WO2013175950A1 - Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet forming body, method of manufacturing these, and electronic device - Google Patents

Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet forming body, method of manufacturing these, and electronic device Download PDF

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Publication number
WO2013175950A1
WO2013175950A1 PCT/JP2013/062624 JP2013062624W WO2013175950A1 WO 2013175950 A1 WO2013175950 A1 WO 2013175950A1 JP 2013062624 W JP2013062624 W JP 2013062624W WO 2013175950 A1 WO2013175950 A1 WO 2013175950A1
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mass
conductive filler
meth
thermally conductive
acrylic acid
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PCT/JP2013/062624
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French (fr)
Japanese (ja)
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明子 北川
拓朗 熊本
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日本ゼオン株式会社
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Priority to JP2014516740A priority Critical patent/JPWO2013175950A1/en
Priority to CN201380024397.1A priority patent/CN104284957A/en
Priority to KR1020147028711A priority patent/KR20150010937A/en
Publication of WO2013175950A1 publication Critical patent/WO2013175950A1/en

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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet.
  • the present invention relates to an electronic device provided with a shaped molded body.
  • thermo conductivity feeling a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • a pressure-sensitive adhesive composition ”) and a sheet-like member hereinafter referred to as“ thermally conductive pressure-sensitive adhesive sheet-like molded body ”.
  • the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are required not only to have excellent heat conductivity but also to be flame retardant depending on applications.
  • Patent Document 1 describes a technique of adding a phosphate ester as a flame retardant. Yes.
  • the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article that are provided with flame retardancy and in which bleed of liquid components is suppressed, a method for producing these, and the thermal process. It is an object of the present invention to provide a conductive pressure-sensitive adhesive composition or an electronic device including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
  • the first aspect of the present invention is a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer ( ⁇ 1), and a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more.
  • thermally conductive filler (B2) subjected to titanate treatment 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2).
  • a mixed composition comprising 200 parts by mass or more and 600 parts by mass or less and phosphoric acid ester (C) in the range of 40 parts by mass or more and 120 parts by mass or less, (meth) acrylate monomer ( ⁇ 1) Polymerization reaction of polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and derived from (meth) acrylate polymer (A1) and / or (meth) acrylate monomer ( ⁇ 1) It is a heat conductive pressure sensitive adhesive composition (F) by which crosslinking reaction of the polymer containing these structural units is performed.
  • (meth) acryl means “acryl and / or methacryl”.
  • the “thermally conductive filler” is added to improve the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) described later. It means a filler having a thermal conductivity of 0.5 W / m ⁇ K or more.
  • the “titanate treatment” means a surface treatment performed using a titanate coupling agent.
  • the “(meth) acrylate monomer ( ⁇ 1) and a polymerization reaction of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds” refers to a (meth) acrylate monomer ( Copolymerization reaction between ⁇ 1) and polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, polymerization reaction of (meth) acrylate monomer ( ⁇ 1), and polymerizable unsaturated bond Among the polymerization reactions of a plurality of multifunctional monomers (D), it means one or a plurality of polymerization reactions.
  • (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer ( ⁇ 1) -derived polymer cross-linking reaction means (meth) acrylic acid ester Cross-linking reaction between polymers (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylate monomer ( ⁇ 1), and (meth) acrylate polymer (A1) and ( Among crosslinking reactions with a polymer containing a structural unit derived from a (meth) acrylate monomer ( ⁇ 1), it means one or a plurality of crosslinking reactions.
  • the “polymer containing a structural unit derived from a (meth) acrylate monomer ( ⁇ 1)” means a polymer obtained by a polymerization reaction between (meth) acrylate monomers ( ⁇ 1), and ( It includes a polymer obtained by a copolymerization reaction between a (meth) acrylic acid ester monomer ( ⁇ 1) and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds.
  • the second aspect of the present invention is a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer ( ⁇ 1) and a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more.
  • thermally conductive filler (B2) subjected to titanate treatment 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2).
  • the third aspect of the present invention is a polyfunctional monomer (D) having a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer ( ⁇ 1) and a plurality of polymerizable unsaturated bonds. ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more.
  • thermally conductive filler (B2) subjected to titanate treatment 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2).
  • the fourth aspect of the present invention is a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer ( ⁇ 1), and a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more.
  • thermally conductive filler (B2) subjected to titanate treatment 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2).
  • the thermally conductive filler (B1) is a metal hydroxide and a metal oxide having a BET specific surface area of 1.0 m 2 / g or more and not subjected to titanate treatment. And at least one selected from the group consisting of the thermally conductive filler (B2) is a titanate-treated metal hydroxide, the thermally conductive filler (B3) is the thermally conductive filler (B1), and the thermal conductivity. It is preferably at least one selected from the group consisting of metal hydroxides, metal oxides and carbon-containing conductive fillers other than the conductive filler (B2), and the heat conductive filler (B1) has a BET specific surface area.
  • (meth) acrylic resin composition (A) is 5 to 25 mass% of (meth) acrylic acid ester polymer (A1), (meth) acrylic acid ester monomer ( ⁇ 1) 74.8 mass. % To 94.8% by mass and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds is preferably contained in an amount of 0.2% by mass to 13% by mass.
  • a radiator and the thermally conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the radiator, or the radiator and the radiator. It is the electronic device provided with the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of the 2nd aspect of the said this invention bonded.
  • a thermally conductive pressure-sensitive adhesive composition excellent in flame retardancy and suppressed bleeding a thermally conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the thermally conductive pressure-sensitive adhesive
  • An electronic device provided with the agent composition or the thermally conductive pressure-sensitive adhesive sheet-like molded product can be provided.
  • the thermally conductive pressure-sensitive adhesive composition (F) of the present invention has a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer ( ⁇ 1), and a plurality of polymerizable unsaturated bonds.
  • a (meth) acrylic resin composition (A) containing a functional monomer (D) hereinafter sometimes simply referred to as “polyfunctional monomer (D)”
  • polyfunctional monomer (D) hereinafter sometimes simply referred to as “polyfunctional monomer (D)”
  • thermally conductive filler (B1) not treated with titanate
  • thermally conductive filler (B2) a thermally conductive filler treated with titanate
  • thermally conductive filler (B3) other than thermally conductive filler (B1) and thermally conductive filler (B2)
  • Thermal conductive filler (B3) And a phosphate ester (C) in a mixed composition, a copolymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer (D). , (Meth) acrylic acid ester monomer ( ⁇ 1) polymerization reaction and / or polyfunctional monomer (D) polymerization reaction, and (meth) acrylic acid ester polymer Cross-linking reaction between (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylic acid ester monomer ( ⁇ 1), and (meth) acrylic acid ester polymers (A1) and (meth) At least one of the crosslinking reactions among the crosslinking reactions with the polymer containing a structural unit derived from the acrylate monomer ( ⁇ 1) is performed.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is (meth) acrylic acid after shape
  • Copolymerization reaction of ester monomer ( ⁇ 1) and polyfunctional monomer (D) polymerization reaction of (meth) acrylic acid ester monomer ( ⁇ 1), and polyfunctional monomer (D)
  • the reaction is performed at least It become one.
  • the materials constituting the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) will be described below.
  • the (meth) acrylic resin composition (A) used in the present invention comprises a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer ( ⁇ 1), and a polyfunctional monomer (D ) Is included.
  • a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G) a polymerization reaction and a crosslinking reaction are performed as mentioned above.
  • the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer (D) are the (meth) acrylic acid ester polymer. It is mixed and / or partially combined with the component (A1).
  • the amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1) used is (mass) acrylic resin composition (A) being 100% by mass
  • the meth) acrylate polymer (A1) is preferably 5% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 74.8% by mass or more and 94.8% by mass or less.
  • the (meth) acrylic acid ester polymer (A1) is 10% by mass or more and 20% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is 79.5% by mass or more and 89.5% by mass or less. Is more preferable.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are formed. Easy to do.
  • the amount of the polyfunctional monomer (D) used is preferably 0.2% by mass or more and 13% by mass or less based on 100% by mass of the (meth) acrylic resin composition (A).
  • the content is more preferably 0.2% by mass or more and 10% by mass or less, and further preferably 0.5% by mass or more and 5% by mass or less.
  • the (meth) acrylate polymer (A1) that can be used in the present invention is not particularly limited, but a (meth) acrylate monomer unit that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain (a1) and a monomer unit (a2) having an organic acid group.
  • the (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer is not particularly limited.
  • ethyl acrylate the glass transition temperature of the homopolymer is -24 ° C
  • n-propyl acrylate (-37 ° C)
  • n-butyl acrylate (-54 ° C)
  • sec-butyl acrylate (-22 ° C)
  • n-octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), 2-methoxyethyl acrylate (-50 ° C) ), 3-methoxypropyl acrylate (-75 ° C), 3-methoxybutyl acrylate (-56 ° C), ethoxymethyl acrylate (-50
  • n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is more preferable.
  • 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 or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1).
  • it is used for polymerization in such an amount that it is more preferably 85% by mass or more and 99.5% by mass or less.
  • the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the viscosity of the polymerization system at the time of polymerization can be easily maintained within an appropriate range.
  • the monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, but representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group.
  • 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, and ⁇ , ⁇ such as itaconic acid, maleic acid, and fumaric acid.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be exemplified.
  • the monomer having a sulfonic acid group examples include allyl sulfonic acid, methacryl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, and the like. These salts can be mentioned.
  • the monomer (a2m) among the monomers having an organic acid group exemplified above, a monomer having a carboxyl group is more preferable, and a monomer having acrylic acid or methacrylic acid is particularly preferable. . These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.
  • the monomer unit (a2) derived from the monomer unit (a2) is preferably 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1). More preferably, it is used for the polymerization in such an amount that it is 0.5 to 15% by mass.
  • the usage-amount of the monomer (a2m) which has an organic acid group exists in the said range, it will become easy to maintain the viscosity of the polymerization system at the time of superposition
  • the monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer (A1) 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 (A1) is produced.
  • the (meth) acrylic acid ester polymer (A1) may contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group.
  • the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.
  • Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.
  • Examples of the monomer having 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) having a functional group other than the organic acid group one type may be used alone, or two or more types may be used in combination.
  • the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferable to use it for polymerization in such an amount.
  • the monomer (a3m) of 10% by mass or less it becomes easy to keep the viscosity of the polymerization system during polymerization in an appropriate range.
  • the (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • a monomer derived from the monomer (a4m) copolymerizable with the above-described monomer may be contained.
  • the monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), ⁇ , ⁇ -ethylenic monomers. Saturated polycarboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, etc. Can be mentioned.
  • the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester examples include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
  • 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-butadiene (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. 2-chloro-1,3-butadiene, cyclopentadiene and the like.
  • 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 monomer (a4m) one type may be used alone, or two or more types may be used in combination.
  • the amount of the monomer unit (a4) derived therefrom is preferably 10% by mass or less, more preferably 5% by mass or less in the (meth) acrylate polymer (A1). It is subjected to polymerization in such an amount.
  • the (meth) acrylic acid ester polymer (A1) has the above-mentioned (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • Monomer (a2m) a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
  • the polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. .
  • solution polymerization is preferable, 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 is more preferable.
  • the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once.
  • the method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator.
  • the thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
  • 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 usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
  • 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.
  • 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 (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. It is more preferable that it is in the range of 200,000 or more and 500,000 or less.
  • 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 (meth) acrylate monomer ( ⁇ 1) is not particularly limited as long as it contains the (meth) acrylate monomer, but forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
  • 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 ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer ( ⁇ 1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer ( ⁇ 1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • the (meth) acrylic acid ester monomer ( ⁇ 1) is a (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is good also as a mixture of the monomer (a6m) which has a polymerizable organic acid group.
  • Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to.
  • a monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 30% by mass or less, and more preferably 10% by mass or less.
  • the (meth) acrylic acid ester monomer ( ⁇ 1) in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture containing the monomer (a7m) copolymerizable with these.
  • Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m).
  • the body can be mentioned.
  • a monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 20% by mass or less, and more preferably 15% by mass or less.
  • Polyfunctional monomer (D) As the polyfunctional monomer (D), one that can be copolymerized with the monomer contained in the (meth) acrylic acid ester monomer ( ⁇ 1) is used.
  • the polyfunctional monomer (D) preferably has a plurality of polymerizable unsaturated bonds, and preferably has the unsaturated bond at the terminal.
  • intramolecular and / or intermolecular crosslinking is introduced into the copolymer, and the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive are introduced.
  • the cohesive force as a pressure-sensitive adhesive of the adhesive sheet-like molded body (G) can be increased.
  • polyfunctional monomer (D) examples include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditri Multifunctional (meth) acrylates such as methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (tri Other substituted triazines, such as Rorome
  • a polyfunctional monomer (D) may be used individually by 1 type, and may use 2 or more types together.
  • ⁇ Polymerization initiator> When obtaining the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G), the components contained in the (meth) acrylic resin composition (A) are polymerized as described above. . In order to accelerate the polymerization reaction, it is preferable to use a polymerization initiator.
  • the polymerization initiator include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator.
  • an organic peroxide thermal polymerization initiator is used. Is preferably used.
  • acylphosphine oxide compounds are preferred.
  • Preferred examples of the acylphosphine oxide compound that is a photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • azo-based thermal polymerization initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.
  • organic peroxide thermal polymerization initiator examples include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone.
  • hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone.
  • organic peroxide thermal polymerization initiators those having a 1-minute half-life temperature of 100 ° C. or more and 170 ° C. or less are preferable.
  • the amount of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). More preferably, it is 0.3 to 2 parts by mass.
  • the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is 95% by mass or more, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the monomer odor from remaining on the surface. Moreover, by making the usage-amount of a polymerization initiator into the said range, a polymerization reaction will advance too much and will cause material destruction, without a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) becoming a smooth sheet form. It becomes easy to prevent the situation.
  • the heat conductive filler (B1) used in the present invention is a heat conductive filler not subjected to titanate treatment having a BET specific surface area of 1.0 m 2 / g or more.
  • the upper limit of the BET specific surface area of the heat conductive filler (B1) is not particularly limited, but the mixture is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). From the viewpoint of suppressing an excessive increase in the viscosity of the composition, it is preferably 10 m 2 / g or less.
  • BET specific surface area means that measured by the following method. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring apparatus, and a sample cell containing a sample (an object to be measured for BET specific surface area) is immersed in liquid nitrogen to adsorb nitrogen gas to the sample surface. After reaching adsorption equilibrium, the sample cell is placed in a water bath and warmed to room temperature, and nitrogen adhering to the sample is desorbed. Since the mixing ratio of the gas before and after passing through the sample cell changes during the adsorption and desorption of nitrogen gas, this change is detected by a thermal conductivity detector (TCD) using a gas with a constant mixing ratio of nitrogen and helium as a control.
  • TCD thermal conductivity detector
  • the adsorption amount and desorption amount of nitrogen gas are obtained.
  • a unit amount of nitrogen gas is introduced into the apparatus for calibration, and the surface area value corresponding to the value detected by TCD is obtained to obtain the surface area of the sample.
  • the BET specific surface area can be obtained by dividing the surface area by the mass of the sample.
  • a liquid such as a phosphate ester (C) described later from the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is obtained. It is thought that a component can be prevented from flowing out.
  • the increase in viscosity of the resin composition can be suppressed by adding the titanate-treated thermally conductive filler (B2) as compared to the case of adding a filler not treated with titanate.
  • the present inventors have further found that the titanate-treated thermally conductive filler (B2) has an effect of suppressing bleeding of the liquid component.
  • the present invention by using the heat conductive filler (B1) and the heat conductive filler (B2) together in appropriate amounts, bleeding of the liquid component can be suppressed while suppressing an increase in the viscosity of the mixed composition. .
  • the heat conductive filler (B1) has a BET specific surface area of 1.0 m 2 / g or more and is not subjected to titanate treatment. When added, the heat conductive pressure-sensitive adhesive composition (F) and the heat conduction are added.
  • the heat conductivity of the pressure-sensitive adhesive sheet-like molded body (G) can be improved as compared with the case where it is not added, and the filler is not particularly limited as long as the thermal conductivity is 0.5 W / m ⁇ K or more.
  • thermally conductive filler (B1) include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; metal oxides such as aluminum oxide (alumina), magnesium oxide, and zinc oxide; carbonic acid Metal carbonates such as calcium and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate hydrate; silica; Among these, metal hydroxides, metal oxides, and metal carbonates are preferable, metal hydroxides and metal oxides are more preferable, aluminum hydroxide and aluminum oxide are further preferable, and aluminum oxide is particularly preferable.
  • a heat conductive filler (B1) may be used individually by 1 type, and may use 2 or more types together.
  • the average particle size of the thermally conductive filler (B1) used in the present invention is preferably 0.5 ⁇ m or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m or less.
  • the “average particle diameter” means that measured by the method described below. That is, a laser type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) is used, and measurement is performed by a microsorting control method (a method in which the measurement target particles are allowed to pass only in the measurement region and the measurement reliability is improved). According to this measurement method, when the measurement target particles 0.01 g to 0.02 g are flowed into the cell, the measurement target particles flowing in the measurement region are irradiated with the semiconductor laser light having a wavelength of 670 nm. By measuring the scattering and diffraction of laser light with a measuring instrument, the average particle size and particle size distribution are calculated from the diffraction principle of Franhofer.
  • the amount of the heat conductive filler (B1) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) 120 parts by mass or more and 450 parts by mass or less, preferably 150 parts by mass or more and 450 parts by mass or less, and more preferably 150 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass.
  • the mixed composition is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G).
  • the thermally conductive filler (B2) used in the present invention is a titanate-treated thermally conductive filler.
  • the titanate treatment method in the heat conductive filler (B2) is not particularly limited, and can be performed using a known titanate coupling agent.
  • titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite).
  • Titanate bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacryl titanate, isopropyltris (dioctylphosphate) titanate, Isopropyltricumylf Niruchitaneto, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, and diisostearoyl ethylene titanate.
  • the heat conductive filler (B2) is titanate-treated, and by adding the heat conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G),
  • the filler is not particularly limited as long as it can be improved as compared with the case where it is not added and the thermal conductivity is 0.5 W / m ⁇ K or more.
  • thermally conductive filler (B2) include those obtained by subjecting the following thermally conductive filler to titanate treatment.
  • Metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide; metal oxides such as aluminum oxide (alumina), magnesium oxide, zinc oxide
  • Metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate hydrate; dosonite; silica; .
  • a heat conductive filler (B2) may be used individually by 1 type, and may use 2 or more types together.
  • the average particle size of the thermally conductive filler (B2) used in the present invention is preferably 1 ⁇ m or more and 80 ⁇ m or less, and more preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the amount of the heat conductive filler (B2) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) It is 120 to 500 mass parts with respect to 100 mass parts, It is preferable that it is 150 to 450 mass parts, and it is more preferable that it is 150 to 400 mass parts.
  • the mixed composition is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G).
  • the thermally conductive filler (B3) used in the present invention is a thermally conductive filler other than the thermally conductive filler (B1) and the thermally conductive filler (B2).
  • the heat conductive filler (B3) one that is not titanate-treated and whose BET specific surface area is out of the range of the heat conductive filler (B1) can be used.
  • thermally conductive filler (B3) include metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide; aluminum oxide ( Alumina), metal oxides such as magnesium oxide and zinc oxide; metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate water Examples thereof include: Japanese; dosonite; silica; carbon-containing conductive fillers such as expanded graphite, artificial graphite, carbon black, and carbon fiber.
  • metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide
  • aluminum oxide ( Alumina) metal oxides such as magnesium oxide and zinc oxide
  • metal carbonates such as calcium carbonate and aluminum carbonate
  • a heat conductive filler (B3) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the heat conductive filler (B3) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) It is 200 mass parts or more and 600 mass parts or less with respect to 100 mass parts, it is preferable that they are 200 mass parts or more and 550 mass parts or less, and it is more preferable that they are 250 mass parts or more and 550 mass parts or less.
  • the mixed composition is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G).
  • the hardness of the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) increases, and the shape followability (adhesion to the adherend) decreases.
  • the content of the heat conductive filler (B3) is less than the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet are obtained by using the heat conductive filler (B3).
  • the quantity of a carbon containing conductive filler is 1 mass part with respect to 100 mass parts of (meth) acrylic resin compositions (A). The amount is preferably 30 parts by mass or less.
  • phosphate ester (C) phosphate ester (C) will be described.
  • phosphoric ester (C) it becomes easy to give the flame retardance excellent in the heat conductive pressure-sensitive-adhesive composition (F) and the heat conductive pressure-sensitive-adhesive sheet-like molded object (G).
  • the phosphate ester (C) used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
  • a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
  • the viscosity of the phosphate ester is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to the following procedure.
  • a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
  • (1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
  • (2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
  • the container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the phosphate ester in the container.
  • the rotation speed is selected from 20, 10, 4, and 2.
  • the rotation speed is selected from 20, 10, 4, and 2.
  • the value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa ⁇ s].
  • the coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.
  • the phosphate ester (C) used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester (C) is liquid when mixed, the workability is good and the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is formed. It becomes easy. When molding the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded product (G) containing the phosphoric ester (C), heat is applied in an environment of 15 ° C. or higher and 100 ° C. or lower.
  • the glass transition temperature of the (meth) acrylic resin composition (A) is set to be equal to or higher than the volatilization or polymerization of monomers contained in the (meth) acrylic resin composition (A). Since it becomes easy to prevent the reaction from starting, the environmental performance and workability can be improved.
  • a condensed phosphate ester or a non-condensed phosphate ester can be used as the phosphate ester (C).
  • condensed phosphate ester means one having a plurality of phosphate ester moieties in one molecule
  • non-condensed phosphate ester means one phosphate ester moiety in one molecule. It means something that exists only. Specific examples of phosphate esters that satisfy the conditions described so far are listed below.
  • condensed phosphate ester examples include aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyalkylene bisdichloroalkyl And halogen-containing condensed phosphates such as phosphates; non-aromatic non-halogen-based condensed phosphates; Of these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no risk of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.
  • aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyal
  • non-condensed phosphate ester examples include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris ( ⁇ -chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.
  • phosphate ester (C) one type may be used alone, or two or more types may be used in combination.
  • the amount of the phosphoric acid ester (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is the (meth) acrylic resin composition (A ) Is 40 parts by mass or more and 120 parts by mass or less, more preferably 50 parts by mass or more and 100 parts by mass or less, and still more preferably 60 parts by mass or more and 100 parts by mass or less.
  • ⁇ Other additives> In addition to the above-described substances, the above-described effects due to the addition of the above-described substances are hindered in the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention.
  • Various known additives can be added within the range.
  • Known additives include: foaming agents (including foaming aids); glass fibers; external cross-linking agents; pigments; other fillers such as clay; nanoparticles such as fullerenes and carbon nanotubes; polyphenols, hydroquinones, Antioxidants such as hindered amines; thickeners such as acrylic polymer particles and fine silica;
  • the thermally conductive filler (B1) having a large BET specific surface area and the titanate treatment were provided while providing flame retardancy by adding the phosphate ester (C).
  • a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded product (G) in which bleeding of the liquid component is suppressed are obtained.
  • the manufacturing method of such a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) is demonstrated.
  • the thermally conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing each of the substances described so far to prepare a mixed composition, and then (meth) acrylic acid ester monomer ( ⁇ 1) and Polymerization reaction of polyfunctional monomer (D) and crosslinking of polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer ( ⁇ 1) It can be obtained by performing at least the reaction.
  • the method for producing the heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises the (meth) acrylic acid ester polymer (A1), the (meth) acrylic acid ester monomer ( ⁇ 1), and the polyfunctional single monomer.
  • Mixed composition comprising (meth) acrylic resin composition (A) containing monomer (D), thermally conductive filler (B1), thermally conductive filler (B2), and thermally conductive filler (B3)
  • the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate
  • the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is prepared by mixing each of the substances described so far to prepare a mixed composition, and molding the mixed composition into a sheet shape, or While forming the mixed composition into a sheet, the polymerization reaction of the (meth) acrylate monomer ( ⁇ 1) and the polyfunctional monomer (D), the (meth) acrylate polymer (A1) and It can be obtained by performing at least a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1).
  • the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention includes (meth) acrylic acid ester polymer (A1), (meth) acrylic acid ester monomer ( ⁇ 1) and polyfunctional.
  • heating is preferably performed when the polymerization and the crosslinking reaction are performed.
  • heating for example, hot air, an electric heater, infrared rays, or the like can be used.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer (D) proceeds.
  • the temperature range varies depending on the type of polymerization initiator used, but is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 130 ° C. or higher and 180 ° C. or lower.
  • the method for molding the mixed composition into a sheet shape is not particularly limited. Suitable methods include, for example, a method of forming a sheet by applying the mixed composition onto a process paper such as a polyester film subjected to a release treatment, and the mixed composition between two release-processed papers. There are a method of forming a sheet by pressing between rolls with a sandwich, and a method of forming the sheet by extruding the mixed composition using an extruder and controlling the thickness through a die at that time. Can be mentioned.
  • the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 5 mm or less. By reducing the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded article (G), the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded article (G) can be reduced. From this viewpoint, the upper limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 2 mm. On the other hand, the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (G) is preferably 0.1 mm.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate.
  • the material which comprises the said base material is not specifically limited.
  • Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone.
  • Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc.
  • a heat-resistant polymer film can be used.
  • the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention can be used as some electronic components with which an electronic device is equipped. In that case, it can also be directly molded on a base material such as a radiator and provided as a part of the electronic component.
  • the electronic device and electronic component include electroluminescence (EL), a component around a heat generating part in a device having a light emitting diode (LED) light source, a component around a power device such as an automobile, a fuel cell, a solar cell, and a battery.
  • Devices and parts having heat generating parts such as mobile phones, personal digital assistants (PDAs), notebook computers, liquid crystals, surface conduction electron-emitting device displays (SED), plasma display panels (PDP), or integrated circuits (ICs) Can be mentioned.
  • PDAs personal digital assistants
  • SED surface conduction electron-emitting device displays
  • PDP plasma display panels
  • ICs integrated circuits
  • an LED light source is exemplified below. Examples of usage can be mentioned.
  • LED light source is directly attached to the LED light source; sandwiched between the LED light source and the heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.);
  • Examples of LED light source applications include backlight devices for display devices having transmissive liquid crystal panels (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; Lighting; and the like.
  • LED light source examples include the following. That is, PDP panel; IC heating part; Cold cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High luminance light emitting LED light source; High luminance light emitting organic EL light source; And so on.
  • examples of the method of using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention include affixing to the housing of the apparatus.
  • affixing to the housing of the apparatus.
  • a device provided in an automobile or the like it is affixed inside a casing provided in the automobile; affixed outside the casing provided in the automobile; a heat generating part (inside the casing provided in the automobile) Connecting the car navigation / fuel cell / heat exchanger) and the housing; affixing to a heat sink connected to the heat generating part (car navigation / fuel cell / heat exchanger) in the housing of the automobile; Etc.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention can be used in the same manner.
  • personal computers homes; TVs; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Organic EL display; laptop computer; PDA; fuel cell; semiconductor device; rice cooker; washing machine; laundry dryer; optical semiconductor device combining optical semiconductor elements and phosphors; Is mentioned.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention are not limited to the above-described usage methods, and may be used in other methods depending on the application. Is also possible.
  • used for heat uniformity of carpets and warm mats, etc . used as LED light source / heat source sealant; used as solar cell sealant; used as solar cell backsheet Used between the backsheet of the solar cell and the roof; used inside the heat insulating layer inside the vending machine; used inside the housing of the organic EL lighting with a desiccant or a hygroscopic agent; organic EL lighting Use with desiccant and hygroscopic agent on the heat conductive layer inside the housing of the LED; Use with desiccant and hygroscopic agent on the heat conductive layer and heat dissipation layer inside the housing of the organic EL lighting Used for heat conduction layer inside the housing of organic EL lighting, epoxy heat dissipation layer, and on top of it with desiccant and moisture absorbent; cooling equipment, clothing, towels, sheets, etc.
  • the member Used as a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer
  • Pressing member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as it is
  • used as a heat transfer part for heat flow control on which the object to be processed of the film forming apparatus is placed used between the outer layer of the radioactive substance storage container and the interior; a box body with a solar panel that absorbs sunlight Can be used between the reflective sheet of the CCFL backlight and the aluminum chassis.
  • the heat-conductive pressure-sensitive adhesive composition (F) of the present invention described so far, the heat-conductive pressure-sensitive adhesive sheet-like molded product (G), the method for producing the heat-conductive pressure-sensitive adhesive composition (F), and
  • the heat conductive filler (B1) has a BET specific surface area of 1.0 m 2 / g or more, is not subjected to titanate treatment, and is metal hydroxide.
  • the thermally conductive filler (B2) is a titanate-treated metal hydroxide
  • the thermally conductive filler (B3) is a thermally conductive filler.
  • It is preferably at least one selected from the group consisting of metal hydroxides, metal oxides and carbon-containing conductive fillers other than (B1) and the heat conductive filler (B2), and the heat conductive filler (B1).
  • BE A specific surface area of 1.0 m 2 / g or more, not titanate processed, at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, heat conductive filler (B2) is titanate processed hydroxide It is aluminum, and the heat conductive filler (B3) is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide and expanded graphite other than the heat conductive filler (B1) and the heat conductive filler (B2).
  • (meth) acrylic resin composition (A) is 5 to 25 mass% of (meth) acrylic acid ester polymer (A1), (meth) acrylic acid ester monomer ( ⁇ 1) 74.8 mass. % To 94.8% by mass and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds is preferably contained in an amount of 0.2% by mass to 13% by mass.
  • a heat conductive pressure-sensitive adhesive sheet-shaped molded body having a thickness of 1 mm was prepared, and then the heat conductive pressure-sensitive adhesive sheet-shaped molded body was cut into a size of 30 mm ⁇ 30 mm, and then oil-repellent paper was used. The sheet was sandwiched and compressed until the heat-conductive pressure-sensitive adhesive sheet-like molded product had a thickness of 0.5 mm, and was allowed to stand for 10 seconds. Thereafter, the position of the oil collecting paper was changed, and the above compression and standing were repeated (total 5 times).
  • ⁇ Flame retardance> As described later, after preparing a heat conductive pressure-sensitive adhesive sheet-like molded body having a thickness of 1 mm, five test pieces were prepared by cutting the sheet into strips having a width of 10 mm and a length of 150 mm. A Bunsen burner air and gas flow rate was adjusted to produce a blue flame of about 20 mm in height, and a burner flame was applied to the lower end of a vertically supported specimen (so that it crossed the flame about 10 mm) and held for 10 seconds. After that, the test piece and the burner flame were released. Thereafter, as soon as the flame of the test piece disappeared, the burner flame was applied to the test piece and held for another 10 seconds, and then the test piece and the burner flame were separated.
  • the flame- and flame-free combustion durations after the first and second flame contact and the presence / absence of combustion drops (drip) were evaluated, and UL-94 (flame retardant standard) was determined. That is, the flaming combustion duration after the end of the first and second flame contact, the total of the flammable combustion duration and the flameless combustion duration after the end of the second flame contact, The determination was made based on the total flame-free combustion time and the presence or absence of combustion drops (drip). In both the first and second times, the flammable combustion was completed within 10 seconds, and the total of the second flammable combustion duration and the flameless combustion time was within 30 seconds. The total flame burning time was within 50 seconds, and there was no burning fallen thing as V-0. The results are shown in Table 2. If this evaluation satisfies the V-0 condition, it can be said that the flame retardancy is excellent. In addition, about the comparative example, since it was inferior in said other evaluation, flame retardance evaluation was not performed.
  • 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 parts 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 (A1-1).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) 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 the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
  • a polyfunctional monomer (light acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) 0.8 mixed with pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate in a ratio of 60: 35: 5.
  • a polyfunctional monomer (light acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.) containing pentaerythritol tetraacrylate as a main component and containing pentaerythritol tetraacrylate and pentaerythritol diacrylate, and acrylic acid 2 -84 parts of ethylhexyl (2EHA) and 1.0 part of organic peroxide thermal polymerization initiator (1,6-bis (t-butylperoxycarbonyloxy) hexane (1 minute half-life temperature is 150 ° C)) And weigh them with an electronic balance. (Meth) were mixed with an acrylic acid ester polymer (A1-1) 15 parts.
  • a thermostatic bath (Viscomate 150III, manufactured by Toki Sangyo Co., Ltd.) and a Hobart mixer (ACM-5LVT type, manufactured by Kodaira Seisakusho Co., Ltd., capacity: 5 L) were used.
  • the temperature control of the Hobart container was set to 40 ° C.
  • the rotation speed scale was set to 3
  • stirring was performed for 10 minutes. This process is referred to as a first mixing process.
  • the mixed composition obtained through the first and second mixing steps is hung on a release PET film having a thickness of 75 ⁇ m, and another release PET film having a thickness of 75 ⁇ m is further dropped on the mixed composition. Covered.
  • This laminate in which the mixed composition was sandwiched between release PET films was passed through a roll having a distance of 1.15 mm between the two, and formed into a sheet shape. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes.
  • the (meth) acrylic acid ester monomer and the polyfunctional monomer are polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester
  • the monomer polymer was subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1).
  • sheet heat conductive pressure-sensitive adhesive sheet-like molded body
  • Examples 2 to 7 and Comparative Examples 1 to 6 The sheets (G2 to G7) according to Examples 2 to 7 and Comparative Example 1 were the same as Example 1, except that the composition of each substance in the second mixing step was changed as shown in Tables 2 and 3. Sheets 6 to 6 (GC1 to GC6) were produced. The evaluation results of these sheets are shown in Tables 2 and 3. Details of the fillers used in Examples 2 to 7 and Comparative Examples 1 to 6 are as follows. In Examples 6 and 7 using expanded graphite, fillers other than expanded graphite were mixed in the second mixing step, and then expanded graphite was mixed.

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Abstract

A mixed composition contains, in prescribed amounts: (A) a (meth)acrylic resin composition containing (A1) a (meth)acrylic acid ester polymer, (α1) (meth)acrylic acid ester monomers, and (D) polyfunctional monomers having multiple polymerizable unsaturated bonds; (B1) a thermally conductive filler that has a BET specific surface area of 1.0 m2/g or greater and is not titanate-treated; (B2) a titanate-treated thermally conductive filler; (B3) a thermally conductive filler other than the thermally conductive filler (B1) and the thermally conductive filler (B2); and a phosphate ester (C). A thermally conductive pressure-sensitive adhesive composition and thermally conductive pressure-sensitive adhesive sheet forming body which suppress bleeding of the liquid component while being flame retardant are provided by producing in the aforementioned mixed composition a polymerization reaction of the (meth)acrylic acid ester monomers (α1) and the polyfunctional monomers (D), and a crosslinking reaction of the (meth)acrylic acid ester polymers (A1) and/or polymers containing the structural units derived from the (meth)acrylic acid ester monomers (α1).

Description

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、及び電子機器Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded product, production method thereof, and electronic device
　本発明は、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、及びこれらの製造方法、並びに、該熱伝導性感圧接着剤組成物又は該熱伝導性感圧接着性シート状成形体を備えた電子機器に関する。 The present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet. The present invention relates to an electronic device provided with a shaped molded body.
　近年、プラズマディスプレイパネル（ＰＤＰ）、集積回路（ＩＣ）チップ等のような電子部品は、その高性能化に伴って発熱量が増大している。その結果、電子部品や電子部品を備えた電子機器には温度上昇による機能障害対策を講じる必要が生じている。電子部品等の温度上昇による機能障害対策として一般的には、金属製のヒートシンク、放熱板、放熱フィン等の放熱体を発熱体に取り付ける方法が採られている。また、放熱体を発熱体に固定する際、発熱体から放熱体への熱伝導を効率よく行うために、熱伝導性に加えて感圧接着性も備えた組成物（以下、「熱伝導性感圧接着剤組成物」という。）やシート状の部材（以下、「熱伝導性感圧接着性シート状成形体」という。）が一般的に用いられている。 In recent years, electronic parts such as a plasma display panel (PDP), an integrated circuit (IC) chip and the like have increased in calorific value as their performance has increased. As a result, it is necessary to take countermeasures against functional failures due to temperature rise in electronic components and electronic devices equipped with electronic components. In general, as a countermeasure against a functional failure due to a temperature rise of an electronic component or the like, a method of attaching a heat radiating body such as a metal heat sink, a heat radiating plate or a heat radiating fin to the heat generating body is employed. In addition, when fixing the radiator to the heating element, in order to efficiently conduct heat conduction from the heating element to the radiator, a composition having a pressure-sensitive adhesive property in addition to thermal conductivity (hereinafter referred to as “thermal conductivity feeling”). A pressure-sensitive adhesive composition ”) and a sheet-like member (hereinafter referred to as“ thermally conductive pressure-sensitive adhesive sheet-like molded body ”) are generally used.
　上記熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体には、優れた熱伝導性が求められることは勿論のこと、用途によっては難燃性も求められる。難燃性に優れた熱伝導性感圧接着剤組成物や熱伝導性感圧接着性シート状成形体に関する技術として、例えば特許文献１には、難燃剤としてリン酸エステルを添加する技術が記載されている。 The heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are required not only to have excellent heat conductivity but also to be flame retardant depending on applications. As a technique relating to a heat conductive pressure-sensitive adhesive composition excellent in flame retardancy and a heat conductive pressure-sensitive adhesive sheet-like molded article, for example, Patent Document 1 describes a technique of adding a phosphate ester as a flame retardant. Yes.
特開２０１１－１１１５４４号公報JP 2011-111544 A
　上記のように、熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体に難燃性を備えさせるためには、難燃剤を添加することが考えられる。しかしながら、熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体の使用時にこれらが押し潰された際、リン酸エステルのような液状の難燃剤が多量に添加されていると液状成分がブリードする虞があった。 As described above, in order to provide the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded product with flame retardancy, it is conceivable to add a flame retardant. However, when these are crushed during use of the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded product, a large amount of a liquid flame retardant such as phosphate ester is added. There was a risk that the liquid component would bleed.
　そこで、本発明は、難燃性を備えつつ、液状成分のブリードが抑制された熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体と、これらの製造方法と、該熱伝導性感圧接着剤組成物又は該熱伝導性感圧接着性シート状成形体を備えた電子機器とを提供することを課題とする。 Accordingly, the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article that are provided with flame retardancy and in which bleed of liquid components is suppressed, a method for producing these, and the thermal process. It is an object of the present invention to provide a conductive pressure-sensitive adhesive composition or an electronic device including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
　本発明の第１の態様は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、を含む混合組成物中において、（メタ）アクリル酸エステル単量体（α１）及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とが行われてなる、熱伝導性感圧接着剤組成物（Ｆ）である。 The first aspect of the present invention is a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more. 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2). ) In a mixed composition comprising 200 parts by mass or more and 600 parts by mass or less and phosphoric acid ester (C) in the range of 40 parts by mass or more and 120 parts by mass or less, (meth) acrylate monomer (α1) Polymerization reaction of polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and derived from (meth) acrylate polymer (A1) and / or (meth) acrylate monomer (α1) It is a heat conductive pressure sensitive adhesive composition (F) by which crosslinking reaction of the polymer containing these structural units is performed.
　本明細書中において「（メタ）アクリル」とは、「アクリル、及び／又は、メタクリル」を意味する。また、「熱伝導性フィラー」とは、添加することによって熱伝導性感圧接着剤組成物（Ｆ）や後に説明する熱伝導性感圧接着性シート状成形体（Ｇ）の熱伝導性を向上させることができ、熱伝導率が０．５Ｗ／ｍ・Ｋ以上であるフィラーを意味する。また、「チタネート処理」とは、チタネート系カップリング剤を用いて行う表面処理を意味する。また、「（メタ）アクリル酸エステル単量体（α１）及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応」とは、（メタ）アクリル酸エステル単量体（α１）と重合性不飽和結合を複数有する多官能性単量体（Ｄ）との共重合反応、（メタ）アクリル酸エステル単量体（α１）の重合反応、及び、重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応のうち、一又は複数の重合反応を意味する。また、「（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応」とは、（メタ）アクリル酸エステル重合体（Ａ１）同士の架橋反応、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体同士の架橋反応、及び、（メタ）アクリル酸エステル重合体（Ａ１）と（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体との架橋反応のうち、一又は複数の架橋反応を意味する。なお、「（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体」とは、（メタ）アクリル酸エステル単量体（α１）同士の重合反応による重合体、及び、（メタ）アクリル酸エステル単量体（α１）と重合性不飽和結合を複数有する多官能性単量体（Ｄ）との共重合反応による重合体を含むものである。 In the present specification, “(meth) acryl” means “acryl and / or methacryl”. The “thermally conductive filler” is added to improve the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) described later. It means a filler having a thermal conductivity of 0.5 W / m · K or more. The “titanate treatment” means a surface treatment performed using a titanate coupling agent. The “(meth) acrylate monomer (α1) and a polymerization reaction of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds” refers to a (meth) acrylate monomer ( Copolymerization reaction between α1) and polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, polymerization reaction of (meth) acrylate monomer (α1), and polymerizable unsaturated bond Among the polymerization reactions of a plurality of multifunctional monomers (D), it means one or a plurality of polymerization reactions. In addition, “(meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) -derived polymer cross-linking reaction” means (meth) acrylic acid ester Cross-linking reaction between polymers (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylate monomer (α1), and (meth) acrylate polymer (A1) and ( Among crosslinking reactions with a polymer containing a structural unit derived from a (meth) acrylate monomer (α1), it means one or a plurality of crosslinking reactions. The “polymer containing a structural unit derived from a (meth) acrylate monomer (α1)” means a polymer obtained by a polymerization reaction between (meth) acrylate monomers (α1), and ( It includes a polymer obtained by a copolymerization reaction between a (meth) acrylic acid ester monomer (α1) and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds.
　本発明の第２の態様は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、を含む混合組成物をシート状に成形した後、又は該混合組成物をシート状に成形しながら、（メタ）アクリル酸エステル単量体（α１）及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とが行われてなる、熱伝導性感圧接着性シート状成形体（Ｇ）である。 The second aspect of the present invention is a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1) and a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more. 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2). ) 200 parts by mass or more and 600 parts by mass or less and the phosphoric acid ester (C) 40 parts by mass or more and 120 parts by mass or less, after forming the mixed composition into a sheet form, or the mixed composition into a sheet form In While molding, polymerization reaction of (meth) acrylate monomer (α1) and polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and (meth) acrylate polymer (A1) And / or a thermally conductive pressure-sensitive adhesive sheet-like molded article (G) obtained by carrying out a crosslinking reaction of a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer (α1).
　本発明の第３の態様は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、を含む混合組成物を作製する工程、並びに、該混合組成物中において、（メタ）アクリル酸エステル単量体（α１）及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを行う工程、を含む、熱伝導性感圧接着剤組成物（Ｆ）の製造方法である。 The third aspect of the present invention is a polyfunctional monomer (D) having a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1) and a plurality of polymerizable unsaturated bonds. ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more. 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2). ) 200 parts by mass or more and 600 parts by mass or less and a phosphoric ester (C) 40 parts by mass or more and 120 parts by mass or less, and in the mixture composition, A) polymerization reaction of the acrylate monomer (α1) and the polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and the (meth) acrylate polymer (A1) and / or (meta) And a step of performing a crosslinking reaction of a polymer containing a structural unit derived from an acrylate monomer (α1). A method for producing a thermally conductive pressure-sensitive adhesive composition (F).
　本発明の第４の態様は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、を含む混合組成物を作製する工程、並びに、該混合組成物をシート状に成形した後、又は、該混合組成物をシート状に成形しながら、（メタ）アクリル酸エステル単量体（α１）及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを行う工程、を含む、熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法である。 The fourth aspect of the present invention is a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer having a plurality of polymerizable unsaturated bonds (D ) Containing 100 parts by mass of (meth) acrylic resin composition (A) and 200 parts by mass or more of non-titanate thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g or more. 120 parts by mass or more and 500 parts by mass or less of the thermally conductive filler (B2) subjected to titanate treatment, and a thermally conductive filler (B3) other than the thermally conductive filler (B1) and the thermally conductive filler (B2). ) 200 parts by mass or more and 600 parts by mass or less and a phosphoric ester (C) 40 parts by mass or more and 120 parts by mass or less, and a step of forming the mixture composition into a sheet shape Polymerization reaction of the polyfunctional monomer (D) having a plurality of (meth) acrylic acid ester monomers (α1) and polymerizable unsaturated bonds, after forming the mixed composition into a sheet shape And a step of performing a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1). It is a manufacturing method of a pressure-adhesive sheet-like molded object (G).
　上記本発明の第１乃至第４の態様において、熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、金属水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種であり、熱伝導性フィラー（Ｂ２）が、チタネート処理された金属水酸化物であり、熱伝導性フィラー（Ｂ３）が、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の、金属水酸化物、金属酸化物及び炭素含有導電性フィラーからなる群より選ばれる少なくとも１種であることが好ましく、熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、水酸化アルミニウム及び酸化アルミニウムからなる群より選ばれる少なくとも１種であり、熱伝導性フィラー（Ｂ２）がチタネート処理された水酸化アルミニウムであり、熱伝導性フィラー（Ｂ３）が、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛から選ばれる少なくとも１種であることがより好ましい。
  また、（メタ）アクリル樹脂組成物（Ａ）が、（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上２５質量％以下、（メタ）アクリル酸エステル単量体（α１）７４．８質量％以上９４．８質量％以下、及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）０．２質量％以上１３質量％以下を含むことが好ましい。 In the first to fourth aspects of the present invention, the thermally conductive filler (B1) is a metal hydroxide and a metal oxide having a BET specific surface area of 1.0 m 2 / g or more and not subjected to titanate treatment. And at least one selected from the group consisting of the thermally conductive filler (B2) is a titanate-treated metal hydroxide, the thermally conductive filler (B3) is the thermally conductive filler (B1), and the thermal conductivity. It is preferably at least one selected from the group consisting of metal hydroxides, metal oxides and carbon-containing conductive fillers other than the conductive filler (B2), and the heat conductive filler (B1) has a BET specific surface area. 1.0 m 2 / g or more, at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, not treated with titanate, and a thermally conductive filler (B 2) is titanate-treated aluminum hydroxide, and the heat conductive filler (B3) is aluminum hydroxide, aluminum oxide and expanded graphite other than the heat conductive filler (B1) and the heat conductive filler (B2). More preferably, at least one selected from the group consisting of:
Moreover, (meth) acrylic resin composition (A) is 5 to 25 mass% of (meth) acrylic acid ester polymer (A1), (meth) acrylic acid ester monomer (α1) 74.8 mass. % To 94.8% by mass and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds is preferably contained in an amount of 0.2% by mass to 13% by mass.
　本発明の第５の態様は、放熱体及び該放熱体に貼合された上記本発明の第１の態様の熱伝導性感圧接着剤組成物（Ｆ）、又は、放熱体及び該放熱体に貼合された上記本発明の第２の態様の熱伝導性感圧接着性シート状成形体（Ｇ）、を備えた電子機器である。 According to a fifth aspect of the present invention, there is provided a radiator and the thermally conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the radiator, or the radiator and the radiator. It is the electronic device provided with the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of the 2nd aspect of the said this invention bonded.
　本発明によれば、難燃性に優れ、ブリードが抑制された熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体と、これらの製造方法と、該熱伝導性感圧接着剤組成物又は該熱伝導性感圧接着性シート状成形体を備えた電子機器とを提供することができる。 According to the present invention, a thermally conductive pressure-sensitive adhesive composition excellent in flame retardancy and suppressed bleeding, a thermally conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the thermally conductive pressure-sensitive adhesive An electronic device provided with the agent composition or the thermally conductive pressure-sensitive adhesive sheet-like molded product can be provided.
　１．熱伝導性感圧接着剤組成物（Ｆ）、熱伝導性感圧接着性シート状成形体（Ｇ）
  本発明の熱伝導性感圧接着剤組成物（Ｆ）は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および重合性不飽和結合を複数有する多官能性単量体（Ｄ）（以下、単に「多官能性単量体（Ｄ）」という場合がある。）、を含む（メタ）アクリル樹脂組成物（Ａ）と、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）（以下、単に「熱伝導性フィラー（Ｂ１）」という場合がある。）と、チタネート処理された熱伝導性フィラー（Ｂ２）（以下、単に「熱伝導性フィラー（Ｂ２）」という場合がある。）と、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）（以下、単に「熱伝導性フィラー（Ｂ３）」という場合がある。）と、リン酸エステル（Ｃ）と、を含む混合組成物中において、（メタ）アクリル酸エステル単量体（α１）と多官能性単量体（Ｄ）との共重合反応、（メタ）アクリル酸エステル単量体（α１）の重合反応、及び、多官能性単量体（Ｄ）の重合反応のうち少なくともいずれかの重合反応、並びに、（メタ）アクリル酸エステル重合体（Ａ１）同士の架橋反応、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体同士の架橋反応、及び、（メタ）アクリル酸エステル重合体（Ａ１）と（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体との架橋反応のうち少なくともいずれかの架橋反応が、少なくとも行われてなるものである。 1. Thermally conductive pressure-sensitive adhesive composition (F), thermally conductive pressure-sensitive adhesive sheet-like molded body (G)
The thermally conductive pressure-sensitive adhesive composition (F) of the present invention has a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a plurality of polymerizable unsaturated bonds. A (meth) acrylic resin composition (A) containing a functional monomer (D) (hereinafter sometimes simply referred to as “polyfunctional monomer (D)”), and a BET specific surface area of 1. 0 m 2 / g or more of a thermally conductive filler (B1) not treated with titanate (hereinafter sometimes simply referred to as “thermally conductive filler (B1)”), and a thermally conductive filler treated with titanate (B2). ) (Hereinafter sometimes simply referred to as “thermally conductive filler (B2)”) and thermally conductive filler (B3) other than thermally conductive filler (B1) and thermally conductive filler (B2) (hereinafter simply referred to as “thermally conductive filler (B2)”). "Thermal conductive filler (B3)" And a phosphate ester (C) in a mixed composition, a copolymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D). , (Meth) acrylic acid ester monomer (α1) polymerization reaction and / or polyfunctional monomer (D) polymerization reaction, and (meth) acrylic acid ester polymer Cross-linking reaction between (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylic acid ester monomer (α1), and (meth) acrylic acid ester polymers (A1) and (meth) At least one of the crosslinking reactions among the crosslinking reactions with the polymer containing a structural unit derived from the acrylate monomer (α1) is performed.
　また、本発明の熱伝導性感圧接着性シート状成形体（Ｇ）は、上記混合組成物をシート状に成形した後、又は上記混合組成物をシート状に成形しながら、（メタ）アクリル酸エステル単量体（α１）と多官能性単量体（Ｄ）との共重合反応、（メタ）アクリル酸エステル単量体（α１）の重合反応、及び、多官能性単量体（Ｄ）の重合反応のうち少なくともいずれかの重合反応、並びに、（メタ）アクリル酸エステル重合体（Ａ１）同士の架橋反応、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体同士の架橋反応、及び、（メタ）アクリル酸エステル重合体（Ａ１）と（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体との架橋反応のうち少なくともいずれかの架橋反応が、少なくとも行われてなるものである。 Moreover, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is (meth) acrylic acid after shape | molding the said mixed composition in a sheet form, or shape | molding the said mixed composition in a sheet form. Copolymerization reaction of ester monomer (α1) and polyfunctional monomer (D), polymerization reaction of (meth) acrylic acid ester monomer (α1), and polyfunctional monomer (D) A polymer containing a structural unit derived from a (meth) acrylate monomer (α1), a crosslinking reaction between (meth) acrylate polymers (A1), and Cross-linking reaction between each other and at least one of cross-linking reaction between the (meth) acrylic acid ester polymer (A1) and the cross-linking reaction between the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (α1). The reaction is performed at least It become one.
　このような熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を構成する物質について以下に説明する。 The materials constituting the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) will be described below.
　＜（メタ）アクリル樹脂組成物（Ａ）＞
  本発明に用いる（メタ）アクリル樹脂組成物（Ａ）は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）、及び多官能性単量体（Ｄ）を含んでいる。なお、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を得る際には、上述したように重合反応及び架橋反応が行われる。当該重合反応及び架橋反応を行うことによって（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体及び多官能性単量体（Ｄ）は、（メタ）アクリル酸エステル重合体（Ａ１）の成分と混合及び／又は一部結合する。 <(Meth) acrylic resin composition (A)>
The (meth) acrylic resin composition (A) used in the present invention comprises a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer (D ) Is included. In addition, when obtaining a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G), a polymerization reaction and a crosslinking reaction are performed as mentioned above. By performing the polymerization reaction and the crosslinking reaction, the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D) are the (meth) acrylic acid ester polymer. It is mixed and / or partially combined with the component (A1).
　本発明において、（メタ）アクリル酸エステル重合体（Ａ１）及び（メタ）アクリル酸エステル単量体（α１）の使用量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量％として、（メタ）アクリル酸エステル重合体（Ａ１）が５質量％以上２５質量％以下、（メタ）アクリル酸エステル単量体（α１）が７４．８質量％以上９４．８質量％以下であることが好ましく、（メタ）アクリル酸エステル重合体（Ａ１）が１０質量％以上２０質量％以下、（メタ）アクリル酸エステル単量体（α１）が７９．５質量％以上８９．５質量％以下であることがより好ましい。（メタ）アクリル酸エステル単量体（α１）の含有比率を上記範囲とすることによって、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を成形することが容易になる。 In the present invention, the amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (α1) used is (mass) acrylic resin composition (A) being 100% by mass, The meth) acrylate polymer (A1) is preferably 5% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer (α1) is preferably 74.8% by mass or more and 94.8% by mass or less. The (meth) acrylic acid ester polymer (A1) is 10% by mass or more and 20% by mass or less, and the (meth) acrylic acid ester monomer (α1) is 79.5% by mass or more and 89.5% by mass or less. Is more preferable. By setting the content ratio of the (meth) acrylic acid ester monomer (α1) within the above range, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are formed. Easy to do.
　また、本発明において多官能性単量体（Ｄ）の使用量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量％として、０．２質量％以上１３質量％以下であることが好ましく、０．２質量％以上１０質量％以下であることがより好ましく、０．５質量％以上５質量％以下であることがさらに好ましい。多官能性単量体（Ｄ）の使用量を上記範囲とすることによって、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に感圧接着剤としての適正な凝集力を付与し易くなる。以下、（メタ）アクリル樹脂組成物（Ａ）に含まれる成分についてより詳細に説明する。 In the present invention, the amount of the polyfunctional monomer (D) used is preferably 0.2% by mass or more and 13% by mass or less based on 100% by mass of the (meth) acrylic resin composition (A). The content is more preferably 0.2% by mass or more and 10% by mass or less, and further preferably 0.5% by mass or more and 5% by mass or less. By making the usage-amount of a polyfunctional monomer (D) into the said range, it is a pressure sensitive adhesive to a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G). It becomes easy to give appropriate cohesive force as. Hereinafter, the components contained in the (meth) acrylic resin composition (A) will be described in more detail.
　（（メタ）アクリル酸エステル重合体（Ａ１））
  本発明に用いることができる（メタ）アクリル酸エステル重合体（Ａ１）は特に限定されないが、ガラス転移温度が－２０℃以下となる単独重合体を形成する（メタ）アクリル酸エステル単量体単位（ａ１）、及び、有機酸基を有する単量体単位（ａ２）を含有することが好ましい。 ((Meth) acrylic acid ester polymer (A1))
The (meth) acrylate polymer (A1) that can be used in the present invention is not particularly limited, but a (meth) acrylate monomer unit that forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is preferable to contain (a1) and a monomer unit (a2) having an organic acid group.
　上記（メタ）アクリル酸エステル単量体の単位（ａ１）を与える（メタ）アクリル酸エステル単量体（ａ１ｍ）は特に限定されないが、例えば、アクリル酸エチル（単独重合体のガラス転移温度は、－２４℃）、アクリル酸ｎ－プロピル（同－３７℃）、アクリル酸ｎ－ブチル（同－５４℃）、アクリル酸ｓｅｃ－ブチル（同－２２℃）、アクリル酸ｎ－ヘプチル（同－６０℃）、アクリル酸ｎ－ヘキシル（同－６１℃）、アクリル酸ｎ－オクチル（同－６５℃）、アクリル酸２－エチルヘキシル（同－５０℃）、アクリル酸２－メトキシエチル（同－５０℃）、アクリル酸３－メトキシプロピル（同－７５℃）、アクリル酸３－メトキシブチル（同－５６℃）、アクリル酸エトキシメチル（同－５０℃）、メタクリル酸ｎ－オクチル（同－２５℃）、メタクリル酸ｎ－デシル（同－４９℃）などを挙げることができる。中でも、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸２－メトキシエチルが好ましく、アクリル酸ｎ－ブチル、アクリル酸２－エチルヘキシルがより好ましく、アクリル酸２－エチルヘキシルがさらに好ましい。 The (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer is not particularly limited. For example, ethyl acrylate (the glass transition temperature of the homopolymer is -24 ° C), n-propyl acrylate (-37 ° C), n-butyl acrylate (-54 ° C), sec-butyl acrylate (-22 ° C), n-heptyl acrylate (-60) ° C), n-hexyl acrylate (-61 ° C), n-octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), 2-methoxyethyl acrylate (-50 ° C) ), 3-methoxypropyl acrylate (-75 ° C), 3-methoxybutyl acrylate (-56 ° C), ethoxymethyl acrylate (-50 ° C), n-octyl methacrylate (same) 25 ° C.), and the like methacrylic acid n- decyl (the -49 ° C.). Among them, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is more preferable.
　これらの（メタ）アクリル酸エステル単量体（ａ１ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 These (meth) acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
　（メタ）アクリル酸エステル単量体（ａ１ｍ）は、それから導かれる単量体単位（ａ１）が、（メタ）アクリル酸エステル重合体（Ａ１）中、好ましくは８０質量％以上９９．９質量％以下、より好ましくは８５質量％以上９９．５質量％以下となるような量で重合に供する。（メタ）アクリル酸エステル単量体（ａ１ｍ）の使用量が上記範囲内であると、重合時の重合系の粘度を適正な範囲に保つことが容易になる。 In the (meth) acrylic acid ester monomer (a1m), the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1). Hereinafter, it is used for polymerization in such an amount that it is more preferably 85% by mass or more and 99.5% by mass or less. When the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the viscosity of the polymerization system at the time of polymerization can be easily maintained within an appropriate range.
　次に、有機酸基を有する単量体単位（ａ２）について説明する。有機酸基を有する単量体単位（ａ２）を与える単量体（ａ２ｍ）は特に限定されないが、その代表的なものとして、カルボキシル基、酸無水物基、スルホン酸基などの有機酸基を有する単量体を挙げることができる。また、これらのほか、スルフェン酸基、スルフィン酸基、燐酸基などを含有する単量体も使用することができる。 Next, the monomer unit (a2) having an organic acid group will be described. The monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, but representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. The monomer which has can be mentioned. In addition to these, monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.
　カルボキシル基を有する単量体の具体例としては、例えば、アクリル酸、メタクリル酸、クロトン酸などのα，β－エチレン性不飽和モノカルボン酸や、イタコン酸、マレイン酸、フマル酸などのα，β－エチレン性不飽和多価カルボン酸の他、イタコン酸モノメチル、マレイン酸モノブチル、フマル酸モノプロピルなどのα，β－エチレン性不飽和多価カルボン酸部分エステルなどを挙げることができる。また、無水マレイン酸、無水イタコン酸などの、加水分解などによりカルボキシル基に誘導することができる基を有するものも同様に使用することができる。 Specific examples of the monomer having a carboxyl group include, for example, α, β-ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and α, β such as itaconic acid, maleic acid, and fumaric acid. In addition to β-ethylenically unsaturated polyvalent carboxylic acid, α, β-ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be exemplified. Moreover, what has group which can be induced | guided | derived to a carboxyl group by hydrolysis etc., such as maleic anhydride and itaconic anhydride, can be used similarly.
　スルホン酸基を有する単量体の具体例としては、アリルスルホン酸、メタクリルスルホン酸、ビニルスルホン酸、スチレンスルホン酸、アクリルアミド－２－メチルプロパンスルホン酸などのα，β－不飽和スルホン酸、及び、これらの塩を挙げることができる。 Specific examples of the monomer having a sulfonic acid group include allyl sulfonic acid, methacryl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, α, β-unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, and the like. These salts can be mentioned.
　単量体（ａ２ｍ）としては、上に例示した有機酸基を有する単量体のうち、カルボキシル基を有する単量体がより好ましく、中でも、アクリル酸又はメタクリル酸を有する単量体が特に好ましい。これらの単量体は工業的に安価で容易に入手することができ、他の単量体成分との共重合性も良く、生産性の点でも好ましい。なお、単量体（ａ２ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 As the monomer (a2m), among the monomers having an organic acid group exemplified above, a monomer having a carboxyl group is more preferable, and a monomer having acrylic acid or methacrylic acid is particularly preferable. . These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.
　有機酸基を有する単量体（ａ２ｍ）は、それから導かれる単量体単位（ａ２）が（メタ）アクリル酸エステル重合体（Ａ１）中、好ましくは０．１質量％以上２０質量％以下、より好ましくは０．５質量％以上１５質量％以下となるような量で重合に供する。有機酸基を有する単量体（ａ２ｍ）の使用量が上記範囲内であると、重合時の重合系の粘度を適正な範囲に保つことが容易になる。 In the monomer (a2m) having an organic acid group, the monomer unit (a2) derived from the monomer unit (a2) is preferably 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1). More preferably, it is used for the polymerization in such an amount that it is 0.5 to 15% by mass. When the usage-amount of the monomer (a2m) which has an organic acid group exists in the said range, it will become easy to maintain the viscosity of the polymerization system at the time of superposition | polymerization in an appropriate range.
　なお、有機酸基を有する単量体単位（ａ２）は、前述のように、有機酸基を有する単量体（ａ２ｍ）の重合によって、（メタ）アクリル酸エステル重合体（Ａ１）中に導入するのが簡便であり好ましいが、（メタ）アクリル酸エステル重合体（Ａ１）を生成後に、公知の高分子反応により、有機酸基を導入してもよい。 The monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer (A1) by polymerization of the monomer (a2m) having an organic acid group as described above. Although it is simple and preferable to carry out, an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer (A1) is produced.
　また、（メタ）アクリル酸エステル重合体（Ａ１）は、有機酸基以外の官能基を有する単量体（ａ３ｍ）から誘導される単量体単位（ａ３）を含有していてもよい。上記有機酸基以外の官能基としては、水酸基、アミノ基、アミド基、エポキシ基、メルカプト基などを挙げることができる。 Further, the (meth) acrylic acid ester polymer (A1) may contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group. Examples of the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.
　水酸基を有する単量体としては、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸３－ヒドロキシプロピルなどの、（メタ）アクリル酸ヒドロキシアルキルエステルなどを挙げることができる。 Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.
　アミノ基を有する単量体としては、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノメチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、アミノスチレンなどを挙げることができる。 Examples of the monomer having an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
　アミド基を有する単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミドなどのα，β－エチレン性不飽和カルボン酸アミド単量体などを挙げることができる。 Examples of monomers having an amide group include α, β-ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.
　エポキシ基を有する単量体としては、（メタ）アクリル酸グリシジル、アリルグリシジルエーテルなどを挙げることができる。 Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
　有機酸基以外の官能基を有する単量体（ａ３ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 As the monomer (a3m) having a functional group other than the organic acid group, one type may be used alone, or two or more types may be used in combination.
　これらの有機酸基以外の官能基を有する単量体（ａ３ｍ）は、それから導かれる単量体単位（ａ３）が、（メタ）アクリル酸エステル重合体（Ａ１）中、１０質量％以下となるような量で重合に使用することが好ましい。１０質量％以下の単量体（ａ３ｍ）を使用することにより、重合時の重合系の粘度を適正な範囲に保つことが容易になる。 In the monomer (a3m) having a functional group other than these organic acid groups, the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferable to use it for polymerization in such an amount. By using the monomer (a3m) of 10% by mass or less, it becomes easy to keep the viscosity of the polymerization system during polymerization in an appropriate range.
　（メタ）アクリル酸エステル重合体（Ａ１）は、上述したガラス転移温度が－２０℃以下となる単独重合体を形成する（メタ）アクリル酸エステル単量体単位（ａ１）、有機酸基を有する単量体単位（ａ２）、及び、有機酸基以外の官能基を有する単量体単位（ａ３）以外に、上述した単量体と共重合可能な単量体（ａ４ｍ）から誘導される単量体単位（ａ４）を含有していてもよい。 The (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower, and an organic acid group. In addition to the monomer unit (a2) and the monomer unit (a3) having a functional group other than an organic acid group, a monomer derived from the monomer (a4m) copolymerizable with the above-described monomer. The monomer unit (a4) may be contained.
　単量体（ａ４ｍ）は、特に限定されないが、その具体例として、上記（メタ）アクリル酸エステル単量体（ａ１ｍ）以外の（メタ）アクリル酸エステル単量体、α，β－エチレン性不飽和多価カルボン酸完全エステル、アルケニル芳香族単量体、共役ジエン系単量体、非共役ジエン系単量体、シアン化ビニル単量体、カルボン酸不飽和アルコールエステル、オレフィン系単量体などを挙げることができる。 The monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), α, β-ethylenic monomers. Saturated polycarboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, etc. Can be mentioned.
　上記（メタ）アクリル酸エステル単量体（ａ１ｍ）以外の（メタ）アクリル酸エステル単量体の具体例としては、アクリル酸メチル（単独重合体のガラス転移温度は、１０℃）、メタクリル酸メチル（同１０５℃）、メタクリル酸エチル（同６３℃）、メタクリル酸ｎ－プロピル（同２５℃）、メタクリル酸ｎ－ブチル（同２０℃）などを挙げることができる。 Specific examples of the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.
　α，β－エチレン性不飽和多価カルボン酸完全エステルの具体例としては、フマル酸ジメチル、フマル酸ジエチル、マレイン酸ジメチル、マレイン酸ジエチル、イタコン酸ジメチルなどを挙げることができる。 Specific examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid complete ester include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
　アルケニル芳香族単量体の具体例としては、スチレン、α－メチルスチレン、メチルα－メチルスチレン、ビニルトルエン、及び、ジビニルベンゼンなどを挙げることができる。 Specific examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl α-methylstyrene, vinyl toluene, and divinylbenzene.
　共役ジエン系単量体の具体例としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン（イソプレンと同義）、１，３－ペンタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロロ－１，３－ブタジエン、シクロペンタジエンなどを挙げることができる。 Specific examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. 2-chloro-1,3-butadiene, cyclopentadiene and the like.
　非共役ジエン系単量体の具体例としては、１，４－ヘキサジエン、ジシクロペンタジエン、エチリデンノルボルネンなどを挙げることができる。 Specific examples of the non-conjugated diene monomer include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.
　シアン化ビニル単量体の具体例としては、アクリロニトリル、メタクリロニトリル、α－クロロアクリロニトリル、α－エチルアクリロニトリルなどを挙げることができる。 Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.
　カルボン酸不飽和アルコールエステル単量体の具体例としては、酢酸ビニルなどを挙げることができる。 Specific examples of the carboxylic acid unsaturated alcohol ester monomer include vinyl acetate.
　オレフィン系単量体の具体例としては、エチレン、プロピレン、ブテン、ペンテンなどを挙げることができる。 Specific examples of the olefin monomer include ethylene, propylene, butene, pentene and the like.
　単量体（ａ４ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 As the monomer (a4m), one type may be used alone, or two or more types may be used in combination.
　単量体（ａ４ｍ）は、それから導かれる単量体単位（ａ４）の量が、（メタ）アクリル酸エステル重合体（Ａ１）中、好ましくは１０質量％以下、より好ましくは５質量％以下となるような量で重合に供する。 In the monomer (a4m), the amount of the monomer unit (a4) derived therefrom is preferably 10% by mass or less, more preferably 5% by mass or less in the (meth) acrylate polymer (A1). It is subjected to polymerization in such an amount.
　（メタ）アクリル酸エステル重合体（Ａ１）は、上述した、ガラス転移温度が－２０℃以下となる単独重合体を形成する（メタ）アクリル酸エステル単量体（ａ１ｍ）、有機酸基を有する単量体（ａ２ｍ）、必要に応じて使用する、有機酸基以外の官能基を含有する単量体（ａ３ｍ）、及び、必要に応じて使用するこれらの単量体と共重合可能な単量体（ａ４ｍ）を共重合することによって特に好適に得ることができる。 The (meth) acrylic acid ester polymer (A1) has the above-mentioned (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower, and an organic acid group. Monomer (a2m), a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
　（メタ）アクリル酸エステル重合体（Ａ１）を得る際の重合方法は特に限定されず、溶液重合、乳化重合、懸濁重合、塊状重合などのいずれであってもよく、これら以外の方法でもよい。ただしこれらの重合方法の中で溶液重合が好ましく、中でも重合溶媒として、酢酸エチル、乳酸エチルなどのカルボン酸エステルやベンゼン、トルエン、キシレンなどの芳香族溶媒を用いた溶液重合がより好ましい。重合に際して、単量体は、重合反応容器に分割添加してもよいが、全量を一括添加するのが好ましい。重合開始の方法は、特に限定されないが、重合開始剤として熱重合開始剤を用いるのが好ましい。当該熱重合開始剤は特に限定されず、例えば過酸化物重合開始剤やアゾ化合物重合開始剤を用いることができる。 The polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. . However, among these polymerization methods, solution polymerization is preferable, 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 is more preferable. In the polymerization, the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once. The method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator. The thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
　過酸化物重合開始剤としては、ｔ－ブチルヒドロペルオキシドのようなヒドロペルオキシドや、ベンゾイルペルオキシド、シクロヘキサノンペルオキシドのようなペルオキシドの他、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムなどの過硫酸塩などを挙げることができる。これらの過酸化物は、還元剤と適宜組み合わせて、レドックス系触媒として使用することもできる。 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.
　アゾ化合物重合開始剤としては、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）などを挙げることができる。 As azo compound polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) And so on.
　重合開始剤の使用量は特に限定されないが、単量体１００質量部に対して０．０１質量部以上５０質量部以下の範囲であることが好ましい。 Although the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
　これらの単量体のその他の重合条件（重合温度、圧力、撹拌条件など）は、特に制限がない。 Other polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
　重合反応終了後、必要により、得られた重合体を重合媒体から分離する。分離の方法は特に限定されない。例えば、溶液重合の場合、重合溶液を減圧下に置き、重合溶媒を留去することによって、（メタ）アクリル酸エステル重合体（Ａ１）を得ることができる。 After completion of the polymerization reaction, the obtained polymer is separated from the polymerization medium if necessary. The separation method is not particularly limited. For example, 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.
　（メタ）アクリル酸エステル重合体（Ａ１）の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフ法（ＧＰＣ法）で測定して、標準ポリスチレン換算で１０万以上１００万以下の範囲にあることが好ましく、２０万以上５０万以下の範囲にあることが、より好ましい。（メタ）アクリル酸エステル重合体（Ａ１）の重量平均分子量は、重合の際に使用する重合開始剤の量や、連鎖移動剤の量を適宜調整することによって制御することができる。 The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. It is more preferable that it is in the range of 200,000 or more and 500,000 or less. 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.
　（（メタ）アクリル酸エステル単量体（α１））
  （メタ）アクリル酸エステル単量体（α１）は、（メタ）アクリル酸エステル単量体を含有するものであれば特に限定されないが、ガラス転移温度が－２０℃以下となる単独重合体を形成する（メタ）アクリル酸エステル単量体（ａ５ｍ）を含有するものであることが好ましい。 ((Meth) acrylic acid ester monomer (α1))
The (meth) acrylate monomer (α1) is not particularly limited as long as it contains the (meth) acrylate monomer, but forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
　ガラス転移温度が－２０℃以下となる単独重合体を形成する（メタ）アクリル酸エステル単量体（ａ５ｍ）の例としては、（メタ）アクリル酸エステル重合体（Ａ１）の合成に用いる（メタ）アクリル酸エステル単量体（ａ１ｍ）と同様の（メタ）アクリル酸エステル単量体を挙げることができる。（メタ）アクリル酸エステル単量体（ａ５ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 As an example of 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) ) The same (meth) acrylate monomer as the acrylate monomer (a1m) can be mentioned. A (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
　（メタ）アクリル酸エステル単量体（α１）における（メタ）アクリル酸エステル単量体（ａ５ｍ）の比率は、好ましくは５０質量％以上１００質量％以下、より好ましくは７５質量％以上１００質量％以下である。（メタ）アクリル酸エステル単量体（α１）における（メタ）アクリル酸エステル単量体（ａ５ｍ）の比率を上記範囲とすることによって、感圧接着性や柔軟性に優れた熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を得やすくなる。 The ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer (α1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer (α1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
　また、（メタ）アクリル酸エステル単量体（α１）は、ガラス転移温度が－２０℃以下となる単独重合体を形成する（メタ）アクリル酸エステル単量体（ａ５ｍ）、及び、これらと共重合可能な有機酸基を有する単量体（ａ６ｍ）の混合物としてもよい。 The (meth) acrylic acid ester monomer (α1) is a (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is good also as a mixture of the monomer (a6m) which has a polymerizable organic acid group.
　上記単量体（ａ６ｍ）の例としては、（メタ）アクリル酸エステル重合体（Ａ１）の合成に用いる単量体（ａ２ｍ）として例示したものと同様の有機酸基を有する単量体を挙げることができる。単量体（ａ６ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to. A monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.
　（メタ）アクリル酸エステル単量体（α１）における単量体（ａ６ｍ）の比率は、３０質量％以下が好ましく、より好ましくは１０質量％以下である。（メタ）アクリル酸エステル単量体（α１）における単量体（ａ６ｍ）の比率を上記範囲とすることによって、感圧接着性や柔軟性に優れた熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を得やすくなる。 The ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer (α1) is preferably 30% by mass or less, and more preferably 10% by mass or less. By setting the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer (α1) to the above range, the heat conductive pressure-sensitive adhesive composition (F) excellent in pressure-sensitive adhesiveness and flexibility. And it becomes easy to obtain a heat conductive pressure-sensitive-adhesive sheet-like molded object (G).
　（メタ）アクリル酸エステル単量体（α１）は、（メタ）アクリル酸エステル単量体（ａ５ｍ）及び所望により共重合させることができる有機酸基を有する単量体（ａ６ｍ）の他に、これらと共重合可能な単量体（ａ７ｍ）も含む混合物としてもよい。 The (meth) acrylic acid ester monomer (α1), in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture containing the monomer (a7m) copolymerizable with these.
　上記単量体（ａ７ｍ）の例としては、（メタ）アクリル酸エステル重合体（Ａ１）の合成に用いる単量体（ａ３ｍ）、及び単量体（ａ４ｍ）として例示したものと同様の単量体を挙げることができる。単量体（ａ７ｍ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m). The body can be mentioned. A monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.
　（メタ）アクリル酸エステル単量体（α１）における単量体（ａ７ｍ）の比率は、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。 The ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer (α1) is preferably 20% by mass or less, and more preferably 15% by mass or less.
　（多官能性単量体（Ｄ））
  多官能性単量体（Ｄ）としては、（メタ）アクリル酸エステル単量体（α１）に含まれる単量体と共重合可能なものを用いる。また、多官能性単量体（Ｄ）は重合性不飽和結合を複数有しており、該不飽和結合を末端に有することが好ましい。このような多官能性単量体（Ｄ）を用いることによって、共重合体に分子内及び／又は分子間架橋を導入して、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の感圧接着剤としての凝集力を高めることができる。 (Polyfunctional monomer (D))
As the polyfunctional monomer (D), one that can be copolymerized with the monomer contained in the (meth) acrylic acid ester monomer (α1) is used. The polyfunctional monomer (D) preferably has a plurality of polymerizable unsaturated bonds, and preferably has the unsaturated bond at the terminal. By using such a polyfunctional monomer (D), intramolecular and / or intermolecular crosslinking is introduced into the copolymer, and the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive are introduced. The cohesive force as a pressure-sensitive adhesive of the adhesive sheet-like molded body (G) can be increased.
　通常、ラジカル熱重合などの重合時には、多官能性単量体（Ｄ）を用いずともある程度の架橋反応は進行する。しかしながら、より確実にしかも所望の量の架橋構造を形成させるためには多官能性単量体（Ｄ）を用いることが好ましい。 Usually, at the time of polymerization such as radical thermal polymerization, a certain degree of crosslinking reaction proceeds without using the polyfunctional monomer (D). However, it is preferable to use the polyfunctional monomer (D) in order to form a desired amount of a crosslinked structure more reliably.
　多官能性単量体（Ｄ）としては、例えば１，６－ヘキサンジオールジ（メタ）アクリレート、１，２－エチレングリコールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどの多官能性（メタ）アクリレートや、２，４－ビス（トリクロロメチル）－６－ｐ－メトキシスチレン－５－トリアジンなどの置換トリアジンの他、４－アクリルオキシベンゾフェノンのようなモノエチレン系不飽和芳香族ケトンなどを用いることができる。中でも、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレートが好ましい。多官能性単量体（Ｄ）は、一種を単独で使用してもよく、二種以上を併用してもよい。 Examples of the polyfunctional monomer (D) include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditri Multifunctional (meth) acrylates such as methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (tri Other substituted triazines, such as Roromechiru) -6-p-methoxystyrene-5-triazine, etc. monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used. Among these, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable. A polyfunctional monomer (D) may be used individually by 1 type, and may use 2 or more types together.
　＜重合開始剤＞
  熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を得る際、上述したように（メタ）アクリル樹脂組成物（Ａ）に含まれる成分が重合する。当該重合反応を促進するため、重合開始剤を用いることが好ましい。当該重合開始剤としては、光重合開始剤、アゾ系熱重合開始剤、有機過酸化物熱重合開始剤などが挙げられる。ただし、得られる熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に強い粘着力を付与する等の観点からは、有機過酸化物熱重合開始剤を用いることが好ましい。 <Polymerization initiator>
When obtaining the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G), the components contained in the (meth) acrylic resin composition (A) are polymerized as described above. . In order to accelerate the polymerization reaction, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator. However, from the viewpoint of imparting strong adhesive force to the obtained heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), an organic peroxide thermal polymerization initiator is used. Is preferably used.
　光重合開始剤としては、公知の各種光重合開始剤を用いることができる。その中でも、アシルホスフィンオキサイド系化合物が好ましい。好ましい光重合開始剤であるアシルホスフィンオキサイド系化合物としては、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドなどが挙げられる。 As the photopolymerization initiator, various known photopolymerization initiators can be used. Of these, acylphosphine oxide compounds are preferred. Preferred examples of the acylphosphine oxide compound that is a photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
　アゾ系熱重合開始剤としては、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）などが挙げられる。 As the azo-based thermal polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.
　有機過酸化物熱重合開始剤としては、ｔ－ブチルヒドロペルオキシドのようなヒドロペルオキシドや、ベンゾイルペルオキシド、シクロヘキサノンペルオキシド、１，６－ビス（ｔ－ブチルペルオキシカルボニルオキシ）ヘキサン、１，１－ビス（ｔ－ブチルペルオキシ）－３，３，５－トリメチルシクロヘキサノンのようなペルオキシドなどを挙げることができる。ただし、熱分解時に臭気の原因となる揮発性物質を放出しないものが好ましい。また、有機過酸化物熱重合開始剤の中でも、１分間半減期温度が１００℃以上かつ１７０℃以下のものが好ましい。 Examples of the organic peroxide thermal polymerization initiator include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone. However, those that do not release volatile substances that cause odor during thermal decomposition are preferred. Among organic peroxide thermal polymerization initiators, those having a 1-minute half-life temperature of 100 ° C. or more and 170 ° C. or less are preferable.
　上記重合開始剤の使用量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．０１質量部以上１０質量部以下であることが好ましく、０．１質量部以上５質量部以下であることがより好ましく、０．３質量部以上２質量部以下であることがさらに好ましい。重合開始剤の使用量を上記範囲とすることによって、（メタ）アクリル酸エステル単量体（α１）の重合転化率を適正な範囲にし易くなり、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に単量体臭が残ることを防止し易くなる。
なお、（メタ）アクリル酸エステル単量体（α１）の重合転化率は、９５質量％以上であることが好ましい。（メタ）アクリル酸エステル単量体（α１）の重合転化率が９５質量％以上であれば、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に単量体臭が残ることを防止し易くなる。また、重合開始剤の使用量を上記範囲とすることによって、重合反応が過度に進行して熱伝導性感圧接着性シート状成形体（Ｇ）が平滑なシート状にならずに材料破壊を起こすという事態を防止し易くなる。 The amount of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). More preferably, it is 0.3 to 2 parts by mass. By making the usage-amount of a polymerization initiator into the said range, it becomes easy to make the polymerization conversion of a (meth) acrylic acid ester monomer ((alpha) 1) into an appropriate range, and a heat conductive pressure sensitive adhesive composition (F) and It becomes easy to prevent the monomer odor from remaining in the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
The polymerization conversion rate of the (meth) acrylic acid ester monomer (α1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer (α1) is 95% by mass or more, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the monomer odor from remaining on the surface. Moreover, by making the usage-amount of a polymerization initiator into the said range, a polymerization reaction will advance too much and will cause material destruction, without a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) becoming a smooth sheet form. It becomes easy to prevent the situation.
　＜熱伝導性フィラー（Ｂ１）＞
  次に熱伝導性フィラー（Ｂ１）について説明する。本発明に用いる熱伝導性フィラー（Ｂ１）は、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラーである。熱伝導性フィラー（Ｂ１）のＢＥＴ比表面積の上限は特に限定されないが、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の前駆体である混合組成物の過度な粘度上昇を抑制する観点から、１０ｍ２／ｇ以下であることが好ましい。 <Thermal conductive filler (B1)>
Next, the heat conductive filler (B1) will be described. The heat conductive filler (B1) used in the present invention is a heat conductive filler not subjected to titanate treatment having a BET specific surface area of 1.0 m 2 / g or more. The upper limit of the BET specific surface area of the heat conductive filler (B1) is not particularly limited, but the mixture is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). From the viewpoint of suppressing an excessive increase in the viscosity of the composition, it is preferably 10 m 2 / g or less.
　なお、本発明において「ＢＥＴ比表面積」とは、以下の方法で計測したものを意味する。まず、窒素およびヘリウムの混合ガスをＢＥＴ比表面積測定装置内に導入し、試料（ＢＥＴ比表面積の測定対象物）を入れた試料セルを液体窒素に浸して、窒素ガスを試料表面に吸着させる。吸着平衡に達した後、試料セルを水浴に入れ常温まで温め、試料に付着していた窒素を脱着させる。窒素ガスの吸着、脱着時に試料セルを通過する前後のガスの混合比は変化するので、この変化を窒素およびヘリウムの混合比が一定のガスを対照として熱伝導度検出器（ＴＣＤ）で検知し、窒素ガスの吸着量および脱着量を求める。測定前に単位量の窒素ガスを装置内に導入してキャリブレーションを行い、ＴＣＤで検出した値に対応する表面績の値を求めておくことにより、その試料の表面積を求める。また、表面積をその試料の質量で除すことにより、ＢＥＴ比表面積を求めることができる。 In the present invention, “BET specific surface area” means that measured by the following method. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring apparatus, and a sample cell containing a sample (an object to be measured for BET specific surface area) is immersed in liquid nitrogen to adsorb nitrogen gas to the sample surface. After reaching adsorption equilibrium, the sample cell is placed in a water bath and warmed to room temperature, and nitrogen adhering to the sample is desorbed. Since the mixing ratio of the gas before and after passing through the sample cell changes during the adsorption and desorption of nitrogen gas, this change is detected by a thermal conductivity detector (TCD) using a gas with a constant mixing ratio of nitrogen and helium as a control. Then, the adsorption amount and desorption amount of nitrogen gas are obtained. Before the measurement, a unit amount of nitrogen gas is introduced into the apparatus for calibration, and the surface area value corresponding to the value detected by TCD is obtained to obtain the surface area of the sample. Further, the BET specific surface area can be obtained by dividing the surface area by the mass of the sample.
　ＢＥＴ比表面積が大きなフィラーを添加することによって、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）から後述するリン酸エステル（Ｃ）のような液状成分が流出することを抑制できると考えられる。 By adding a filler having a large BET specific surface area, a liquid such as a phosphate ester (C) described later from the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is obtained. It is thought that a component can be prevented from flowing out.
　しかしながら、ＢＥＴ比表面積が大きなフィラーを多量に添加すると、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の前駆体である混合組成物の粘度が過度に上昇し、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を成形することが困難になる。そこで、本発明では、ＢＥＴ比表面積が大きな熱伝導性フィラー（Ｂ１）と後述するチタネート処理された熱伝導性フィラー（Ｂ２）とを併用している。チタネート処理された熱伝導性フィラー（Ｂ２）を添加することによって、チタネート処理されていないフィラーを添加する場合に比べて樹脂組成物の粘度上昇を抑えられることは知られていた。本発明者らは、さらに、チタネート処理された熱伝導性フィラー（Ｂ２）には液状成分のブリードを抑制する効果があることを見出した。本発明によれば、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）を適量ずつ併用することによって、混合組成物の粘度上昇と抑制しつつ、液状成分のブリードを抑制することができる。 However, when a large amount of a filler having a large BET specific surface area is added, the viscosity of the heat conductive pressure-sensitive adhesive composition (F) and the mixture composition which is a precursor of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is low. It will rise too much and it will become difficult to shape | mold a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G). Therefore, in the present invention, a thermally conductive filler (B1) having a large BET specific surface area and a titanate-treated thermally conductive filler (B2) described later are used in combination. It has been known that the increase in viscosity of the resin composition can be suppressed by adding the titanate-treated thermally conductive filler (B2) as compared to the case of adding a filler not treated with titanate. The present inventors have further found that the titanate-treated thermally conductive filler (B2) has an effect of suppressing bleeding of the liquid component. According to the present invention, by using the heat conductive filler (B1) and the heat conductive filler (B2) together in appropriate amounts, bleeding of the liquid component can be suppressed while suppressing an increase in the viscosity of the mixed composition. .
　熱伝導性フィラー（Ｂ１）は、ＢＥＴ比表面積が１．０ｍ２／ｇ以上であり、チタネート処理されていないものであり、添加することによって熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の熱伝導性を、添加しない場合よりも向上させることができ、熱伝導率が０．５Ｗ／ｍ・Ｋ以上であるフィラーであれば特に限定されない。 The heat conductive filler (B1) has a BET specific surface area of 1.0 m 2 / g or more and is not subjected to titanate treatment. When added, the heat conductive pressure-sensitive adhesive composition (F) and the heat conduction are added. The heat conductivity of the pressure-sensitive adhesive sheet-like molded body (G) can be improved as compared with the case where it is not added, and the filler is not particularly limited as long as the thermal conductivity is 0.5 W / m · K or more.
　熱伝導性フィラー（Ｂ１）の具体例としては、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、などの金属水酸化物；酸化アルミニウム（アルミナ）、酸化マグネシウム、酸化亜鉛などの金属酸化物；炭酸カルシウム、炭酸アルミニウムなどの金属炭酸塩；窒化ホウ素、窒化アルミニウムなどの金属窒化物；ホウ酸亜鉛水和物；カオリンクレー；アルミン酸カルシウム水和物；シリカ；等を挙げることができる。この中でも、金属水酸化物、金属酸化物及び金属炭酸塩が好ましく、金属水酸化物、金属酸化物がより好ましく、水酸化アルミニウム、酸化アルミニウムがさらに好ましく、酸化アルミニウムが特に好ましい。熱伝導性フィラー（Ｂ１）は一種を単独で使用してもよく、二種以上を併用してもよい。 Specific examples of the thermally conductive filler (B1) include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; metal oxides such as aluminum oxide (alumina), magnesium oxide, and zinc oxide; carbonic acid Metal carbonates such as calcium and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate hydrate; silica; Among these, metal hydroxides, metal oxides, and metal carbonates are preferable, metal hydroxides and metal oxides are more preferable, aluminum hydroxide and aluminum oxide are further preferable, and aluminum oxide is particularly preferable. A heat conductive filler (B1) may be used individually by 1 type, and may use 2 or more types together.
　本発明に用いる熱伝導性フィラー（Ｂ１）の平均粒径は、０．５μｍ以上５０μｍ以下であることが好ましく、１μｍ以上３０μｍ以下であることがより好ましい。 The average particle size of the thermally conductive filler (B1) used in the present invention is preferably 0.5 μm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less.
　なお、本発明において「平均粒径」とは、以下に説明する方法で測定したものを意味する。すなわち、レーザー式粒度測定機（株式会社セイシン企業製）を用い、マイクロソーティング制御方式（測定領域内にのみ測定対象粒子を通過させ、測定の信頼性を向上させる方式）により測定する。この測定方法によれば、セル中に測定対象粒子０．０１ｇ～０．０２ｇが流されることで、測定領域内に流れてくる測定対象粒子に波長６７０ｎｍの半導体レーザー光が照射され、その際のレーザー光の散乱と回折が測定機にて測定されることにより、フランホーファの回折原理から、平均粒径及び粒径分布が算出される。 In the present invention, the “average particle diameter” means that measured by the method described below. That is, a laser type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) is used, and measurement is performed by a microsorting control method (a method in which the measurement target particles are allowed to pass only in the measurement region and the measurement reliability is improved). According to this measurement method, when the measurement target particles 0.01 g to 0.02 g are flowed into the cell, the measurement target particles flowing in the measurement region are irradiated with the semiconductor laser light having a wavelength of 670 nm. By measuring the scattering and diffraction of laser light with a measuring instrument, the average particle size and particle size distribution are calculated from the diffraction principle of Franhofer.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に使用する熱伝導性フィラー（Ｂ１）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、１２０質量部以上４５０質量部以下であり、１５０質量部以上４５０質量部以下であることが好ましく、１５０質量部以上４００質量部以下であることがより好ましい。熱伝導性フィラー（Ｂ１）の含有量が上記範囲を超えると、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の前駆体である混合組成物の粘度が過剰に増大し、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を成形し難くなったり、成形できたとしても熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の硬度が増大して形状追随性（被着体への密着性）が低下したりする虞がある。一方、熱伝導性フィラー（Ｂ１）の含有量が上記範囲未満であると、熱伝導性フィラー（Ｂ１）を用いることによって熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）からの液状成分のブリードを抑制する効果が不十分となる虞がある。 The amount of the heat conductive filler (B1) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) 120 parts by mass or more and 450 parts by mass or less, preferably 150 parts by mass or more and 450 parts by mass or less, and more preferably 150 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass. When the content of the heat conductive filler (B1) exceeds the above range, the mixed composition is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G). Even if the viscosity of the resin increases excessively, it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), or even if it can be molded, the heat conductive pressure-sensitive adhesive There is a possibility that the hardness of the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) increases, and the shape followability (adhesion to the adherend) decreases. On the other hand, when the content of the heat conductive filler (B1) is less than the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet are obtained by using the heat conductive filler (B1). There is a possibility that the effect of suppressing bleeding of the liquid component from the shaped molded body (G) is insufficient.
　＜熱伝導性フィラー（Ｂ２）＞
  次に熱伝導性フィラー（Ｂ２）について説明する。本発明に用いる熱伝導性フィラー（Ｂ２）は、チタネート処理された熱伝導性フィラーである。熱伝導性フィラー（Ｂ２）におけるチタネート処理の方法は特に限定されず、公知のチタネート系カップリング剤を用いて行うことができる。 <Thermal conductive filler (B2)>
Next, the heat conductive filler (B2) will be described. The thermally conductive filler (B2) used in the present invention is a titanate-treated thermally conductive filler. The titanate treatment method in the heat conductive filler (B2) is not particularly limited, and can be performed using a known titanate coupling agent.
　チタネート系カップリング剤としては、例えば、イソプロピルトリイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリス（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート、イソプロピルトリ（Ｎ－アミドエチル・アミノエチル）チタネート、ジクミルフェニルオキシアセテートチタネート、及びジイソステアロイルエチレンチタネート等が挙げられる。 Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacryl titanate, isopropyltris (dioctylphosphate) titanate, Isopropyltricumylf Niruchitaneto, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, and diisostearoyl ethylene titanate.
　熱伝導性フィラー（Ｂ２）は、チタネート処理されており、添加することによって熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の熱伝導性を、添加しない場合よりも向上させることができ、熱伝導率が０．５Ｗ／ｍ・Ｋ以上であるフィラーであれば特に限定されない。 The heat conductive filler (B2) is titanate-treated, and by adding the heat conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), The filler is not particularly limited as long as it can be improved as compared with the case where it is not added and the thermal conductivity is 0.5 W / m · K or more.
　熱伝導性フィラー（Ｂ２）の具体例としては、以下の熱伝導性フィラーにチタネート処理を施したものが挙げられる。水酸化アルミニウム、水酸化ガリウム、水酸化インジウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどの金属水酸化物；酸化アルミニウム（アルミナ）、酸化マグネシウム、酸化亜鉛などの金属酸化物；炭酸カルシウム、炭酸アルミニウムなどの金属炭酸塩；窒化ホウ素、窒化アルミニウムなどの金属窒化物；ホウ酸亜鉛水和物；カオリンクレー；アルミン酸カルシウム水和物；ドーソナイト；シリカ；等を挙げることができる。この中でも、金属水酸化物、金属酸化物及び金属炭酸塩が好ましく、金属水酸化物がより好ましく、水酸化アルミニウムが特に好ましい。熱伝導性フィラー（Ｂ２）は一種を単独で使用してもよく、二種以上を併用してもよい。 Specific examples of the thermally conductive filler (B2) include those obtained by subjecting the following thermally conductive filler to titanate treatment. Metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide; metal oxides such as aluminum oxide (alumina), magnesium oxide, zinc oxide Metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate hydrate; dosonite; silica; . Among these, metal hydroxides, metal oxides, and metal carbonates are preferable, metal hydroxides are more preferable, and aluminum hydroxide is particularly preferable. A heat conductive filler (B2) may be used individually by 1 type, and may use 2 or more types together.
　本発明に用いる熱伝導性フィラー（Ｂ２）の平均粒径は、１μｍ以上８０μｍ以下であることが好ましく、５μｍ以上５０μｍ以下であることがより好ましい。 The average particle size of the thermally conductive filler (B2) used in the present invention is preferably 1 μm or more and 80 μm or less, and more preferably 5 μm or more and 50 μm or less.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に使用する熱伝導性フィラー（Ｂ２）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、１２０質量部以上５００質量部以下であり、１５０質量部以上４５０質量部以下であることが好ましく、１５０質量部以上４００質量部以下であることがより好ましい。熱伝導性フィラー（Ｂ２）の含有量が上記範囲を超えると、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の前駆体である混合組成物の粘度が過剰に増大し、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を成形し難くなったり、成形できたとしても熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の硬度が増大して形状追随性（被着体への密着性）が低下したりする虞がある。一方、熱伝導性フィラー（Ｂ２）の含有量が上記範囲未満であると、熱伝導性フィラー（Ｂ２）を用いることによって熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）からの液状成分のブリードを抑制する効果が不十分となる虞がある。 The amount of the heat conductive filler (B2) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) It is 120 to 500 mass parts with respect to 100 mass parts, It is preferable that it is 150 to 450 mass parts, and it is more preferable that it is 150 to 400 mass parts. When the content of the heat conductive filler (B2) exceeds the above range, the mixed composition is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G). Even if the viscosity of the resin increases excessively, it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), or even if it can be molded, the heat conductive pressure-sensitive adhesive There is a possibility that the hardness of the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) increases, and the shape followability (adhesion to the adherend) decreases. On the other hand, when the content of the heat conductive filler (B2) is less than the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet are obtained by using the heat conductive filler (B2). There is a possibility that the effect of suppressing bleeding of the liquid component from the shaped molded body (G) is insufficient.
　＜熱伝導性フィラー（Ｂ３）＞
  次に熱伝導性フィラー（Ｂ３）について説明する。本発明に用いる熱伝導性フィラー（Ｂ３）は、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラーである。熱伝導性フィラー（Ｂ３）としては、チタネート処理されておらず、ＢＥＴ比表面積が上記熱伝導性フィラー（Ｂ１）の範囲を外れるものを用いることができる。 <Thermal conductive filler (B3)>
Next, a heat conductive filler (B3) is demonstrated. The thermally conductive filler (B3) used in the present invention is a thermally conductive filler other than the thermally conductive filler (B1) and the thermally conductive filler (B2). As the heat conductive filler (B3), one that is not titanate-treated and whose BET specific surface area is out of the range of the heat conductive filler (B1) can be used.
　熱伝導性フィラー（Ｂ３）の具体例としては、水酸化アルミニウム、水酸化ガリウム、水酸化インジウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどの金属水酸化物；酸化アルミニウム（アルミナ）、酸化マグネシウム、酸化亜鉛などの金属酸化物；炭酸カルシウム、炭酸アルミニウムなどの金属炭酸塩；窒化ホウ素、窒化アルミニウムなどの金属窒化物；ホウ酸亜鉛水和物；カオリンクレー；アルミン酸カルシウム水和物；ドーソナイト；シリカ；膨張化黒鉛、人造黒鉛、カーボンブラック、炭素繊維などの、炭素含有導電性フィラー；等を挙げることができる。この中でも、金属水酸化物、金属酸化物及び炭素含有導電性フィラーが好ましく、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛がより好ましく、水酸化アルミニウム及び酸化アルミニウムがさらに好ましく、水酸化アルミニウムが特に好ましい。熱伝導性フィラー（Ｂ３）は一種を単独で使用してもよく、二種以上を併用してもよい。 Specific examples of the thermally conductive filler (B3) include metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide; aluminum oxide ( Alumina), metal oxides such as magnesium oxide and zinc oxide; metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate water Examples thereof include: Japanese; dosonite; silica; carbon-containing conductive fillers such as expanded graphite, artificial graphite, carbon black, and carbon fiber. Among these, metal hydroxides, metal oxides, and carbon-containing conductive fillers are preferable, aluminum hydroxide, aluminum oxide, and expanded graphite are more preferable, aluminum hydroxide and aluminum oxide are more preferable, and aluminum hydroxide is particularly preferable. . A heat conductive filler (B3) may be used individually by 1 type, and may use 2 or more types together.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に使用する熱伝導性フィラー（Ｂ３）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、２００質量部以上６００質量部以下であり、２００質量部以上５５０質量部以下であることが好ましく、２５０質量部以上５５０質量部以下であることがより好ましい。熱伝導性フィラー（Ｂ３）の含有量が上記範囲を超えると、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の前駆体である混合組成物の粘度が過剰に増大し、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を成形し難くなったり、成形できたとしても熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の硬度が増大して形状追随性（被着体への密着性）が低下したりする虞がある。一方、熱伝導性フィラー（Ｂ３）の含有量が上記範囲未満であると、熱伝導性フィラー（Ｂ３）を用いることによって熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）からの液状成分のブリードを抑制する効果が不十分となる虞がある。また、熱伝導性フィラー（Ｂ３）が上述した炭素含有導電性フィラーを含む場合、炭素含有導電性フィラーの量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、１質量部以上３０質量部以下であることが好ましい。 The amount of the heat conductive filler (B3) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) It is 200 mass parts or more and 600 mass parts or less with respect to 100 mass parts, it is preferable that they are 200 mass parts or more and 550 mass parts or less, and it is more preferable that they are 250 mass parts or more and 550 mass parts or less. When the content of the heat conductive filler (B3) exceeds the above range, the mixed composition is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G). Even if the viscosity of the resin increases excessively, it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), or even if it can be molded, the heat conductive pressure-sensitive adhesive There is a possibility that the hardness of the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) increases, and the shape followability (adhesion to the adherend) decreases. On the other hand, when the content of the heat conductive filler (B3) is less than the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet are obtained by using the heat conductive filler (B3). There is a possibility that the effect of suppressing bleeding of the liquid component from the shaped molded body (G) is insufficient. Moreover, when a heat conductive filler (B3) contains the carbon containing conductive filler mentioned above, the quantity of a carbon containing conductive filler is 1 mass part with respect to 100 mass parts of (meth) acrylic resin compositions (A). The amount is preferably 30 parts by mass or less.
　＜リン酸エステル（Ｃ）＞
  次にリン酸エステル（Ｃ）について説明する。リン酸エステル（Ｃ）を用いることによって、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に優れた難燃性を付与し易くなる。 <Phosphate ester (C)>
Next, phosphate ester (C) will be described. By using phosphoric ester (C), it becomes easy to give the flame retardance excellent in the heat conductive pressure-sensitive-adhesive composition (F) and the heat conductive pressure-sensitive-adhesive sheet-like molded object (G).
　本発明に用いるリン酸エステル（Ｃ）は、２５℃における粘度が３０００ｍＰａ・ｓ以上であることが好ましい。リン酸エステル（Ｃ）の粘度を上記範囲とすることで、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）の成形性が悪くなることを防止し易くなる。なお、本発明においてリン酸エステル（Ｃ）の「粘度」とは、以下に説明する方法によって測定した粘度を意味する。 The phosphate ester (C) used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa · s or more. By making the viscosity of the phosphoric ester (C) within the above range, it is prevented that the moldability of the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is deteriorated. It becomes easy to do. In the present invention, the “viscosity” of the phosphate ester (C) means the viscosity measured by the method described below.
　（リン酸エステルの粘度測定方法）
  リン酸エステルの粘度測定には、Ｂ型粘度計（東京計器株式会社製）を用いて、以下に示す手順で行う。
（１）常温の環境でリン酸エステルを３００ｍｌ計量し、５００ｍｌの容器に入れる。
（２）攪拌用ロータＮｏ．１、２、３、４、５、６、７から、いずれかを選択し、粘度計に取り付ける。
（３）リン酸エステルが入った容器を粘度計の上に置き、ロータを該容器内のリン酸エステルに沈める。このとき、ロータの目印となる凹みが丁度、リン酸エステルの液状界面にくるように沈める。
（４）回転数を２０、１０、４、２の中から選択する。
（５）攪拌スイッチを入れ、１分後の数値を読み取る。
（６）読み取った数値に、係数Ａを掛け算した値が粘度［ｍＰａ・ｓ］となる。
なお、係数Ａは、下記表１に示すように、選択したロータＮｏ．と回転数とから決まる。 (Method for measuring viscosity of phosphate ester)
The viscosity of the phosphate ester is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to the following procedure.
(1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
(2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
(3) The container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the phosphate ester in the container. At this time, the dent which becomes a mark of a rotor sinks so that it may just come to the liquid interface of phosphate ester.
(4) The rotation speed is selected from 20, 10, 4, and 2.
(5) Turn on the stirring switch and read the value after 1 minute.
(6) The value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa · s].
The coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　また、本発明に用いるリン酸エステル（Ｃ）は、大気圧下での１５℃以上１００℃以下の温度領域において常に液体であることが好ましい。リン酸エステル（Ｃ）は、混合する際に液体であれば、作業性が良く、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）を成形することが容易になる。リン酸エステル（Ｃ）を含んだ熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）を成形する際、１５℃以上１００℃以下の環境で、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）を構成する各物質を混合することが好ましい。混合時の温度を上記範囲とすることによって、（メタ）アクリル樹脂組成物（Ａ）のガラス転移温度以上とし、（メタ）アクリル樹脂組成物（Ａ）に含まれる単量体等の揮発あるいは重合反応が始まってしまうことを防止し易くなるため、環境性及び作業性を良くすることができる。 Further, it is preferable that the phosphate ester (C) used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester (C) is liquid when mixed, the workability is good and the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is formed. It becomes easy. When molding the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded product (G) containing the phosphoric ester (C), heat is applied in an environment of 15 ° C. or higher and 100 ° C. or lower. It is preferable to mix each substance which comprises a conductive pressure sensitive adhesive composition (F) or a heat conductive pressure sensitive adhesive sheet-like molded object (G). By setting the temperature during mixing in the above range, the glass transition temperature of the (meth) acrylic resin composition (A) is set to be equal to or higher than the volatilization or polymerization of monomers contained in the (meth) acrylic resin composition (A). Since it becomes easy to prevent the reaction from starting, the environmental performance and workability can be improved.
　本発明には、リン酸エステル（Ｃ）として、縮合リン酸エステルも非縮合リン酸エステルも用いることができる。ここでいう「縮合リン酸エステル」とは、１分子内にリン酸エステル部位が複数存在するものを意味し、「非縮合リン酸エステル」とは、１分子内にリン酸エステル部位が１つだけ存在するものを意味する。これまでに説明した条件を満たすリン酸エステルの具体例を以下に列記する。 In the present invention, either a condensed phosphate ester or a non-condensed phosphate ester can be used as the phosphate ester (C). As used herein, “condensed phosphate ester” means one having a plurality of phosphate ester moieties in one molecule, and “non-condensed phosphate ester” means one phosphate ester moiety in one molecule. It means something that exists only. Specific examples of phosphate esters that satisfy the conditions described so far are listed below.
　縮合リン酸エステルの具体例としては、１，３－フェニレンビス（ジフェニルホスフェート）、ビスフェノールＡビス（ジフェニルホスフェート）、レゾルシノールビス（ジフェニルホスフェート）などの芳香族縮合リン酸エステル；ポリオキシアルキレンビスジクロロアルキルホスフェートなどの含ハロゲン系縮合リン酸エステル；非芳香族非ハロゲン系縮合リン酸エステル；などが挙げられる。これらの中でも、比重が比較的小さく、有害物質（ハロゲンなど）の放出の危険がなく、入手も容易であることなどから、芳香族縮合リン酸エステルが好ましく、１，３－フェニレンビス（ジフェニルホスフェート）、ビスフェノールＡビス（ジフェニルホスフェート）がより好ましい。 Specific examples of the condensed phosphate ester include aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyalkylene bisdichloroalkyl And halogen-containing condensed phosphates such as phosphates; non-aromatic non-halogen-based condensed phosphates; Of these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no risk of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.
　非縮合リン酸エステルの具体例としては、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジル－２，６－キシレニルホスフェート、２－エチルヘキシルジフェニルホスフェートなどの芳香族リン酸エステル；トリス（β－クロロプロピル）ホスフェート、トリスジクロロプロピルホスフェート、トリス（トリブロモネオペンチル）ホスフェートなどの含ハロゲン系リン酸エステル；などが挙げられる。この中でも、有害物質（ハロゲンなど）が発生しないことなどから、芳香族リン酸エステルが好ましい。 Specific examples of the non-condensed phosphate ester include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris (β-chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.
　リン酸エステル（Ｃ）は、一種を単独で用いてもよく、二種以上を併用してもよい。 As the phosphate ester (C), one type may be used alone, or two or more types may be used in combination.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に使用するリン酸エステル（Ｃ）の量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量部として４０質量部以上１２０質量部以下であり、５０質量部以上１００質量部以下であることがより好ましく、６０質量部以上１００質量部以下であることがさらに好ましい。リン酸エステル（Ｃ）の含有量を上記範囲とすることによって、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）に優れた難燃性を付与しやすくなる。 The amount of the phosphoric acid ester (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is the (meth) acrylic resin composition (A ) Is 40 parts by mass or more and 120 parts by mass or less, more preferably 50 parts by mass or more and 100 parts by mass or less, and still more preferably 60 parts by mass or more and 100 parts by mass or less. By setting the content of the phosphate ester (C) in the above range, excellent flame retardancy is imparted to the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It becomes easy to do.
　＜その他の添加剤＞
  本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）には、上述した物質以外にも、上述した物質を配合することによる上記効果を妨げない範囲で、公知の各種添加剤を添加することもできる。公知の添加剤としては、発泡剤（発泡助剤を含む。）；ガラス繊維；外部架橋剤；顔料；クレーなどのその他の充填材；フラーレン、カーボンナノチューブなどのナノ粒子；ポリフェノール系、ハイドロキノン系、ヒンダードアミン系などの酸化防止剤；アクリル系ポリマー粒子、微粒シリカなどの増粘剤；などを挙げることができる。 <Other additives>
In addition to the above-described substances, the above-described effects due to the addition of the above-described substances are hindered in the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention. Various known additives can be added within the range. Known additives include: foaming agents (including foaming aids); glass fibers; external cross-linking agents; pigments; other fillers such as clay; nanoparticles such as fullerenes and carbon nanotubes; polyphenols, hydroquinones, Antioxidants such as hindered amines; thickeners such as acrylic polymer particles and fine silica;
　これまでに説明したように、本発明によれば、リン酸エステル（Ｃ）を添加することによって難燃性を備えさせつつ、ＢＥＴ比表面積が大きな熱伝導性フィラー（Ｂ１）及びチタネート処理された熱伝導性フィラー（Ｂ２）を適量添加することによって、液状成分のブリードを抑制された熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を得ることができる。以下、このような熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法について説明する。 As explained so far, according to the present invention, the thermally conductive filler (B1) having a large BET specific surface area and the titanate treatment were provided while providing flame retardancy by adding the phosphate ester (C). By adding an appropriate amount of the heat conductive filler (B2), a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded product (G) in which bleeding of the liquid component is suppressed are obtained. Can do. Hereinafter, the manufacturing method of such a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) is demonstrated.
　２．製造方法
  本発明の熱伝導性感圧接着剤組成物（Ｆ）は、これまでに説明した各物質を混合して混合組成物を作製した後、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを少なくとも行うことにより得ることができる。 2. Production Method The thermally conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing each of the substances described so far to prepare a mixed composition, and then (meth) acrylic acid ester monomer (α1) and Polymerization reaction of polyfunctional monomer (D) and crosslinking of polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) It can be obtained by performing at least the reaction.
　すなわち、本発明の熱伝導性感圧接着剤組成物（Ｆ）の製造方法は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）と、熱伝導性フィラー（Ｂ１）と、熱伝導性フィラー（Ｂ２）と、熱伝導性フィラー（Ｂ３）とを含む混合組成物を作製する工程、並びに、該混合組成物中において、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを少なくとも行う工程を含んでいる。なお、その他に使用できる物質や、各物質の好ましい含有比率等は上述した通りであり、ここでは詳細な説明を省略する。 That is, the method for producing the heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises the (meth) acrylic acid ester polymer (A1), the (meth) acrylic acid ester monomer (α1), and the polyfunctional single monomer. Mixed composition comprising (meth) acrylic resin composition (A) containing monomer (D), thermally conductive filler (B1), thermally conductive filler (B2), and thermally conductive filler (B3) In the mixed composition, the polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D), and the (meth) acrylic acid ester polymer ( A1) and / or a step of performing at least a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1). In addition, the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate | omitted here.
　本発明の熱伝導性感圧接着性シート状成形体（Ｇ）は、これまでに説明した各物質を混合して混合組成物を作製し、該混合組成物をシート状に成形した後、又は該混合組成物をシート状に成形しながら、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを少なくとも行うことにより得ることができる。 The heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is prepared by mixing each of the substances described so far to prepare a mixed composition, and molding the mixed composition into a sheet shape, or While forming the mixed composition into a sheet, the polymerization reaction of the (meth) acrylate monomer (α1) and the polyfunctional monomer (D), the (meth) acrylate polymer (A1) and It can be obtained by performing at least a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1).
　すなわち、本発明の熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法は、（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）および多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）と、熱伝導性フィラー（Ｂ１）と、熱伝導性フィラー（Ｂ２）と、熱伝導性フィラー（Ｂ３）とを含む混合組成物を作製する工程、並びに、該混合組成物をシート状に成形した後、又は、該混合組成物をシート状に成形しながら、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体（Ｄ）の重合反応と、（メタ）アクリル酸エステル重合体（Ａ１）及び／又は（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを少なくとも行う工程を含んでいる。なお、その他に使用できる物質や、各物質の好ましい含有比率等は上述した通りであり、ここでは詳細な説明を省略する。 That is, the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention includes (meth) acrylic acid ester polymer (A1), (meth) acrylic acid ester monomer (α1) and polyfunctional. Containing (meth) acrylic resin composition (A) containing heat conductive monomer (D), heat conductive filler (B1), heat conductive filler (B2), and heat conductive filler (B3) (Meth) acrylic acid ester monomer (α1) and polyfunctional after the step of producing the composition, and after forming the mixed composition into a sheet or while forming the mixed composition into a sheet And a crosslinking reaction of a polymer containing a structural unit derived from a (meth) acrylic acid ester polymer (A1) and / or a (meth) acrylic acid ester monomer (α1) At least the step of performing. In addition, the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate | omitted here.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法において、上記重合及び架橋反応を行う際には、加熱することが好ましい。当該加熱には、例えば、熱風、電気ヒーター、赤外線などを用いることができる。このときの加熱温度は、重合開始剤が効率良く分解し、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体（Ｄ）の重合が進行する温度が好ましい。温度範囲は、用いる重合開始剤の種類等により異なるが、１００℃以上２００℃以下が好ましく、１３０℃以上１８０℃以下がより好ましい。 In the production method of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention, heating is preferably performed when the polymerization and the crosslinking reaction are performed. For the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. The heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D) proceeds. The temperature range varies depending on the type of polymerization initiator used, but is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 130 ° C. or higher and 180 ° C. or lower.
　また、本発明の熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法において、上記混合組成物をシート状に成形する方法は特に限定されない。好適な方法としては、例えば、離型処理したポリエステルフィルムなどの工程紙の上に上記混合組成物を塗布してシートを成形する方法、二枚の離型処理した工程紙間に上記混合組成物を挟んでロールの間を通して押圧することでシートを成形する方法、及び、押出機を用いて上記混合組成物を押出し、その際にダイスを通して厚さを制御することでシートを成形する方法などが挙げられる。 Further, in the method for producing the heat conductive pressure-sensitive adhesive sheet-shaped body (G) of the present invention, the method for molding the mixed composition into a sheet shape is not particularly limited. Suitable methods include, for example, a method of forming a sheet by applying the mixed composition onto a process paper such as a polyester film subjected to a release treatment, and the mixed composition between two release-processed papers. There are a method of forming a sheet by pressing between rolls with a sandwich, and a method of forming the sheet by extruding the mixed composition using an extruder and controlling the thickness through a die at that time. Can be mentioned.
　熱伝導性感圧接着性シート状成形体（Ｇ）の厚さは０．０５ｍｍ以上５ｍｍ以下にすることができる。熱伝導性感圧接着性シート状成形体（Ｇ）の厚さを薄くすることによって、熱伝導性感圧接着性シート状成形体（Ｇ）の厚み方向の熱抵抗を低くすることができる。かかる観点から、熱伝導性感圧接着性シート状成形体（Ｇ）の厚さの上限は、好ましくは２ｍｍである。一方、熱伝導性感圧接着性シート状成形体（Ｇ）の厚さの下限は、好ましくは０．１ｍｍである。熱伝導性感圧接着性シート状成形体（Ｇ）にある程度の厚さをもたせることによって、当該熱伝導性感圧接着性シート状成形体（Ｇ）を発熱体及び放熱体に貼付する際に空気を巻き込むことを防止し易くなり、結果として熱抵抗の増加を防止し、被着体への貼り付け工程における作業性を良好にし易くなる。 The thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 5 mm or less. By reducing the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded article (G), the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded article (G) can be reduced. From this viewpoint, the upper limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 2 mm. On the other hand, the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (G) is preferably 0.1 mm. By applying a certain thickness to the heat conductive pressure-sensitive adhesive sheet-like molded body (G), air is applied when the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) is applied to the heating element and the heat radiating body. It becomes easy to prevent entrainment, and as a result, increase in thermal resistance is prevented, and workability in the step of attaching to the adherend is easily improved.
　また、熱伝導性感圧接着性シート状成形体（Ｇ）は、基材の片面又は両面に成形することもできる。当該基材を構成する材料は特に限定されない。当該基材の具体例としては、アルミニウム、銅、ステンレス鋼、ベリリウム銅などの熱伝導性に優れる金属、及び、合金の箔状物や、熱伝導性シリコーンなどのそれ自体熱伝導性に優れるポリマーからなるシート状物や、熱伝導性添加物を含有させた熱伝導性プラスチックフィルムや、各種不織布や、ガラスクロスや、ハニカム構造体などを挙げることができる。プラスチックフィルムとしては、ポリイミド、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリテトラフルオロエチレン、ポリエーテルケトン、ポリエーテルスルホン、ポリメチルペンテン、ポリエーテルイミド、ポリスルホン、ポリフェニレンスルフィド、ポリアミドイミド、ポリエステルイミド、芳香族ポリアミドなどの耐熱性ポリマーのフィルムを使用することができる。 Also, the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate. The material which comprises the said base material is not specifically limited. Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone. And a sheet-like material made of the above, a heat-conductive plastic film containing a heat-conductive additive, various non-woven fabrics, a glass cloth, and a honeycomb structure. Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc. A heat-resistant polymer film can be used.
　３．使用例
  本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）は、電子機器に備えられる電子部品の一部として用いることができる。その際、放熱体のような基材上に直接的に成形して電子部品の一部として提供することもできる。当該電子機器及び電子部品の具体例としては、エレクトロルミネッセンス（ＥＬ）、発光ダイオード（ＬＥＤ）光源を有する機器における発熱部周囲の部品、自動車等のパワーデバイス周囲の部品、燃料電池、太陽電池、バッテリー、携帯電話、携帯情報端末（ＰＤＡ）、ノートパソコン、液晶、表面伝導型電子放出素子ディスプレイ（ＳＥＤ）、プラズマディスプレイパネル（ＰＤＰ）、又は集積回路（ＩＣ）などの発熱部を有する機器や部品を挙げることができる。 3. Use example The heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention can be used as some electronic components with which an electronic device is equipped. In that case, it can also be directly molded on a base material such as a radiator and provided as a part of the electronic component. Specific examples of the electronic device and electronic component include electroluminescence (EL), a component around a heat generating part in a device having a light emitting diode (LED) light source, a component around a power device such as an automobile, a fuel cell, a solar cell, and a battery. , Devices and parts having heat generating parts such as mobile phones, personal digital assistants (PDAs), notebook computers, liquid crystals, surface conduction electron-emitting device displays (SED), plasma display panels (PDP), or integrated circuits (ICs) Can be mentioned.
　なお、本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の電子機器への使用方法の一例としては、ＬＥＤ光源を例にすると下記に記述するような使用方法を挙げることができる。すなわちＬＥＤ光源に直接貼り付ける；ＬＥＤ光源と放熱材料（ヒートシンク、ファン、ペルチェ素子、ヒートパイプ、グラファイトシート等）との間に挟みこむ；ＬＥＤ光源に接続された放熱材料（ヒートシンク、ファン、ペルチェ素子、ヒートパイプ、グラファイトシート等）に貼り付ける；ＬＥＤ光源を取り囲む筐体として使用する；ＬＥＤ光源を取り囲む筐体に貼り付ける；ＬＥＤ光源と筐体との隙間を埋める；等の方法である。ＬＥＤ光源の用途例としては、透過型の液晶パネルを有する表示装置のバックライト装置（テレビ、携帯、ＰＣ、ノートＰＣ、ＰＤＡ等）；車両用灯具；工業用照明；商業用照明；一般住宅用照明；等が挙げられる。 In addition, as an example of the usage method for the electronic device of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention, an LED light source is exemplified below. Examples of usage can be mentioned. That is, it is directly attached to the LED light source; sandwiched between the LED light source and the heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); The heat dissipation material connected to the LED light source (heat sink, fan, Peltier element) , Heat pipe, graphite sheet, etc.); used as a housing surrounding the LED light source; pasted on a housing surrounding the LED light source; filling a gap between the LED light source and the housing; Examples of LED light source applications include backlight devices for display devices having transmissive liquid crystal panels (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; Lighting; and the like.
　また、ＬＥＤ光源以外の具体例としては、以下のものが挙げられる。すなわち、ＰＤＰパネル；ＩＣ発熱部；冷陰極管（ＣＣＦＬ）；有機ＥＬ光源；無機ＥＬ光源；高輝度発光ＬＥＤ光源；高輝度発光有機ＥＬ光源；高輝度発光無機ＥＬ光源；ＣＰＵ；ＭＰＵ；半導体素子；等である。 Further, specific examples other than the LED light source include the following. That is, PDP panel; IC heating part; Cold cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High luminance light emitting LED light source; High luminance light emitting organic EL light source; And so on.
　更に本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の使用方法としては、装置の筐体に貼り付けること等を挙げることができる。例えば、自動車等に備えられる装置に使用する場合、自動車に備えられる筐体の内部に貼り付ける；自動車に備えられる筐体の外側に貼り付ける；自動車に備えられる筐体の内部にある発熱部（カーナビ／燃料電池／熱交換器）と該筐体とを接続する；自動車に備えられる筐体の内部にある発熱部（カーナビ／燃料電池／熱交換器）に接続した放熱板に貼り付ける；こと等が挙げられる。 Furthermore, examples of the method of using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention include affixing to the housing of the apparatus. For example, when used in a device provided in an automobile or the like, it is affixed inside a casing provided in the automobile; affixed outside the casing provided in the automobile; a heat generating part (inside the casing provided in the automobile) Connecting the car navigation / fuel cell / heat exchanger) and the housing; affixing to a heat sink connected to the heat generating part (car navigation / fuel cell / heat exchanger) in the housing of the automobile; Etc.
　なお、自動車以外にも、同様の方法で本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を使用することができる。その対象としては、例えばパソコン；住宅；テレビ；携帯電話機；自動販売機；冷蔵庫；太陽電池；表面伝導型電子放出素子ディスプレイ（ＳＥＤ）；有機ＥＬディスプレイ；無機ＥＬディスプレイ；有機ＥＬ照明；無機ＥＬ照明；有機ＥＬディスプレイ；ノートパソコン；ＰＤＡ；燃料電池；半導体装置；炊飯器；洗濯機；洗濯乾燥機；光半導体素子と蛍光体とを組み合わせた光半導体装置；各種パワーデバイス；ゲーム機；キャパシタ；等が挙げられる。 In addition to the automobile, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention can be used in the same manner. For example, personal computers; homes; TVs; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Organic EL display; laptop computer; PDA; fuel cell; semiconductor device; rice cooker; washing machine; laundry dryer; optical semiconductor device combining optical semiconductor elements and phosphors; Is mentioned.
　更に、本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）は上記の使用方法に留まらず、用途に応じて他の方法で使用することも可能である。例えば、カーペットや温暖マット等の熱の均一化のために使用する；ＬＥＤ光源／熱源の封止剤として使用する；太陽電池セルの封止剤として使用する；太陽電池のバックシ－トとして使用する；太陽電池のバックシ－トと屋根との間に使用する；自動販売機内部の断熱層の内側に使用する；有機ＥＬ照明の筐体内部に、乾燥剤や吸湿剤と共に使用する；有機ＥＬ照明の筐体内部の熱伝導層及びその上に、乾燥剤や吸湿剤と共に使用する；有機ＥＬ照明の筐体内部の熱伝導層、放熱層、及びその上に、乾燥剤や吸湿剤と共に使用する；有機ＥＬ照明の筐体内部の熱伝導層、エポキシ系の放熱層、及びその上に、乾燥剤や吸湿剤と共に使用する；人や動物を冷やすための装置、衣類、タオル、シート等の冷却部材に対し、身体と反対の面に使用する；電子写真複写機、電子写真プリンタ等の画像成形装置に搭載する定着装置の加圧部材に使用する；電子写真複写機、電子写真プリンタ等の画像成形装置に搭載する定着装置の加圧部材そのものとして使用する；製膜装置の処理対象体を載せる熱流制御用伝熱部として使用する；放射性物質格納容器の外層と内装の間に使用する；太陽光線を吸収するソーラパネルを設置したボックス体の中に使用する；ＣＣＦＬバックライトの反射シートとアルミシャーシの間に使用する；こと等を挙げることができる。 Furthermore, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention are not limited to the above-described usage methods, and may be used in other methods depending on the application. Is also possible. For example, used for heat uniformity of carpets and warm mats, etc .; used as LED light source / heat source sealant; used as solar cell sealant; used as solar cell backsheet Used between the backsheet of the solar cell and the roof; used inside the heat insulating layer inside the vending machine; used inside the housing of the organic EL lighting with a desiccant or a hygroscopic agent; organic EL lighting Use with desiccant and hygroscopic agent on the heat conductive layer inside the housing of the LED; Use with desiccant and hygroscopic agent on the heat conductive layer and heat dissipation layer inside the housing of the organic EL lighting Used for heat conduction layer inside the housing of organic EL lighting, epoxy heat dissipation layer, and on top of it with desiccant and moisture absorbent; cooling equipment, clothing, towels, sheets, etc. for cooling humans and animals Used on the opposite side of the body to the member Used as a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer; Pressing member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as it is; used as a heat transfer part for heat flow control on which the object to be processed of the film forming apparatus is placed; used between the outer layer of the radioactive substance storage container and the interior; a box body with a solar panel that absorbs sunlight Can be used between the reflective sheet of the CCFL backlight and the aluminum chassis.
　これまでに説明した本発明の熱伝導性感圧接着剤組成物（Ｆ）、熱伝導性感圧接着性シート状成形体（Ｇ）、熱伝導性感圧接着剤組成物（Ｆ）の製造方法、及び、熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法において、熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、金属水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種であり、熱伝導性フィラー（Ｂ２）が、チタネート処理された金属水酸化物であり、熱伝導性フィラー（Ｂ３）が、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の、金属水酸化物、金属酸化物及び炭素含有導電性フィラーからなる群より選ばれる少なくとも１種であることが好ましく、熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、水酸化アルミニウム及び酸化アルミニウムからなる群より選ばれる少なくとも１種であり、熱伝導性フィラー（Ｂ２）がチタネート処理された水酸化アルミニウムであり、熱伝導性フィラー（Ｂ３）が、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）以外の、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛からなる群より選ばれる少なくとも１種であることがより好ましい。また、（メタ）アクリル樹脂組成物（Ａ）が、（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上２５質量％以下、（メタ）アクリル酸エステル単量体（α１）７４．８質量％以上９４．８質量％以下、及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）０．２質量％以上１３質量％以下を含むことが好ましい。 The heat-conductive pressure-sensitive adhesive composition (F) of the present invention described so far, the heat-conductive pressure-sensitive adhesive sheet-like molded product (G), the method for producing the heat-conductive pressure-sensitive adhesive composition (F), and In the method for producing a heat conductive pressure-sensitive adhesive sheet-like molded body (G), the heat conductive filler (B1) has a BET specific surface area of 1.0 m 2 / g or more, is not subjected to titanate treatment, and is metal hydroxide. And at least one selected from the group consisting of an oxide and a metal oxide, the thermally conductive filler (B2) is a titanate-treated metal hydroxide, and the thermally conductive filler (B3) is a thermally conductive filler. It is preferably at least one selected from the group consisting of metal hydroxides, metal oxides and carbon-containing conductive fillers other than (B1) and the heat conductive filler (B2), and the heat conductive filler (B1). But BE A specific surface area of 1.0 m 2 / g or more, not titanate processed, at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, heat conductive filler (B2) is titanate processed hydroxide It is aluminum, and the heat conductive filler (B3) is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide and expanded graphite other than the heat conductive filler (B1) and the heat conductive filler (B2). It is more preferable that Moreover, (meth) acrylic resin composition (A) is 5 to 25 mass% of (meth) acrylic acid ester polymer (A1), (meth) acrylic acid ester monomer (α1) 74.8 mass. % To 94.8% by mass and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds is preferably contained in an amount of 0.2% by mass to 13% by mass.
　以下に、実施例にて本発明をさらに詳しく説明するが、本発明は実施例に限定されるものではない。なお、ここで用いる「部」や「％」は、特に断らない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The “parts” and “%” used here are based on mass unless otherwise specified.
　＜混合組成物の粘度＞
  後に説明するようにして混合組成物を作成後、Ｂ型粘度計（東京計器株式会社製）を用いて、該混合組成物の粘度を測定した。粘度の測定方法は、上述したリン酸エステル（Ｃ）の粘度の測定方法と同様である。その結果を表２および表３に示した。混合組成物の粘度が高すぎると、熱伝導性感圧接着性シート状成形体を作製することが困難になる。 <Viscosity of mixed composition>
After preparing the mixed composition as described later, the viscosity of the mixed composition was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The measuring method of a viscosity is the same as the measuring method of the viscosity of phosphate ester (C) mentioned above. The results are shown in Tables 2 and 3. When the viscosity of the mixed composition is too high, it becomes difficult to produce a heat conductive pressure-sensitive adhesive sheet-like molded body.
　＜外観クレータ＞
  後に説明するようにして熱伝導性感圧接着性シート状成形体を作製後、該熱伝導性感圧接着性シート状成形体の外観を目視で観察した。その結果を表２および表３に示した。表２において、クレータを確認できなかった場合を「○」とし、クレータが確認された場合を「×」とした。 <Appearance crater>
After producing a heat conductive pressure-sensitive adhesive sheet-like molded article as described later, the appearance of the heat conductive pressure-sensitive adhesive sheet-like molded article was visually observed. The results are shown in Tables 2 and 3. In Table 2, the case where the crater was not confirmed was set as “◯”, and the case where the crater was confirmed was set as “x”.
　＜ブリード量＞
  後に説明するようにして厚さ１ｍｍの熱伝導性感圧接着性シート状成形体を作製後、該熱伝導性感圧接着性シート状成形体を３０ｍｍ×３０ｍｍの大きさに裁断し、油とり紙で挟持し、熱伝導性感圧接着性シート状成形体が０．５ｍｍの厚さになるまで圧縮し、１０秒間、静置した。その後、油とり紙の位置を変えて上記圧縮及び静置を繰り返した（合計５回）。その後、油とり紙の重量を測定し、熱伝導性感圧接着性シート状成形体を挟持する前の油とり紙の重量との差を、ブリード量とした。その結果を表２および表３に示した。ブリード量が少ないほど、液状成分の流出が抑制されているといえる。なお、上記外観クレータの評価でクレータが確認されたものについては、ブリード量の評価を行っていない。 <Bleed amount>
As described later, a heat conductive pressure-sensitive adhesive sheet-shaped molded body having a thickness of 1 mm was prepared, and then the heat conductive pressure-sensitive adhesive sheet-shaped molded body was cut into a size of 30 mm × 30 mm, and then oil-repellent paper was used. The sheet was sandwiched and compressed until the heat-conductive pressure-sensitive adhesive sheet-like molded product had a thickness of 0.5 mm, and was allowed to stand for 10 seconds. Thereafter, the position of the oil collecting paper was changed, and the above compression and standing were repeated (total 5 times). Thereafter, the weight of the oil collecting paper was measured, and the difference from the weight of the oil collecting paper before sandwiching the heat conductive pressure-sensitive adhesive sheet-like molded product was taken as the bleed amount. The results are shown in Tables 2 and 3. It can be said that the smaller the bleed amount, the more the liquid component is prevented from flowing out. In addition, about the thing by which the crater was confirmed by the evaluation of the said external crater, the bleed amount is not evaluated.
　＜難燃性＞
  後に説明するようにして厚さ１ｍｍの熱伝導性感圧接着性シート状成形体を作製後、これを幅１０ｍｍ×長さ１５０ｍｍの短冊状に裁断した試験片を５本用意した。ブンゼンバーナーの空気およびガスの流量を調整して高さ２０ｍｍ程度の青色炎をつくり、垂直に支持した試験片の下端にバーナーの炎をあてて（炎と約１０ｍｍ交わるように）１０秒間保った後、試験片とバーナー炎を離した。その後、試験片の炎が消えれば直ちにバーナー炎を試験片にあて、更に１０秒間保持した後、試験片とバーナー炎を離した。１回目と２回目の接炎終了後の有炎及び無炎燃焼持続時間や燃焼滴下物（ドリップ）の有無を評価し、ＵＬ－９４（難燃性規格）の判定を行った。すなわち、１回目と２回目の接炎終了後の有炎燃焼持続時間、２回目の接炎終了後の有炎燃焼持続時間及び無炎燃焼持続時間の合計、５本の試験片の有炎及び無炎燃焼時間の合計、並びに燃焼滴下物（ドリップ）の有無で判定した。１回目、２回目ともに１０秒以内に有炎燃焼を終え、２回目の有炎燃焼持続時間と無炎燃焼時間の合計が３０秒以内であって、更に５本の試験片の有炎及び無炎燃焼時間の合計が５０秒以内であり、燃焼落下物がないものをＶ－０とした。その結果を表２に示した。この評価によってＶ－０の条件を満たしていれば、難燃性に優れていると言える。なお、比較例については上記の他の評価において劣っていたため、難燃性の評価は行っていない。 <Flame retardance>
As described later, after preparing a heat conductive pressure-sensitive adhesive sheet-like molded body having a thickness of 1 mm, five test pieces were prepared by cutting the sheet into strips having a width of 10 mm and a length of 150 mm. A Bunsen burner air and gas flow rate was adjusted to produce a blue flame of about 20 mm in height, and a burner flame was applied to the lower end of a vertically supported specimen (so that it crossed the flame about 10 mm) and held for 10 seconds. After that, the test piece and the burner flame were released. Thereafter, as soon as the flame of the test piece disappeared, the burner flame was applied to the test piece and held for another 10 seconds, and then the test piece and the burner flame were separated. The flame- and flame-free combustion durations after the first and second flame contact and the presence / absence of combustion drops (drip) were evaluated, and UL-94 (flame retardant standard) was determined. That is, the flaming combustion duration after the end of the first and second flame contact, the total of the flammable combustion duration and the flameless combustion duration after the end of the second flame contact, The determination was made based on the total flame-free combustion time and the presence or absence of combustion drops (drip). In both the first and second times, the flammable combustion was completed within 10 seconds, and the total of the second flammable combustion duration and the flameless combustion time was within 30 seconds. The total flame burning time was within 50 seconds, and there was no burning fallen thing as V-0. The results are shown in Table 2. If this evaluation satisfies the V-0 condition, it can be said that the flame retardancy is excellent. In addition, about the comparative example, since it was inferior in said other evaluation, flame retardance evaluation was not performed.
　＜熱伝導性感圧接着性シート状成形体の作製＞
  （実施例１）
  反応器に、アクリル酸２－エチルヘキシル９４％とアクリル酸６％とからなる単量体混合物１００部、２，２’－アゾビスイソブチロニトリル０．０３部及び酢酸エチル７００部を入れて均一に溶解し、窒素置換後、８０℃で６時間重合反応を行った。重合転化率は９７％であった。得られた重合体を減圧乾燥して酢酸エチルを蒸発させ、粘性のある固体状の（メタ）アクリル酸エステル重合体（Ａ１－１）を得た。（メタ）アクリル酸エステル重合体（Ａ１－１）の重量平均分子量（Ｍｗ）は２７０，０００、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）は３．１であった。重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、テトラヒドロフランを溶離液とするゲルパーミエーションクロマトグラフィーにより、標準ポリスチレン換算で求めた。 <Preparation of heat conductive pressure-sensitive adhesive sheet-like molded body>
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 parts 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 (A1-1). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) 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 the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
　次に、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート及びペンタエリスリトールジアクリレートを６０：３５：５の割合で混合した多官能性単量体（ライトアクリレートＰＥ－３Ａ、共栄社化学株式会社製）０．８部と、ペンタエリスリトールテトラアクリレートを主成分としてペンタエリスリトールテトラアクリレート及びペンタエリスリトールジアクリレートを含む多官能性単量体（ライトアクリレートＰＥ－４Ａ、共栄社化学株式会社製）０．２部と、アクリル酸２－エチルヘキシル（２ＥＨＡ）８４部と、有機過酸化物熱重合開始剤（１，６－ビス（ｔ－ブチルペルオキシカルボニルオキシ）ヘキサン（１分間半減期温度は１５０℃である。））１．０部と、を電子天秤で計量し、これらを上記（メタ）アクリル酸エステル重合体（Ａ１－１）１５部と混合した。混合には、恒温槽（ビスコメイト １５０ＩＩＩ、東機産業株式会社製）及びホバートミキサー（ＡＣＭ－５ＬＶＴ型、株式会社小平製作所製、容量：５Ｌ）を用いた。ホバート容器の温調は４０℃に設定し、回転数目盛を３にして１０分間攪拌した。この工程を第１混合工程という。 Next, a polyfunctional monomer (light acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) 0.8 mixed with pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate in a ratio of 60: 35: 5. Part, 0.2 part of a polyfunctional monomer (light acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.) containing pentaerythritol tetraacrylate as a main component and containing pentaerythritol tetraacrylate and pentaerythritol diacrylate, and acrylic acid 2 -84 parts of ethylhexyl (2EHA) and 1.0 part of organic peroxide thermal polymerization initiator (1,6-bis (t-butylperoxycarbonyloxy) hexane (1 minute half-life temperature is 150 ° C)) And weigh them with an electronic balance. (Meth) were mixed with an acrylic acid ester polymer (A1-1) 15 parts. For the mixing, a thermostatic bath (Viscomate 150III, manufactured by Toki Sangyo Co., Ltd.) and a Hobart mixer (ACM-5LVT type, manufactured by Kodaira Seisakusho Co., Ltd., capacity: 5 L) were used. The temperature control of the Hobart container was set to 40 ° C., the rotation speed scale was set to 3, and stirring was performed for 10 minutes. This process is referred to as a first mixing process.
　次に、リン酸エステル（レオフォス６５、味の素ファインテクノ株式会社製、化合物名：リン酸トリアリールイソプロピル化物）８０部と、チタネート処理されていない微細アルミナ（昭和電工株式会社製、商品名「ＡＬ－４７－Ｈ」、平均粒径：２μｍ、ＢＥＴ比表面積：１．８ｍ２／ｇ）３００部と、チタネート処理された水酸化アルミニウム（日本軽金属株式会社製、商品名「Ｂ３０３Ｔ」、平均粒径：１５μｍ）３００部と、チタネート処理されていない水酸化アルミニウム（日本軽金属株式会社製、商品名「ＢＦ０８３」、平均粒径：８μｍ、ＢＥＴ比表面積：０．８ｍ２／ｇ）１５０部及びチタネート処理されていないアルミナ（電気化学工業株式会社製、商品名「ＤＡＭ－７０」、平均粒径：７０μｍ、ＢＥＴ比表面積：０．１ｍ２／ｇ）２５０部と、を計量して上記ホバート容器に投入し、ホバート容器の温調を４０℃に設定し、回転数目盛を５にして１０分間攪拌した。この工程を第２混合工程という。 Next, 80 parts of phosphoric acid ester (Reophos 65, manufactured by Ajinomoto Fine-Techno Co., Ltd., compound name: triaryl isopropylated product) and fine alumina not treated with titanate (manufactured by Showa Denko KK, trade name “AL- 47-H ”, average particle size: 2 μm, BET specific surface area: 1.8 m 2 / g) and titanate-treated aluminum hydroxide (trade name“ B303T ”manufactured by Nippon Light Metal Co., Ltd.), average particle size: 15 parts by weight, 300 parts by weight, aluminum hydroxide not subjected to titanate treatment (trade name “BF083” manufactured by Nippon Light Metal Co., Ltd., average particle diameter: 8 μm, BET specific surface area: 0.8 m 2 / g) and titanate-treated Alumina (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DAM-70”, average particle size: 70 μm, BET specific surface area: 0.0. m 2 / g) was weighed and 250 parts, was charged to the Hobart container, to set the temperature control of the Hobart vessel 40 ° C., and stirred for 10 minutes with a rotational speed scale to 5. This process is referred to as a second mixing process.
　次に、上記第１及び第２混合工程を経て得た混合組成物を、厚さ７５μｍの離型ＰＥＴフィルム上に垂らし、当該混合組成物上にさらに、厚さ７５μｍの他の離型ＰＥＴフィルムを被せた。混合組成物が離型ＰＥＴフィルムに挟持されたこの積層体を、両者の間隔を１．１５ｍｍにしたロールの間を通し、シート状に成形した。その後、当該積層体をオーブンに投入し、１５０℃で１５分間加熱した。この加熱工程によって、（メタ）アクリル酸エステル単量体及び多官能性単量体を重合反応させ、またほぼ同時に、（メタ）アクリル酸エステル重合体（Ａ１－１）及び（メタ）アクリル酸エステル単量体の重合体を架橋反応させ、熱伝導性感圧接着性シート状成形体（以下、単に「シート」と表記する。）（Ｇ１）を得た。なお、シート（Ｇ１）中の残存単量体量から（メタ）アクリル酸エステル単量体の重合転化率を計算したところ、９９．９％であった。このシート（Ｇ１）の評価結果を表２に示した。 Next, the mixed composition obtained through the first and second mixing steps is hung on a release PET film having a thickness of 75 μm, and another release PET film having a thickness of 75 μm is further dropped on the mixed composition. Covered. This laminate in which the mixed composition was sandwiched between release PET films was passed through a roll having a distance of 1.15 mm between the two, and formed into a sheet shape. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes. By this heating step, the (meth) acrylic acid ester monomer and the polyfunctional monomer are polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester The monomer polymer was subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet | seat (G1). The evaluation results of this sheet (G1) are shown in Table 2.
　（実施例２～７、及び比較例１～６）
  第２混合工程における各物質の配合を表２および表３に示したように変更した以外は実施例１と同様にして、実施例２～７に係るシート（Ｇ２～Ｇ７）、及び比較例１～６に係るシート（ＧＣ１～ＧＣ６）を作製した。これらのシートの評価結果を表２および表３に示した。実施例２～７、及び比較例１～６で用いたフィラーの詳細は下記の通りである。なお、膨張化黒鉛を用いた実施例６および７では、膨張化黒鉛以外のフィラーを第２混合工程で混合し、その後、膨張化黒鉛を混合した。膨張化黒鉛を混合する際には、上記ホバート容器の温調を４０℃に設定し、回転数目盛を３にして１０分間、－０．１ＭＰａＧで真空脱泡しながら攪拌した。
・チタネート処理されていない水酸化アルミニウム（Ｂ１０３）
  日本軽金属株式会社製、商品名「Ｂ１０３」、平均粒径：８μｍ、ＢＥＴ比表面積：３ｍ２／ｇ
・チタネート処理された水酸化アルミニウム（Ｂ１０３Ｔ）
  日本軽金属株式会社製、商品名「Ｂ１０３Ｔ」、平均粒径：８μｍ
・チタネート処理されていない水酸化アルミニウム（Ｂ３０３）
  日本軽金属株式会社製、商品名「Ｂ３０３」、平均粒径：３０μｍ
・チタネート処理されていない膨張化黒鉛（ＥＣ５００）
  伊藤黒鉛工業株式会社製、商品名「ＥＣ５００」、平均粒径：３０μｍ、ＢＥＴ比表面積：０．２ｍ２／ｇ (Examples 2 to 7 and Comparative Examples 1 to 6)
The sheets (G2 to G7) according to Examples 2 to 7 and Comparative Example 1 were the same as Example 1, except that the composition of each substance in the second mixing step was changed as shown in Tables 2 and 3. Sheets 6 to 6 (GC1 to GC6) were produced. The evaluation results of these sheets are shown in Tables 2 and 3. Details of the fillers used in Examples 2 to 7 and Comparative Examples 1 to 6 are as follows. In Examples 6 and 7 using expanded graphite, fillers other than expanded graphite were mixed in the second mixing step, and then expanded graphite was mixed. When the expanded graphite was mixed, the temperature control of the Hobart container was set to 40 ° C., the rotation speed scale was set to 3, and stirring was performed for 10 minutes while vacuum degassing at −0.1 MPaG.
· Aluminum hydroxide not treated with titanate (B103)
Nippon Light Metal Co., Ltd., trade name “B103”, average particle size: 8 μm, BET specific surface area: 3 m 2 / g
・ Titanate-treated aluminum hydroxide (B103T)
Nippon Light Metal Co., Ltd., trade name “B103T”, average particle size: 8 μm
-Aluminum hydroxide not treated with titanate (B303)
Nippon Light Metal Co., Ltd., trade name “B303”, average particle size: 30 μm
・ Expanded graphite not treated with titanate (EC500)
Product name “EC500” manufactured by Ito Graphite Industries Co., Ltd., average particle size: 30 μm, BET specific surface area: 0.2 m 2 / g
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に示したように、実施例にかかるシート（Ｇ１～Ｇ７）はいずれも混合組成物の粘度が適度で成形が容易であり、難燃性に優れており、ブリードが抑制されていた。一方、表３に示したように、比較例１にかかるシート（ＧＣ１）は、チタネート処理された熱伝導性フィラー（Ｂ２）の添加量が不十分であり、ブリードを十分に抑制しきれなかった。また、比較例２にかかるシート（ＧＣ２）では、チタネート処理された熱伝導性フィラー（Ｂ２）に代えて、チタネート処理されていない熱伝導性フィラー（Ｂ３）の添加量を増やしたことによって混合組成物の粘度が過剰に上昇し、成形性が悪かった。また、比較例３にかかるシート（ＧＣ３）では、ＢＥＴ比表面積が大きなチタネート処理されていない熱伝導性フィラー（Ｂ１）を添加しておらず、ブリードを抑制できなかった。また、比較例４にかかるシート（ＧＣ４）では、ＢＥＴ比表面積が大きなチタネート処理されていない熱伝導性フィラー（Ｂ１）の添加量が多すぎたため、混合組成物の粘度が過剰に上昇し、成形性が悪かった。一方、比較例５にかかるシート（ＧＣ５）では、ＢＥＴ比表面積が大きなチタネート処理されていない熱伝導性フィラー（Ｂ１）の添加量が少なすぎたため、ブリードを抑制できなかった。また、比較例６にかかるシート（ＧＣ６）では、チタネート処理された熱伝導性フィラー（Ｂ２）の添加量が多すぎたため、混合組成物の粘度が過剰に上昇し、成形性が悪かった。 As shown in Table 2, in all the sheets (G1 to G7) according to the examples, the viscosity of the mixed composition was appropriate, the molding was easy, the flame retardancy was excellent, and bleeding was suppressed. On the other hand, as shown in Table 3, in the sheet (GC1) according to Comparative Example 1, the amount of the titanate-treated thermally conductive filler (B2) was insufficient, and the bleed could not be sufficiently suppressed. . Moreover, in the sheet | seat (GC2) concerning the comparative example 2, it replaces with the heat conductive filler (B2) by which the titanate process was carried out, and was mixed composition by increasing the addition amount of the heat conductive filler (B3) which has not been a titanate process. The viscosity of the product increased excessively and the moldability was poor. Moreover, in the sheet | seat (GC3) concerning the comparative example 3, the heat conductive filler (B1) with which BET specific surface area with a large BET specific surface area was not added was not added, but a bleed | breed could not be suppressed. In addition, in the sheet (GC4) according to Comparative Example 4, the addition amount of the heat conductive filler (B1) not subjected to the titanate treatment having a large BET specific surface area was excessive, so that the viscosity of the mixed composition was excessively increased and molded. The nature was bad. On the other hand, in the sheet (GC5) according to Comparative Example 5, the amount of the thermally conductive filler (B1) not subjected to the titanate treatment having a large BET specific surface area was too small, so that bleeding could not be suppressed. Moreover, in the sheet | seat (GC6) concerning the comparative example 6, since there was too much addition amount of the heat conductive filler (B2) by which the titanate process was carried out, the viscosity of the mixed composition increased excessively and the moldability was bad.

Claims (17)

  1. 　（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）、及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、
    　チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、
    　前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、
    　リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、
    を含む混合組成物中において、前記（メタ）アクリル酸エステル単量体（α１）及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、前記（メタ）アクリル酸エステル重合体（Ａ１）及び／又は前記（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とが行われてなる、熱伝導性感圧接着剤組成物（Ｆ）。     A (meth) acrylic resin comprising a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds 100 parts by mass of the composition (A),
    A BET specific surface area of 1.0 m 2 / g or more and a heat conductive filler (B1) not subjected to titanate treatment is 200 parts by mass or more and 450 parts by mass or less,
    120 to 500 parts by mass of the titanate-treated thermally conductive filler (B2),
    The thermal conductive filler (B3) other than the thermal conductive filler (B1) and the thermal conductive filler (B2) is 200 parts by mass or more and 600 parts by mass or less,
    40 mass parts or more and 120 mass parts or less of phosphate ester (C),
    In a mixed composition containing the (meth) acrylic acid ester monomer (α1) and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and the (meth) acrylic Thermally conductive pressure-sensitive adhesive composition (A) comprising a crosslinking reaction of a polymer containing a structural unit derived from the acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1). F).
  2. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、金属水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）が、チタネート処理された金属水酸化物であり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、金属水酸化物、金属酸化物及び炭素含有導電性フィラーからなる群より選ばれる少なくとも１種である、
    請求項１に記載の熱伝導性感圧接着剤組成物（Ｆ）。     The thermally conductive filler (B1) is at least one selected from the group consisting of metal hydroxides and metal oxides having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is a titanate-treated metal hydroxide,
    The thermally conductive filler (B3) is selected from the group consisting of metal hydroxides, metal oxides, and carbon-containing conductive fillers other than the thermally conductive filler (B1) and the thermally conductive filler (B2). At least one,
    The heat conductive pressure-sensitive-adhesive composition (F) of Claim 1.
  3. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、水酸化アルミニウム及び酸化アルミニウムからなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）がチタネート処理された水酸化アルミニウムであり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛からなる群より選ばれる少なくとも１種である、
    請求項１又は２に記載の熱伝導性感圧接着剤組成物（Ｆ）。     The thermally conductive filler (B1) is at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is titanate-treated aluminum hydroxide,
    The thermally conductive filler (B3) is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide and expanded graphite other than the thermally conductive filler (B1) and the thermally conductive filler (B2). is there,
    The heat conductive pressure-sensitive adhesive composition (F) according to claim 1 or 2.
  4. 　前記（メタ）アクリル樹脂組成物（Ａ）が、前記（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上２５質量％以下、前記（メタ）アクリル酸エステル単量体（α１）７４．８質量％以上９４．８質量％以下、及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）０．２質量％以上１３質量％以下を含む、
    請求項１乃至３のいずれか１項に記載の熱伝導性感圧接着剤組成物（Ｆ）。     The (meth) acrylic resin composition (A) is 5% by mass to 25% by mass of the (meth) acrylic acid ester polymer (A1), and the (meth) acrylic acid ester monomer (α1) 74.8. Including 0.2% by mass or more and 13% by mass or less of polyfunctional monomer (D) having a plurality of the polymerizable unsaturated bonds, and not less than 9% by mass and not more than 94.8% by mass,
    The heat conductive pressure-sensitive adhesive composition (F) according to any one of claims 1 to 3.
  5. 　（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）、及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、
    　チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、
    　前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、
    　リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、
    を含む混合組成物をシート状に成形した後、又は前記混合組成物をシート状に成形しながら、前記（メタ）アクリル酸エステル単量体（α１）及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、前記（メタ）アクリル酸エステル重合体（Ａ１）及び／又は前記（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とが行われてなる、熱伝導性感圧接着性シート状成形体（Ｇ）。     A (meth) acrylic resin comprising a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds 100 parts by mass of the composition (A),
    A BET specific surface area of 1.0 m 2 / g or more and a heat conductive filler (B1) not subjected to titanate treatment is 200 parts by mass or more and 450 parts by mass or less,
    120 to 500 parts by mass of the titanate-treated thermally conductive filler (B2),
    The thermal conductive filler (B3) other than the thermal conductive filler (B1) and the thermal conductive filler (B2) is 200 parts by mass or more and 600 parts by mass or less,
    40 mass parts or more and 120 mass parts or less of phosphate ester (C),
    A plurality of (meth) acrylic acid ester monomers (α1) and a plurality of the polymerizable unsaturated bonds after forming the mixed composition containing a sheet into a sheet or while forming the mixed composition into a sheet Polymerization reaction of functional monomer (D) and polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) A heat conductive pressure-sensitive adhesive sheet-like molded body (G) obtained by performing a crosslinking reaction.
  6. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、金属水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）が、チタネート処理された金属水酸化物であり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、金属水酸化物、金属酸化物及び炭素含有導電性フィラーからなる群より選ばれる少なくとも１種である、
    請求項５に記載の熱伝導性感圧接着性シート状成形体（Ｇ）。     The thermally conductive filler (B1) is at least one selected from the group consisting of metal hydroxides and metal oxides having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is a titanate-treated metal hydroxide,
    The thermally conductive filler (B3) is selected from the group consisting of metal hydroxides, metal oxides, and carbon-containing conductive fillers other than the thermally conductive filler (B1) and the thermally conductive filler (B2). At least one,
    The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 5.
  7. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、水酸化アルミニウム及び酸化アルミニウムからなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）がチタネート処理された水酸化アルミニウムであり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛からなる群より選ばれる少なくとも１種である、
    請求項５又は６に記載の熱伝導性感圧接着性シート状成形体（Ｇ）。     The thermally conductive filler (B1) is at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is titanate-treated aluminum hydroxide,
    The thermally conductive filler (B3) is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide and expanded graphite other than the thermally conductive filler (B1) and the thermally conductive filler (B2). is there,
    The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 5 or 6.
  8. 　前記（メタ）アクリル樹脂組成物（Ａ）が、前記（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上２５質量％以下、前記（メタ）アクリル酸エステル単量体（α１）７４．８質量％以上９４．８質量％以下、及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）０．２質量％以上１３質量％以下を含む、
    請求項５乃至７のいずれか１項に記載の熱伝導性感圧接着性シート状成形体（Ｇ）。     The (meth) acrylic resin composition (A) is 5% by mass to 25% by mass of the (meth) acrylic acid ester polymer (A1), and the (meth) acrylic acid ester monomer (α1) 74.8. Including 0.2% by mass or more and 13% by mass or less of polyfunctional monomer (D) having a plurality of the polymerizable unsaturated bonds, and not less than 9% by mass and not more than 94.8% by mass,
    The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of any one of Claims 5 thru | or 7.
  9. 　（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）、及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、
    　チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、
    　前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、
    　リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、
    を含む混合組成物を作製する工程、並びに、
    　前記混合組成物中において、前記（メタ）アクリル酸エステル単量体（α１）及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、前記（メタ）アクリル酸エステル重合体（Ａ１）及び／又は前記（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを行う工程、
    を含む、熱伝導性感圧接着剤組成物（Ｆ）の製造方法。     A (meth) acrylic resin comprising a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds 100 parts by mass of the composition (A),
    A BET specific surface area of 1.0 m 2 / g or more and a heat conductive filler (B1) not subjected to titanate treatment is 200 parts by mass or more and 450 parts by mass or less,
    120 to 500 parts by mass of the titanate-treated thermally conductive filler (B2),
    The thermal conductive filler (B3) other than the thermal conductive filler (B1) and the thermal conductive filler (B2) is 200 parts by mass or more and 600 parts by mass or less,
    40 mass parts or more and 120 mass parts or less of phosphate ester (C),
    Producing a mixed composition comprising:
    In the mixed composition, a polymerization reaction of the (meth) acrylic acid ester monomer (α1) and a polyfunctional monomer (D) having a plurality of the polymerizable unsaturated bonds, and the (meth) acrylic acid A step of performing a crosslinking reaction of the ester polymer (A1) and / or a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1),
    The manufacturing method of a heat conductive pressure sensitive adhesive composition (F) containing this.
  10. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、金属水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）が、チタネート処理された金属水酸化物であり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、金属水酸化物、金属酸化物及び炭素含有導電性フィラーからなる群より選ばれる少なくとも１種である、
    請求項９に記載の熱伝導性感圧接着剤組成物（Ｆ）の製造方法。     The thermally conductive filler (B1) is at least one selected from the group consisting of metal hydroxides and metal oxides having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is a titanate-treated metal hydroxide,
    The thermally conductive filler (B3) is selected from the group consisting of metal hydroxides, metal oxides, and carbon-containing conductive fillers other than the thermally conductive filler (B1) and the thermally conductive filler (B2). At least one,
    The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of Claim 9.
  11. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、水酸化アルミニウム及び酸化アルミニウムからなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）がチタネート処理された水酸化アルミニウムであり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛からなる群より選ばれる少なくとも１種である、
    請求項９又は１０に記載の熱伝導性感圧接着剤組成物（Ｆ）の製造方法。     The thermally conductive filler (B1) is at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is titanate-treated aluminum hydroxide,
    The thermally conductive filler (B3) is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide and expanded graphite other than the thermally conductive filler (B1) and the thermally conductive filler (B2). is there,
    The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of Claim 9 or 10.
  12. 　前記（メタ）アクリル樹脂組成物（Ａ）が、前記（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上２５質量％以下、前記（メタ）アクリル酸エステル単量体（α１）７４．８質量％以上９４．８質量％以下、及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）０．２質量％以上１３質量％以下を含む、
    請求項９乃至１１のいずれか１項に記載の熱伝導性感圧接着剤組成物（Ｆ）の製造方法。     The (meth) acrylic resin composition (A) is 5% by mass to 25% by mass of the (meth) acrylic acid ester polymer (A1), and the (meth) acrylic acid ester monomer (α1) 74.8. Including 0.2% by mass or more and 13% by mass or less of polyfunctional monomer (D) having a plurality of the polymerizable unsaturated bonds, and not less than 9% by mass and not more than 94.8% by mass,
    The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of any one of Claims 9 thru | or 11.
  13. 　（メタ）アクリル酸エステル重合体（Ａ１）、（メタ）アクリル酸エステル単量体（α１）、及び重合性不飽和結合を複数有する多官能性単量体（Ｄ）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない熱伝導性フィラー（Ｂ１）を２００質量部以上４５０質量部以下と、
    　チタネート処理された熱伝導性フィラー（Ｂ２）を１２０質量部以上５００質量部以下と、
    　前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の熱伝導性フィラー（Ｂ３）を２００質量部以上６００質量部以下と、
    　リン酸エステル（Ｃ）を４０質量部以上１２０質量部以下と、
    を含む混合組成物を作製する工程、並びに、
    　前記混合組成物をシート状に成形した後、又は、前記混合組成物をシート状に成形しながら、前記（メタ）アクリル酸エステル単量体（α１）及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）の重合反応と、前記（メタ）アクリル酸エステル重合体（Ａ１）及び／又は前記（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体の架橋反応とを行う工程、
    を含む、熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法。     A (meth) acrylic resin comprising a (meth) acrylic acid ester polymer (A1), a (meth) acrylic acid ester monomer (α1), and a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds 100 parts by mass of the composition (A),
    A BET specific surface area of 1.0 m 2 / g or more and a heat conductive filler (B1) not subjected to titanate treatment is 200 parts by mass or more and 450 parts by mass or less,
    120 to 500 parts by mass of the titanate-treated thermally conductive filler (B2),
    The thermal conductive filler (B3) other than the thermal conductive filler (B1) and the thermal conductive filler (B2) is 200 parts by mass or more and 600 parts by mass or less,
    40 mass parts or more and 120 mass parts or less of phosphate ester (C),
    Producing a mixed composition comprising:
    A plurality of the (meth) acrylic acid ester monomer (α1) and the polymerizable unsaturated bond are formed after the mixed composition is formed into a sheet or while the mixed composition is formed into a sheet. Polymerization reaction of functional monomer (D) and polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) A step of performing a crosslinking reaction,
    The manufacturing method of a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) including this.
  14. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、金属水酸化物及び金属酸化物からなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）が、チタネート処理された金属水酸化物であり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、金属水酸化物、金属酸化物及び炭素含有導電性フィラーからなる群より選ばれる少なくとも１種である、
    請求項１３に記載の熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法。     The thermally conductive filler (B1) is at least one selected from the group consisting of metal hydroxides and metal oxides having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is a titanate-treated metal hydroxide,
    The thermally conductive filler (B3) is selected from the group consisting of metal hydroxides, metal oxides, and carbon-containing conductive fillers other than the thermally conductive filler (B1) and the thermally conductive filler (B2). At least one,
    The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 13.
  15. 　前記熱伝導性フィラー（Ｂ１）が、ＢＥＴ比表面積が１．０ｍ２／ｇ以上の、チタネート処理されていない、水酸化アルミニウム及び酸化アルミニウムからなる群より選ばれる少なくとも１種であり、
    　前記熱伝導性フィラー（Ｂ２）がチタネート処理された水酸化アルミニウムであり、
    　前記熱伝導性フィラー（Ｂ３）が、前記熱伝導性フィラー（Ｂ１）及び前記熱伝導性フィラー（Ｂ２）以外の、水酸化アルミニウム、酸化アルミニウム及び膨張化黒鉛からなる群より選ばれる少なくとも１種である、
    請求項１３又は１４に記載の熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法。     The thermally conductive filler (B1) is at least one selected from the group consisting of aluminum hydroxide and aluminum oxide, having a BET specific surface area of 1.0 m 2 / g or more, not treated with titanate,
    The thermally conductive filler (B2) is titanate-treated aluminum hydroxide,
    The thermally conductive filler (B3) is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide and expanded graphite other than the thermally conductive filler (B1) and the thermally conductive filler (B2). is there,
    The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 13 or 14.
  16. 　前記（メタ）アクリル樹脂組成物（Ａ）が、前記（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上２５質量％以下、前記（メタ）アクリル酸エステル単量体（α１）７４．８質量％以上９４．８質量％以下、及び前記重合性不飽和結合を複数有する多官能性単量体（Ｄ）０．２質量％以上１３質量％以下を含む、
    請求項１３乃至１５のいずれか１項に記載の熱伝導性感圧接着性シート状成形体（Ｇ）の製造方法。     The (meth) acrylic resin composition (A) is 5% by mass to 25% by mass of the (meth) acrylic acid ester polymer (A1), and the (meth) acrylic acid ester monomer (α1) 74.8. Including 0.2% by mass or more and 13% by mass or less of polyfunctional monomer (D) having a plurality of the polymerizable unsaturated bonds, and not less than 9% by mass and not more than 94.8% by mass,
    The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of any one of Claim 13 thru | or 15.
  17. 　放熱体及び該放熱体に貼合された請求項１乃至４のいずれか１項に記載の熱伝導性感圧接着剤組成物（Ｆ）、又は、放熱体及び該放熱体に貼合された請求項５乃至８のいずれか１項に記載の熱伝導性感圧接着性シート状成形体（Ｇ）、を備えた電子機器。 The heat conductive pressure-sensitive-adhesive composition (F) of any one of Claims 1 thru | or 4 bonded by the heat radiator and this heat radiator, or the claim bonded by the heat radiator and this heat radiator. Item 9. An electronic apparatus comprising the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) according to any one of Items 5 to 8.
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