WO2009157315A1 - Composition adhésive sensible à la pression thermoconductrice et feuille adhésive sensible à la pression thermoconductrice - Google Patents

Composition adhésive sensible à la pression thermoconductrice et feuille adhésive sensible à la pression thermoconductrice Download PDF

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Publication number
WO2009157315A1
WO2009157315A1 PCT/JP2009/060676 JP2009060676W WO2009157315A1 WO 2009157315 A1 WO2009157315 A1 WO 2009157315A1 JP 2009060676 W JP2009060676 W JP 2009060676W WO 2009157315 A1 WO2009157315 A1 WO 2009157315A1
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Prior art keywords
sensitive adhesive
conductive pressure
heat conductive
adhesive composition
meth
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PCT/JP2009/060676
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English (en)
Japanese (ja)
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拓朗 熊本
亮子 西岡
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日本ゼオン株式会社
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Priority to JP2010517877A priority Critical patent/JP5621592B2/ja
Publication of WO2009157315A1 publication Critical patent/WO2009157315A1/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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • the present invention relates to a heat conductive pressure sensitive adhesive composition and a heat conductive pressure sensitive adhesive sheet formed from the heat conductive pressure sensitive adhesive composition.
  • Patent Document 1 discloses that a heat conductive pressure sensitive adhesive composition containing a flame retardant inorganic compound, expanded graphite powder, and the like, wherein the main component is selected from a resin and the like, and the heat conductive pressure sensitive A heat conductive pressure sensitive adhesive sheet comprising an adhesive composition is disclosed, and such a heat conductive pressure sensitive adhesive sheet has good flame retardancy, hardness, adhesive properties and thermal conductivity, and a balance of these properties. It is said to be excellent.
  • Patent Document 2 discloses a sheet obtained by curing an acrylic copolymer with a crosslinking agent, and it is difficult to add an inorganic compound having crystal water such as expanded graphite and aluminum hydroxide as a filler.
  • a flammable heat conductive sheet is disclosed, and such a flame retardant heat conductive sheet is said to be able to achieve both high flame retardant properties and heat conductivity.
  • the flame resistance of the heat conductive pressure-sensitive adhesive sheet disclosed in the above-mentioned Patent Document 1 is that V-2 of UL-94 (flame retardant standard) is achieved. Although it is not insufficient as performance required when used, in recent years, further flame retardancy is being demanded.
  • the flame-retardant heat conductive sheet disclosed in Patent Document 2 needs to contain a large amount of aluminum hydroxide in order to achieve both high flame resistance and heat conductivity.
  • the content of aluminum hydroxide is increased, there is a problem that the hardness of the sheet becomes too high and the shape followability is inferior.
  • the present invention achieves a high thermal conductivity while providing the basic performance required as a heat conductive pressure-sensitive adhesive sheet such as thermal conductivity and shape followability in an excellent balance, and further flame retardant. It is an object of the present invention to provide a heat conductive pressure-sensitive adhesive sheet having improved properties and a heat conductive pressure-sensitive adhesive composition that is the basis of the heat conductive pressure-sensitive adhesive sheet.
  • the present inventors have made a sheet of a heat conductive pressure-sensitive adhesive composition containing a combustion inhibitor, expanded graphite, and heat conductive fibers. It has been found that the above-mentioned problems can be solved by molding, and the present invention has been completed.
  • At least one polymer (S) selected from the group consisting of rubber, elastomer and resin, combustion inhibitor (B), expanded graphite powder (C), heat A thermally conductive pressure-sensitive adhesive composition (E) comprising conductive fibers (D) is provided.
  • the “combustion inhibitor” is not particularly limited as long as it is a substance having a function capable of suppressing the combustion of the heat conductive pressure-sensitive adhesive sheet (F) by being added to the polymer (S).
  • a known flame retardant can be used.
  • thermalally conductive fiber means a fiber having high thermal conductivity, and specific examples include carbon fiber and metal fiber.
  • the heat conductive pressure sensitive adhesive composition (E) contains the combustion inhibitor (B), the expanded graphite powder (C) and the heat conductive fiber (D) in the heat conductive pressure sensitive adhesive composition (E).
  • the thermally conductive pressure-sensitive adhesive sheet (F) made of) is combusted, the expanded graphite powder (C) swells and entangles with the thermally conductive fibers (D) to form a heat insulating layer. Furthermore, since the combustion rate of the heat conductive pressure-sensitive adhesive sheet (F) is suppressed by the combustion inhibitor (B), combustion does not spread before the heat insulating layer is formed, and combustion can be prevented in the heat insulating layer. Therefore, the heat conductive pressure sensitive adhesive composition (E) contains the combustion inhibitor (B), the expanded graphite powder (C) and the heat conductive fiber (D), so that the heat conductive pressure sensitive adhesive sheet ( The flame retardancy of F) can be improved.
  • the polymer (S) is preferably a (meth) acrylic acid ester polymer (A1).
  • the combustion inhibitor (B) is preferably made of aluminum hydroxide.
  • the combustion inhibitor (B) is more preferably composed of aluminum hydroxide and phosphate ester.
  • the expanded graphite powder (C) preferably has an average particle size of 30 ⁇ m to 500 ⁇ m.
  • the average particle size of the expanded graphite powder means that a laser type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) is used and a microsorting control method (measuring particles are allowed to pass only within the measurement region, and the measurement reliability is Means a value measured by a method for improving the property).
  • a laser type particle size measuring machine manufactured by Seishin Enterprise Co., Ltd.
  • a microsorting control method means a value measured by a method for improving the property.
  • the heat conductive fiber (D) is a carbon fiber.
  • the heat conductive fiber (D) is a carbon fiber
  • the fiber length of the carbon fiber is 0.5 mm to 25 mm
  • the fiber diameter of the carbon fiber is preferably 1 ⁇ m to 30 ⁇ m.
  • the polymer (S) is a (meth) acrylic acid ester polymer (A1)
  • a (meth) acrylic acid ester monomer It is preferable to contain a body (A2m).
  • the graphite powder (C) preferably contains 10 to 150 parts by mass and the thermally conductive fiber (D) 0.5 to 50 parts by mass.
  • molding the heat conductive pressure-sensitive-adhesive composition (E) of 1st this invention in a sheet form is provided. Provided.
  • the heat conductive pressure-sensitive adhesive composition (E) is composed of (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid.
  • An ester monomer (A2m) is contained, and the (meth) acrylic acid ester polymer (A1) is formed while the heat conductive pressure-sensitive adhesive composition (E) is formed into a sheet shape or after being formed into a sheet shape. ) Obtained by polymerizing the (meth) acrylic acid ester monomer (A2m), and a sheet-like molded product of the solidified product (E ′) of the thermally conductive pressure-sensitive adhesive composition (E). It is.
  • the thermal conductivity and shape followability, etc. including the basic performance required as a heat conductive pressure-sensitive adhesive sheet in an excellent balance and further improved in flame retardancy are provided.
  • a pressure-sensitive adhesive sheet and a heat-conductive pressure-sensitive adhesive composition that is the basis of the heat-conductive pressure-sensitive adhesive sheet can be obtained.
  • the heat conductive pressure-sensitive adhesive composition (E) of the present invention comprises at least one polymer (S) selected from the group consisting of rubber, elastomer and resin, a combustion inhibitor (B), and expanded graphite powder ( C) and heat conductive fiber (D) are contained. And in order to shape
  • Polymer (S) As what comprises a polymer (S), at least 1 type arbitrarily selected from rubber
  • the rubber, elastomer and resin are preferably selected from those having adhesiveness and / or tackiness.
  • an adhesive agent can be used in combination with rubber, elastomer and resin having no adhesiveness and / or tackiness.
  • Conjugated diene polymers such as natural rubber, polybutadiene rubber, polyisoprene rubber; butyl rubber; styrene-butadiene random copolymer, styrene-isoprene random copolymer, styrene-butadiene-isoprene random copolymer, styrene-butadiene block copolymer Polymers, styrene-isoprene block copolymers, styrene-butadiene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, aromatic vinyl-conjugated diene copolymers; styrene-butadiene copolymers Hydrogenated aromatic vinyl-conjugated diene copolymer such as hydrogenated product; vinyl cyanide compound-conjugated diene copolymer such as acrylonitrile-
  • Polyepichlorohydride Polyepihalohydrin rubber such as phosphorus rubber and polyepibromohydrin rubber
  • Polyalkylene oxide such as polyethylene oxide and polypropylene oxide
  • Ethylene-propylene-diene copolymer (EPDM) Silicone rubber; Silicone resin; Fluoro rubber; Fluoro resin
  • Polyethylene ethylene- ⁇ -olefin copolymer such as ethylene-propylene copolymer and ethylene-butene copolymer
  • ⁇ -olefin polymer such as polypropylene, poly-1-butene and poly-1-octene
  • poly Polyvinyl halide resins such as polyvinyl chloride resins and polyvinyl bromide resins
  • Polyvinylidene chloride resins such as polyvinylidene chloride resins and polyvinylidene bromide resins
  • styrene-isoprene block copolymer polyethyl acrylate, poly (n-butyl acrylate), poly (acrylic acid 2 -Ethylhexyl), poly [acrylic acid- (n-butyl acrylate)], poly [acrylic acid- (2-ethylhexyl acrylate)], poly [acrylic acid- (n-butyl acrylate)-(acrylic acid 2- Ethylhexyl)], poly [methacrylic acid- (n-butyl acrylate)], poly [methacrylic acid- (2-ethylhexyl acrylate)], poly [methacrylic acid- (n-butyl acrylate)-(acrylic acid 2- Ethylhexyl)], poly [acrylic acid-methacrylic acid-methacrylic acid-methacrylic acid,
  • More preferable examples include poly [acrylic acid- (2-ethylhexyl acrylate)], poly [methacrylic acid- (2-ethylhexyl acrylate)], and poly [acrylic acid-methacrylic acid- (2-ethylhexyl acrylate)]. It is done.
  • the above substances listed as specific examples of rubber, elastomer, and resin may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester polymer (A1) is particularly preferable, as will be described in detail later.
  • Various known materials can be used as the adhesiveness-adhesive agent blended into the polymer (S) as desired.
  • petroleum resin, terpene resin, phenol resin and rosin resin can be mentioned, and among these, petroleum resin is preferable. These may be used individually by 1 type and may use 2 or more types together.
  • petroleum resins include C5 petroleum resins obtained from pentene, pentadiene, isoprene, etc .; C9 petroleum resins obtained from indene, methylindene, vinyltoluene, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc .; C5-C9 copolymerized petroleum resins obtained from monomers; petroleum resins obtained from cyclopentadiene and dicyclopentadiene; hydrides of these petroleum resins; maleic anhydride, maleic acid, fumaric acid, (meth) of these petroleum resins And modified petroleum resins modified with acrylic acid, phenol, and the like.
  • terpene resins examples include ⁇ -pinene resins, ⁇ -pinene resins, and aromatic-modified terpene resins obtained by copolymerizing terpenes such as ⁇ -pinene and ⁇ -pinene with aromatic monomers such as styrene. .
  • phenol resin a condensate of phenols and formaldehyde can be used.
  • the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and the like. These phenols and formaldehyde are subjected to an addition reaction with an alkali catalyst, or an acid catalyst is used for a condensation reaction. The novolak obtained by this can be illustrated.
  • the rosin phenol resin etc. which are obtained by adding phenol to an rosin with an acid catalyst and heat-polymerizing can also be illustrated.
  • rosin resins include gum rosin, wood rosin or tall oil rosin, stabilized rosin or polymerized rosin disproportionated or hydrogenated using the rosin, maleic anhydride, maleic acid, fumaric acid, (meth) acrylic acid, Examples thereof include modified rosin modified with phenol and the like, and esterified products thereof.
  • the alcohol used for esterification to obtain the esterified product is preferably a polyhydric alcohol, and examples thereof include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and neopentyl glycol, glycerin, trimethylolethane, Examples include trihydric alcohols such as trimethylolpropane, tetrahydric alcohols such as pentaerythritol and diglycerin, and hexahydric alcohols such as dipentaerythritol. These may be used alone or in combination of two or more. You may use together.
  • the softening point of these adhesiveness-imparting agents is not particularly limited, but a liquid having a high softening point of 200 ° C. or lower can be appropriately selected and used at room temperature.
  • the (meth) acrylic acid ester polymer (A1) is not particularly limited, but the (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and It is preferable to contain a monomer unit (a2) having an organic acid group.
  • the (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is not particularly limited.
  • ethyl acrylate glass transition temperature of homopolymer is -24 ° C
  • propyl acrylate propyl acrylate (-37 ° C)
  • sec-butyl acrylate (same as above) -22 ° C)
  • octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), acrylic acid 2 -Methoxyethyl (at -50 ° C), 3-methoxypropyl acrylate (at -75 ° C), 3-methoxybut
  • acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
  • the monomer unit (a1) derived therefrom is preferably 80% by mass to 99.9% by mass in the (meth) acrylic acid ester polymer (A1). %, More preferably 85 to 99.5% by weight.
  • the heat-sensitive pressure-sensitive adhesive sheet (F) obtained therefrom is excellent in pressure-sensitive adhesiveness around room temperature.
  • the monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, and representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. In addition to these, monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.
  • the monomer having a carboxyl group include, for example, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, ⁇ , such as itaconic acid, maleic acid, and fumaric acid.
  • ⁇ -ethylenically unsaturated polyvalent carboxylic acid ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid partial esters such as methyl itaconate, butyl maleate and propyl fumarate can be used.
  • the monomer having a sulfonic acid group examples include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.
  • monomers having an organic acid group monomers having a carboxyl group are more preferable, and acrylic acid and methacrylic acid are particularly preferable. These are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. These monomers (a2m) having an organic acid group may be used alone or in combination of two or more.
  • the monomer unit (a2) derived therefrom is 20% by mass to 0.1% by mass in the (meth) acrylic acid ester polymer (A1), preferably Is preferably used in the polymerization in an amount of 15 mass% to 0.5 mass%.
  • the viscosity of the polymerization system during polymerization can be maintained within an appropriate range.
  • the monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer by polymerization of the monomer (a2m) having an organic acid group as described above.
  • an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer is formed.
  • the (meth) acrylic acid ester polymer (A1) may contain a polymer unit (a3) derived from a monomer (a3m) containing a functional group other than an organic acid group.
  • Examples of functional groups other than organic acid groups include hydroxyl groups, amino groups, amide groups, epoxy groups, mercapto groups, and the like.
  • Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
  • Examples of the monomer containing an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
  • Examples of monomers having an amide group include ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
  • the monomer (a3m) containing a functional group other than the organic acid group may be used alone or in combination of two or more.
  • the monomer (a3m) having a functional group other than these organic acid groups is such that the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferred to be used in the polymerization in an appropriate amount. By using 10 mass% or less of monomer (a3m), the viscosity at the time of superposition
  • the (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower.
  • the monomer unit (a2) and the monomer unit (a3) containing a functional group other than the organic acid group it is derived from a monomer (a4m) copolymerizable with these monomers.
  • the monomer unit (a4) may be contained.
  • a monomer (a4m) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the monomer unit (a4) derived from the monomer (a4m) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the acrylate polymer (A1).
  • the monomer (a4m) is not particularly limited, and as a specific example thereof, a (meth) acrylic acid ester monomer (a1m) other than (meth) acrylate monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or less. ) Acrylic acid ester monomer, ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer Carboxylic acid unsaturated alcohol ester, olefinic monomer and the like.
  • the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower include methyl acrylate (single The glass transition temperature of the polymer is 10 ° C., methyl methacrylate (105 ° C.), ethyl methacrylate (63 ° C.), propyl methacrylate (25 ° C.), butyl methacrylate (20 ° C.), and the like. be able to.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete esters such as methyl itaconate, butyl maleate and propyl fumarate include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, itacon Examples include dimethyl acid.
  • alkenyl aromatic monomer examples include styrene, ⁇ -methylstyrene, methyl ⁇ -methylstyrene, vinyl toluene, and divinylbenzene.
  • conjugated diene monomer examples include 1,3-butadiene, 2-methyl-1,3-monobutadiene (synonymous with isoprene), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene.
  • Examples include 2-chloro-1,3-butadiene and cyclopentadiene.
  • non-conjugated diene monomer examples include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
  • olefin monomer examples include ethylene, propylene, butene, pentene and the like.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is preferably in the range of 100,000 to 400,000 as measured by gel permeation chromatography (GPC method). It is more preferable that it is in the range of from 300,000.
  • the (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and a monomer having an organic acid group (A2m), a monomer containing a functional group other than an organic acid group (a3m) used as required, and a monomer copolymerizable with these monomers used as needed ( a4m) can be obtained particularly preferably by copolymerization.
  • the polymerization method is not particularly limited, and any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like may be used.
  • Solution polymerization is preferred, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene as the polymerization solvent is more preferred.
  • the monomer may be added to the polymerization reaction vessel in a divided manner, but it is preferable to add the whole amount at once.
  • the polymerization initiation method is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator (H).
  • the thermal polymerization initiator is not particularly limited, and may be either a peroxide or an azo compound.
  • Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
  • the amount of the polymerization initiator (H) used is not particularly limited, but is preferably in the range of 0.01 to 50 parts by mass with respect to 100 parts by mass of the monomer.
  • polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
  • the obtained polymer is separated from the polymerization medium if necessary.
  • the separation method is not particularly limited, but in the case of solution polymerization, the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
  • the heat conductive pressure-sensitive adhesive composition (E) of the present invention may further contain a (meth) acrylic acid ester monomer (A2m) in addition to the (meth) acrylic acid ester polymer (A1). More preferred.
  • the heat conductive pressure-sensitive adhesive composition (E) of the present invention is formed into a heat conductive pressure-sensitive adhesive sheet (F), (meth) in the heat conductive pressure-sensitive adhesive composition (E).
  • the acrylate monomer (A2m) is polymerized and converted to a (meth) acrylate polymer.
  • the (meth) acrylic acid ester monomer (A2m) is not particularly limited as long as it contains a (meth) acrylic acid ester monomer, but a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m) to form.
  • a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) )
  • a (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
  • the (meth) acrylic acid ester monomer (A2m) may be used as a mixture of the (meth) acrylic acid ester monomer (a5m) and a monomer copolymerizable therewith.
  • Particularly preferred (meth) acrylate monomer (A2m) includes (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group. It consists of a monomer (a6m) having
  • the monomer (a6m) having an organic acid group a monomer having an organic acid group similar to that exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1).
  • a polymer can be mentioned.
  • the monomer having an organic acid group (a6m) one type may be used alone, or two or more types may be used in combination.
  • the ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer (A2m) is preferably 70% by mass to 99.9% by mass, more preferably 75% by mass to 99%. % By mass.
  • the ratio of the (meth) acrylic acid ester monomer (a5m) is in the above range, the pressure-sensitive adhesiveness and flexibility of the heat conductive pressure-sensitive adhesive sheet (F) are excellent.
  • the ratio of the monomer (a6m) having an organic acid group in the (meth) acrylic acid ester monomer (A2m) is preferably 30% by mass to 0.1% by mass, more preferably 25% by mass to 1% by mass. %.
  • the ratio of the monomer having an organic acid group (a6m) is in the above range, the hardness of the heat conductive pressure sensitive adhesive sheet is appropriate, and the pressure sensitive adhesive property at high temperature (100 ° C.) is good. It becomes.
  • the (meth) acrylic acid ester monomer (A2m) is a monomer capable of copolymerizing with the (meth) acrylic acid ester monomer (a5m) and the monomer having an organic acid group (a6m).
  • a body (a7m) can be contained in 20 mass% or less.
  • Examples of the monomer (a7m) include a monomer (a3m), a monomer (a4m) used in the synthesis of the (meth) acrylic acid ester polymer (A1), or a polyfunctional monomer shown below.
  • the monomer similar to what is illustrated as a body can be mentioned.
  • a polyfunctional monomer having two or more polymerizable unsaturated bonds can also be used.
  • intramolecular and / or intermolecular crosslinking can be introduced into the copolymer to increase the cohesive force as a pressure-sensitive adhesive.
  • pen erythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable.
  • the (meth) acrylic acid ester monomer (A2m) preferably contains the above polyfunctional monomer.
  • the polyfunctional monomer is preferably contained in an amount of 0.5% by mass to 5% by mass, more preferably 1% by mass to 3% by mass with respect to 100% by mass of the (meth) acrylic acid ester monomer (A2m). It is desirable to do.
  • the amount of the (meth) acrylic acid ester monomer (A2m) contained in the heat conductive pressure-sensitive adhesive composition (E) is (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester alone.
  • the total amount of the monomer (A2m) is 20% by mass to 70% by mass, preferably 30% by mass to 60% by mass, and more preferably 40% by mass to 55% by mass, based on 100% by mass.
  • the pressure-sensitive adhesive retention of the heat conductive pressure-sensitive adhesive sheet (F) may be inferior.
  • the heat conductive pressure-sensitive adhesive composition (E) of the present invention contains a combustion inhibitor (B).
  • the flame retardant (B) that can be used in the present invention is not particularly limited, and both organic flame retardants and inorganic flame retardants can be used. However, it is preferable to use one that takes into consideration the reduction of environmental burden and safety. From such a viewpoint, halides and hazardous materials are excluded, and aluminum hydroxide, magnesium hydroxide, calcium hydroxide, 2 water are excluded. Japanese gypsum, zinc borate, kaolin clay, calcium aluminate, calcium carbonate, aluminum carbonate, dosonite, phosphate ester, hydrotalcite, antimony oxide and the like.
  • These combustion inhibitors (B) may be used individually by 1 type, and may use 2 or more types together.
  • the shape of the combustion inhibitor (B) is not particularly limited, and may be any of a spherical shape, a needle shape, a fiber shape, a scale shape, a dendritic shape, a flat plate shape, and an indefinite shape.
  • the combustion inhibitor (B) that can be used in the present invention
  • aluminum hydroxide excellent flame retardancy can be imparted to the heat conductive pressure-sensitive adhesive composition (E) and the heat conductive pressure-sensitive adhesive sheet (F) of the present invention.
  • the heat conductive pressure sensitive adhesive sheet (F ) can be further imparted with flame retardancy.
  • one having a particle size of 0.2 ⁇ m to 150 ⁇ m, preferably 0.7 ⁇ m to 100 ⁇ m is usually used. Those having an average particle diameter of 1 ⁇ m to 80 ⁇ m are preferable.
  • the average particle size is less than 1 ⁇ m, the viscosity of the heat conductive pressure-sensitive adhesive composition (E) is increased, and at the same time, the hardness is increased, and the shape followability of the heat conductive pressure-sensitive adhesive sheet (F) is decreased. There is a risk of causing it.
  • the average particle size exceeds 80 ⁇ m the surface of the heat conductive pressure-sensitive adhesive sheet (F) is roughened, which may cause a decrease in the adhesive holding power.
  • phosphate ester examples include, but are not limited to, tri (o-isopropyl) phenyl phosphate, tri (m-isopropyl) phenyl phosphate, tri (p-isopropyl) phenyl phosphate, tri (diisopropyl) phenyl phosphate, tri ( Isopropylated products of triphenyl phosphate such as triisopropyl) phenyl phosphate, tri (tetraisopropyl) phenyl phosphate, tri (pentaisopropyl) phenyl phosphate; triphenyl phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bisdiphenyl phosphate, cresyl diphenyl phosphate Isopropyl chloride, tricresyl phosphate, trixylenyl phosphate, etc.
  • Triaryl phosphates other than chloride trialkyl phosphates such as triisobutyl phosphate and trioctyl phosphate; tri (alkoxyalkyl) phosphates such as tris (butoxyethyl) phosphate; phosphoric acids such as diaryl phosphate and dialkyl phosphate Diesters; phosphoric acid monoesters such as monoaryl phosphates and monoalkyl phosphates; and the like.
  • tri (o-isopropyl) phenyl phosphate tri (m-isopropyl) phenyl phosphate, tri (p-isopropyl) phenyl phosphate, tri (diisopropyl) phenyl phosphate, tri (triisopropyl) phenyl phosphate, tri (tetraisopropyl) phenyl
  • isopropylated products of triphenyl phosphate such as phosphate, tri (pentaisopropyl) phenyl phosphate.
  • aluminum hydroxide is used as the combustion inhibitor (B)
  • hydroxylation is performed with respect to 100 parts by mass of the total amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (A2m).
  • the aluminum content is preferably 50 to 450 parts by mass. More preferred is 100 to 400 parts by mass, and still more preferred is 200 to 400 parts by mass.
  • the total amount of (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (A2m) is 100 parts by mass.
  • the aluminum hydroxide content is preferably 50 to 400 parts by mass, and the phosphate ester content is preferably 10 to 100 parts by mass. More preferably, the aluminum hydroxide content is 100 to 350 parts by mass, and the phosphate ester content is 30 to 95 parts by mass. More preferably, the aluminum hydroxide content is 200 to 350 parts by mass, and the phosphate ester content is 40 to 95 parts by mass.
  • the thermally conductive pressure-sensitive adhesive composition (E) of the present invention contains expanded graphite powder (C).
  • expanded graphite powder examples include a process comprising heat-treating acid-treated graphite at 500 ° C. to 1200 ° C. to expand it to 100 ml / g to 300 ml / g and then pulverizing it. Can be mentioned. More preferably, the graphite is treated with a strong acid, sintered in an alkali, and then again treated with a strong acid at 500 ° C. to 1200 ° C. to remove the acid and to 100 ml / g to 300 ml / g. What was obtained through the process including expanding and then crushing can be mentioned.
  • the temperature of the heat treatment is particularly preferably 800 ° C. to 1000 ° C.
  • the average particle diameter of the expanded graphite powder (C) used in the present invention is preferably 30 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 400 ⁇ m, and further preferably 250 ⁇ m to 350 ⁇ m.
  • the average particle size of the expanded graphite powder (C) is less than the lower limit of the above range, the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (E) is difficult to improve, or the heat conductive pressure-sensitive adhesive sheet (F ),
  • the expanded graphite powder (C) passes through the gaps between the entangled thermal conductive fibers (D), and the improvement in flame retardancy of the thermal conductive pressure-sensitive adhesive sheet (F) cannot be expected. There is a fear.
  • the average particle diameter of the expanded graphite powder (C) exceeds the upper limit of the above range, the presence of large domains on the surface of the molded product makes it easy to form voids at the interface with the adherend, and thermal conductivity. In addition, there is a possibility that the adhesiveness may be lowered and the moldability may be deteriorated.
  • the average particle size of the expanded graphite powder (C) is measured using a laser-type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) and a micro-sorting control method (measuring particles are allowed to pass only within the measurement region to ensure measurement reliability. (Measure to improve).
  • a laser-type particle size measuring machine manufactured by Seishin Enterprise Co., Ltd.
  • a micro-sorting control method measuring particles are allowed to pass only within the measurement region to ensure measurement reliability. (Measure to improve).
  • 0.01 g to 0.02 g of the expanded graphite powder (C) to be measured is caused to flow in the cell, so that the expanded graphite powder (C) flowing into the measurement region has a semiconductor with a wavelength of 670 nm.
  • the content of the expanded graphite powder (C) is preferably 10 parts by mass with respect to 100 parts by mass of the total amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (A2m). From 150 parts by weight, more preferably from 30 parts by weight to 120 parts by weight, and even more preferably from 50 parts by weight to 100 parts by weight.
  • the thermal conductivity of the heat conductive pressure-sensitive adhesive sheet (F) tends to be low, whereas if it exceeds the upper limit of the above range, The thermal conductivity of the heat conductive pressure-sensitive adhesive sheet (F) does not increase so much even if the added number of the expanded graphite powder (C) is increased, which is uneconomical.
  • Thermally conductive fiber (D) The heat conductive pressure sensitive adhesive composition (E) of the present invention contains a heat conductive fiber (D).
  • the heat conductive fiber (D) that can be used in the present invention may be a fiber having high heat conductivity, and specific examples include carbon fiber and metal fiber. However, it is preferable to use carbon fiber from the viewpoint of moldability when the heat conductive pressure-sensitive adhesive composition (E) is used as the heat conductive pressure-sensitive adhesive sheet (F).
  • the thermally conductive pressure sensitive adhesive composition (E) As described above, by adding the expanded graphite powder (C) and the thermally conductive fiber (D) to the thermally conductive pressure sensitive adhesive composition (E), from the thermally conductive pressure sensitive adhesive composition (E).
  • the expanded graphite powder (C) swells and entangles with the heat conductive fiber (D) to form a heat insulating layer. It is thought that it is possible to prevent dripping from occurring during combustion of the conductive sheet (F).
  • the combustion of the heat conductive pressure-sensitive adhesive sheet (F) is suppressed by containing the above-described combustion inhibitor (B) in the heat conductive pressure-sensitive adhesive composition (E), and expanded graphite powder. Time until the said heat insulation layer formed of (C) and a heat conductive fiber (D) is formed can be earned.
  • the fiber length of the thermally conductive fiber (D) that can be used in the present invention is preferably 0.5 mm to 25 mm, more preferably 1 mm to 20 mm, and still more preferably 3 mm to 10 mm.
  • the fiber diameter of the heat conductive fiber (D) that can be used in the present invention is preferably 1 ⁇ m to 30 ⁇ m, more preferably 3 ⁇ m to 20 ⁇ m, and even more preferably 5 ⁇ m to 10 ⁇ m.
  • the heat conductive fiber (D) When the fiber length and fiber diameter of the heat conductive fiber (D) are less than the lower limit of the above range, the heat conductive fiber (D) is difficult to be entangled, and the flame resistance of the heat conductive pressure sensitive adhesive sheet (F) is improved. There is a possibility that it cannot be planned. On the other hand, when the fiber length and fiber diameter of the heat conductive fiber (D) exceed the upper limit of the above range, the moldability may be deteriorated.
  • polymerization initiator (H) examples include organic peroxide thermal polymerization initiators, photopolymerization initiators, azo thermal polymerization initiators, and the like. Adhesive strength of the resulting heat conductive pressure-sensitive adhesive sheet (F) From the viewpoint of the above, an organic peroxide thermal polymerization initiator is preferably used.
  • organic peroxide thermal polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( Examples thereof include peroxides such as t-butylperoxy) -3,3,5-trimethylcyclohexanone, but it is preferable not to release volatile substances that cause odor during thermal decomposition.
  • the organic peroxide thermal polymerization initiators those having a one-minute half-life temperature of 120 ° C. or more and 170 ° C. or less are preferable.
  • the amount of the organic peroxide thermal polymerization initiator used is preferably based on 100 parts by mass of the total amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (A2m).
  • the amount is 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass.
  • the polymerization conversion rate of the (meth) acrylic acid ester monomer (A2m) is preferably 95% by mass or more. If the polymerization conversion rate is too low, a monomer odor remains in the obtained heat conductive pressure-sensitive adhesive sheet (F), which is not preferable.
  • Pyrolytic organic foaming agent (J) A foaming agent can also be added to the heat conductive pressure sensitive adhesive composition (E) of the present invention in order to foam the heat conductive pressure sensitive adhesive sheet (F) obtained therefrom.
  • a thermally decomposable organic foaming agent (J) is preferable.
  • a thermally decomposable organic foaming agent (J) what has a decomposition start temperature of 80 degreeC or more and 200 degrees C or less is preferable.
  • thermally decomposable organic foaming agent (J) examples include 4,4'-oxybis (benzenesulfonylhydrazide).
  • foaming aid examples include zinc stearate, a mixture of stearic acid and zinc white (zinc oxide), zinc laurate, a mixture of lauric acid and zinc white, zinc palmitate, a mixture of palmitic acid and zinc white, stearin Examples include sodium acid, sodium laurate, sodium palmitate, potassium stearate, potassium laurate, and potassium palmitate.
  • External cross-linking agent An external cross-linking agent is added to the heat-conductive pressure-sensitive adhesive composition (E) of the present invention in order to increase cohesion as a pressure-sensitive adhesive and to improve heat resistance.
  • a crosslinked structure can be introduced into the polymer obtained by polymerizing the (meth) acrylate monomer (A2m) in the presence of the acrylate polymer (A1).
  • external crosslinking agents include polyfunctional isocyanate crosslinking agents such as tolylene diisocyanate, trimethylolpropane diisocyanate, diphenylmethane triisocyanate; epoxy crosslinking such as diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether Melamine resin crosslinking agent; amino resin crosslinking agent; metal salt crosslinking agent; metal chelate crosslinking agent; peroxide crosslinking agent;
  • polyfunctional isocyanate crosslinking agents such as tolylene diisocyanate, trimethylolpropane diisocyanate, diphenylmethane triisocyanate
  • epoxy crosslinking such as diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether Melamine resin crosslinking agent; amino resin crosslinking agent; metal salt crosslinking agent; metal chelate crosslink
  • the external crosslinking agent is obtained by polymerizing the (meth) acrylic acid ester monomer (A2m) in the presence of the (meth) acrylic acid ester polymer (A1), and then added to this. By performing heat treatment or radiation irradiation treatment, a cross-link is formed within and / or between the molecules of the copolymer.
  • the heat conductive pressure-sensitive adhesive composition (E) of the present invention may further contain various known additives such as pigments, other fillers, anti-aging agents, and thickeners, if necessary. It can contain in the range which does not impair the effect of invention.
  • the pigment can be used regardless of organic type or inorganic type such as carbon black other than the expanded graphite powder (C), titanium dioxide and the like.
  • examples of other fillers include inorganic compounds such as clay.
  • Antioxidants such as polyphenols, hydroquinones, and hindered amines can be used as the anti-aging agents, although they are not usually used because they are likely to inhibit radical polymerization.
  • As the thickener inorganic polymer fine particles such as acrylic polymer particles and fine silica, and reactive inorganic compounds such as magnesium oxide can be used.
  • Thermally conductive pressure sensitive adhesive sheet (F) The heat conductive pressure sensitive adhesive sheet (F) of the present invention is formed by molding a heat conductive pressure sensitive adhesive composition (E) into a sheet shape.
  • the heat conductive pressure-sensitive adhesive composition (E) is a (meth) acrylate polymer (A1) and a (meth) acrylate ester. Presence of the (meth) acrylic acid ester polymer (A1) while forming the heat conductive pressure sensitive adhesive composition (E) into a sheet or after forming into a sheet A sheet-like molded body of the solidified product (E ′) of the heat conductive pressure-sensitive adhesive composition (E) obtained by polymerizing the (meth) acrylic acid ester monomer (A2m) below.
  • the heat conductive pressure-sensitive adhesive composition (E) can be regarded as substantially equivalent to the solidified product (E ′).
  • the heat conductive pressure-sensitive adhesive composition (E) that does not contain a liquid component such as a (meth) acrylic acid ester monomer (A2m) is considered to be equivalent to the solidified product (E ′). it can.
  • the heat conductive pressure-sensitive adhesive composition (E) when the content of a liquid component represented by a monomer or the like in the heat conductive pressure-sensitive adhesive composition (E) is 5% by mass or less.
  • the heat conductive pressure-sensitive adhesive composition (E) is molded as it is without solidifying the liquid component (for example, polymerization of the monomer), and the heat conductive pressure-sensitive adhesive sheet ( F).
  • the heat conductive pressure-sensitive adhesive sheet (F) of the present invention may be composed of only the heat conductive pressure-sensitive adhesive composition (E) or its solidified product (E ′). It may be a composite comprising a thermally conductive pressure-sensitive adhesive composition (E) or a solidified product (E ′) layer formed on both sides.
  • the thickness of the layer of the heat conductive pressure-sensitive adhesive composition (E) or its solidified product (E ′) in the heat conductive pressure-sensitive adhesive sheet (F) of the present invention is not particularly limited, but is usually 50 ⁇ m to 3 mm. is there. If it is thinner than 50 ⁇ m, air is likely to be involved when affixing to the heat generator and the heat radiating body, and as a result, sufficient thermal conductivity may not be obtained. On the other hand, if it is thicker than 3 mm, the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet (F) becomes large, and there is a possibility that the heat dissipation is impaired.
  • the base material is not particularly limited.
  • the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and foils of alloys and polymers having excellent thermal conductivity such as thermal conductive silicone.
  • a sheet-like material, a heat conductive plastic film containing a heat conductive filler, various nonwoven fabrics, glass cloth, a honeycomb structure, or the like can be used.
  • Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc.
  • a film made of a heat-resistant polymer can be used.
  • the method for forming the heat conductive pressure-sensitive adhesive composition (E) or the solidified product (E ′) thereof into a sheet is not particularly limited. Suitable methods include, for example, a casting method in which the heat conductive pressure-sensitive adhesive composition (E) is applied onto a process paper such as a peeled polyester film, the heat conductive pressure-sensitive adhesive composition (E) or The solidified product (E ′) is sandwiched between two exfoliated process papers if necessary and passed between rolls, and the thickness is controlled through a die when extruding using an extruder. And the like.
  • the pressurizing condition is usually 10 MPa or less, preferably 1 MPa or less. Pressurization exceeding 10 MPa is not preferable because the foamed cell may be crushed when the thermally conductive pressure-sensitive adhesive sheet (F) is foamed.
  • the pressing time may be selected in accordance with the temperature conditions and the type and amount of the polymerization initiator to be used, but is preferably within 1 hour in consideration of productivity.
  • the heat conductive pressure sensitive adhesive composition (E) is suitably obtained by heating the heat conductive pressure sensitive adhesive composition (E) with hot air, an electric heater, infrared rays or the like. be able to.
  • the heating temperature at this time is preferably such that the organic peroxide thermal polymerization initiator decomposes efficiently and the polymerization of the (meth) acrylic acid ester monomer (A2m) proceeds.
  • the temperature range varies depending on the type of organic peroxide thermal polymerization initiator used, but is preferably 100 ° C. to 200 ° C., more preferably 130 ° C. to 180 ° C.
  • the heat conductive pressure sensitive adhesive sheet (F) is obtained by forming the heat conductive pressure sensitive adhesive composition (E) into a sheet shape and heating it to a temperature of 100 ° C. or higher and 200 ° C. or lower. It is preferable that it is a sheet-like molded object formed by forming the pressure-adhesive composition (E) into a sheet and polymerizing the (meth) acrylic acid ester monomer (A2m).
  • the heat conductive pressure-sensitive adhesive sheet (F) of the present invention can be directly formed on a base material such as a radiator and provided as a part of an electronic component.
  • thermo conductivity of heat conductive pressure sensitive adhesive sheet A sample was prepared by cutting a heat conductive pressure-sensitive adhesive sheet (F) having a thickness of 1 mm into a size of 50 mm width ⁇ 110 mm length with scissors. The release PET of this sample was peeled off, and a wrap film was affixed to the surface where the release PET was peeled off so that air would not enter. The size of the wrap film may be larger than the adhesive surface of the sample. And the heat conductivity was measured using the sample which stuck this wrap film. The thermal conductivity (unit: W / m ⁇ K) was measured by an unsteady hot wire comparison method using a rapid thermal conductivity meter (trade name “QTM-500”, manufactured by Kyoto Electronics Industry Co., Ltd.). For the reference plate, quartz (current value: 4A), zirconia (current value: 6A), and mullite (current value: 9A) were used in this order.
  • Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 part 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
  • the raw materials used are shown in Table 1.
  • the mixing was performed using a Hobart mixer (trade name “ACM-5LVT type, capacity: 5 L”) manufactured by Kodaira Seisakusho under the following conditions.
  • Mixing conditions Using a thermostatic bath (trade name “Viscomate 150III”, manufactured by Toki Sangyo Co., Ltd.), the temperature control of the Hobart container was set to 40 ° C. 1.
  • Mix in the rotation speed memory 3 ⁇ 10 minutes 2.
  • a polyester film with a release agent is laid on the bottom of the mold having a length of 400 mm, a width of 400 mm, and a depth of 2 mm, and then the heat conductive pressure-sensitive adhesive composition (E1) is poured into the mold. Then, it was covered with a polyester film with a release agent. This was taken out of the mold and polymerized in a hot air oven at 155 ° C. for 30 minutes to obtain a heat conductive pressure sensitive adhesive sheet (F1) whose both surfaces were covered with a polyester film with a release agent. The results are shown in Table 2. The polymerization conversion rate of the (meth) acrylic acid ester monomer mixture (A2m) was calculated from the residual monomer amount in the heat conductive pressure-sensitive adhesive sheet (F1) and found to be 99.9%.
  • Example 2 As shown in Table 1, the heat conductive pressure-sensitive adhesive composition (E2) and the heat conductive pressure sensitive were the same as in Example 1 except that the carbon fiber (D) content was changed from 5 parts to 1 part. An adhesive sheet (F2) was obtained. The results are shown in Table 2.
  • Example 3 As shown in Table 1, the heat conductive pressure-sensitive adhesive composition (E3) and the heat conductive pressure sensitive were the same as in Example 1 except that the carbon fiber (D) content was changed from 5 parts to 30 parts. An adhesive sheet (F3) was obtained. The results are shown in Table 2.
  • Example 4 As shown in Table 1, a heat conductive pressure-sensitive adhesive composition (E4) was used in the same manner as in Example 1 except that the phosphate ester was not contained and the content of aluminum hydroxide was changed from 300 parts to 350 parts. ) And a heat conductive pressure sensitive adhesive sheet (F4). The results are shown in Table 2.
  • Table 1 shows the compositions of the thermally conductive pressure-sensitive adhesive compositions prepared in Examples and Comparative Examples.
  • the heat conductive pressure-sensitive adhesive sheets of Examples 1 to 3 have high thermal conductivity and extremely excellent flame retardancy.
  • the heat conductive pressure sensitive adhesive sheet of Example 4 uses only aluminum hydroxide as the combustion inhibitor (B), so that the hardness is higher than that of the heat conductive pressure sensitive adhesive sheets of Examples 1 to 3.
  • the flame retardancy is slightly inferior, but it can be seen that it has sufficient thermal conductivity and flame retardancy.
  • the heat conductivity is high, but the flame retardancy is poor.
  • the heat conductive pressure-sensitive-adhesive sheet of the comparative example 2 which does not contain expanded graphite powder (C) has low heat conductivity, and is inferior in flame retardance. Furthermore, the thermally conductive pressure-sensitive adhesive sheet of Comparative Example 3 which does not contain expanded graphite powder and the content of aluminum hydroxide exceeds the upper limit of the range defined in the present invention showed excellent flame retardancy. However, the thermal conductivity was inferior and the shape following property was low because the hardness was too high.

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Abstract

Cette invention concerne une feuille adhésive sensible à la pression thermoconductrice douée d'une thermoconductivité élevée et d'une excellente propriété retardatrice d'inflammation. Une composition adhésive sensible à la pression thermoconductrice constituant la feuille adhésive sensible à la pression thermoconductrice est également décrite. Une composition adhésive sensible à la pression thermoconductrice (E) selon l'invention contient au moins un polymère (S) choisi dans le groupe constitué par les caoutchoucs, les élastomères et les résines, un inhibiteur de combustion (B), une poudre de graphite expansée (C) et des fibres thermoconductrices (D). Une feuille adhésive sensible à la pression thermoconductrice (F) est un corps moulé en forme de feuille de la composition adhésive sensible à la pression thermoconductrice (E) ou une forme solidifiée (E') de la composition adhésive sensible à la pression thermoconductrice.
PCT/JP2009/060676 2008-06-25 2009-06-11 Composition adhésive sensible à la pression thermoconductrice et feuille adhésive sensible à la pression thermoconductrice WO2009157315A1 (fr)

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WO2011102170A1 (fr) * 2010-02-19 2011-08-25 日本ゼオン株式会社 Composition d'adhésif autocollant thermiquement conducteur, feuille adhésive autocollante thermiquement conductrice et composant électronique
WO2012014794A1 (fr) * 2010-07-30 2012-02-02 国立大学法人東北大学 Organe de conversion photoélectrique
WO2012132656A1 (fr) * 2011-03-29 2012-10-04 日本ゼオン株式会社 Composition adhésive sensible à la pression, thermoconductrice, corps formé d'une feuille adhésive sensible à la pression, thermoconductrice, procédé de production de ceux-ci, et composant électronique
WO2012132657A1 (fr) * 2011-03-29 2012-10-04 日本ゼオン株式会社 Composition adhésive sensible à la pression, thermoconductrice, corps formé d'une feuille adhésive sensible à la pression, thermoconductrice, procédé de production de ceux-ci, et composant électronique
EP2726567A1 (fr) * 2011-06-30 2014-05-07 3M Innovative Properties Company Composition adhésive, ruban adhésif et structure d'adhérence
CN104284957A (zh) * 2012-05-23 2015-01-14 日本瑞翁株式会社 导热性压敏粘接剂组合物、导热性压敏粘接性片状成型体、它们的制造方法、和电子设备
JP2016216587A (ja) * 2015-05-19 2016-12-22 日立マクセル株式会社 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
WO2019123336A1 (fr) * 2017-12-22 2019-06-27 3M Innovative Properties Company Adhésifs et articles thermoconducteurs et leurs procédés de fabrication
JP2021532233A (ja) * 2018-07-24 2021-11-25 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA 難燃性接着剤組成物
CN113930168A (zh) * 2021-10-29 2022-01-14 深圳陆祥科技股份有限公司 一种阻燃绝缘电气胶带及其制备方法

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WO2011102170A1 (fr) * 2010-02-19 2011-08-25 日本ゼオン株式会社 Composition d'adhésif autocollant thermiquement conducteur, feuille adhésive autocollante thermiquement conductrice et composant électronique
JP5713000B2 (ja) * 2010-02-19 2015-05-07 日本ゼオン株式会社 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート、及び電子部品
WO2012014794A1 (fr) * 2010-07-30 2012-02-02 国立大学法人東北大学 Organe de conversion photoélectrique
WO2012132657A1 (fr) * 2011-03-29 2012-10-04 日本ゼオン株式会社 Composition adhésive sensible à la pression, thermoconductrice, corps formé d'une feuille adhésive sensible à la pression, thermoconductrice, procédé de production de ceux-ci, et composant électronique
JPWO2012132657A1 (ja) * 2011-03-29 2014-07-24 日本ゼオン株式会社 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート状成形体、これらの製造方法、及び電子部品
WO2012132656A1 (fr) * 2011-03-29 2012-10-04 日本ゼオン株式会社 Composition adhésive sensible à la pression, thermoconductrice, corps formé d'une feuille adhésive sensible à la pression, thermoconductrice, procédé de production de ceux-ci, et composant électronique
EP2726567A1 (fr) * 2011-06-30 2014-05-07 3M Innovative Properties Company Composition adhésive, ruban adhésif et structure d'adhérence
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