WO2013115338A1 - Feuille adhésive thermoconductrice ignifuge - Google Patents

Feuille adhésive thermoconductrice ignifuge Download PDF

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Publication number
WO2013115338A1
WO2013115338A1 PCT/JP2013/052268 JP2013052268W WO2013115338A1 WO 2013115338 A1 WO2013115338 A1 WO 2013115338A1 JP 2013052268 W JP2013052268 W JP 2013052268W WO 2013115338 A1 WO2013115338 A1 WO 2013115338A1
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Prior art keywords
flame
meth
sensitive adhesive
retardant
acrylate
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PCT/JP2013/052268
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English (en)
Japanese (ja)
Inventor
憲司 古田
好夫 寺田
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日東電工株式会社
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Priority to CN201380007731.2A priority Critical patent/CN104093803A/zh
Priority to KR1020147017788A priority patent/KR20140126694A/ko
Publication of WO2013115338A1 publication Critical patent/WO2013115338A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a flame-retardant heat conductive adhesive sheet having both flame retardancy and heat conductivity.
  • a heat conductive pressure-sensitive adhesive sheet improves heat conductivity as compared with a base pressure-sensitive adhesive by including a heat conductive filler in an acrylic pressure-sensitive adhesive.
  • a high adhesive force (adhesive strength) can be imparted to a heat conductive adhesive sheet by using boron nitride particles having a specific particle diameter and an acrylic polymer component (see, for example, Patent Document 1 below). .
  • heat conductive adhesive sheet is widely used in electronic component applications such as sealing chip components and forming an insulating layer between a circuit on which a heat generating component is mounted and a heat sink.
  • electronic component applications such as sealing chip components and forming an insulating layer between a circuit on which a heat generating component is mounted and a heat sink.
  • high flame retardancy is required.
  • a sensitivity comprising 100 parts by mass of an acrylic copolymer prepared from a monomer mixture in which 0.5 to 10 parts by mass of a polar vinyl monomer such as acrylic acid is essential, and 10 to 100 parts by mass of a tackifier resin.
  • Electrically insulating heat conductive difficulty containing 50 to 250 parts by weight of a hydrated metal compound having both functions of heat conductive particles and non-halogen flame retardant with respect to 100 parts by weight of the pressure-sensitive adhesive composition
  • a flammable pressure sensitive adhesive and a pressure sensitive adhesive tape have been proposed (see, for example, Patent Document 2 below).
  • a heat conductive difficulty containing an acrylic polymer, a flame retardant having thermal conductivity and containing no halogen for example, aluminum hydroxide
  • a heat conductive filler for example, aluminum oxide
  • the heat conductive adhesive sheet by holding it with a base material of a plastic film such as a polyolefin film, the heat conductive adhesive sheet is applied while following an adherend having a special shape such as an uneven surface or a curved surface. It has also been proposed to suppress wrinkles, tears, elongation, etc. that occur when trying to attach (see, for example, Patent Document 4 below).
  • JP 2010-174173 A Japanese Patent Laid-Open No. 11-269438 JP 2002-294192 A JP 2001-168246 A
  • a plastic film such as a polyolefin film used as a base material is often flammable, for example, satisfies the flame retardancy of UL94 VTM-0 standard. There is a problem that it is difficult.
  • An object of the present invention is to provide a flame-retardant heat conductive pressure-sensitive adhesive sheet that is excellent in thermal conductivity and flame retardancy, and that is excellent in ease of sticking to an adherend.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet of the present invention is a flame-retardant heat-conductive pressure-sensitive adhesive sheet having a base material and a flame-retardant heat-conductive pressure-sensitive adhesive layer provided on at least one side of the base material.
  • the base material includes a polyester film, and the ratio of the thickness of the base material to the total thickness of the flame-retardant heat-conductive adhesive sheet is less than 0.2, and the thermal resistance is 10 cm 2 ⁇ K / W or less. It is characterized by being.
  • Such a flame-retardant thermally conductive pressure-sensitive adhesive sheet can ensure excellent thermal conductivity and flame retardancy, and can improve adhesion to an adherend.
  • the thickness of the base material is 5 ⁇ m or more and less than 50 ⁇ m.
  • the total thickness of the flame-retardant heat conductive adhesive sheet is 120 to 1000 ⁇ m.
  • the tensile elastic modulus is 10 MPa or more.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet of the present invention excellent heat conductivity and flame retardancy can be ensured, and furthermore, excellent sticking property can be ensured.
  • FIG. 1 is a schematic cross-sectional view partially showing an example of the flame-retardant heat-conductive pressure-sensitive adhesive sheet of the present invention.
  • FIG. 1 (a) shows a flame-retardant heat-conductive pressure-sensitive adhesive layer on one surface of a substrate.
  • FIG. 1B shows a configuration in which a flame-retardant thermally conductive adhesive layer is formed on both sides of the substrate, and
  • FIG. 1C shows a flame-retardant on one side of the substrate.
  • the structure by which the heat conductive adhesive layer was formed and the non-flame retardant heat conductive adhesive layer was formed in the other surface of a base material is shown.
  • 2A and 2B are explanatory diagrams of a thermal property evaluation apparatus that measures thermal conductivity and thermal resistance in the embodiment.
  • FIG. 2A is a front view
  • FIG. 2B is a side view.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet of the present invention is a flame-retardant heat-conductive pressure-sensitive adhesive sheet having a base material and a flame-retardant heat-conductive pressure-sensitive adhesive layer provided on at least one side of the base material,
  • the ratio of the thickness of the base material to the total thickness of the flame-retardant heat-conductive pressure-sensitive adhesive sheet is less than 0.2, and the thermal resistance is 10 cm 2 ⁇ K / W or less.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet of the present invention includes a flame-retardant heat-conductive pressure-sensitive adhesive layer on at least one surface of a substrate including a polyester film.
  • Such a flame-retardant thermally conductive pressure-sensitive adhesive sheet may have either a form in which both surfaces are adhesive surfaces (adhesive surface) or a form in which only one surface is an adhesive surface.
  • a flame-retardant heat conductive pressure-sensitive adhesive sheet having an adhesive surface only on one side where a flame-retardant heat-conductive pressure-sensitive adhesive layer is formed on one side of the substrate, As shown in FIG. 1 (b) or FIG. 1 (c), both surfaces are adhesive surfaces, and at least one of the adhesive surfaces is formed of a flame retardant thermal conductive pressure-sensitive adhesive layer.
  • An adhesive sheet etc. are mentioned.
  • sheet is used as a concept including shapes such as “tape”, “sheet”, and “film”. Further, a punching process or a cutting process may be performed in a shape according to the purpose of use.
  • FIG. 1 is a schematic cross-sectional view partially showing an example of the flame-retardant heat-conductive adhesive sheet of the present invention.
  • FIG. 1, 11, 12, and 13 are flame-retardant heat-conductive pressure-sensitive adhesive sheets each having a flame-retardant heat-conductive pressure-sensitive adhesive layer provided on at least one surface of a substrate including a polyester film, and 2 is flame-retardant.
  • a heat conductive adhesive layer, 3 is a base material, 4 is an adhesive layer (non-flame-retardant heat conductive adhesive layer).
  • the flame-retardant heat conductive adhesive sheet 12 shown in FIG. 1B has a configuration in which the flame-retardant heat conductive adhesive layer 2 is provided on both surfaces of the base material 3.
  • the flame-retardant heat conductive adhesive sheet 13 shown in FIG. 1 (c) has the flame-retardant heat conductive adhesive layer 2 formed on one surface of the substrate 3, and the pressure-sensitive adhesive layer on the other surface. (Non-flame retardant thermally conductive pressure-sensitive adhesive layer) 4 is formed.
  • the flame-retardant heat conductive adhesive layer 2 is formed on one surface of the substrate 3 shown in FIG. 1A, the flame-retardant heat conductive adhesive layer 2 is not formed.
  • a treatment layer for preventing dirt and scratches may be formed on the other surface of the substrate 3.
  • the treatment layer for preventing dirt for example, a layer obtained by treating the surface of the substrate with silicone or fluorine having a low surface tension to make it difficult to get dirt can be used.
  • the surface tension is not particularly limited, but is preferably 50 dyne / cm or less, more preferably 40 dyne / cm or less, and still more preferably 30 dyne / cm or less.
  • examples of the treatment layer for preventing scratches include a hard coat layer.
  • the pencil hardness of the hard coat layer is, for example, H or higher, preferably 2H or higher, more preferably 3H or higher.
  • the flame-retardant heat conductive adhesive sheet of this invention may be formed in the form wound by roll shape, and may be formed in the form by which the sheet
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet has a form wound in a roll shape or is laminated, the flame-retardant heat conductive pressure-sensitive adhesive layer is prevented from coming into direct contact with the release liner. be able to.
  • the thickness (total thickness) of the flame-retardant heat conductive adhesive sheet of the present invention is, for example, 100 to 1000 ⁇ m, preferably 120 to 1000 ⁇ m. If the thickness (total thickness) of the sheet is within the above range, an excellent tensile elastic modulus can be ensured, and adhesion to an adherend can be improved.
  • the thickness (total thickness) of a flame-retardant heat conductive adhesive sheet is the thickness of the base material which comprises a flame-retardant heat conductive adhesive sheet, and a flame-retardant heat conductive adhesive layer.
  • the thickness of the release liner (described later) is not included.
  • the flame-retardant heat conductive adhesive sheet (base material and flame-retardant heat conductive pressure-sensitive adhesive layer) of the present invention is preferably substantially free of halogen-based flame retardant components from the viewpoint of reducing environmental burden. It is desirable.
  • the phrase “substantially free of a halogen-based flame retardant component” means that no halogen-based flame retardant component is used at all or that it is below the detection limit in a generally used evaluation method.
  • the substrate includes a polyester film.
  • the polyester film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and the like.
  • Polyester film base materials have the advantage of higher breaking strength, Young's modulus, and dielectric breakdown voltage than base materials such as polyolefin films, polyamide films, and polyimide films.
  • the thickness of the substrate is, for example, from 1 ⁇ m to less than 100 ⁇ m, preferably from 5 ⁇ m to less than 50 ⁇ m, and more preferably from 10 ⁇ m to less than 40 ⁇ m.
  • the thickness of the substrate is within the above range, flame retardancy satisfying the flame retardancy standard of UL94 VTM-0 can be obtained. Furthermore, it is possible to ensure an excellent tensile elastic modulus, and it is possible to improve the adherence to the adherend.
  • the flame resistance standard of UL94 VTM-0 may not be satisfied.
  • the thickness of the base material is less than the above lower limit, a tape drip phenomenon may occur during fire spreading, and the flame retardancy standard of UL94 VTM-0 may not be satisfied. Further, if the thickness of the base material is not less than the above upper limit, the base material including the polyester film may burn and may not satisfy the flame resistance standard of UL94 VTM-0.
  • the ratio between the thickness of the substrate containing the polyester film and the thickness of the flame-retardant heat conductive adhesive layer Is less than 0.2, preferably less than 0.15, more preferably less than 0.1, usually 0.0025 or more.
  • the heat conductivity may be impaired.
  • the base material of this invention may be a polyester film single-piece
  • a substrate for example, a paper-based substrate such as paper, for example, a fiber-based substrate such as cloth, unemployed cloth, a net, for example, a metal-based substrate such as a metal foil, a metal plate, for example, Plastic base materials such as plastic films and sheets, for example, rubber base materials such as rubber sheets, foams such as foam sheets, and laminates thereof (particularly between plastic base materials and other base materials)
  • a paper-based substrate such as paper
  • a fiber-based substrate such as cloth, unemployed cloth
  • a net for example, a metal-based substrate such as a metal foil, a metal plate
  • Plastic base materials such as plastic films and sheets, for example, rubber base materials such as rubber sheets, foams such as foam sheets, and laminates thereof (particularly between plastic base materials and other base materials)
  • An appropriate thin leaf body such as a laminate, a laminate of plastic films or sheets, or the like can be used.
  • ⁇ -olefin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA) is used as a monomer component.
  • An olefin resin such as polyvinyl chloride (PVC), for example, vinyl acetate resin, for example, polyphenylene sulfide (PPS), for example, polyamide (nylon), amide resin such as wholly aromatic polyamide (aramid),
  • PVC polyvinyl chloride
  • PPS polyphenylene sulfide
  • nylon polyamide
  • amide resin such as wholly aromatic polyamide (aramid)
  • polyimide resin for example, polyetheretherketone (PEEK) and the like can be mentioned.
  • the surface of the base material containing the polyester film is a conventional surface treatment, for example, corona treatment, chromic acid treatment, ozone exposure treatment, flame exposure treatment, in order to improve the adhesion with the flame retardant heat conductive adhesive layer, etc.
  • An oxidation treatment by a chemical or physical method such as a high piezoelectric exposure treatment or an ionizing radiation treatment may be applied, or a coating treatment or the like may be performed by a primer or a release agent.
  • the heat resistance of a flame-retardant heat conductive adhesive sheet is 10 cm ⁇ 2 > * K / W or less, Preferably, it is 6 cm ⁇ 2 > * K / W or less, More preferably, it is 4 cm ⁇ 2 > * K / W or less.
  • the heat resistance of the flame-retardant heat conductive adhesive sheet exceeds 10 cm 2 ⁇ K / W, the function as the heat conductive sheet cannot be sufficiently exhibited.
  • the flame retardancy of the flame retardant thermally conductive pressure-sensitive adhesive sheet of the present invention needs to satisfy the UL94 VTM-0 standard. If the UL94 VTM-0 standard is satisfied, there is an advantage that vertical fire spread can be suppressed even when ignited, and the flame-retardant heat conductive adhesive sheet can be used as, for example, a heat conductive member of an electronic device. (Flame retardant thermal conductive adhesive layer)
  • the flame-retardant heat conductive pressure-sensitive adhesive layer used in the flame-retardant heat conductive sheet of the present invention is not particularly limited, and a conventionally known flame-retardant heat conductive pressure-sensitive adhesive layer can be used.
  • the flame-retardant heat-conductive pressure-sensitive adhesive layer refers to a pressure-sensitive adhesive layer that satisfies, for example, UL94 VTM-2, preferably VTM-1, more preferably VTM-0.
  • An acrylic pressure-sensitive adhesive layer is preferred because it is easy to achieve both thermal conductivity and flame retardancy and is excellent in adhesive properties such as adhesive strength and holding power.
  • the (a) acrylic polymer constituting the flame-retardant thermally conductive pressure-sensitive adhesive layer is obtained by copolymerizing a monomer component containing (meth) acrylic acid alkyl ester as a main component and a polar group-containing monomer. An acrylic polymer is given.
  • the acrylic polymer can be used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid alkyl ester constituting the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic.
  • (meth) acrylic acid C 2-12 alkyl ester more preferably (meth) acrylic acid C 4-9 alkyl ester can be used from the viewpoint of easily balancing the adhesive properties.
  • the above (meth) acrylic acid alkyl ester is used as a main component in the monomer component constituting the acrylic polymer.
  • the proportion of the (meth) acrylic acid alkyl ester is, for example, 60% by mass or more (for example, 60 to 99% by mass), preferably 80% by mass or more (for example, based on the total amount of monomer components for preparing the acrylic polymer). 80 to 98% by mass).
  • the (a) acrylic polymer in the present invention preferably contains a polar group-containing monomer as a monomer component in an amount of 5% by mass or more in the monomer component.
  • the polar group-containing monomer is contained in the monomer component in an amount of 5% by mass or more, the adhesion of the flame-retardant heat conductive pressure-sensitive adhesive layer to the adherend is improved, or the flame-retardant heat conductive pressure-sensitive adhesive layer is aggregated. You can increase your power.
  • Examples of the polar group-containing monomer include nitrogen-containing monomers, hydroxyl group-containing monomers, sulfonic acid group-containing monomers, and phosphoric acid group-containing monomers.
  • the polar group-containing monomers can be used alone or in combination of two or more.
  • a nitrogen-containing monomer and a hydroxyl group-containing monomer are preferable because high adhesiveness and holding power are obtained.
  • a polar group containing monomer is mentioned later in detail, Preferably, a carboxyl group containing monomer is not contained.
  • examples of the nitrogen-containing monomer include N- (2-hydroxyethyl) (meth) acrylamide (HEAA), N- (2-hydroxypropyl) (meth) acrylamide, N- (1-hydroxypropyl) (meta) ) Acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, N- (4-hydroxybutyl) N-hydroxyalkyl (meth) acrylamides such as (meth) acrylamide, for example, cyclic (meth) acrylamides such as N- (meth) acryloylmorpholine, N-acryloylpyrrolidine, such as (meth) acrylamide, N-substituted (meth) Acrylamide (eg N-eth N-alkyl (meth) acrylamides such as (meth) acrylamide and Nn-buty
  • nitrogen-containing monomers are preferably N- (2-hydroxyethyl) (meth) acrylamide, N-vinyl-2-pyrrolidone, N- (meta) from the viewpoint of good adhesion at the initial stage of application. ) Acryloylmorpholine, N, N-diethyl (meth) acrylamide.
  • Examples of the hydroxyl group-containing monomer in the present invention include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate. , 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate, and the like.
  • hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferred because they have good wettability to the adherend.
  • sulfonic acid group-containing monomers include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) And acryloyloxynaphthalene sulfonic acid.
  • examples of the phosphate group-containing monomer include 2-hydroxyethylacryloyl phosphate.
  • the proportion of the polar group-containing monomer is 5% by mass or more, for example, 5 to 30% by mass, preferably 6 to 25% by mass, based on the total amount of monomer components for preparing the acrylic polymer. .
  • the amount of the polar group-containing monomer used is 5% by mass or more, good holding power can be obtained.
  • the use amount of the polar group-containing monomer is less than 5% by mass, the cohesive force of the flame-retardant thermally conductive pressure-sensitive adhesive layer is lowered, and a high holding power may not be obtained, which exceeds 30% by mass. In some cases, the cohesive force of the flame-retardant heat-conductive pressure-sensitive adhesive layer becomes excessively high, and the adhesiveness of the flame-retardant heat-conductive pressure-sensitive adhesive layer is lowered.
  • a polyfunctional monomer can be used as a monomer component as necessary.
  • a crosslinked structure can be introduced into the acrylic polymer, and the cohesive force required as a flame-retardant thermally conductive pressure-sensitive adhesive layer can be adjusted.
  • polyfunctional monomer examples include hexanediol (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol diester.
  • (Meth) acrylate pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) Acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, dibutyl (meth) acrylate, hexidyl (meth) acrylate, etc. And the like.
  • ⁇ Multifunctional monomers can be used alone or in combination of two or more.
  • the ratio of the polyfunctional monomer is 2% by mass or less, for example, 0.01 to 2% by mass, preferably 0.02 to 1% by mass, based on the total amount of monomer components for preparing the acrylic polymer. It is.
  • the amount of the polyfunctional monomer used exceeds 2% by mass with respect to the total amount of monomer components for preparing the acrylic polymer, the cohesive force of the flame-retardant heat-conductive adhesive layer becomes too high and flame-retardant heat conduction In some cases, the adhesiveness of the adhesive layer is reduced.
  • the cohesive force of the flame-retardant thermally conductive pressure-sensitive adhesive layer may be reduced.
  • the (a) acrylic polymer can use other monomers as a monomer component as necessary.
  • other monomers for example, various properties of the pressure-sensitive adhesive and the structure of the acrylic polymer can be more appropriately controlled.
  • Other monomers include monomers having an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether, such as 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, and (meth) acrylic.
  • an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether, such as 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, and (meth) acrylic.
  • Monomers having an alkoxy group such as methoxyethylene glycol acid and methoxypolypropylene glycol (meth) acrylate, for example, monomers having a cyano group such as acrylonitrile and methacrylonitrile, for example, styrenes such as styrene and ⁇ -methylstyrene Monomers, for example, ⁇ -olefins such as ethylene, propylene, isoprene, butadiene, isobutylene, isocyanates such as 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, etc.
  • Monomers having an ate group for example, vinyl ester monomers such as vinyl acetate and vinyl propionate, for example, vinyl ether monomers such as vinyl ether, for example, (meth) acryl having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate Monomers having a halogen atom such as acid esters such as fluorine (meth) acrylate, such as monomers having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, such as silicone (meth) Monomers having a siloxane bond, such as acrylates, for example, alkyl (meth) acrylates having an alkyl group having 21 or more carbon atoms, such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylic (Meth) acrylates having an alicyclic hydrocarbon group, such as phenyl (meth) acryl
  • a monomer having an alkoxy group is preferably used. More preferably, 2-methoxyethyl acrylate is used.
  • the wettability of a flame-retardant heat conductive adhesive layer can be improved, and the heat from a to-be-adhered body (heat generation source) can be conducted efficiently.
  • the proportion of other monomers is suitably 30% by mass or less, preferably 20% by mass or less, based on the total amount of monomer components for preparing the acrylic polymer. It may be a monomer component not contained.
  • the content of the monomer having an alkoxy group is, for example, 5% by mass to 20% by mass, and preferably 8% by mass to 15% by mass with respect to the total amount of monomer components for preparing the acrylic polymer. be able to.
  • the acrylic polymer preferably contains substantially no carboxyl group-containing monomer as a monomer component.
  • the “carboxyl group-containing monomer” is a monomer having one or more carboxyl groups (may be in the form of anhydrides) in one molecule, such as (meth) acrylic acid, itaconic acid, maleic acid.
  • examples include acids, fumaric acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the monomer component of the acrylic polymer “substantially free of carboxyl group-containing monomer” means that the monomer component does not contain any carboxyl group-containing monomer or the content is 0.1% by mass of the monomer component. It means the following.
  • the fluidity of the pressure-sensitive adhesive composition may be reduced, making it difficult to prepare a pressure-sensitive adhesive sheet.
  • the acrylic polymer becomes pseudo-crosslinked (hardens)
  • the fluidity is lowered and the adhesive property is lowered by reducing the wettability.
  • an acrylic polymer can be obtained by copolymerizing the above monomer components.
  • the method of copolymerization is not particularly limited, and it can be cured by heat or ultraviolet rays using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator).
  • a photopolymerization initiator is preferably used because of the advantage that the polymerization time can be shortened, and a monomer component is copolymerized by using polymerization using ultraviolet rays, and acrylic resin is used. A base polymer is obtained.
  • a polymerization initiator can be used individually or in combination of 2 or more types.
  • the polymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive agents.
  • An oxime photopolymerization initiator, a benzoin photopolymerization initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, or the like can be used.
  • examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples include 1-one and anisole methyl ether.
  • examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
  • the benzoin photopolymerization initiator includes, for example, benzoin.
  • examples of the benzyl photopolymerization initiator include benzyl.
  • examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • ketal photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, decylthioxanthone, and the like.
  • the amount of the photopolymerization initiator used is not particularly limited, but can be selected, for example, from 0.01 to 5 parts by mass, preferably from 0.05 to 3 parts by mass with respect to 100 parts by mass of the monomer component.
  • the photopolymerization initiator In activating the photopolymerization initiator, it is important to irradiate the mixture of the monomer component and the photopolymerization initiator with ultraviolet rays.
  • the irradiation energy of the ultraviolet rays, the irradiation time, etc. are not particularly limited as long as the photopolymerization initiator can be activated to cause the monomer component to react.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2-methylpropionic acid).
  • Azo polymerization initiators such as 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, examples For example, peroxide polymerization initiators such as dibenzoyl peroxide, t-butyl permaleate,
  • the amount of the thermal polymerization initiator used is not particularly limited as long as it can be conventionally used as a polymerization initiator.
  • the monomer component and the thermal polymerization initiator are dissolved in an appropriate solvent (for example, toluene or ethyl acetate) and, for example, 20 to 100 ° C. (typically 40 to 80 ° C.). ) By heating at a polymerization temperature of about.
  • an appropriate solvent for example, toluene or ethyl acetate
  • 20 to 100 ° C. typically 40 to 80 ° C.
  • the acrylic polymer has a glass transition temperature (Tg) of about ⁇ 10 ° C. or lower (typically about ⁇ 10 ° C. to ⁇ 70 ° C.), preferably ⁇ 20 ° C. or lower (
  • the monomer component is preferably about ⁇ 20 ° C. to ⁇ 70 ° C., and the composition and blending of the monomer component are preferably such that the Tg of the acrylic polymer obtained by polymerizing the monomer component is in the above range. Adjust the amount.
  • the Tg of the acrylic polymer refers to a value obtained from the Fox formula based on the Tg of the homopolymer of each monomer constituting the monomer component and the weight fraction (copolymerization composition) of the monomer.
  • the value of Tg of the homopolymer can be obtained from various known materials (such as “Adhesion Technology Handbook” of Nikkan Kogyo Shimbun).
  • the (b) hydrated metal compound contained in the flame retardant thermally conductive pressure-sensitive adhesive layer has a decomposition start temperature in the range of 150 to 500 ° C., and has a general formula M m O n ⁇ XH 2 O (where M is A metal, m, n are an integer of 1 or more determined by the valence of the metal, and X is a compound represented by water containing crystal water) or a double salt containing the above compound.
  • Examples of the (b) hydrated metal compound in the present invention include aluminum hydroxide [Al 2 O 3 .3H 2 O; or Al (OH) 3 ], boehmite [Al 2 O 3 .H 2 O; or AlOOH].
  • These hydrated metal compounds may be used alone or in combination of two or more.
  • aluminum hydroxide is preferable because of its high thermal conductivity and high flame retardancy.
  • the shape of the (b) hydrated metal compound used in the present invention is not particularly limited, and may be a bulk shape, a needle shape, a plate shape, or a layer shape.
  • the bulk shape includes, for example, a spherical shape, a rectangular parallelepiped shape, a crushed shape, or a deformed shape thereof.
  • the particle diameter of the hydrated metal compound (b) is 0.1 to 1000 ⁇ m, preferably 1 to 100 ⁇ m as the primary average particle diameter in the case of a bulk (spherical) hydrated metal compound. Preferably, it is 5 to 80 ⁇ m.
  • the primary average particle diameter exceeds 1000 ⁇ m, there is a problem that the hydrated metal compound exceeds the thickness of the flame-retardant heat conductive pressure-sensitive adhesive layer and causes thickness variation.
  • the primary average particle diameter is a volume-based value obtained by the particle size distribution measurement method in the laser scattering method. Specifically, it is calculated
  • the maximum length is 0.1 to 1000 ⁇ m, preferably 1 to 100 ⁇ m, more preferably 5 to 45 ⁇ m.
  • aspect ratios are, for example, 1 to 10000, preferably 1 to 1000.
  • the aspect ratio is expressed by major axis length / minor axis length or major axis length / thickness.
  • the aspect ratio is expressed by diagonal length / thickness or long side length / thickness.
  • the hydrated metal compound is used in combination of two or more hydrated metal compounds having different particle diameters.
  • the particle diameter means the primary average particle diameter or the maximum length.
  • the thermally conductive particles are more closely packed in the flame retardant thermally conductive pressure-sensitive adhesive layer. As a result, the heat conduction path is easily constructed, and the heat conductivity is improved.
  • the blending ratio is, for example, 1:10 to 10: 1, preferably 1: 5 to 5: 1, and more preferably 1: 2 to 2: 1.
  • the (b) hydrated metal compound a general commercially available product can be used.
  • the aluminum hydroxide for example, the trade name “Hijilite H-100-ME” (primary average particle) Diameter 75 ⁇ m) (made by Showa Denko KK), trade name “Hijilite H-10” (primary average particle diameter 55 ⁇ m) (made by Showa Denko KK), trade name “Hijilite H-32” (primary average particle diameter 8 ⁇ m) ) (Manufactured by Showa Denko KK), trade name “Hijilite H-42” (primary average particle diameter 1 ⁇ m) (manufactured by Showa Denko KK), etc., trade name “B103ST” (primary average particle diameter 8 ⁇ m)
  • trade name “KISUMA 5A” primary average particle diameter 1 ⁇ m
  • Kyowa Chemical Industry Co., Ltd. can be used.
  • the content of the (b) hydrated metal compound constituting the flame-retardant heat conductive pressure-sensitive adhesive layer of the present invention is not particularly limited, but is 100 parts by mass of the acrylic polymer in the flame-retardant heat conductive pressure-sensitive adhesive layer. On the other hand, it is 100 to 500 parts by mass, preferably 200 to 450 parts by mass, and more preferably 300 to 400 parts by mass.
  • the content of the hydrated metal compound is 100 to 500 parts by mass with respect to 100 parts by mass of the acrylic polymer, high thermal conductivity and flame retardancy can be obtained.
  • the content of the hydrated metal compound is less than 100 parts by mass, sufficient thermal conductivity and flame retardancy may not be imparted, and if it exceeds 500 parts by mass, the flexibility is low. Thus, the adhesive strength and holding power may be reduced.
  • thermally conductive particles in order to improve thermal conductivity, other thermally conductive particles may be contained.
  • thermally conductive particles examples include boron nitride, aluminum nitride, silicon nitride, gallium nitride, silicon carbide, silicon dioxide, aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, tin oxide, and oxide. Copper, nickel oxide, antimonic acid doped tin oxide, calcium carbonate, barium titanate, potassium titanate, copper, silver, gold, nickel, aluminum, platinum, carbon black, carbon tube (carbon nanotube), carbon fiber, diamond, etc. Can be mentioned.
  • heat conductive particles general commercial products can be used.
  • trade name “HP-40” manufactured by Mizushima Alloy Iron Company
  • trade name “PT620” for example, the product name “AS-50” (manufactured by Showa Denko KK), etc.
  • the aluminum oxide, and the antimonate doped tin for example, the product name “SN-100S” (manufactured by Ishihara Sangyo Co., Ltd.) ), Trade name “SN-100P” (Ishihara Sangyo Co., Ltd.), trade name “SN-100D (water-dispersed product)” (Ishihara Sangyo Co., Ltd.), etc.
  • the content is not particularly limited, but for example 100 parts by weight or less with respect to 100 parts by weight of the acrylic polymer in the flame retardant heat conductive pressure-sensitive adhesive layer,
  • the amount is preferably 1 to 270 parts by mass, more preferably 5 to 280 parts by mass.
  • the flexibility of the flame retardant heat conductive pressure-sensitive adhesive layer may be lowered or the flame retardancy may be lowered.
  • a dispersant is preferably used in the flame-retardant heat conductive adhesive layer of the present invention in order to stably disperse the hydrated metal compound and the heat conductive particles without agglomerating.
  • phosphate ester is mentioned.
  • the phosphoric acid ester include phosphoric acid monoesters including polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether or polyoxyethylene alkyl aryl ether, phosphoric acid including polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether Examples thereof include diesters and phosphoric acid triesters, and derivatives thereof.
  • phosphate ester dispersants may be used alone or in combination of two or more.
  • polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester and phosphate diester are preferably used.
  • Such dispersants are, for example, trade name “Plisurf A212E” (Daiichi Kogyo Seiyaku Co., Ltd.), trade name “Plisurf A210G” (Daiichi Kogyo Seiyaku Co., Ltd.), trade name “Plisurf A212C” (No. 1).
  • the blending amount of the dispersant is not particularly limited, but is, for example, 0.01 to 10 parts by weight, preferably 0.05 parts by weight to 5 parts by weight, more preferably 100 parts by weight of the acrylic polymer. 0.1 parts by mass to 3 parts by mass.
  • other flame retardants may be contained within a range that does not adversely affect adhesiveness and thermal conductivity.
  • Examples of the flame retardant that can be used in the present invention include metal carbonates such as basic magnesium carbonate, magnesium carbonate-calcium, calcium carbonate, barium carbonate, and dolomite, such as barium metaborate, magnesium oxide, ammonium polyphosphate, Examples include zinc borate, tin compounds, organic phosphorus, red phosphorus, carbon black, and silicone flame retardants.
  • metal carbonates such as basic magnesium carbonate, magnesium carbonate-calcium, calcium carbonate, barium carbonate, and dolomite, such as barium metaborate, magnesium oxide, ammonium polyphosphate
  • Examples include zinc borate, tin compounds, organic phosphorus, red phosphorus, carbon black, and silicone flame retardants.
  • the content is not particularly limited, but it is 250 parts by mass or less with respect to 100 parts by mass of the acrylic polymer in the flame retardant thermally conductive pressure-sensitive adhesive layer.
  • the adhesion of the flame retardant thermally conductive pressure-sensitive adhesive layer may be significantly reduced or the thermal conductivity may be lowered due to the bleeding out of the monomer.
  • the content of the flame retardant is preferably 1 to 270 parts by mass, and more preferably 5 to 280 parts by mass with respect to 100 parts by mass of the acrylic polymer.
  • the total amount thereof is the acrylic polymer 100 in the flame retardant heat conductive pressure-sensitive adhesive layer.
  • the amount is 100 to 500 parts by weight, preferably 200 to 450 parts by weight, and more preferably 300 to 400 parts by weight with respect to parts by weight.
  • the flame retardant thermally conductive adhesive sheet has a high heat Conductivity and flame retardancy can be obtained.
  • the content of the hydrated metal compound, the thermally conductive particles and / or the flame retardant is less than 100 parts by mass, sufficient thermal conductivity and flame retardancy may not be imparted. If it exceeds the mass part, the flexibility becomes low, and the adhesive force and holding force of the flame-retardant heat conductive adhesive layer may be reduced.
  • the content of the hydrated metal compound is such that the hydrated metal compound, the heat conductive particles and / or It is 50 mass% or more with respect to the total amount of a flame retardant, Preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more.
  • the flame-retardant heat conductive adhesive sheet can obtain high heat conductivity and flame retardance.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet may not be able to impart sufficient heat conductivity and flame resistance. (Bubbles)
  • the flame-retardant heat conductive pressure-sensitive adhesive layer can also contain bubbles.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheet can be provided with thickness and cushioning properties, and the followability to the uneven surface of the adherend is improved.
  • the bubble content can be appropriately selected within a range that does not impair the heat conduction characteristics of the flame-retardant heat-conductive adhesive sheet, but is usually 5 to the total volume of the flame-retardant heat-conductive pressure-sensitive adhesive layer. It is 50% by volume, preferably 10 to 40% by volume, more preferably 12 to 35% by volume.
  • the amount of bubbles is less than 5% by volume, the adhesion to the adherend and the unevenness followability are often poor.
  • the air bubbles mixed in the flame-retardant heat conductive adhesive layer are closed-cell type bubbles, but the closed-cell type bubbles and open-cell type bubbles are mixed. Also good.
  • such bubbles usually have a spherical shape, but may have an irregular spherical shape.
  • the average bubble diameter (diameter) of the bubbles is not particularly limited, and can be selected, for example, from 1 to 1000 ⁇ m, preferably from 10 to 500 ⁇ m, more preferably from 30 to 300 ⁇ m.
  • the gas component contained in the bubbles is not particularly limited, and is an air other than an inert gas such as nitrogen, carbon dioxide, or argon.
  • a gas component that forms bubbles sometimes referred to as “bubble-forming gas”
  • Various gas components such as can be used.
  • the bubble-forming gas is preferably nitrogen from the viewpoint of not inhibiting the reaction or from the viewpoint of cost.
  • the method of mixing the bubbles is not particularly limited, but is preferably a mixture of monomer components containing (meth) acrylic acid alkyl ester as a main component and containing a polar group-containing monomer in an amount of 5% by mass or more, or partial polymerization thereof.
  • C mixing bubbles with a precursor composition of a flame retardant thermally conductive pressure-sensitive adhesive layer containing a product and a hydrated metal compound (hereinafter sometimes referred to as “precursor composition”) Then, a precursor composition containing bubbles is prepared, and this is irradiated with ultraviolet rays to form a flame-retardant heat conductive adhesive layer.
  • a stator with many fine teeth on a disk with a through hole in the center is opposed to a stator with teeth, and the same fine teeth as the stator are on the disk.
  • a device equipped with a rotor is opposed to a stator with teeth, and the same fine teeth as the stator are on the disk.
  • a precursor composition is introduced between the teeth on the stator and the teeth on the rotor, and a gas component (bubble forming gas) for forming bubbles through the through-holes while rotating the rotor at a high speed is the precursor.
  • a gas component bubble forming gas
  • a bubble-containing precursor composition in which a bubble-forming gas is finely dispersed and mixed in the precursor composition can be obtained.
  • a fluorine-based surfactant can be added to the precursor composition containing bubbles.
  • Using a fluorosurfactant reduces the adhesion and frictional resistance between the hydrated metal compound and the acrylic polymer in the flame retardant thermally conductive adhesive layer, and reduces the stress between the hydrated metal compound and the acrylic polymer. Are dispersed, and the flame-retardant heat-conductive pressure-sensitive adhesive layer obtains a high adhesive force.
  • the effect of improving the bubble mixing property and bubble stability in the flame-retardant thermally conductive pressure-sensitive adhesive layer can also be obtained.
  • fluorine-based surfactant a fluorine-based surfactant having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group in the molecule is used.
  • the oxy C 2-3 alkylene group is represented by the formula: —R—O— (where R is a linear or branched alkylene group having 2 or 3 carbon atoms).
  • the fluorosurfactant is not particularly limited as long as it has an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group, but is preferably a nonionic surfactant from the viewpoint of dispersibility with respect to an acrylic polymer. Is good.
  • the oxy C 2-3 alkylene group in the molecule of the fluorosurfactant includes an oxyethylene group (—CH 2 CH 2 O—), an oxypropylene group [—CH 2 CH (CH 3 ) O—], and the like. Any one of these may be used, or two or more may be used.
  • a fluorine-type surfactant can be used individually or in combination of 2 or more types.
  • a perfluoro group is mentioned.
  • the perfluoro group may be monovalent or divalent or higher. Further, the fluorinated hydrocarbon group may have a double bond or a triple bond, and may be linear or have a branched structure or a cyclic structure.
  • the number of carbon atoms of the fluorinated hydrocarbon group is not particularly limited, and is, for example, 1 or 2 or more, preferably 3 to 30, more preferably 4 to 20.
  • One or two or more of these fluorinated hydrocarbon groups are introduced into the surfactant molecule.
  • Examples of the oxy C 2-3 alkylene group include alcohols in which a hydrogen atom is bonded to a terminal oxygen atom, ethers bonded to other hydrocarbon groups, and esters bonded to other hydrocarbon groups via a carbonyl group. Form may be sufficient.
  • a form having the above oxy-C 2-3 alkylene group structure in a part of the cyclic structure such as cyclic ethers and lactones may be used.
  • the structure of the fluorosurfactant is not particularly limited.
  • a copolymer containing, as monomer components, a monomer having an oxy C 2-3 alkylene group and a monomer having a fluorinated hydrocarbon group is mentioned.
  • Examples of the block copolymer include polyoxyethylene perfluoroalkyl ether, polyoxyethylene perfluoroalkylate, polyoxyethylene perfluoroalkylate, Examples include propylene perfluoroalkyl ether, polyoxyisopropylene perfluoroalkyl ether, polyoxyethylene sorbitan perfluoroalkylate, polyoxyethylene polyoxypropylene block copolymer perfluoroalkylate, and polyoxyethylene glycol perfluoroalkylate.
  • graft copolymer examples include, for example, a vinyl compound having a polyoxyalkylene group and a fluorinated hydrocarbon group.
  • a copolymer with a vinyl compound, an acrylic copolymer, etc. are mentioned, Preferably an acrylic copolymer is mentioned.
  • Examples of the vinyl compound having a polyoxyalkylene group include polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and polyoxyethylene polyoxypropylene (meth) acrylate. Can be mentioned.
  • vinyl compounds having a fluorinated hydrocarbon group examples include perfluoroalkyl (meth) acrylates such as perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluoropentyl (meth) acrylate, and fluorine.
  • perfluoroalkyl (meth) acrylates such as perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluoropentyl (meth) acrylate, and fluorine.
  • (Meth) acrylic acid ester containing a fluorinated hydrocarbon examples include perfluoroalkyl (meth) acrylates such as perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluoropentyl (meth) acrylate, and fluorine.
  • the fluorosurfactant may have a structure such as an alicyclic hydrocarbon group or an aromatic hydrocarbon group in the molecule, and does not impair dispersibility in the acrylic polymer. And may have various functional groups such as a carboxyl group, a sulfonic acid group, a cyano group, an amide group, and an amino group.
  • the fluorosurfactant is a vinyl copolymer
  • a monomer component copolymerizable with a vinyl compound having a polyoxyalkylene group and a vinyl compound having a fluorinated hydrocarbon group is used as the monomer component. It may be used.
  • Such monomers can be used alone or in combination of two or more.
  • Examples of the copolymerizable monomer component include (meth) acrylic acid C 1-20 alkyl esters such as undecyl (meth) acrylate and dodecyl (meth) acrylate, and alicyclic rings such as cyclopentyl (meth) acrylate.
  • (Meth) acrylic acid ester which has a formula hydrocarbon group for example, (meth) acrylic acid ester which has aromatic hydrocarbon groups, such as phenyl (meth) acrylate, etc. are mentioned.
  • carboxyl group-containing monomers such as maleic acid and crotonic acid
  • sulfonic acid group-containing monomers such as sodium vinyl sulfonate
  • aromatic vinyl compounds such as styrene and vinyl toluene, such as ethylene and butadiene Olefins or dienes
  • vinyl ethers such as vinyl alkyl ethers
  • amide group-containing monomers such as acrylamide
  • amino group-containing monomers such as (meth) acryloylmorpholine
  • examples thereof include glycidyl group-containing monomers such as methyl glycidyl acrylate, for example, isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate.
  • polyfunctional copolymerizable monomers polyfunctional copolymerizable monomers (polyfunctional monomer), such as dipentaerythritol hexa (meth) acrylate and divinylbenzen
  • the weight average molecular weight of the fluorosurfactant is not particularly limited, but when the weight average molecular weight is less than 20000 (for example, 500 or more and less than 20000), an acrylic polymer in the flame-retardant thermally conductive pressure-sensitive adhesive layer, The effect of reducing adhesion between the heat conductive particles and frictional resistance is high.
  • the mixing property of the bubbles and the mixed bubbles Increased stability.
  • Fluorosurfactants having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of less than 20,000 include, as a specific example, a trade name “Futgent 251” (manufactured by Neos), trade name "FTX-218" (manufactured by Neos), product name "Megafac F-477” (manufactured by Dainippon Ink and Chemicals), product name “megafuck F-470” (manufactured by Dainippon Ink and Chemicals), product Name “Surflon S-381” (manufactured by Sey Chemical Co., Ltd.), Product name “Surflon S-383” (manufactured by Sey Chemical Company), Product name “Surflon S-393” (manufactured by Sey Chemical Company), Product name “Surflon KH- 20 ”(manufactured by Sey Chemical Co., Ltd.) and the
  • a specific example of a fluorosurfactant having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of 20000 or more is the trade name “F-top EF-352” (manufactured by Gemco). Trade name “F-top EF-801” (manufactured by Gemco), trade name “Unidyne TG-656” (manufactured by Daikin Industries), and the like.
  • Any fluorosurfactant can be suitably used in the present invention.
  • the amount of use (solid content) of the fluorosurfactant is not particularly limited. For example, it is 0 with respect to 100 parts by mass of the total monomer components for forming the acrylic polymer of the flame retardant thermally conductive pressure-sensitive adhesive layer. It can be selected in the range of 0.01 to 5 parts by mass, preferably 0.02 to 3 parts by mass, more preferably 0.03 to 2 parts by mass.
  • the amount is less than 0.01 parts by mass, it is difficult to obtain the stability of the bubbles, and if it exceeds 5 parts by mass, the adhesion performance may be deteriorated.
  • the degree of adhesion and frictional resistance between the dispersant for stably dispersing the hydrated metal compound and the acrylic polymer in the hydrated metal compound and the flame-retardant thermally conductive adhesive layer are reduced.
  • a fluorine-based surfactant that exhibits stress dispersibility can be used in combination.
  • the hydrated metal compound aggregates in the flame retardant thermally conductive adhesive layer in a smaller amount of fluorosurfactant than when used alone.
  • the heat conductivity is improved without stabilization.
  • the stress dispersibility of the flame retardant thermally conductive pressure-sensitive adhesive layer is also improved, and higher adhesive strength can be expected.
  • the blending amount is not particularly limited, but the ratio (weight ratio) of the dispersant to the fluorosurfactant is 1:20 to 20: 0.01, preferably 1:10 to 10: 0.01, more preferably 1: 5 to 5: 0.01.
  • the step of mixing the precursor composition of the flame retardant thermally conductive adhesive layer and the bubbles is preferably a series of steps. It is set as the last process of a flame-retardant heat conductive adhesive layer formation process. In the above step, more preferably, the viscosity of the precursor composition before mixing the bubbles is increased.
  • the viscosity of the precursor composition is not particularly limited as long as it is a viscosity capable of stably holding the mixed bubbles, but is, for example, 5 to 50 Pa ⁇ s, preferably 10 to 40 Pa ⁇ s.
  • the measurement conditions are a BH viscometer, the rotor is a No. 5 rotor, the rotation speed is 10 rpm, and the temperature is 30 ° C.).
  • the viscosity of the precursor composition is less than 5 Pa ⁇ s, the viscosity is too low, and the mixed bubbles may immediately coalesce and come out of the system, while exceeding 50 Pa ⁇ s. If it is, when the flame-retardant heat-conductive pressure-sensitive adhesive layer is formed, the viscosity is too high and coating becomes difficult.
  • the viscosity of the precursor composition is, for example, a method of blending various polymer components such as acrylic rubber and a thickening additive, a monomer component for forming an acrylic polymer (for example, for forming an acrylic polymer) It can be adjusted by a method of partially polymerizing a monomer component such as (meth) acrylic acid ester, etc. to obtain a partial polymer.
  • a monomer component for forming an acrylic polymer for example, a monomer component such as (meth) acrylic acid ester for forming an acrylic polymer
  • a polymerization initiator for example, photopolymerization
  • thermal polymerization initiator thermal polymerization initiator, etc.
  • a precursor of viscosity suitable for stably containing bubbles by blending the syrup with a hydrated metal compound and, if necessary, a monomer, a dispersant, a fluorosurfactant and various additives (described later).
  • a body composition can be prepared.
  • a precursor composition containing stable bubbles can be obtained.
  • a fluorosurfactant or a hydrated metal compound may be appropriately blended in advance during monomer mixing.
  • a crosslinking agent can be used in addition to the above-described method of blending the polyfunctional monomer and introducing a crosslinked structure into the acrylic polymer. It is.
  • a commonly used crosslinking agent can be used.
  • a melamine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned, Especially preferably, an isocyanate type crosslinking agent and an epoxy type crosslinking agent are mentioned.
  • tolylene diisocyanate hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate
  • examples include triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
  • a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule specifically 2-isocyanatoethyl (meth) acrylate, etc. should be used as an isocyanate crosslinking agent. Can do.
  • Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Examples include glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N′-diamine glycidylaminomethyl) cyclohexane. It is done.
  • the content thereof is not particularly limited, but is 0.01 to 5 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the acrylic polymer in the flame-retardant heat conductive adhesive layer. 0.01 to 3 parts by mass, and more preferably 0.01 to 2 parts by mass.
  • the flame-retardant heat-conductive pressure-sensitive adhesive layer of the present invention can contain a tackifier resin in order to improve the adhesion.
  • tackifying resin Preferably, hydrogenation type tackifying resin is mentioned. Such a resin hardly inhibits the ultraviolet copolymerization of the acrylic polymer even when used in combination with the acrylic polymer.
  • hydrogenated tackifying resins include hydrogenation to tackifying resins such as petroleum resins, terpene resins, coumarone / indene resins, styrene resins, rosin resins, alkylphenol resins, and xylene resins.
  • the derivatives can be selected.
  • the hydrogenated petroleum resin can be selected from, for example, aromatic, dicyclopentadiene, aliphatic, and aromatic-dicyclopentadiene copolymer.
  • the hydrogenated terpene resin can be selected from, for example, a terpene phenol resin and an aromatic terpene resin. Among these, Preferably, petroleum-type resin or terpene-type resin is mentioned.
  • the softening point of the tackifier resin is preferably 80 to 200 ° C, more preferably 100 to 200 ° C.
  • a tackifier resin when used, its content is not particularly limited, but is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the acrylic polymer in the flame-retardant heat conductive adhesive layer. More preferably, it is 2 to 40 parts by mass, and particularly preferably 3 to 30 parts by mass.
  • the addition amount of the tackifying resin exceeds 50 parts by mass, the cohesive force may be reduced.
  • the addition amount is less than 1 part by mass, the effect of improving the adhesive force of the flame-retardant thermally conductive pressure-sensitive adhesive layer cannot be obtained. There is a case.
  • an acrylic oligomer can be contained in order to improve adhesiveness.
  • the acrylic oligomer (a) is a polymer having a glass transition temperature (Tg) higher than that of the acrylic polymer and a small weight average molecular weight, functions as a tackifier resin, and is polymerized at the time of polymerization using ultraviolet rays. It has the advantage that it is difficult to cause inhibition.
  • the acrylic oligomer has a glass transition temperature (Tg) of, for example, about 0 ° C. or higher and 300 ° C. or lower, preferably about 20 ° C. or higher and 300 ° C. or lower, more preferably about 40 ° C. or higher and 300 ° C. or lower. is there.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) is less than about 0 ° C.
  • the cohesive strength of the flame retardant thermally conductive pressure-sensitive adhesive layer at room temperature or higher is lowered, and the retention characteristics and high temperature of the flame retardant thermally conductive pressure sensitive adhesive layer are reduced.
  • the adhesive strength in the area may be reduced.
  • Tg of the acrylic oligomer can be calculated based on the Fox equation in the same manner as the Tg of the acrylic polymer (a).
  • the weight average molecular weight of the acrylic oligomer is, for example, 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000.
  • the weight average molecular weight is 30000 or more, the effect of improving the adhesive strength of the flame-retardant thermally conductive pressure-sensitive adhesive sheet may not be sufficiently obtained.
  • the adhesive strength and holding characteristics of the flame-retardant heat conductive pressure-sensitive adhesive sheet may be deteriorated.
  • the measurement of the weight average molecular weight of the acrylic oligomer can be obtained by polystyrene conversion by the GPC method.
  • the measurement is performed with a tetrahydrofuran solvent using a TSKgelGMH-H (20) ⁇ 2 column on HPLC 8020 manufactured by Tosoh Corporation under a flow rate of about 0.5 ml / min.
  • examples of the monomer constituting the acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate.
  • Such (meth) acrylic acid esters can be used alone or in combination of two or more.
  • the (meth) acrylic oligomer is preferably a (meth) acrylic acid alkyl ester having a branched structure of an alkyl group such as isobutyl (meth) acrylate or t-butyl (meth) acrylate, (meth) Esters of (meth) acrylic acid with cycloaliphatic alcohols such as cyclohexyl acrylate and isobornyl (meth) acrylate, aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate As represented by (meth) acrylate having a cyclic structure such as, an acrylic monomer having a relatively bulky structure is included as a monomer unit.
  • an acrylic monomer having a relatively bulky structure is included as a monomer unit.
  • those having a ring structure are highly effective, and those containing a plurality of rings are more effective.
  • UV rays ultraviolet rays
  • monomers having saturated bonds are less likely to cause polymerization inhibition.
  • Such a monomer is preferably (meth) acrylate or alicyclic alcohol in which the alkyl group has a branched structure.
  • the acrylic oligomer for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA) Copolymers of cyclohexyl methacrylate (CHMA) and acryloylmorpholine (ACMO), copolymers of cyclohexyl methacrylate (CHMA) and diethylacrylamide (DEAA), 1-adamantyl acrylate (ADA) and methacrylic acid Copolymer of methyl (MMA) or copolymer of dicyclopentanyl methacrylate (DCPMA) and isobornyl methacrylate (IBXMA), dicyclopentanyl methacrylate (DC MA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate
  • an acrylic oligomer when used, its content is not particularly limited, but it is, for example, 1 to 70 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the acrylic polymer in the flame-retardant heat conductive adhesive layer. Is 2 to 50 parts by mass, more preferably 3 to 40 parts by mass. When the addition amount of the acrylic oligomer exceeds 70 parts by mass, the cohesive force of the flame retardant thermally conductive pressure-sensitive adhesive layer may be reduced.
  • the elastic modulus of the flame-retardant heat-conductive pressure-sensitive adhesive layer becomes too high, which may cause problems such as a decrease in adhesion at low temperatures and loss of adhesion at room temperature.
  • the amount of the acrylic oligomer added is less than 1 part by mass, the effect of improving the adhesive strength may not be obtained.
  • a silane coupling agent can be used for the flame-retardant heat-conductive pressure-sensitive adhesive layer of the present invention for the purpose of improving adhesive strength, durability, and affinity between the hydrated metal compound and the acrylic polymer.
  • silane coupling agent known ones can be appropriately used without particular limitation.
  • silane coupling agents may be used alone or in combination of two or more.
  • the content of the silane coupling agent is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and more preferably 100 parts by mass of the acrylic polymer. 0.05 to 2 parts by mass.
  • the flame retardant thermally conductive adhesive layer includes (a) an acrylic polymer, (b) a hydrated metal compound, and the above-described bubbles and various components, as well as a flame retardant thermally conductive adhesive layer. Depending on the application, an appropriate additive may be contained.
  • a flame-retardant heat conductive pressure-sensitive adhesive sheet of the present invention a flame-retardant heat conductive pressure-sensitive adhesive composition containing at least (a) an acrylic polymer and (b) a hydrated metal compound is used.
  • a flame-retardant heat conductive pressure-sensitive adhesive composition containing at least (a) an acrylic polymer and (b) a hydrated metal compound is used.
  • a monomer component for forming an acrylic polymer for example, a polymerization initiator (for example, a photopolymerization initiator, a thermal polymerization initiator, etc.), and an appropriate solvent (toluene, ethyl acetate, etc.) are mixed to form a monomer.
  • a polymerization initiator for example, a photopolymerization initiator, a thermal polymerization initiator, etc.
  • an appropriate solvent toluene, ethyl acetate, etc.
  • the monomer solution is subjected to a polymerization reaction according to the type of polymerization initiator to prepare a polymer solution containing an acrylic polymer copolymerized with monomer components, and then a hydrated metal compound and various additives as necessary. Is added to prepare a flame retardant thermally conductive pressure-sensitive adhesive composition having a viscosity suitable for coating.
  • a flame-retardant heat conductive adhesive layer can be formed by applying the flame-retardant heat conductive pressure-sensitive adhesive composition on a predetermined surface and performing drying or curing as necessary.
  • a monomer mixture for preparing an acrylic polymer and a photopolymerization initiator are mixed to prepare a monomer mixture, and the monomer mixture is irradiated with ultraviolet rays.
  • a composition (syrup) containing a partial polymer obtained by polymerizing only a part of the monomer components are prepared.
  • the above syrup is mixed with a hydrated metal compound and, if necessary, a monomer, a dispersant, a fluorosurfactant and various additives to prepare a precursor composition having a viscosity suitable for coating.
  • the flame retardant thermally conductive pressure-sensitive adhesive layer can be formed by applying the precursor composition on a predetermined surface and then curing it by irradiating with ultraviolet rays.
  • a precursor composition in which bubbles are mixed with the precursor composition is obtained.
  • the flame retardant thermally conductive pressure-sensitive adhesive layer having bubbles can be formed by curing by irradiation with ultraviolet rays. .
  • a flame retardant thermally conductive pressure-sensitive adhesive layer can be prepared by coating a coating liquid on a substrate or a release liner containing a polyester film, and drying and then bonding another release liner.
  • Examples of the method for forming the flame retardant thermally conductive pressure-sensitive adhesive layer in the present invention include a roll coat, a kiss roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, a dip roll coat, a bar coat, a knife coat, and an air.
  • Examples thereof include an extrusion coating method such as knife coating, curtain coating, lip coating, and die coater.
  • the thickness of the flame-retardant thermally conductive pressure-sensitive adhesive layer is not particularly limited, and can be selected, for example, from 1 to 950 ⁇ m, preferably from 20 to 200 ⁇ m, more preferably from 30 to 100 ⁇ m.
  • the thickness of the flame-retardant heat-conductive pressure-sensitive adhesive layer is less than 10 ⁇ m, sufficient adhesion and holding power may not be obtained. On the other hand, if the thickness is greater than 950 ⁇ m, sufficient heat conductivity is obtained. You may not be able to.
  • the flame retardant thermally conductive adhesive sheet has a tensile modulus of, for example, 0.1 MPa or more, preferably 10 MPa or more, more preferably 20 MPa or more, and usually less than 1000 MPa.
  • the flame-retardant heat-conductive pressure-sensitive adhesive sheet may be stretched when pasted, resulting in poor pasting.
  • the tensile modulus is measured according to the description in the evaluation of Examples (described later).
  • Adhesive layer non-flame retardant thermally conductive adhesive layer
  • a pressure-sensitive adhesive layer other than the above-mentioned flame-retardant heat-conductive pressure-sensitive adhesive layer (non-flame-retardant heat-conductive pressure-sensitive adhesive) unless the effects of the present invention are impaired.
  • Agent layer may be impaired.
  • the pressure-sensitive adhesive layer is a known pressure-sensitive adhesive (for example, acrylic pressure-sensitive adhesive, rubber pressure-sensitive adhesive, vinyl alkyl ether pressure-sensitive adhesive, silicone pressure-sensitive adhesive, polyester pressure-sensitive adhesive, polyamide pressure-sensitive adhesive, urethane pressure-sensitive adhesive, fluorine And a pressure-sensitive adhesive layer, an epoxy pressure-sensitive adhesive, etc.).
  • a known pressure-sensitive adhesive for example, acrylic pressure-sensitive adhesive, rubber pressure-sensitive adhesive, vinyl alkyl ether pressure-sensitive adhesive, silicone pressure-sensitive adhesive, polyester pressure-sensitive adhesive, polyamide pressure-sensitive adhesive, urethane pressure-sensitive adhesive, fluorine And a pressure-sensitive adhesive layer, an epoxy pressure-sensitive adhesive, etc.
  • a non-flame retardant heat conductive adhesive layer is not specifically limited, According to the objective, the usage method, etc., it can select suitably.
  • a release liner may be used to protect the adhesive surface (adhesive surface) of the pressure-sensitive adhesive layer such as the flame-retardant heat-conductive pressure-sensitive adhesive layer or the non-flame-retardant heat-conductive pressure-sensitive adhesive layer.
  • a release liner is not necessarily provided.
  • the release liner is used by being peeled off when the pressure-sensitive adhesive layer is attached to the adherend.
  • Conventional release paper can be used as such a release liner.
  • a fluorine-based polymer for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinyl fluoride.
  • Low-adhesive substrates made of vinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc., and nonpolar polymers (eg, olefin resins such as polyethylene and polypropylene)
  • a release liner having a release treatment layer formed on at least one surface of a release liner substrate.
  • Such release liner base materials include polyester films (polyethylene terephthalate film, etc.), olefin resin films (polyethylene film, polypropylene film, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon films), rayon films.
  • plastic base film synthetic resin film
  • papers quality paper, Japanese paper, kraft paper, glassine paper, synthetic paper, topcoat paper, etc.
  • these are laminated by laminating or coextrusion. (2 to 3 layer composite).
  • the release treatment agent constituting the release treatment layer is not particularly limited, and for example, a silicone release treatment agent, a fluorine release treatment agent, a long-chain alkyl release treatment agent, or the like can be used.
  • the release treatment agents can be used alone or in combination of two or more.
  • the thickness of the release liner, the formation method, etc. are not particularly limited. According to the flame-retardant heat conductive pressure-sensitive adhesive sheet of the present invention, since it is excellent in heat conductivity and flame retardancy, it is suitable for applications such as hard disks, LED lighting, lithium ion batteries, etc., taking advantage of the characteristics.
  • the monomer component is 82 parts by mass of 2-ethylhexyl acrylate and 12 parts by mass of 2-methoxyethyl acrylate, and the polar group-containing monomer is 5 parts by mass of N-vinyl-2-pyrrolidone (NVP) and hydroxyethylacrylamide (HEAA).
  • NDP N-vinyl-2-pyrrolidone
  • HEAA hydroxyethylacrylamide
  • the mixture of the monomer mixture and the photopolymerization initiator is irradiated with ultraviolet rays, and a part thereof is polymerized until the viscosity (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30 ° C.) reaches about 20 Pa ⁇ s.
  • a composition (syrup) was prepared.
  • a hydrated metal compound 175 parts by mass of a trade name “Hijilite H-32” (shape: crushed, particle size: 8 ⁇ m, manufactured by Showa Denko KK) which is aluminum hydroxide powder and a product which is aluminum hydroxide powder
  • a precursor composition was prepared by adding 175 parts by mass of “Hijilite H-10” (shape: crushed, particle size: 55 ⁇ m) (manufactured by Showa Denko KK).
  • the precursor composition was dried and separated between the release treated surfaces of two release liners made of polyethylene terephthalate (trade name “Diafoil MRF38” (Mitsubishi Chemical Polyester Film Co., Ltd.)). It applied so that the thickness after hardening might be set to 54 micrometers.
  • the precursor composition is sandwiched between release liners made of polyethylene terephthalate.
  • ultraviolet rays with an illuminance of about 5 mW / cm 2 were irradiated from both sides for 3 minutes to polymerize the monomer component to obtain an acrylic polymer, and a flame-retardant heat conductive adhesive layer was produced.
  • the glass transition temperature of the acrylic polymer was ⁇ 62.8 ° C.
  • the release liner on one side of the flame-retardant heat-conductive adhesive layer is peeled off, and the flame-retardant heat-conductive adhesive layer is a polyethylene terephthalate film with a thickness of 12 ⁇ m, trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.). ).
  • the total thickness (excluding the thickness of the release liner, including the polyethylene terephthalate film and the flame-retardant heat conductive adhesive layer provided on both sides thereof. That is, the polyethylene terephthalate film has a thickness of 12 ⁇ m and each flame-retardant property.
  • a flame-retardant heat-conductive pressure-sensitive adhesive sheet having a thickness of 54 ⁇ m (the same applies hereinafter) of a heat-conductive pressure-sensitive adhesive layer was prepared.
  • Example 2 In Example 1, a flame-retardant heat conductive adhesive sheet having a total thickness of 250 ⁇ m was prepared in the same manner as in Example 1 except that the thickness of the flame-retardant heat conductive adhesive layer was 119 ⁇ m. .
  • Example 3 a flame-retardant heat conductive adhesive sheet having a total thickness of 500 ⁇ m was prepared in the same manner as in Example 1 except that the thickness of the flame-retardant heat conductive adhesive layer was 244 ⁇ m. .
  • Example 4 In Example 1, the flame retardant thermally conductive pressure-sensitive adhesive layer had a thickness of 112.5 ⁇ m, and a polyethylene terephthalate film having a thickness of 25 ⁇ m as a base material, trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.) was used. Others were the same formulation as in Example 1, and a flame-retardant thermally conductive adhesive sheet with a total thickness of 250 ⁇ m was prepared.
  • Example 5 the flame retardant thermally conductive pressure-sensitive adhesive layer had a thickness of 237.5 ⁇ m, and a polyethylene terephthalate film having a thickness of 25 ⁇ m was used as a substrate, trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.). Others were the same formulation as in Example 1, and a flame-retardant thermally conductive adhesive sheet having a total thickness of 500 ⁇ m was prepared.
  • Example 6 In Example 1, the thickness of the flame-retardant heat-conductive adhesive layer was set to 106 ⁇ m, and a polyethylene terephthalate film having a thickness of 38 ⁇ m was used as a substrate, trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.) A flame-retardant thermally conductive pressure-sensitive adhesive sheet having a total thickness of 250 ⁇ m was prepared in the same manner as in Example 1.
  • Example 7 In Example 1, except that the thickness of the flame-retardant heat conductive pressure-sensitive adhesive layer was 59 ⁇ m, and a polyethylene terephthalate film having a thickness of 2 ⁇ m was used as a substrate, the trade name “Lumirror 2DC-61” (manufactured by Toray Industries, Inc.) A flame-retardant thermally conductive pressure-sensitive adhesive sheet having the same formulation as in Example 1 and a total thickness of 120 ⁇ m was prepared.
  • Example 8 In Example 1, except that the thickness of the flame-retardant heat conductive adhesive layer was 122.5 ⁇ m and a polyethylene terephthalate film having a thickness of 5 ⁇ m was used as the base material, the total thickness was the same as in Example 1. Produced a flame-retardant thermally conductive pressure-sensitive adhesive sheet having a thickness of 250 ⁇ m.
  • Example 9 In Example 1, except that the thickness of the flame-retardant heat conductive adhesive layer was 102.5 ⁇ m and a polyethylene terephthalate film having a thickness of 45 ⁇ m was used as the base material, the total thickness was the same as in Example 1.
  • Example 1 Produced a flame-retardant thermally conductive pressure-sensitive adhesive sheet having a thickness of 250 ⁇ m.
  • the thickness of the flame-retardant heat-conductive adhesive layer was 231 ⁇ m, and a polyethylene terephthalate film having a thickness of 38 ⁇ m was used as the base material, and the trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.) was used.
  • a flame retardant thermally conductive pressure-sensitive adhesive sheet having a total thickness of 500 ⁇ m was prepared in the same manner as in Example 1.
  • Example 2 the thickness of the flame-retardant heat conductive adhesive layer was set to 100 ⁇ m, and a polyethylene terephthalate film having a thickness of 50 ⁇ m as a base material, a trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.) was used. A flame-retardant thermally conductive pressure-sensitive adhesive sheet having a total thickness of 250 ⁇ m was prepared in the same manner as in Example 1.
  • Example 3 the thickness of the flame-retardant heat conductive adhesive layer was set to 41 ⁇ m, and a polyethylene terephthalate film having a thickness of 38 ⁇ m was used as a base material, trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.).
  • Example 4 the thickness of the flame retardant thermally conductive pressure-sensitive adhesive layer was 47.5 ⁇ m, and a polyethylene terephthalate film having a thickness of 25 ⁇ m was used as a substrate, trade name “Lumirror S-10” (manufactured by Toray Industries, Inc.). Others were the same formulation as in Example 1, and a flame-retardant thermally conductive adhesive sheet with a total thickness of 120 ⁇ m was prepared. (Test evaluation) The following test was done about the flame-retardant heat conductive adhesive sheet obtained by each Example and each comparative example. The test results are shown in Table 1. (Thermal resistance) The measurement of thermal resistance was performed using the thermal characteristic evaluation apparatus shown in FIG.
  • the heating element H is disposed on the upper block L
  • the radiator C is disposed below the block L on the lower side.
  • the pair of blocks L bonded together with the flame-retardant heat conductive adhesive sheet S is positioned between a pair of pressure adjusting screws T penetrating the heating element H and the radiator C.
  • a load cell R is disposed between the pressure adjusting screw T and the heating element H, and is configured to measure the pressure when the pressure adjusting screw T is tightened. Was used as a pressure applied to the flame-retardant heat-conductive adhesive sheet S.
  • three probes P (diameter 1 mm) of a contact displacement meter were installed so as to penetrate the lower block L and the flame-retardant heat conductive adhesive sheet S from the radiator C side. At this time, the upper end portion of the probe P is in contact with the lower surface of the upper block L, and the distance between the upper and lower blocks L (the thickness of the adhesive sheet S) can be measured.
  • the temperature sensor D was attached to the heating element H and the upper and lower blocks L. Specifically, the temperature sensor D was attached to one place of the heating element H, and the temperature sensors D were attached to the five places of each block L at intervals of 5 mm in the vertical direction.
  • the pressure adjusting screw T is tightened to apply pressure to the flame-retardant heat conductive adhesive sheet S, the temperature of the heating element H is set to 80 ° C., and the temperature of the radiator C is set to 20 ° C. Cooling water was circulated.
  • the temperature of the upper and lower blocks L is measured by each temperature sensor D, and the thermal conductivity (W / m ⁇ K) and temperature gradient of the upper and lower blocks L are measured.
  • the temperature at the interface between the upper and lower blocks L and the flame-retardant heat conductive adhesive sheet S was calculated. Then, using these, the thermal conductivity (W / m ⁇ K) and thermal resistance (cm 2 ⁇ K / W) at the above pressure were calculated using the following thermal conductivity equation (Fourier's law).
  • the flame-retardant heat-conductive adhesive sheet S (20 mm ⁇ 20 mm) of each Example and each Comparative Example was loaded into the evaluation apparatus in the same manner as in the case of measuring the thermal resistance.
  • the pressure adjusting screw T is tightened and sandwiched between the upper and lower blocks, and a pressure of 25 N / cm 2 (250 kPa) is applied to the flame-retardant heat-conductive adhesive sheet S. While setting the amount to be constant 30 W, cooling water at 20 ° C. was circulated through the radiator C. At that time, the case where the temperature change of the thermocouple was 0.02 ° C. or less in 30 seconds was regarded as a stable state, and the temperature of the thermocouple on the heater side closest to the sheet was read as the module temperature.
  • the initial longitudinal length is 20 mm
  • the initial width is 10 mm
  • a tensile test was performed at a measurement temperature of 23 ° C., a distance between chucks of 20 mm, and a tensile speed of 300 mm / min, and the amount of change (mm) in elongation of the evaluation sample was measured.
  • a tangent line was drawn at the initial rising portion of the obtained SS curve, and the tensile strength when the tangent line corresponds to 100% elongation was divided by the cross-sectional area of the evaluation sample to obtain the tensile elastic modulus.
  • the flame-retardant heat conductive pressure-sensitive adhesive sheets prepared in each Example and each Comparative Example were cut into a size of 200 mm ⁇ 50 mm, the release films on both sides were peeled off and wound into a cylindrical shape, and five test pieces were obtained. One end of the test piece was held vertically and suspended. The burner flame was first applied to the free end for 3 seconds, separated from the flame, and then applied for an additional 3 seconds. Each of the obtained sheets was evaluated for pass / fail of UL94VTM-0 according to the following evaluation criteria.
  • Example 5 and Comparative Example 2 the thickness of the test piece was 500 ⁇ m.
  • the evaluation was performed in the same procedure as in the other examples.
  • the total flammable combustion time (the total of the combustion time after applying the first flame and the combustion time after applying the second flame) of each test piece is within 10 seconds.
  • the total of the total flammable combustion time of each test piece is within 50 seconds.
  • the flaming combustion time and the flameless combustion time of each test piece after applying the flame for the second time are within 30 seconds.
  • Combustion dripping material falls from one of the test pieces and does not ignite the cotton placed below. (5) Any test piece does not burn up to its suspended part.
  • ⁇ The number of evaluation items satisfying the above (1) to (5) is 5 or more.
  • the flame-retardant heat conductive adhesive sheets of Examples 1 to 9 are polyesters having a ratio of the thickness of the base material to the total thickness of the flame-retardant heat conductive adhesive sheets of less than 0.2. It can be seen that the film is used and has high flame retardancy (UL94VTM-0). It can also be seen that the thermal resistance is 10 cm 2 ⁇ K / W or more, and the thermal conductivity is high.
  • Comparative Examples 2 to 4 use a polyester film in which the ratio of the thickness of the base material to the total thickness of the flame-retardant heat-conductive adhesive sheet is 0.2 or more, and UL94 VTM-0 flame-retardant standards Not satisfied. Moreover, since the thermal resistance is more than 10 cm ⁇ 2 > * K / W, the comparative example 1 is inferior in heat conductivity, and does not fully function as a heat conductive sheet.
  • the flame-retardant heat-conductive adhesive sheet of the present invention is suitable for applications such as hard disks, LED lighting, and lithium ion batteries.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne une feuille adhésive thermoconductrice ignifuge comprenant : un matériau de base; et une couche adhésive thermoconductrice ignifuge disposée sur au moins une surface du matériau de base. Le matériau de base comprend un film de polyester, le rapport entre l'épaisseur du matériau de base et l'épaisseur totale de la feuille adhésive thermoconductrice ignifuge étant inférieur à 0,2, et la résistance à la chaleur étant inférieure ou égale à 10 cm2⋅K/W.
PCT/JP2013/052268 2012-02-02 2013-01-31 Feuille adhésive thermoconductrice ignifuge WO2013115338A1 (fr)

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JP6454139B2 (ja) * 2014-11-26 2019-01-16 マクセルホールディングス株式会社 粘着組成物前駆体、粘着組成物及びその製造方法、粘着シート及びその製造方法、並びに粘着シートを含む電子機器
JP6607370B2 (ja) * 2015-06-12 2019-11-20 Ｄｉｃ株式会社 粘着テープ及び物品
JP2019206629A (ja) * 2018-05-29 2019-12-05 綜研化学株式会社 粘着剤組成物、粘着シートおよび画像表示装置
KR102500214B1 (ko) * 2021-08-23 2023-02-17 삼성디스플레이 주식회사 열 확산 시트를 포함한 표시 장치
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CN110183977A (zh) * 2018-02-22 2019-08-30 琳得科株式会社 粘着片卷绕体
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