive filler, but it is similar to aluminum nitride which is easily reacting with water resulting in worst wet fastness.
  • Magnesium carbonate is not stable and tends to decompose into magnesium oxide under high temperature.
  • the thermal conductive filler rises the cost of the thermal interface material (eg. lots of thermal conductive filler is needed), heat deterioration (eg. poor heat resistance), surface seepage (eg. poor moisture tolerance) or some limitation between the conductors (eg. epoxy resin) of the thermal interface material
  • the present invention provides a thermal interface material filled with graphene which could effectively conduct the heat generated by an electronic element to the outside of the thermal dissipating element, moreover, it possesses great electrical insulating property which could be widely used in electric and electronic area, for example, to be used as CPU and thermal dissipating element of high-power transistor chip.
  • the present invention provides an insulated thermal interface material for applying between an electronic element and a thermal dissipating element.
  • the abovementioned thermal dissipating element at least comprises a base, a first filler and a second filler.
  • the base is a polymer
  • the first filler is a graphene and the first filler and the second filler dispersed in the base.
  • the first filler is a graphene with a length-to-thickness ratio or a width-to-thickness ratio of 50 ⁇ 10000 and selected from a group consisting of a graphene, a graphene doped with nitrogen, a graphene doped with oxygen, a graphene doped with both nitrogen and oxygen, multilayer graphene stacking via van der Waals interaction, multilayer graphene doped with nitrogen and stacking via van der Waals interaction, multilayer graphene doped with oxygen stacking via van der Waals interaction and multilayer graphene doped with both nitrogen and oxygen stacking via van der Waals interaction.
  • the second filler is a thermal conductive inorganic powder and selected from a group consisting of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon carbide, tin oxide, silicon nitride, aluminum oxide whisker, aluminum nitride whisker, silicon carbide whisker, magnesium oxide whisker and silicon nitride whisker.
  • the base is a silicone rubber and at least contains an organic polysiloxane compound, a curing agent and an adhesion promoter, the weight percentage of the organic polysiloxane compound, the curing agent, the adhesion promoter, the first filler and the second filler are 91 ⁇ 99.55%, 0.1 ⁇ 5%, 0.1 ⁇ 3%, 0.0025 ⁇ 0.005% and 0.25 ⁇ 0.5%, respectively.
  • the second filler has an average granularity of 20 ⁇ 50 ⁇ m.
  • the organic polysiloxane compound has a degree of polymerization of 200 ⁇ 12000 and is represented by the following formula:
  • R 1 is a single-valence C 1 ⁇ C 10 hydrocarbon group and selected from a group consisting of an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkyl group substituted by halogen and an alkenyl group, and “a” further represents a positive number of 1.9-2.05.
  • the curing agent is an organic peroxide or a curing agent applying in an alkylation reaction of silane.
  • the adhesion promoter at least comprises a silicon compound with a plurality of substitutes and the substitutes could be selected from a group consisting of a cycloalkyl group, an alkoxyl group, a methyl group, a vinyl group and a silane group.
  • the base is a curing epoxy resin and selected from a group consisting of a linear polyepoxide with epoxide as an end group, a polyepoxide with epoxide at backbond and a polyepoxide with epoxide as side chain.
  • the insulated thermal interface material further comprising a particulate thermoplastic polymer, wherein the weight percentage of the base, the particulate thermoplastic polymer, the first filler and the second filler are 90 ⁇ 97%, 1 ⁇ 2%, 0.001 ⁇ 0.005% and 0.1 ⁇ 1%, respectively.
  • the particulate thermoplastic polymer comprises a polymer with a glass transition temperature of at least 60° C.
  • the particulate thermoplastic polymer comprises has an average molecular weight higher than 7000.
  • the particulate thermoplastic polymer is selected from a group consisting of a poly(methyl methacrylate) and a methyl methacrylate/methacrylic acid copolymer.
  • the particulate thermoplastic polymer has an average granularity of 0.25 ⁇ 250 ⁇ m.
  • the insulated thermal interface material further comprising a curing agent
  • the curing agent contains a dicyandiamide and its derivatives or a metal imidazole compound represented by the following formula:
  • M is a metal and selected from a group consisting of Ag (I), Cu (I), Cu (II), Cd (II), Zn (II), Hg (II), Ni (II) and Co (II), and L is a compound represented by the following formula:
  • R 1 , R 2 and R 3 could be selected from a group consisting of hydrogen atom, alkyl group and aryl group, and m is the valence of metal.
  • the thermal conductivity of the insulated thermal interface material is higher than 3 W/mK.
  • the insulated thermal interface material further comprising an additive
  • the additive could be selected from a group consisting of coupling agent, lubricant, flow controlling agent, thickener, accelerant, chain-extenders, flexibilizer, dispersant and co-curing agent.
  • FIG. 1A to FIG. 1C are diagrams showing the structure of an insulated thermal interface material according to a first embodiment of the present invention.
  • FIG. 2A to FIG. 2C are diagrams showing the structure of an insulated thermal interface material according to a second embodiment of the present invention.
  • the present invention provides an insulated thermal interface material filled with graphene which could effectively conduct the heat generated by an electronic element to the outside of a thermal dissipating element by percentage collocated of the components, moreover, it could further possesses great electrical insulating property.
  • the present invention provides an insulated thermal interface material which could be used between an electronic element and a thermal dissipating element.
  • the electronic element could be a power transistor, a metal oxide semiconductor transistor, a field effect transistor, a thyristor, a rectifier and a transformer, but the present invention is not limited thereto.
  • the abovementioned insulated thermal interface material at least comprises a base, a first filler and a second filler.
  • the base is a polymer
  • the first filler is a graphene.
  • the first filler and the second filler dispersed in the base.
  • the first filler is a graphene with a length-to-thickness ratio or a width-to-thickness ratio of 50 ⁇ 10000 and selected from a group consisting of a graphene, a graphene doped with nitrogen, a graphene doped with oxygen, a graphene doped with both nitrogen and oxygen, multilayer graphene stacking via van der Waals interaction, multilayer graphene doped with nitrogen stacking via van der Waals interaction, multilayer graphene doped with oxygen stacking via van der Waals interaction and multilayer graphene doped with both nitrogen and oxygen stacking via van der Waals interaction.
  • the second filler is a thermal conductive inorganic powder and selected from a group consisting of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon carbide, tin oxide, silicon nitride, aluminum oxide whisker, aluminum nitride whisker, silicon carbide whisker, magnesium oxide whisker and silicon nitride whisker.
  • the second filler is not limited thereto and could use any kind of powder which possesses conductivity and insulativity and can be used to improve the conductivity and insulativity of the insulated thermal interface material.
  • the thermal conductive powder could be used alone or combined with two or more components.
  • the base is a silicone rubber or an epoxy resin.
  • the percentage of other components varies with different bases, but the thermal interface material disclosed in the present invention at least comprises the first filler and the second filler.
  • the two embodiments of the base will be illustrated as the following.
  • the base is a silicone rubber and at least contains an organic polysiloxane compound, a curing agent and an adhesion promoter.
  • the organic polysiloxane compound has a polymerization degree of between 200 ⁇ 12000 and can be represented by the following formula (I):
  • R 1 is a single-valence C 1 ⁇ C 10 hydrocarbon group and selected from a group consisting of an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkyl group substituted by halogen and an alkenyl group.
  • “a” further represents a positive number of 1.9-2.05.
  • R 1 when R 1 is an alkyl group, it could be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl group.
  • R 1 when R 1 is a cycloalkyl group, it could be cyclopentyl or cyclohexyl group.
  • R 1 is an aryl group, it could be phenyl, tolyl, xylyl or naphthyl group.
  • R 1 when R 1 is an aralkyl group, it could be phenethyl or hydrocinnamyl group.
  • R 1 When R 1 is a halogen substituted-alkyl group, it could be 3,3,3-trifluoropropyl or 3-chloropropyl group.
  • R 1 When R 1 is an alkenyl group, it could be vinyl group, allyl group, butenyl group, pentenyl group or hexenyl group.
  • the backbone of the organic polysiloxane compound could be formed by a dimethysiloxane unit or other similar units.
  • the methyl groups of the organic polysiloxane compound can be partially substituted by vinyl group, phenyl group or 3,3,3-trifluoropropyl group.
  • the terminal of the organic polysiloxane compound could be terminated by tri-organic silyl group or hydrocarbon group.
  • tri-organic silyl group comprises trimethylsilyl group, dimethylvinylsilyl group or trivinylsilyl group.
  • the curing agent is an alkylated silane or an organic peroxide.
  • the curing agent is composed of catalysts based on platinum and organicohydrogenpolysiloxane which in average of at least two hydrogen atoms binding to a silicon atom within a single molecule.
  • each molecular of the abovementioned organic polysiloxane compound will have at least two or more alkenyl groups bound on its silicon atom.
  • the organohydrogenpolysiloxane of the curing agent served as crosslinking agent and the addition reaction occurs with the alkenyl group in organic polysiloxane compound.
  • the alkenyl group binding to the silicon atom is preferably vinyl group, and the vinyl group could be at the terminal, side chain or both.
  • at least one vinyl group is binding on the silicon atom at the terminal of molecular chain.
  • the organic polysiloxane compound could be selected from one or more combinations of the group listed below: a copolymer of methylvinylsiloxane and dimethysiloxane terminated with trimethylsiloxanes at both ends of the molecular chain, a polymethylvinylsiloxane terminated with trimethylsiloxanes at both ends of the molecular chain, a co-polymer of methylphenylsiloxane, methylvinylsiloxane and dimethysiloxane terminated with trimethylsiloxanes at both ends of the molecular chain, a polydimethylsiloxane terminated with dimethylvinylsiloxanes at both ends of the molecular chain, a polymethylvinylsiloxane terminated with dimethylvinylsiloxanes at both ends of the molecular chain, a co-polymer of methylvinylsiloxane and dime
  • the catalyst used to promote the curing of compound is based on platinum and organohydrogenpolysiloxanes combinations, and it could be chloroplatinic acid, alcohol solution of chloroplatinic acid, olefin complex of platinum and vinylsiloxane complex of platinum.
  • the amount of catalyst based on platinum in the combinations there are no particular limitations of the amount of catalyst based on platinum in the combinations, as long as it reaches the effective catalytic amount.
  • the curing agent is an organic peroxide
  • it could be selected from a group consisting of benzoperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, ditert-butyl peroxide and benzenecarboperoxoic acid.
  • each molecule at least comprises two vinyl groups.
  • the organic polysiloxane compound could be selected from one or more combinations of the group listed below, but the present invention is not limited thereto: a polydimethylsiloxane terminated with dimethylvinylsiloxanes at both ends of the molecular chain, a polydimethylsiloxane terminated with methylphenylvinylsiloxanes at both ends of the molecular chain, a co-polymer of methylphenylsiloxane and dimethysiloxane terminated with dimethylvinylsiloxanes at both ends of the molecular chain, a co-polymer of methylvinylsiloxane and dimethysiloxane terminated with dimethylvinylsiloxane at both ends of the molecular chain, a co-polymer of methylvinylsiloxane and dimethysiloxane terminated with trimethylsiloxanes at both ends of the molecular chain,
  • the addition of adhesion promoter could offer strong adhesiveness between silicon rubber and further overcome the peeling problem suffered in the prior art to get the abovementioned thermal interface material with a long-term durability.
  • the adhesion promoter at least comprises a silicon compound with a plurality of substitutes, and the substitutes could be selected from a group consisting of a cycloalkyl group, an alkoxyl group, a methyl group, a vinyl group and a silane group.
  • the silicon compound at least contains two abovementioned groups within a molecule.
  • the silicon compound of the adhesion promoter when the curing agent is applied in an alkylation reaction of silane, preferably, the silicon compound of the adhesion promoter contains vinyl group, silane group or both, and epoxide group, alkoxyl group or both.
  • the silicon compound of the adhesion promoter when the curing agent is the organic peroxide, contains methyl group, vinyl group or both, and epoxide group, alkoxyl group or both.
  • the silicon compound which comprises the abovementioned groups is shown below, but the present invention is not limited thereto.
  • the organic polysiloxane compound, the curing agent, the adhesion promoter, the first filler and the second filler of the thermal interface material has a weight percentage of 91-99.55%, 0.1-5%, 0.1-3%, 0.0025-0.005% and 0.25-0.5%, respectively.
  • the overall thermal conductivity of thermal interface material will decrease if the addition amount of the first filler and the second filler are too small. However, it will also be hard to mix and affect the molding processing performance if the addition amount of the first filler and the second filler are too much.
  • the second filler has an average granularity of about 20-50 ⁇ m.
  • the thickness of each composite material could be setup according to the anticipated structure and application when producing the thermal interface material into thin film.
  • the thermal conductivity decreases if the outer layer is too thin or too thick. Therefore, the thickness is 30-800 ⁇ m, preferably, the thickness is in the range of 50-400 ⁇ m.
  • the thermal interface material provided in the present invention further comprising an additive, and it could be selected from a group consisting of coupling agent, chain-extenders, flexibilizer, dispersant and co-curing agent.
  • a mixing device such as kneader, Banbury mixer, planet-type mixer or Shinagawa mixer. If necessary, accompanying of heating to about 100° C. or higher could knead organic polysiloxane compound, first filler and second filler together.
  • kneading process introducing and mixing of the following compound, such as enhancing silicon dioxide including pyrolysis of silicon dioxide or precipitation of silicon dioxide, silicon oil or silicone wetting agent, flame retardant including platinum, titanium oxide or benzotriazole, is applicable in precondition of those addition does not affect the thermal conductivity of outer layer
  • the thermal interface material after second kneading could be used as outer layer coating agent. If needed, addition of solvent including toluene is applicable, and the resulting mixture is mixing in mixing device, such as planet-type mixer or kneader, to form the outer layer coating agent, but the present invention is not limited to single-layer structure. If needed, the abovementioned inner layer (A) compounds including aromatic polyimide could also be combined with thermal interface material (B) into (B)/(A)/(B)/(A)/(B) five-layer structure, or it could also includes isolating layer, such as glass-fiber fabric, graphite flake or aluminum foil, into the structure, but the present invention is not limited thereto.
  • organic polysiloxane compound a polydimethylsiloxane terminated with dimethylvinylsiloxanes at both ends of the molecular chain was used with 8000 average degree of polymerization.
  • the manufacturing method of the thermal interface material is the same as the formulation 1.
  • thermal conductivity and resistance of the thermal interface material provided in the present invention are shown in Table 1, and the thermal conductivity was measured with laser flash method in heat-soaking device under 25° C.:
  • thermal conductivity of thermal interface material is not lower than 3 W/mK, which is far more better than the products currently sold in the market (about 0.5-0.6 W/mK).
  • the electric material usually needs to maintain insulation in order not to be burned due to the excess of the current. Therefore, we also measured the resistance of this thermal interface material and found that the resistance is enormously large to reach basic demands of insulation for electronic component.
  • FIG 1 A to FIG. 1C are diagrams showing the structure of the insulated thermal interface material 10 according to the first embodiment of the present invention.
  • the silicon rubber 13 could store and release elastic energy E 1 due to long backbone structure. Therefore, when first filler 11 moves, rotates and vibrates under heating, it compresses or elongates the spring-like silicon rubber 13 and undergo transfer of thermal energy T and elastic energy F.
  • the thermal conductivity of continuity between the second filler 12 and the first filler 11 results in a synergistic effect of increasing thermal transfer and thermal insulation, which give rise to a satisfying results of thermal conductivity and resistance.
  • the thermal interface material 10 provides in the present invention could be widely used as heat conductive fins inserted between heating electronic device or electric component and heat dissipating component. Moreover, the abovementioned thermal interface material 10 displays great thermal insulativity especially applied in heating apparatus. Meanwhile, although not illustrated, the silicon rubber 13 further comprises the adhesion promoter. Hence, strong interaction occurred when combining this thermal interface material with the abovementioned compounds including aromatic polyimide, that is the great duration of the thermal interface material provides in the present invention.
  • the base is a curing epoxy resin and it could be selected from a group consisting of a linear polyepoxide with epoxide as an end group, a polyepoxide with epoxide at backbond and a polyepoxide with epoxide as side chain. It can comprise the following compound represented by the formula (III):
  • R′ is an alkyl group, alkyl ether or aryl group
  • n is an integer of 2-6.
  • the abovementioned curing epoxy resin at least contains two epoxide groups within every molecule and the average molecular weight is 150-10000.
  • the epoxy resin includes aromatic glycidyl ether (by reacting of polyphenol with excess amount of epichlorohydrin), cycloaliphatic glycidyl ether, hydrogenation of the glycidyl ether, and their mixture.
  • the polyphenols includes resorcinol, pyrocatechol, hydroquinone and polycyclic phenol including p,p′-dihydroxy benzyl, p,p′-dihydroxy biphenyl, p,p′-dihydroxyphenyl sulfone, p,p′-hydroxy benzophenone, 2,2′-dihydroxy-1,1′-dinaphthylmethane and dihydroxy diphenyl methane, dihydroxy diphenyl dimethyl methane, dihydroxy-diphenyl-ethyl methyl methane, dimethyl phenyl methyl propyl methane, dihydroxy-diphenyl-ethyl phenyl methane, dihydroxy-dip
  • the abovementioned thermal interface material could chose to add epoxy compound as reactive diluent which at least contains glycidyl ether at the terminal, preferably a saturated or non-saturated ring skeletons.
  • reactive diluents such as processing helper, toughening and compatible between different materials.
  • reactive diluents could be diglycidyl ether of cyclohexanedimethanol, diglycidyl ether of resorcinol, p-tert-butyl phenyl glycidyl ether, hydroxymethyl phenyl glycidyl ether, diglycidyl ether of neopentyl glycol, trimethylol ethane triglycidyl ether, triglycidyl ether of trimethylolpropane, N,N-diglycidyl-4-glycidyloxyaniline, N,N-diglycidyl glyceryl aniline, N,N,N,N-tetraglycidyl m-xylenedi-amine, multi-diglycidyl ether of vegetable oil, but the present invention is not limited thereto.
  • the insulated thermal interface material further comprises a particulate thermoplastic polymer.
  • the base, the particulate thermoplastic polymer, the first filler and the second filler has a weight percentage of 90-97%, 1-2%, 0.005-0.001% and 0.1-1%, respectively.
  • the abovementioned particulate thermoplastic polymer preferably contains a polymer with glass transition temperature (T g ) of at least 60° C., the average molecular weight is higher than 7000 and could be selected from a group consisting of a poly(methyl methacrylate) and a methyl methacrylate/methacrylic acid copolymer.
  • T g glass transition temperature
  • the average granularity of the particulate thermoplastic polymer is preferably 0.25-250 ⁇ m.
  • the thermal interface material further comprises a curing agent, and the curing agent contains a dicyandiamide and its derivatives or a metal imidazole compound represented by formula (IV):
  • M is a metal which could be selected from a group consisting of Ag (I), Cu (I), Cu (II), Cd (II), Zn (II), Hg (II), Ni (II) and Co (II).
  • L is a compound shown by formula (V):
  • R 1 , R 2 , R 3 could be selected from a group consisting of hydrogen atom, alkyl group and aryl group.
  • m is the valence of metal.
  • the metal imidazole compound is a green imidazole copper (II).
  • the equivalent weight of metal imidazole compound is based on a criteria that it could cure epoxy resin, which preferably be 0.5-3%.
  • the thermal interface material further comprises an additive, and the additive could be selected from a group consisting of coupling agent, lubricant, flow controlling agent, thickener, accelerant, chain-extenders, flexibilizer, dispersant and co-curing agent.
  • the flexibilizer helps to offer the intensity of overlap shear and impact, and the composition is different from the thermoplastic material.
  • Flexibilizer is a polymer which could react with epoxy resin and is cross-linkable.
  • flexibilizer comprises a rubber-phase and a thermoplastic-phase polymer or a material which could form rubber-phase and a thermoplastic-phase compound with epoxy group.
  • flexibilizer could be butadiene acrylonitrile terminated with carboxyl group, a butadiene acrylonitrile terminated with carboxyl group and core-shell polymer or the mixture, but the present invention is not limited thereto.
  • flow controlling agent preferably includes pyrolysis of silicon dioxide and un-pyrolysis silicon dioxide.
  • the adhesion promoter could be used to enhance the attachment of binding agent and the base, and the composition of the adhesion promoter could be varied with the target surface.
  • Adhesion promoter such as dihydric phenol including catechol and dithiobis phenol, is especially useful for the surface of ionic lubricant used to pull the metal raw material during the processing.
  • the weight percentage of coupling agent could be 0.001-0.05%, and 1-2% for lubricant.
  • the coupling agent could be selected from a group consisting of silane coupling agent, titanate coupling agent or aluminate coupling agent, and the lubricant could be selected from a group consisting of stearate, stearic acid amines, low molecular weight polymer or paraffin.
  • additive such as filler (for example, aluminum powder, carbon black, glass bulb, talc, clay, calcium carbonate, barium sulfate, titanium dioxide, silicon dioxide, silicate, glass bead and mica), flame retardant, antistatic agent, thermal conductive or electric conductive granule and foaming agent (azodicaroxamide or expandable polymer microsphere containing hydrocarbon liquid) etc.
  • filler for example, aluminum powder, carbon black, glass bulb, talc, clay, calcium carbonate, barium sulfate, titanium dioxide, silicon dioxide, silicate, glass bead and mica
  • flame retardant for example, aluminum powder, carbon black, glass bulb, talc, clay, calcium carbonate, barium sulfate, titanium dioxide, silicon dioxide, silicate, glass bead and mica
  • flame retardant for example, aluminum powder, carbon black, glass bulb, talc, clay, calcium carbonate, barium sulfate, titanium dioxide, silicon dioxide, silicate, glass bead and mica
  • flame retardant for example, aluminum powder
  • the preparation process of the thermal interface material provides in the present invention is described below. First, one or more epoxy resin was heated under 100-180° C. to melt those resin. Then, the resin was cooled to about 90-50° C. Addition of other epoxy resin, reactive diluents and flexibilizer besides first filler and second filler under high shearing mixing. If the mixture comprises the first filler and the second filler, granules were added and mixed for 1 hour at most till the granules are dispersed. Finally, the filler was added and mixed to obtain the dispersed mixture. The mixture was cooled to below the glass transition temperature of particulate thermoplastic, generally 50-100° C. After that, the curing agent, the adhesion promoter and the particulate thermoplastic were mixed in the epoxy mixture. This epoxy mixture is flowable at this point and could be poured into suitable container for further use.
  • the melted epoxy mixture was cooled to about 50° C. before addition of additives such as reactive diluents and flexibilizer under high shearing mixing. Further adding 0.005% of the first filler, such as graphene doped with nitrogen, and 0.25% of the second filler, such as 50-200 mm sphere aluminum oxide, and mixing for 1 hour till the granules are dispersed. The mixture was further cooled to about 50° C. below the glass transition temperature of particulate thermoplastic, before addition of the curing agent, the adhesion promoter and the particulate thermoplastic into the epoxy mixture.
  • additives such as reactive diluents and flexibilizer under high shearing mixing.
  • the first filler such as graphene doped with nitrogen
  • the second filler such as 50-200 mm sphere aluminum oxide
  • formulations 1 and 2 The only different between formulations 1 and 2 is to change the percentage of the second filler from 0.005% to 0.5%.
  • thermal conductivity and resistance of the thermal interface material provided in the present invention are shown in Table 2, and the thermal conductivity is then measured with laser flash method in heat-soaking device under 25° C.:
  • thermal conductivity of the thermal interface material provides in the present invention is far more better than the products currently sold in the market (about 0.03-0.2 W/mK).
  • the electric material usually needs to maintain insulation in order not to be burned due to the excess of the current. Therefore, we also measured the resistance of this thermal interface material and found that the resistance is enormously large to reach basic demands of insulation for electronic component.
  • FIG. 2A to FIG. 2C are diagrams showing the structure of the insulated thermal interface material 10 according to the second embodiment of the present invention. It is noted that the curing material, the first filler 11 and the second filler 12 , is flowable below the curing temperature and at least a part was diffused into the epoxy resin 14 . Or the first filler 11 and the second filler 12 dispersed in epoxy resin 14 and was separated by the epoxy resin 14 . As shown in the FIG, collocation of the first filler 11 and the second filler 12 , the silicon rubber silicon resin 14 possesses similar structure (benzene ring and epoxy group) comparing to the first filler 11 . Therefore, the thermal energy T could transmit through phonon and the great connection between the first filler 11 and the second filler 12 , resulting in a synergistic effect of increasing thermal transfer and thermal insulation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US13/886,477 2012-05-10 2013-05-03 Insulated thermal interface material Abandoned US20130299140A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TW101116708 2012-05-10
TW101116708A TWI598385B (zh) 2012-05-10 2012-05-10 絕緣化熱介面材料

Publications (1)

Publication Number Publication Date
US20130299140A1 true US20130299140A1 (en) 2013-11-14

Family

ID=49547730

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/886,477 Abandoned US20130299140A1 (en) 2012-05-10 2013-05-03 Insulated thermal interface material

Country Status (2)

Country Link
US (1) US20130299140A1 (zh)
TW (1) TWI598385B (zh)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140287239A1 (en) * 2013-03-20 2014-09-25 Stmicroelectronics S.R.L. Graphene based filler material of superior thermal conductivity for chip attachment in microstructure devices
CN104072966A (zh) * 2014-06-10 2014-10-01 东莞上海大学纳米技术研究院 一种多元复合导热功能母粒及制备方法
US20150083376A1 (en) * 2013-09-25 2015-03-26 Google Inc. Cold-formed sachet modified atmosphere packaging
WO2015103435A1 (en) * 2013-12-31 2015-07-09 Balandin Alexander A Thermal interface materials with alligned fillers
CN105609770A (zh) * 2015-12-26 2016-05-25 黑龙江科技大学 一种n-掺杂石墨烯的制备方法
CN105670228A (zh) * 2016-04-08 2016-06-15 苏州锦腾电子科技有限公司 一种高导热绝缘材料及其制备方法
US9615486B2 (en) 2014-03-26 2017-04-04 General Electric Company Thermal interface devices
CN107501861A (zh) * 2017-08-30 2017-12-22 桂林电子科技大学 一种基于石墨烯的复合热界面材料及其制备方法
TWI623721B (zh) * 2014-05-02 2018-05-11 加川清二 高熱傳導率的散熱片及其製造方法
CN108148558A (zh) * 2016-12-06 2018-06-12 中国科学院金属研究所 一种含石墨烯的导热凝胶及其制备方法和应用
CN108673911A (zh) * 2018-06-21 2018-10-19 上海大学 一种基于石墨烯增韧高性能碳纤维树脂基复合材料电池托盘的制备装置及其制备方法
US10121720B2 (en) 2017-01-03 2018-11-06 Stmicroelectronics S.R.L. Semiconductor device, corresponding apparatus and method
CN108841138A (zh) * 2018-06-07 2018-11-20 上海大学 一种石墨烯增韧树脂基碳纤维复合材料的制备方法
US20180358283A1 (en) * 2015-11-17 2018-12-13 Liqiang Zhang Thermal interface materials including a coloring agent
CN109111740A (zh) * 2017-06-22 2019-01-01 佛山市南海区研毅电子科技有限公司 一种高导热石墨烯热固性绝缘界面材料及其制备方法
US10287471B2 (en) 2014-12-05 2019-05-14 Honeywell International Inc. High performance thermal interface materials with low thermal impedance
CN110054998A (zh) * 2019-02-11 2019-07-26 斯迪克新型材料（江苏）有限公司 石墨烯定向导热双面胶带
CN110054999A (zh) * 2019-02-11 2019-07-26 斯迪克新型材料（江苏）有限公司 防残胶导热双面胶带的制备方法
GB2571791A (en) * 2018-03-09 2019-09-11 Graphitene Ltd Heat-sink formulation and method of manufacture thereof
US10428257B2 (en) 2014-07-07 2019-10-01 Honeywell International Inc. Thermal interface material with ion scavenger
US10428256B2 (en) 2017-10-23 2019-10-01 Honeywell International Inc. Releasable thermal gel
US10501671B2 (en) 2016-07-26 2019-12-10 Honeywell International Inc. Gel-type thermal interface material
US10781349B2 (en) 2016-03-08 2020-09-22 Honeywell International Inc. Thermal interface material including crosslinker and multiple fillers
US11041103B2 (en) 2017-09-08 2021-06-22 Honeywell International Inc. Silicone-free thermal gel
US11072706B2 (en) 2018-02-15 2021-07-27 Honeywell International Inc. Gel-type thermal interface material
US11373921B2 (en) 2019-04-23 2022-06-28 Honeywell International Inc. Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing
CN115504789A (zh) * 2022-09-20 2022-12-23 武汉科技大学 一种高强韧耐磨wc复合材料的制备方法
CN115820183A (zh) * 2022-12-23 2023-03-21 深圳市道尔科技有限公司 一种耐高温高强度、高导热胶的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI697556B (zh) * 2018-06-26 2020-07-01 台灣中油股份有限公司 熱介面材料組成及其製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030234074A1 (en) * 2002-06-25 2003-12-25 Bhagwagar Dorab Edul Thermal interface materials and methods for their preparation and use
US20070246245A1 (en) * 2004-10-28 2007-10-25 Dongchan Ahn Conductive Curable Compositions
US20120263940A1 (en) * 2011-04-14 2012-10-18 Ada Technologies, Inc. Thermal interface materials and systems and devices containing the same
US20140120399A1 (en) * 2012-10-25 2014-05-01 The Regents Of The University Of California Graphene based thermal interface materials and methods of manufacturing the same
US20150065613A1 (en) * 2012-04-26 2015-03-05 Dow Mf Produktions Gmbh & Co. Ohg Epoxy adhesive composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030234074A1 (en) * 2002-06-25 2003-12-25 Bhagwagar Dorab Edul Thermal interface materials and methods for their preparation and use
US20070246245A1 (en) * 2004-10-28 2007-10-25 Dongchan Ahn Conductive Curable Compositions
US20120263940A1 (en) * 2011-04-14 2012-10-18 Ada Technologies, Inc. Thermal interface materials and systems and devices containing the same
US20150065613A1 (en) * 2012-04-26 2015-03-05 Dow Mf Produktions Gmbh & Co. Ohg Epoxy adhesive composition
US20140120399A1 (en) * 2012-10-25 2014-05-01 The Regents Of The University Of California Graphene based thermal interface materials and methods of manufacturing the same

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9892994B2 (en) 2013-03-20 2018-02-13 Stmicroelectronics S.R.L. Graphene based filler material of superior thermal conductivity for chip attachment in microstructure devices
US20140287239A1 (en) * 2013-03-20 2014-09-25 Stmicroelectronics S.R.L. Graphene based filler material of superior thermal conductivity for chip attachment in microstructure devices
US20150083376A1 (en) * 2013-09-25 2015-03-26 Google Inc. Cold-formed sachet modified atmosphere packaging
WO2015103435A1 (en) * 2013-12-31 2015-07-09 Balandin Alexander A Thermal interface materials with alligned fillers
US9615486B2 (en) 2014-03-26 2017-04-04 General Electric Company Thermal interface devices
TWI623721B (zh) * 2014-05-02 2018-05-11 加川清二 高熱傳導率的散熱片及其製造方法
CN104072966A (zh) * 2014-06-10 2014-10-01 东莞上海大学纳米技术研究院 一种多元复合导热功能母粒及制备方法
US10428257B2 (en) 2014-07-07 2019-10-01 Honeywell International Inc. Thermal interface material with ion scavenger
US10287471B2 (en) 2014-12-05 2019-05-14 Honeywell International Inc. High performance thermal interface materials with low thermal impedance
US20180358283A1 (en) * 2015-11-17 2018-12-13 Liqiang Zhang Thermal interface materials including a coloring agent
US10312177B2 (en) * 2015-11-17 2019-06-04 Honeywell International Inc. Thermal interface materials including a coloring agent
CN105609770A (zh) * 2015-12-26 2016-05-25 黑龙江科技大学 一种n-掺杂石墨烯的制备方法
US10781349B2 (en) 2016-03-08 2020-09-22 Honeywell International Inc. Thermal interface material including crosslinker and multiple fillers
CN105670228A (zh) * 2016-04-08 2016-06-15 苏州锦腾电子科技有限公司 一种高导热绝缘材料及其制备方法
US10501671B2 (en) 2016-07-26 2019-12-10 Honeywell International Inc. Gel-type thermal interface material
CN108148558A (zh) * 2016-12-06 2018-06-12 中国科学院金属研究所 一种含石墨烯的导热凝胶及其制备方法和应用
US10121720B2 (en) 2017-01-03 2018-11-06 Stmicroelectronics S.R.L. Semiconductor device, corresponding apparatus and method
CN109111740A (zh) * 2017-06-22 2019-01-01 佛山市南海区研毅电子科技有限公司 一种高导热石墨烯热固性绝缘界面材料及其制备方法
CN107501861A (zh) * 2017-08-30 2017-12-22 桂林电子科技大学 一种基于石墨烯的复合热界面材料及其制备方法
US11041103B2 (en) 2017-09-08 2021-06-22 Honeywell International Inc. Silicone-free thermal gel
US10428256B2 (en) 2017-10-23 2019-10-01 Honeywell International Inc. Releasable thermal gel
US11072706B2 (en) 2018-02-15 2021-07-27 Honeywell International Inc. Gel-type thermal interface material
WO2019170894A1 (en) * 2018-03-09 2019-09-12 Graphitene Limited Heat-sink formulation and method of manufacture thereof
GB2571791A (en) * 2018-03-09 2019-09-11 Graphitene Ltd Heat-sink formulation and method of manufacture thereof
GB2571791B (en) * 2018-03-09 2022-07-13 Graphitene Ltd Heat-sink formulation and method of manufacture thereof
CN108841138A (zh) * 2018-06-07 2018-11-20 上海大学 一种石墨烯增韧树脂基碳纤维复合材料的制备方法
CN108673911A (zh) * 2018-06-21 2018-10-19 上海大学 一种基于石墨烯增韧高性能碳纤维树脂基复合材料电池托盘的制备装置及其制备方法
CN110054999A (zh) * 2019-02-11 2019-07-26 斯迪克新型材料（江苏）有限公司 防残胶导热双面胶带的制备方法
CN110054998A (zh) * 2019-02-11 2019-07-26 斯迪克新型材料（江苏）有限公司 石墨烯定向导热双面胶带
US11373921B2 (en) 2019-04-23 2022-06-28 Honeywell International Inc. Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing
CN115504789A (zh) * 2022-09-20 2022-12-23 武汉科技大学 一种高强韧耐磨wc复合材料的制备方法
CN115820183A (zh) * 2022-12-23 2023-03-21 深圳市道尔科技有限公司 一种耐高温高强度、高导热胶的制备方法

Also Published As

Publication number Publication date
TW201345963A (zh) 2013-11-16
TWI598385B (zh) 2017-09-11

Similar Documents

Publication Publication Date Title
US20130299140A1 (en) Insulated thermal interface material
KR101862413B1 (ko) 경화성 오르가노폴리실록산 조성물 및 반도체 장치
TWI540045B (zh) Thermal conductive silicone rubber composite sheet
JP2013189625A (ja) 高熱伝導性樹脂硬化物、高熱伝導性半硬化樹脂フィルム及び高熱伝導性樹脂組成物
JP5471868B2 (ja) 熱伝導性シリコーンゴム複合シート
JP7073716B2 (ja) 熱伝導性樹脂組成物、熱伝導性シートおよび半導体装置
JP6662458B2 (ja) 熱伝導性シリコーンゴム複合シート
JP7026674B2 (ja) 回路基板用樹脂組成物とそれを用いた金属ベース回路基板
TW201623455A (zh) 矽氧烷組成物
US11028234B2 (en) Addition-curable silicone composition
TW200540221A (en) Resin composition for sealing and semiconductor device sealed with resin
JP2014193965A (ja) 高熱伝導性樹脂組成物、高熱伝導性半硬化樹脂フィルム及び高熱伝導性樹脂硬化物
JP5472055B2 (ja) 熱伝導性シリコーングリース組成物
WO2015059950A1 (ja) ポリイミド樹脂組成物、及びそれを用いた熱伝導性接着フィルム
JP2021109971A (ja) 高温絶縁用途のシリコーン複合材
US20240199817A1 (en) Curable organopolysiloxane composition and semiconductor device
CN115698222A (zh) 二液固化型导热性润滑脂用组合物、导热性润滑脂及电子设备
JP6669258B2 (ja) 熱伝導性シート
WO2014069353A1 (ja) 半導体装置
JP2014189701A (ja) 高熱伝導性樹脂硬化物、高熱伝導性半硬化樹脂フィルム及び高熱伝導性樹脂組成物
CN114729193B (zh) 热传导性硅酮组合物和热传导性硅酮片材
US20240294758A1 (en) Thermally conductive silicone composition and cured product thereof
US20230047058A1 (en) Thermally conductive silicone resin composition
JP2021195478A (ja) 熱伝導性シリコーン組成物、その硬化物、及び放熱シート
JP7532861B2 (ja) 熱伝導性シート

Legal Events

Date Code Title Description
AS Assignment

Owner name: NATIONAL TSING HUA UNIVERSITY, TAIWAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LING, YONG-CHIEN;WANG, CHIH-PING;LIU, JEN-YU;SIGNING DATES FROM 20130825 TO 20130909;REEL/FRAME:031222/0185

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION