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WO2003002644A1 - Feuille thermoconductrice - Google Patents

Feuille thermoconductrice Download PDF

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Publication number
WO2003002644A1
WO2003002644A1 PCT/US2002/016743 US0216743W WO03002644A1 WO 2003002644 A1 WO2003002644 A1 WO 2003002644A1 US 0216743 W US0216743 W US 0216743W WO 03002644 A1 WO03002644 A1 WO 03002644A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermally conductive
conductive sheet
sheet
filler
binder resin
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.)
Ceased
Application number
PCT/US2002/016743
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English (en)
Inventor
Maya Igarashi
Mitsuhiko Okada
Tomoaki Uchiya
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.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of WO2003002644A1 publication Critical patent/WO2003002644A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a thermally conductive sheet and, more particularly, to a thermally conductive sheet which has an excellent thermal conductivity and a well-balanced adhesion performance and is suited for use as a heat transfer medium for electronic parts.
  • heat dissipating materials such as a heat sink, a heat dissipating fin, and a metallic heat dissipating plate have conventionally been mounted to heat generating parts. Furthermore, thermally conductive sheets have been used as heating spacers to operate as a heat transfer medium interposed between the heat generating parts and heat dissipating material.
  • a thermally conductive sheet should have a high thermal conductivity and be sufficiently conformable to the surfaces of heat generating parts having various shapes, such as an IC chip. It is also necessary that the thermally conductive sheet has electrical insulation properties. To satisfy these requirements, almost all of conventional thermally conductive sheets are prepared by mixing silicone rubber with a filler for enhancing the thermal conductivity. As the filler, for example, alumina, silica (quartz), boron nitride and magnesium oxide are used. Specifically, Japanese Unexamined Patent Publication (Kokai) No.
  • a heat dissipating sheet comprising, as a principal component, an inorganic filler and a synthetic rubber, the inorganic filler comprising two components (A) boron nitride and (B) alumina, silica, magnesia, zinc white and mica.
  • Japanese Unexamined Patent Publication (Kokai) No. 7-111300 discloses an insulating heat dissipating sheet having a thickness of not less than 1 ⁇ m and comprising a silicone rubber and a boron nitride powder dispersed in the silicone rubber.
  • These thermally conductive silicone rubber sheets can exhibit high thermal conductivity, but have some problems to be solved.
  • silicone rubber itself has a high price so that the cost of the heat dissipating sheet depends on its high price.
  • a long time is required to form a sheet because silicone rubber exhibits a low curing rate.
  • a thin sheet can not be made with high accuracy because a large amount of the filler is added to improve the thermal conductivity.
  • thermally conductive gel suited for use as a heat dissipating sheet, which is cured in the form of a gel at normal temperature, the thermally conductive gel being prepared by adding a silicone oil and thermally conductive fillers such as boron nitride, silicon nitride, aluminum nitride and magnesium oxide to a condensation type gel such as condensation curing type liquid silicone gel.
  • a two-part curing type silicone gel contains molecules which have no functional group and are not crosslinked. It has been pointed out that those having a low molecular weight can diffuse into electronic apparatuses to exert an adverse influence on the operation of other electronic parts because they are liable to be volatilized.
  • a hard disc whose capacity has recently been increased is broken down when a trace amount of silicone is oxidized and fixed to a head in the hard disc so that it has been known that such a device is a part damaged easily by silicone among electronic parts. Therefore, it has been required to develop a thermally conductive sheet which does not contain any silicone.
  • a heat dissipating sheet using a silicone gel as a binder has tackiness on the surface thereof, but can not be firmly fixed to heat generating parts and a heat dissipating material because it hardly exhibits enough adhesive strength when incorporated into an adhesive sheet to be used for bonding.
  • thermally conductive sheet using, a urethane resin binder in place of the silicone rubber and gel described above also has been used (see, Japanese Unexamined Patent Publication (Kokai) Nos. 2-74545, 5-162296 and 11-111899).
  • all thermally conductive sheets disclosed in these patent publications have an object of improving the thermal conductivity and are not intended to afford a function for a bonding sheet, they have not enough performances for the adhesive sheet similar to the thermally conductive sheet using a silicone rubber and a silicone gel.
  • thermally conductive sheet having thermal conductivity and adhesion properties wherein an acrylic adhesive is used as a binder.
  • a thermally conductive electrical insulating pressure-sensitive adhesive comprising (a) a polymer prepared from a monomer mixture containing (i) an alkyl acrylate or methacrylate and (ii) a polar monomer which is copolymerizable with the alkyl acrylate or methacrylate, and (b) thermally conductive electrical insulating particles dispersed in the polymer in Unexamined Patent Publication (Kokai) No. 6-88061.
  • thermally conductive sheet using such a pressure-sensitive adhesive When using this pressure-sensitive adhesive, there can be obtained effects such as comparatively simple production process, low thermal resistance, excellent adhesion properties and the like.
  • a polymer (resin) is not cured when the thermally conductive electrical insulating particles to be dispersed in the polymer are black particles through which ultraviolet light easily penetrates.
  • the amount of the thermally conductive electrical insulating particles to be added is from about 20 to 30 volume % at most, and it is difficult to further improve the thermal conductivity by mixing a larger amount of the thermally conductive electrical insulating particles.
  • a white thermally conductive particles made of aluminum oxide the center portion of the sheet is not likely to be sufficiently cured by increasing the thickness of the sheet.
  • An object of the present invention is to solve the above-described problems of the prior art and to provide a thermally conductive sheet which has flexibility and is conformable to a special shape such as unevenness and curved surface, thereby making it possible to secure high adhesion and heat dissipation, and to improve the thermal conductivity and obtain well-balanced adhesive performance by mixing a large amount of thermally conductive electric insulating particles with a binder.
  • the present inventors have intensively studied to solve the object described above and obtained such a finding that, when using an acrylic polyurethane resin as a binder resin of a thermally conductive sheet, a thermally conductive filler can be mixed in a high content and a thermally conductive sheet having high thermal conductivity can be provided.
  • the present invention resides in thermally conductive sheet comprising a binder resin and thermally conductive fillers dispersed in said binder resin.
  • the thermally conductive sheet comprises a binder resin and a thermally conductive filler dispersed in the binder resin, characterized in that an acrylic polyurethane resin is used as the binder resin.
  • the acrylic polyurethane resin used herein is prepared by the polyaddition reaction of (a) an acrylic oligomer having at least two hydroxyl groups in a molecule and (b) a polyfunctional isocyanate having at least two isocyanate groups in a molecule, optionally in the presence of a catalyst.
  • an acrylic oligomer having at least two hydroxyl groups in a molecule is used as a polyol component. Since the acrylic oligomer has a function of imparting high adhesive performance to a polyurethane resin prepared therefrom and is also acrylic-based, the cured resin can exhibit sufficiently high heat resistance and weathering resistance without adding an antioxidant.
  • acrylic oligomer having at least two hydroxyl groups in a molecule, useful in the present invention (hereinafter referred to as "acrylic oligomer”), for example, there can be advantageously used an acrylic oligomer that is generally used in an acrylic adhesive.
  • an acrylic oligomer typically has two hydroxyl groups in a molecule, but may be a mixture with those having one or three or more hydroxyl groups.
  • the term "acrylic oligomer” includes both of acrylic and methacrylic oligomers.
  • the acrylic oligomer useful in the present invention usually has an adhesive component and a cohesive component in the molecule.
  • Useful materials for the adhesive component of the acrylic oligomer include, but are not limited to, acrylate monomers such as isooctyl acrylate (IOA), 2-ethylhexyl acrylate (2EHA), n-butyl acrylate (n-BA), methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, ethoxypolyethylene glycol mono(meth)acrylate, ethoxypolypropylene glycol mono(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate and nonylphenoxypolyethylene glycol mono(meth)acrylate.
  • acrylate monomers such as isooctyl acrylate (IOA), 2-ethylhexyl acrylate (2EHA), n-butyl acrylate (n-BA), methoxyethyl (meth
  • Useful materials for the cohesive component of the acrylic oligomer include, but are not limited to, acrylate monomers such as methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), vinyl acetate (VAc) and acrylamide (AAm).
  • acrylate monomers such as methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), vinyl acetate (VAc) and acrylamide (AAm).
  • the method of introducing a hydroxyl group relating to the polyaddition reaction with polyisocyanate into the molecule of the acrylic oligomer includes, for example, method using a polymerization chain transfer agent having a hydroxyl group, method using a polymerization initiator having a hydroxyl group and method of copolymerizing a monomer having a hydroxyl group.
  • the acrylate monomer may be used alone, or two or more of them may be used in combination.
  • a polyether or polyester polyol, conventionally useful as a raw material for a polyurethane resin, may be added to the acrylic oligomer or combination of acrylic oligomers.
  • the viscosity of the acrylic oligomer can vary depending on the characteristics required of the acrylic polyurethane resin to be derived therefrom, but is preferably within a range from about 500 to 10,000 cps. When the viscosity of the acrylic oligomer is less than 500 cps, the adhesion performance of the acrylic polyurethane resin after curing may become poor because of too small molecular weight. On the other hand, when the viscosity of the acrylic oligomer exceeds 10,000 cps, the fluidity of a compound obtained by mixing the oligomer with a thermally conductive filler may be lowered, thereby making it difficult to prepare the acrylic polyurethane resin. Because the viscosity of the acrylic oligomer varies with the composition and molecular weight of its constituent monomers, an optimum viscosity can be obtained by controlling these factors.
  • the polyfunctional isocyanate which is subjected to the polymerization addition reaction with the acrylic oligomer to form an acrylic polyurethane resin, is not specifically limited as far as it has a predetermined number of hydroxyl groups in a molecule, in addition to at least two isocyanate (-NCO) groups, and there can be used an aromatic or aliphatic polyisocyanate compound used generally in the preparation of the polyurethane resin.
  • Preferable polyfunctional isocyanate includes, but is not limited to, hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), tolidine diisocyanate (TODI), naphthalene diisocyanate (NDI) and xylylene diisocyanate (XDI).
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • MDI diphenylenemethane diisocyanate
  • IPDI isophorone diisocyanate
  • TODI tolidine diisocyanate
  • NDI naphthalene diisocyanate
  • XDI xylylene diisocyanate
  • the amount of the polyfunctional isocyanate to be added to the acrylic oligomer varies depending on the desired effect and conditions of the polyaddition reaction to be applied, but is preferably an amount that the equivalent amount of the hydroxyl group of the acrylic oligomer is almost the same as that of the isocyanate group of the polyfunctional isocyanate.
  • the polyfunctional isocyanate is added so that the equivalent amount of the isocyanate group is slightly larger than that of the hydroxyl group, reaction efficiency can be enhanced.
  • the equivalent amount of the isocyanate group is smaller than that of the hydroxyl group, a harmful influence is likely to be exerted on the cured state.
  • the polyaddition reaction between the acrylic oligomer and polyfunctional isocyanate is carried out in the presence of a suitable catalyst.
  • the catalyst used herein may be a catalyst used generally in the preparation of the acrylic polyurethane resin and is not specifically limited.
  • Catalysts includes, for example, organometallic catalysts such as stannous octoate, dibutyltin diacetate and lead octeate; and amine catalyst such as triethylenediamine. These catalysts may be used alone, or two or more kinds of them may be used in combination.
  • the amount of the catalyst can vary depending on the kind of the catalyst and polymerization conditions, but is preferably from about 0.01 to 0.5% wt% based on the amount of the binder component in the thermally conductive compound (polymerizable composition) before curing.
  • the polyaddition reaction can be carried out under various reaction conditions in the presence of the above catalyst.
  • This polymerization process is carried out with heating in consideration of the above starting materials according to the manner used generally in the preparation of the polyurethane resin.
  • the heating can be conducted by putting the starting materials in an oven, or can be conducted by heating using an infrared heater in some cases.
  • the heating temperature varies depending on the kind of the starting material, but is usually from about 25°C to 150°C.
  • the polymerization process described above in order to easily obtain a sheet comprising an acrylic polyurethane resin and a thermally conductive filler dispersed uniformly in the acrylic polyurethane, may be preferably carried out in such a manner that the thermally conductive filler is previously contained in a polymerizable composition including starting materials and the mixture is formed into a sheet before polymerization, and then the sheet is cured with heating.
  • various fillers used generally for a thermally conductive sheet can be used as the thermally conductive filler.
  • An inorganic filler in the form of particles is preferred. Particles of the inorganic filler are not specifically limited as far as they are superior in thermal conductivity and resist settling due to gravity during the storage of the resulting thermally conductive sheet, and also they can be dispersed uniformly in the polymerizable composition on polymerization of the above acrylic oligomer and polyfunctional isocyanate.
  • the particles of the inorganic filler include, but are not limited to, particles of oxides such as aluminum oxide, silicon dioxide and titanium dioxide; particles of carbonates such as silicon carbide; and particles of metals such as copper and aluminum. These particles of inorganic fillers may be used alone, or two or more kinds of them may be used alone.
  • the thermally conductive sheet of the present invention is worthy of note in the respect that a white filler can be used similar to a conventional thermally conductive sheet when the thermally conductive filler is dispersed in a binder resin, and that there can also be used a filler colored in black or other colors, that has never been used by using the technique disclosed in Japanese Unexamined Patent Publication (Kokai) No. 6-88061 (cited above).
  • a conventional thermally conductive sheet since curing of the binder resin depended on photopolymerization, the white filler that does not interfere with light irradiation was exclusively used.
  • the filler is not limited to the white filler because thermal polymerization is conducted. Therefore, not only the degree of freedom in selection of fillers and the like markedly increases, but also a filler capable of contributing drastically to an improvement in the thermal conductivity can be used easily without any limitation.
  • the shape of particles of the thermally conductive filler to be used is not specifically limited and particles include, for example, spherical and flaky particles.
  • the size (average particle diameter) of these particles is usually within a range from about 1 to 200 ⁇ m, and can range from about 10 to 100 ⁇ m.
  • the particle diameter of the filler particles is less than 1 ⁇ m, it may become complicated to prepare the sheet or becomes difficult to uniformly disperse the filler particles in the binder resin.
  • the particle diameter of the filler particles exceeds 200 ⁇ m, it may become necessary to increase the film thickness of the thermally conductive sheet contrary to the requirement to reduce the thickness as much as possible.
  • the same kinds of the filler particles having different particle diameters may be used or different kinds of the filler particles having the same or different particle diameters may be used, if they are preferred.
  • the amount of the thermally conductive filler to be mixed with the binder resin can vary widely depending on the effect of the addition required to the filler, but is generally within a range from about 10 to 70% by volume. When the amount of the filler is less than 10% by volume, the thermal conductivity may become poor. On the other hand, when the amount exceeds 70% by volume, the fluidity of the thermally conductive compound of the present invention may be lowered, thus making it difficult to form into a sheet.
  • additives used generally in the polymer chemistry may be added to the polymerizable composition, if necessary.
  • tackifiers and plasticizers may be added.
  • antioxidants may also be added. Since the polyol component is acrylic-based in the present invention, excellent heat resistance and weathering resistance can be imparted to the resin after curing without adding antioxidants.
  • Other additives include, for example, modifiers, thermal stabilizers, and colorants such as pigments and dyes.
  • the thermally conductive sheet of the present invention can be prepared preferably by mixing an acrylic oligomer, a polyfunctional isocyanate, a catalyst and arbitrary additives in each predetermined amount to obtain a liquid mixture (binder component), and adding a predetermined amount of a thermally conductive filler in the form of particles to the binder component.
  • the thermally conductive filler may also be added on preparation of the liquid mixture, if necessary.
  • the mixture is uniformly kneaded under stirring using a kneader such as planetary mixer. Then, the resulting compound is interposed between two liners (e.g.
  • polyester film treated with silicone treated with a release agent and formed into a sheet by pressing using a press whose gap was controlled to a value to secure a predetermined thickness.
  • the sheet-liked uncured compound may be placed in an oven and cured by heating at a predetermined temperature. As a result, a thermally conductive sheet is obtained.
  • the compound may also be continuously formed into a sheet by passing it through two gap-controlled rolls.
  • a multi-layer structure thermally conductive sheet may also be prepared by passing a core material interposed between layers of the compound through rolls.
  • thermally conductive sheet thus prepared, particles of the thermally conductive filler are dispersed uniformly in the binder component and the particles do not settle during storage to cause non-uniform dispersion.
  • This thermally conductive sheet is a two-part curing type acrylic polyurethane resin wherein the binder is free from a solvent, and a thermally conductive filler can be mixed in a high mixing ratio. Therefore, the thermally conductive sheet can exhibit excellent thermal conductivity of 0.5 W/m • K or more.
  • the acrylic polyurethane resin is not obtained by curing due to irradiation with ultraviolet light
  • a tackifier capable of absorbing visible light and ultraviolet light can be used, thereby making it possible to obtain enhanced adhesion performance.
  • the kind and amount of the tackifier not only the adhesion performance can be freely controlled, but also well-balanced adhesion performance can be realized by selection of the polyfunctional isocyanate and addition of the plasticizer.
  • the thermally conductive sheet of the present invention is also worthy of note in the respect that it can be formed in a different thickness according to the portion applied because of no limitation of the thickness due to the curing reaction.
  • the thermally conductive sheet of the present invention can be usually formed in the form of a thin film having a thickness with a range from 0.01 to 4.0 mm. When the thickness of the sheet is less than 0.01 mm, it may become difficult to obtain enough adhesive strength, resulting in poor heat dissipation properties. On the other hand, when the thickness exceeds 4.0 mm, the heat resistance of the thermally conductive sheet may be enhanced, resulting in deterioration of the heat dissipation properties.
  • the thermally conductive sheet of the present invention is a self-supporting sheet and, therefore, it can be used advantageously as a heating means as it is. If necessary, this sheet may be used in combination with a substrate.
  • a substrate includes, for example, plastic film, woven fabric, nonwoven fabric and metallic foil.
  • Plastic films suitable for use as the substrate are a polyolefin film, and a plastic film having good thermal conductivity, good weathering resistance and comparatively high substrate strength can be used.
  • Preferable polyolefin film includes, but is not limited to, polyethylene film, polypropylene film, ethyl ene -vinyl acetate copolymer (EVA) film, ethylene-acrylic acid copolymer (EAA) film and ionomer film.
  • EAA ethylene-acrylic acid copolymer
  • ionomer film Among these polyolefin films, high crystalline and high density polyethylene and ultra high molecular weight polyethylene can be used most preferably because of high strength even as a thin film and comparatively high thermal conductivity.
  • the thickness of the polyolefin film can vary widely depending on various factors, but is preferably within a range from about 1 to 25 ⁇ m.
  • the metallic foil suited for use as the substrate includes, for example, foils of various metallic materials such as aluminum, copper, gold, silver, lead and stainless steel.
  • foil refers to those substrates having a small thickness, thus including those referred to as metallic sheet and metallic foil.
  • the thickness of the metallic foil can vary widely depending on various factors, but is preferably small as possible similar to the above plastic film and is usually within a range from 1 to 20 ⁇ m.
  • the particles of the thermally conductive filler used herein are prepared by mixing silicon carbide (SiC) (average particle diameter of 75 ⁇ m, manufactured by Nanko Ceramic Co.) with SiC (average particle diameter of 10 ⁇ m, manufactured by Nanko Ceramic Co.) in a weight ratio of 1 :3 as described in Table 1 below.
  • SiC silicon carbide
  • the binder and particles of the filler were uniformly mixed with defoaming under reduced pressure.
  • the resulting mixed solution was interposed between two polyester films (thickness of 50 ⁇ m), the surface of which was treated with silicone, followed by formation into a sheet using a press under the conditions that the thickness of the sheet after forming becomes 1 mm.
  • the resulting sheet was put in an oven at 120° C and heated for three minutes. As a result, a thermally conductive sheet having a thickness of 1 mm was obtained.
  • the thermally conductive sheet thus obtained was evaluated by the following procedures with respect to (1) cured state, (2) thermal resistance, (3) shear force and (4) adhesive force to aluminum (Al). The resulting evaluation results are shown in Table 2 below.
  • thermally conductive sheet was interposed between a central processing unit (CPU) and an aluminum plate, the sheet was pressed against the CPU by applying a fixed pressure and a voltage of 7.0 V was applied to the CPU. After a lapse of five minutes, the difference in temperature between the CPU and aluminum plate and the thermal resistance was calculated by the resulting value.
  • the thermal resistance of the thermally conductive sheet of Example 1 was 1.07 K- in 2 /W (3) Shear force
  • thermally conductive sheet was cut to form a rectangular sample (10 mm X 10 mm), the rectangular sample was interposed between two stainless steel plates and its shear force was measured according to the procedure defined in JIS-Z-0237.
  • the shear force of the thermally conductive sheet of this example (Example 1) was 11.7 N/cm 2 .
  • the thermally conductive sheet was backed with a single-coated tape (product No. #851 A, manufactured by Sumitomo 3M Co.), the sheet was applied to an aluminum plate and the 90° peel adhesive force was measured according to the procedure defined in JIS-Z-0237. The sheet was peeled off at a testing rate of 300 mm/min. The adhesive force to Al of the thermally conductive sheet of Example 1 was 1.6 N/cm.
  • Example 2 The procedure described in Example 1 was repeated. However, in these examples, the binder, the filler and the ratio of the binder to filler were changed as described in Table 1 below in the preparation of the thermally conductive sheet. The satisfactory evaluation results as shown in Table 2 were obtained.
  • COMPARATIVE EXAMPLES 1 to 4 The procedure described in Example 1 was repeated. However, in these examples, the binder, the filler and the ratio of the binder to filler were changed for comparison as described in Table 1 below and, in Comparative Example 3, the thickness of the sheet was increased to 3 mm from 1 mm. As shown in Table 2 below, the evaluation test could not continued because of poor uncured state. Even if the test was conducted, the evaluation results were unsatisfactory.
  • thermoly conductive sheet which has flexibility and is conformable to a special shape such as unevenness and curved surface, thereby making it possible to secure high adhesion and heat dissipation, and which also has excellent thermal conductivity and well- balanced adhesion performance. Since various thermally conductive materials can be mixed with a binder in this thermally conductive sheet, the thermal conductivity of the sheet can be easily controlled.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une feuille thermoconductrice, comprenant une résine liante et des charges thermoconductrices dispersées dans ladite résine liante, caractérisée en ce que cette résine liante est une résine de polyuréthanne acrylique. Cette feuille thermoconductrice est flexible, adaptable et présente une excellente thermoconductivité ainsi qu'une qualité d'adhésion bien équilibrée.
PCT/US2002/016743 2000-06-29 2002-05-24 Feuille thermoconductrice Ceased WO2003002644A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000201480A JP2002030212A (ja) 2000-06-29 2000-06-29 熱伝導性シート
JP00-201480 2001-06-29

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WO2003002644A1 true WO2003002644A1 (fr) 2003-01-09

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7589147B2 (en) 2003-05-19 2009-09-15 Nippon Shokubai Co., Ltd. Resin composition for thermal conductive material and thermal conductive material
US9278867B2 (en) 2010-12-30 2016-03-08 Yava Technologies Inc. Transition metal compound particles and methods of production
CN112877025A (zh) * 2021-02-04 2021-06-01 浙江荣泰科技企业有限公司 一种导热树脂组合物及其制备方法
CN114213982A (zh) * 2021-12-27 2022-03-22 宁波启合新材料科技有限公司 一种无基材导热胶带

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AU2003281446A1 (en) 2002-07-08 2004-01-23 Dynic Corporation Hygroscopic molding
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JP4714432B2 (ja) * 2004-07-09 2011-06-29 スリーエム イノベイティブ プロパティズ カンパニー 熱伝導性シート
JP2007169568A (ja) * 2005-12-26 2007-07-05 Nitto Shinko Kk 熱伝導性粘着剤ならびに該熱伝導性粘着剤が用いられた熱伝導性粘着シート
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JP5153558B2 (ja) * 2008-10-08 2013-02-27 日本ジッパーチュービング株式会社 粘着性熱伝導シート
JP5450216B2 (ja) * 2010-04-06 2014-03-26 日本ジッパーチュービング株式会社 薄肉粘着性熱伝導シート
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US7589147B2 (en) 2003-05-19 2009-09-15 Nippon Shokubai Co., Ltd. Resin composition for thermal conductive material and thermal conductive material
US9278867B2 (en) 2010-12-30 2016-03-08 Yava Technologies Inc. Transition metal compound particles and methods of production
CN112877025A (zh) * 2021-02-04 2021-06-01 浙江荣泰科技企业有限公司 一种导热树脂组合物及其制备方法
CN114213982A (zh) * 2021-12-27 2022-03-22 宁波启合新材料科技有限公司 一种无基材导热胶带

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