WO2013183389A1 - Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded body, method for producing thermally conductive pressure-sensitive adhesive composition, method for producing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic device - Google Patents

Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded body, method for producing thermally conductive pressure-sensitive adhesive composition, method for producing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic device Download PDF

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Publication number
WO2013183389A1
WO2013183389A1 PCT/JP2013/062625 JP2013062625W WO2013183389A1 WO 2013183389 A1 WO2013183389 A1 WO 2013183389A1 JP 2013062625 W JP2013062625 W JP 2013062625W WO 2013183389 A1 WO2013183389 A1 WO 2013183389A1
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meth
less
heat conductive
acid ester
mass
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PCT/JP2013/062625
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French (fr)
Japanese (ja)
Inventor
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 JP2014519886A priority Critical patent/JPWO2013183389A1/en
Priority to CN201380024987.4A priority patent/CN104321400A/en
Priority to KR1020147030510A priority patent/KR20150016496A/en
Publication of WO2013183389A1 publication Critical patent/WO2013183389A1/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
    • 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
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • H01L23/42—Fillings or auxiliary members in containers or encapsulations selected or arranged to facilitate heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C09J133/04—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
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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 above-mentioned heat conductive pressure-sensitive adhesive composition and heat conductive pressure-sensitive adhesive sheet-like molded body are required to be flexible so as to be in close contact with the heat generator and the heat radiator in order to transmit heat from the heat generator to the heat radiator.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded article having excellent flexibility for example, there are a flame-retardant heat dissipation sheet disclosed in Patent Document 1 and a heat conductive sheet disclosed in Patent Document 2.
  • heat is generated by improving flexibility. It is conceivable to improve the adhesion between the body and the radiator. Further, in order to efficiently transfer heat from the heating element to the heat radiating body using the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded body, for example, these are formed into thin thicknesses. It is conceivable to reduce the thermal resistance in the direction. However, the conventional heat conductive pressure-sensitive adhesive composition or heat conductive pressure-sensitive adhesive sheet-like molded product may be easily broken or may have pinholes when it is thinly formed.
  • the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded product that are difficult to break even when molded thinly, their production methods, and the thermally conductive pressure-sensitive adhesive composition.
  • an object of the present invention is to provide an electronic device including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
  • (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) The heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • a mixed composition containing at least part by mass, and at least a polymerization reaction of the (meth) acrylate monomer ( ⁇ 1), and a (meth) acrylate polymer (A1) and / or (meth) acrylate.
  • Polymer and the crosslinking reaction is taking place, including a structural unit derived from ester monomers ([alpha] 1), a thermally conductive pressure-sensitive adhesive composition (F).
  • (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 “polymerization reaction of (meth) acrylate monomer ( ⁇ 1)” means a polymerization reaction to obtain a polymer containing a structural unit derived from (meth) acrylate monomer ( ⁇ 1).
  • (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.
  • (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) The heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) The heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • a step of preparing a mixed composition comprising: less than or equal to parts by mass; and in the mixed composition, at least a polymerization reaction of the (meth) acrylate monomer ( ⁇ 1) and (meth) acrylate polymerization (A1) and / or the process of performing the crosslinking reaction of the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1), to produce a heat conductive pressure-sensitive adhesive composition (F) Is the method.
  • the 4th aspect of this invention is 100 mass parts of (meth) acrylic resin compositions (A) containing the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1).
  • the heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • a step of preparing a mixed composition comprising the mass part or less, and after forming the mixed composition into a sheet or while forming the mixed composition into a sheet, at least a (meth) acrylate ester
  • G heat conductive pressure-sensitive-adhesive sheet-like molded object
  • the heat conductive filler (B1) is a metal oxide having an average particle size of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g
  • the conductive filler (B2) is preferably a metal oxide having an average particle size of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more
  • the thermally conductive filler (B1) has an average particle size of 20 ⁇ m.
  • the (meth) acrylic resin composition (A) is not less than 5% by mass and not more than 25% by mass of the (meth) acrylic acid ester polymer (A1) and not less than 75% by mass of the (meth) acrylic acid ester monomer ( ⁇ 1). It is preferable to contain 95 mass% or less.
  • 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 heat-conductive pressure-sensitive adhesive composition and a heat-conductive pressure-sensitive adhesive sheet-shaped molded body that are difficult to break even when molded thinly, their production methods, and the heat-conductive pressure-sensitive adhesive composition Or the electronic device provided with this heat conductive pressure-sensitive-adhesive sheet-like molded object can be provided.
  • the heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition ((meth) acrylic acid ester polymer (A1)) and a (meth) acrylic acid ester monomer ( ⁇ 1) ( A) and a thermally conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g (hereinafter, simply referred to as “thermally conductive filler (B1)”).
  • thermoconductive filler (B2) having an average particle size of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more (hereinafter sometimes simply referred to as “thermal conductive filler (B2)”).
  • a polyfunctional epoxy compound (C) having a functional group of 2 or more and 10,000 or less hereinafter sometimes simply referred to as “polyfunctional epoxy compound (C)”.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is at least (meth) acryl after shape
  • 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 contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1).
  • 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) is mixed with the component of the (meth) acrylic acid ester polymer (A1) and / or. Partially join.
  • 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 75% by mass or more and 95% by mass or less. More preferably, the acrylic acid ester polymer (A1) is 10% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is 75% by mass or more and 90% by mass or less.
  • 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 components contained in the (meth) acrylic resin composition (A) will be described in more detail below.
  • 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 amount of the soot polymerization initiator used is not particularly limited, but is preferably in the range of 0.01 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the monomer.
  • polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
  • the obtained polymer is separated from the polymerization medium if necessary.
  • the separation method is not particularly limited.
  • 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 preferably in the range of 100,000 to 1,000,000, more preferably in the range of 200,000 to 900,000.
  • a weight average molecular weight (Mw) means what measured the weight average molecular weight of standard polystyrene conversion by molecular weight measurement gel permeation chromatography (GPC) (hereinafter the same).
  • GPC molecular weight measurement gel permeation chromatography
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet form are used.
  • Appropriate strength can be given to the molded body (G) to make it difficult to break.
  • the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molding are used.
  • the body (G) can have appropriate flexibility. That is, by using both in combination, appropriate strength and flexibility can be achieved.
  • the weight average molecular weight (Mw) 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.
  • a polyfunctional monomer can also be used in the (meth) acrylic resin composition (A).
  • the polyfunctional monomer that can be used in the present invention a monomer that is copolymerizable with the monomer contained in the (meth) acrylic acid ester monomer ( ⁇ 1) is used.
  • the polyfunctional monomer 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 adhesive sheet are introduced.
  • the cohesive force as a pressure-sensitive adhesive of the shaped molded body (G) can be increased.
  • a certain degree of crosslinking reaction proceeds without using a polyfunctional monomer.
  • a polyfunctional monomer may be used in order to form a desired amount of a crosslinked structure more reliably.
  • polyfunctional monomer 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, ditrimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloro Other substituted triazines, such as chill)
  • monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used.
  • pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable.
  • a polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polyfunctional monomer used is preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the (meth) acrylic resin composition (A).
  • the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) are suitable as a pressure sensitive adhesive. It becomes easy to give a strong cohesive force.
  • ⁇ 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 having an average particle size of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g.
  • the heat conductive filler with a small BET specific surface area like the heat conductive filler (B1) was used.
  • a thermally conductive filler having a small BET specific surface area it becomes easy to suppress an excessive increase in the viscosity of the mixed composition.
  • BET specific surface area of the thermally conductive filler (B1) is less than 1.0 m 2 / g, preferably not more than 0.05 m 2 / g or more 0.9m 2 / g, 0.08m 2 / g or more 0 More preferably, it is 8 m 2 / g or less.
  • Mixing which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the BET specific surface area of the heat conductive filler (B1) in the above range. Heat of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) molded from the mixed composition while suppressing the viscosity of the composition from becoming excessively high Conductivity can be improved.
  • 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.
  • the average particle size of the heat conductive filler (B1) is 20 ⁇ m or less, preferably 0.05 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average particle size exceeds the above upper limit, when a thin sheet is produced, there is a risk that irregularities due to the filler or pinholes may occur on the surface.
  • 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 heat conductive filler (B1) is not particularly limited as long as the average particle diameter and the BET specific surface area satisfy the above ranges.
  • 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 them, a metal oxide is preferable and aluminum oxide (alumina) is most preferable because it has excellent thermal conductivity and is chemically stable.
  • a heat conductive filler (B1) may be used individually by 1 type, and may use 2 or more types together.
  • 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) It is 300 to 1000 mass parts with respect to 100 mass parts, It is preferable that they are 400 to 900 mass parts, More preferably, it is 500 to 800 mass parts. Mixing that is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B1) to the upper limit or less. It becomes easy to suppress that the viscosity of a composition becomes high too much.
  • the heat conductive filler (B2) used in the present invention is a heat conductive filler having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more.
  • the viscosity of the mixed composition which is a precursor of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G) becomes high too much.
  • the BET specific surface area as in the heat conductive filler (B1) is increased. It is conceivable to use a small thermally conductive filler.
  • a filler having a large specific gravity with respect to the (meth) acrylic resin composition (A) is likely to precipitate in the mixed composition.
  • the mixed composition When air is entrained and included during preparation (mixing) of the mixed composition, it is preferable that the mixed composition is allowed to stand in order to remove the air.
  • the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet is formed while gradually discharging the mixed composition as a coating liquid.
  • a part with extremely high filler content may be formed. When this becomes a cause of trouble, it becomes difficult to continuously produce the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) from the mixed composition. was there.
  • a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet are used by using a heat conductive filler having a relatively large BET specific surface area such as the heat conductive filler (B2).
  • the viscosity of the mixed composition of the precursor of the shaped compact (G) is moderately increased. It is thought that precipitation of fillers having a large specific gravity such as the heat conductive filler (B1) can be suppressed by adding an appropriate amount of the heat conductive filler (B2) to moderately increase the viscosity of the mixed composition.
  • BET specific surface area of the thermally conductive filler (B2) is at 1.0 m 2 / g or more, is preferably from 1.0 m 2 / g or more 100m 2 / g, 1.0m 2 / g or more 10 m 2 / More preferably, it is g or less.
  • 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). It becomes easy to raise the viscosity of a composition moderately, and it becomes easy to suppress precipitation of a filler with large specific gravity with respect to (meth) acrylic resin composition (A).
  • the average particle size of the heat conductive filler (B2) is 20 ⁇ m or less, preferably 0.05 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average particle size exceeds the above upper limit, when a thin sheet is produced, there is a risk that irregularities due to the filler or pinholes may occur on the surface.
  • the heat conductive filler (B2) is not particularly limited as long as the average particle diameter and the BET specific surface area satisfy the above ranges.
  • Specific examples of the thermally conductive filler (B2) 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 them, a metal oxide is preferable and aluminum oxide (alumina) is most preferable because it has excellent thermal conductivity and is chemically stable.
  • a heat conductive filler (B2) may be used individually by 1 type, and may use 2 or more types together.
  • 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) 60 parts by mass or more and 900 parts by mass or less, preferably 70 parts by mass or more and 700 parts by mass or less, and more preferably 80 parts by mass or more and 600 parts by mass or less with respect to 100 parts by mass.
  • Mixing that is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B2) to the upper limit or less.
  • the content of the heat conductive filler (B2) is not less than the above lower limit, the viscosity of the mixed composition is appropriately increased as described above, and the specific gravity of the (meth) acrylic resin composition (A) is increased. It is believed that large fillers can be prevented from precipitating in the mixed composition.
  • the polyfunctional epoxy compound (C) is a polyfunctional epoxy compound having 2 to 10,000 functional groups.
  • the polyfunctional epoxy compound (C) can react with the organic acid group in the (meth) acrylic acid ester polymer (A1) to form a crosslinked structure.
  • the (meth) acrylate monomer ( ⁇ 1) contains a monomer having an organic acid group, it can react with the organic acid group.
  • a crosslinked structure can be formed in the polymer containing the structural unit derived from the monomer ( ⁇ 1).
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) have a certain amount. Since strength is imparted, it is considered that the strength of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be easily secured. Therefore, by using the polyfunctional epoxy compound (C), it is considered that even if the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are thinly formed, it is difficult to break. It is done.
  • the polyfunctional epoxy compound (C) that can be used in the present invention preferably has a viscosity at 25 ° C. of 600 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, and 400 mPa ⁇ s or less. Further preferred.
  • a mixed composition which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It is considered that the polyfunctional epoxy compound (C) is easily dispersed uniformly therein, and the cross-linked structure by the polyfunctional epoxy compound (C) is easily formed uniformly.
  • the viscosity of a polyfunctional epoxy compound (C) means what was measured as demonstrated below.
  • the polyfunctional epoxy compound (C) which can be used for this invention has 2 or more and 10,000 or less functional groups, and it is preferable that the number of functional groups is 2 or more and 1000 or less, and is 2 or more and 10 or less. More preferably.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) have appropriate strength. It becomes easy to prepare.
  • a tetrafunctional epoxy compound is preferable because a crosslinked structure can be effectively formed even in a small amount, and pentaerythritol tetraglycidyl ether is more preferable.
  • a polyfunctional epoxy compound (C) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polyfunctional epoxy compound (C) 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) is 100 parts by mass, 0.05 parts by mass to 4 parts by mass, preferably 0.07 parts by mass to 3 parts by mass, and 0.09 parts by mass to 2 parts by mass. Is more preferable.
  • ⁇ 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; flame retardants such as phosphates;
  • the present invention even if it is thinly formed by using a suitable amount of the polyfunctional epoxy compound (C), the heat conductive filler (B1) and the heat conductive filler (B2), it is It is possible to obtain a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) that are difficult to cut.
  • the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 1.0 mm or less. By thinly forming, the thermal resistance in the thickness direction can be lowered.
  • the upper limit of the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.5 mm.
  • the lower limit of the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.07 mm.
  • the heat conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing the substances described so far to prepare a mixed composition, and then polymerizing the (meth) acrylate monomer ( ⁇ 1). And a cross-linking 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 ( ⁇ 1).
  • the manufacturing method of the heat conductive pressure-sensitive adhesive composition (F) of the present invention includes (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1).
  • 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 (meth) acrylate polymer (A1) and / or (meth) acrylate ester It can be obtained by performing at least a crosslinking reaction of a polymer containing a structural unit derived from the body ( ⁇ 1).
  • the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1)
  • a step of producing a mixed composition comprising a (meth) acrylic resin composition (A), a thermally conductive filler (B1), a thermally conductive filler (B2), and a polyfunctional epoxy compound (C); and The polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1) and the (meth) acrylic acid ester polymer after forming the mixed composition into a sheet or while forming the mixed composition into a sheet
  • the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentione
  • 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) acrylate monomer ( ⁇ 1) 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 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 filler (B2) is preferably a metal oxide having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more, and the heat conductive filler (B1) is The aluminum oxide has an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermally conductive filler (B2) has an average particle diameter of 20 ⁇ m or less and a BET specific surface area of 1.0 m. 2 / g or more of aluminum oxide More preferably.
  • the (meth) acrylic resin composition (A) is not less than 5% by mass and not more than 25% by mass of the (meth) acrylic acid ester polymer (A1) and not less than 75% by mass of the (meth) acrylic acid ester monomer ( ⁇ 1). It is preferable to contain 95 mass% or less.
  • ⁇ Manufacturable thickness> When a mixed composition is prepared as described later, and a heat conductive pressure-sensitive adhesive sheet-like molded body is prepared using 100 ml of the mixed composition as described later, it can be manufactured without a pinhole. The thickness was examined. The results are shown in Tables 2 and 3. This measurement was performed in a range up to a sheet thickness of 150 ⁇ m (lower limit). This thickness does not include the thickness of a release PET film (a release-treated polyethylene terephthalate film; the same applies hereinafter).
  • a heat conductive pressure-sensitive adhesive sheet-like molded article having a thickness of 150 ⁇ m (not including the thickness of the release PET film) sandwiched between the release PET films was prepared. Then, it cut
  • Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.015 part 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 800,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.5.
  • 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 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 performed 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) acrylate polymer (A1-2).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-2) 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 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 is sandwiched between the release PET films is passed through a roll whose spacing is adjusted so that a heat-conductive pressure-sensitive adhesive sheet-like molded product having a desired thickness is obtained.
  • the (meth) acrylic acid ester monomer is polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester polymer (A1-2) And a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer is subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). It was. 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
  • Example 2 to 7 and Comparative Examples 1 to 6 Sheets (G2 to G7) according to Examples 2 to 7 in the same manner as in Example 1 except that the composition of each substance in the first mixing process and the second mixing process was changed as shown in Table 2 and Table 3. And sheets (GC1 to GC6) according to Comparative Examples 1 to 6 were produced.
  • the details of the polyfunctional monomer used in the first mixing step in Comparative Example 1 and the spherical alumina used in the second mixing step in Comparative Example 6 are as follows.
  • Polyfunctional monomer used in Comparative Example 1 Polyfunctional monomer (light acrylate PE-3A) in which pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate were mixed in a ratio of 60: 35: 5 Manufactured by Kyoeisha Chemical Co., Ltd.) -Spherical alumina used in Comparative Example 6 manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DAM-45”, average particle size: 45 ⁇ m, BET specific surface area: 0.2 m 2 / g

Abstract

Provided are: a thermally conductive pressure-sensitive adhesive composition which is obtained by carrying out at least a polymerization reaction of a (meth)acrylic acid ester monomer (α1) and a crosslinking reaction of a (meth)acrylic acid ester polymer (A1) and/or a polymer that has a structural unit derived from the (meth)acrylic acid ester monomer (α1) in a mixed composition that contains a predetermined amount of a (meth)acrylic resin composition (A) that contains the (meth)acrylic acid ester polymer (A1) and the (meth)acrylic acid ester monomer (α1), a predetermined amount of a thermally conductive filler (B1) that has an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m2/g, a predetermined amount of a thermally conductive filler (B2) that has an average particle diameter of 20 μm or less and a BET specific surface area of 1.0 m2/g or more, and a predetermined amount of a polyfunctional epoxy compound (C) that has from 2 to 10,000 (inclusive) functional groups, said thermally conductive pressure-sensitive adhesive composition being not easily torn even if molded into a thin body; and a thermally conductive pressure-sensitive adhesive sheet-like molded body.

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の一般的方法としては、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. As a general method for countermeasures against functional failures due to temperature rise of electronic parts and the like, a method of attaching a heat radiator such as a metal heat sink, a heat radiating plate, and a heat radiating fin to the heat generator is adopted. 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は、発熱体から放熱体へと熱を伝えるために、発熱体及び放熱体に密着できる柔軟性が求められる。柔軟性が優れた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は、例えば、特許文献１に開示された難燃性放熱シートや、特許文献２に開示された熱伝導シートがある。 The above-mentioned heat conductive pressure-sensitive adhesive composition and heat conductive pressure-sensitive adhesive sheet-like molded body are required to be flexible so as to be in close contact with the heat generator and the heat radiator in order to transmit heat from the heat generator to the heat radiator. As a technique regarding the heat conductive pressure-sensitive-adhesive sheet-like molded article having excellent flexibility, for example, there are a flame-retardant heat dissipation sheet disclosed in Patent Document 1 and a heat conductive sheet disclosed in Patent Document 2.
特開２００６－１７６６４０号公報JP 2006-176640 A 特開２０１０－１３２８５６号公報JP 2010-132856 A
　熱伝導性感圧接着剤組成物又は熱伝導性感圧接着性シート状成形体を用いて発熱体から放熱体へと熱を効率良く伝えるためには、上述したように、柔軟性を向上させて発熱体と放熱体との密着性を向上させることが考えられる。また、熱伝導性感圧接着剤組成物又は熱伝導性感圧接着性シート状成形体を用いて発熱体から放熱体へと熱を効率良く伝えるためには、例えば、これらを薄く成形して厚さ方向の熱抵抗を下げることが考えられる。しかしながら、従来の熱伝導性感圧接着剤組成物又は熱伝導性感圧接着性シート状成形体は、薄く成形すると千切れやすくなったり、ピンホールが発生したりする場合があった。 In order to efficiently transfer heat from the heating element to the heat radiating body using the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded body, as described above, heat is generated by improving flexibility. It is conceivable to improve the adhesion between the body and the radiator. Further, in order to efficiently transfer heat from the heating element to the heat radiating body using the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded body, for example, these are formed into thin thicknesses. It is conceivable to reduce the thermal resistance in the direction. However, the conventional heat conductive pressure-sensitive adhesive composition or heat conductive pressure-sensitive adhesive sheet-like molded product may be easily broken or may have pinholes when it is thinly formed.
　そこで、本発明は、薄く成形しても千切れ難い熱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 product that are difficult to break even when molded thinly, their production methods, and the thermally conductive pressure-sensitive adhesive composition. Alternatively, an object of the present invention is to provide 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）及び（メタ）アクリル酸エステル単量体（α１）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４質量部以下と、を含む混合組成物中において、少なくとも（メタ）アクリル酸エステル単量体（α１）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。 In the first aspect of the present invention, 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) The heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 μm or less, and the BET specific surface area. The polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass. In a mixed composition containing at least part by mass, and at least a polymerization reaction of the (meth) acrylate monomer (α1), and a (meth) acrylate polymer (A1) and / or (meth) acrylate. Polymer and the crosslinking reaction is taking place, including a structural unit derived from ester monomers ([alpha] 1), a thermally conductive pressure-sensitive adhesive composition (F).
　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、（メタ）アクリル酸エステル単量体（α１）の重合反応」とは、（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を得る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。 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 “polymerization reaction of (meth) acrylate monomer (α1)” means a polymerization reaction to obtain a polymer containing a structural unit derived from (meth) acrylate monomer (α1). 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.
　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）及び（メタ）アクリル酸エステル単量体（α１）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４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、少なくとも（メタ）アクリル酸エステル単量体（α１）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。 In the second aspect of the present invention, 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) The heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 μm or less, and the BET specific surface area. The polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass. And after polymerization of the mixed composition containing not more than parts by mass into a sheet or while forming the mixed composition into a sheet, polymerization reaction of at least the (meth) acrylate monomer (α1), Meta) Thermally conductive pressure-sensitive adhesive sheet-like molding comprising a cross-linking reaction of a polymer containing a structural unit derived from a lauric acid ester polymer (A1) and / or a (meth) acrylic acid ester monomer (α1) Body (G).
　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）及び（メタ）アクリル酸エステル単量体（α１）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４質量部以下と、を含む混合組成物を作製する工程、並びに、混合組成物中において、少なくとも（メタ）アクリル酸エステル単量体（α１）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。 In the third aspect of the present invention, 100 parts by mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) The heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 μm or less, and the BET specific surface area. The polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass. And a step of preparing a mixed composition comprising: less than or equal to parts by mass; and in the mixed composition, at least a polymerization reaction of the (meth) acrylate monomer (α1) and (meth) acrylate polymerization (A1) and / or the process of performing the crosslinking reaction of the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (α1), to produce a heat conductive pressure-sensitive adhesive composition (F) Is the method.
　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）及び（メタ）アクリル酸エステル単量体（α１）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４質量部以下と、を含む混合組成物を作製する工程、並びに、混合組成物をシート状に成形した後、又は、混合組成物をシート状に成形しながら、少なくとも（メタ）アクリル酸エステル単量体（α１）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 4th aspect of this invention is 100 mass parts of (meth) acrylic resin compositions (A) containing the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer (α1). The heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 μm or less, and the BET specific surface area. The polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass. And a step of preparing a mixed composition comprising the mass part or less, and after forming the mixed composition into a sheet or while forming the mixed composition into a sheet, at least a (meth) acrylate ester A step of performing a polymerization reaction of the body (α1) and 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). Is a manufacturing method of the heat conductive pressure-sensitive-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、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の金属酸化物であり、熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の金属酸化物であることが好ましく、熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の酸化アルミニウムであり、熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の酸化アルミニウム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％以下及び（メタ）アクリル酸エステル単量体（α１）７５質量％以上９５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 heat conductive filler (B1) is a metal oxide having an average particle size of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, The conductive filler (B2) is preferably a metal oxide having an average particle size of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more, and the thermally conductive filler (B1) has an average particle size of 20 μm. And an aluminum oxide having a BET specific surface area of less than 1.0 m 2 / g, a thermally conductive filler (B2) having an average particle diameter of 20 μm or less, and a BET specific surface area of 1.0 m 2 / g or more. More preferably, it is aluminum.
The (meth) acrylic resin composition (A) is not less than 5% by mass and not more than 25% by mass of the (meth) acrylic acid ester polymer (A1) and not less than 75% by mass of the (meth) acrylic acid ester monomer (α1). It is preferable to contain 95 mass% or less.
　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、薄く成形しても千切れ難い熱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 heat-conductive pressure-sensitive adhesive composition and a heat-conductive pressure-sensitive adhesive sheet-shaped molded body that are difficult to break even when molded thinly, their production methods, and the heat-conductive pressure-sensitive adhesive composition Or the electronic device provided with this heat conductive pressure-sensitive-adhesive sheet-like molded object 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）及び（メタ）アクリル酸エステル単量体（α１）を含む（メタ）アクリル樹脂組成物（Ａ）と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）（以下、単に「熱伝導性フィラー（Ｂ１）」という場合がある。）と、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）（以下、単に「熱伝導性フィラー（Ｂ２）」という場合がある。）と、官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）（以下、単に「多官能エポキシ化合物（Ｃ）」という場合がある。）と、を含む混合組成物中において、少なくとも（メタ）アクリル酸エステル単量体（α１）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ものである。 1. Thermally conductive pressure-sensitive adhesive composition (F), thermally conductive pressure-sensitive adhesive sheet-like molded body (G)
The heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition ((meth) acrylic acid ester polymer (A1)) and a (meth) acrylic acid ester monomer (α1) ( A) and a thermally conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g (hereinafter, simply referred to as “thermally conductive filler (B1)”). And a heat conductive filler (B2) having an average particle size of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more (hereinafter sometimes simply referred to as “thermal conductive filler (B2)”). And a polyfunctional epoxy compound (C) having a functional group of 2 or more and 10,000 or less (hereinafter sometimes simply referred to as “polyfunctional epoxy compound (C)”), at least (meth) acrylic acid Ester amount The polymerization reaction of the body (α1) and the crosslinking reaction of the polymer containing the structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1) are performed. It will be.
　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、少なくとも（メタ）アクリル酸エステル単量体（α１）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ものである。 Moreover, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is at least (meth) acryl after shape | molding the said mixed composition in a sheet form, or shape | molding the said mixed composition in a sheet form. Polymerization reaction of acid ester monomer (α1) and crosslinking reaction of polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) And is done.
　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）及び（メタ）アクリル酸エステル単量体（α１）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 contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (α1). 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) is mixed with the component of the (meth) acrylic acid ester polymer (A1) and / or. Partially join.
　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７５質量％以上９５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２５質量％以下、（メタ）アクリル酸エステル単量体（α１）が７５質量％以上９０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。（メタ）アクリル樹脂組成物（Ａ）に含まれる成分について、以下により詳細に説明する。 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 75% by mass or more and 95% by mass or less. More preferably, the acrylic acid ester polymer (A1) is 10% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer (α1) is 75% by mass or more and 90% by mass or less. 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. The components contained in the (meth) acrylic resin composition (A) will be described in more detail below.
　（（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。 The amount of the soot polymerization initiator used is not particularly limited, but is preferably in the range of 0.01 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the monomer.
　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、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９０万以下の範囲にあることが、より好ましい。なお、重量平均分子量（Ｍｗ）とは、分子量測定ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により標準ポリスチレン換算の重量平均分子量を測定したものを意味する（以下、同じ。）。また、（メタ）アクリル酸エステル重合体（Ａ１）として、重量平均分子量（Ｍｗ）が異なる２種の（メタ）アクリル酸エステル重合体を混合して用いることが好ましい。この場合、重量平均分子量（Ｍｗ）が比較的大きな（メタ）アクリル酸エステル重合体（Ａ１）を適量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）に適切な強度を持たせて千切れ難くすることができる。一方、重量平均分子量（Ｍｗ）が比較的小さな（メタ）アクリル酸エステル重合体（Ａ１）を適量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）に適度な柔軟性を持たせることができる。すなわち、両者を併用することによって適度な強度と柔軟性を両立させることができる。 The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is preferably in the range of 100,000 to 1,000,000, more preferably in the range of 200,000 to 900,000. In addition, a weight average molecular weight (Mw) means what measured the weight average molecular weight of standard polystyrene conversion by molecular weight measurement gel permeation chromatography (GPC) (hereinafter the same). Moreover, it is preferable to use as a (meth) acrylic acid ester polymer (A1) a mixture of two (meth) acrylic acid ester polymers having different weight average molecular weights (Mw). In this case, by using an appropriate amount of the (meth) acrylic acid ester polymer (A1) having a relatively large weight average molecular weight (Mw), the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet form are used. Appropriate strength can be given to the molded body (G) to make it difficult to break. On the other hand, by using an appropriate amount of the (meth) acrylic acid ester polymer (A1) having a relatively small weight average molecular weight (Mw), the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molding are used. The body (G) can have appropriate flexibility. That is, by using both in combination, appropriate strength and flexibility can be achieved.
　（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、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) 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）
  本発明において、（メタ）アクリル樹脂組成物（Ａ）には多官能性単量体も用いることができる。本発明に用いることができる多官能性単量体としては、（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、当該多官能性単量体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)
In the present invention, a polyfunctional monomer can also be used in the (meth) acrylic resin composition (A). As the polyfunctional monomer that can be used in the present invention, a monomer that is copolymerizable with the monomer contained in the (meth) acrylic acid ester monomer (α1) is used. The polyfunctional monomer has a plurality of polymerizable unsaturated bonds, and preferably has the unsaturated bond at the terminal. By using such a polyfunctional monomer, 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 adhesive sheet are introduced. The cohesive force as a pressure-sensitive adhesive of the shaped 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を用いてもよい。 Usually, at the time of polymerization such as radical thermal polymerization, a certain degree of crosslinking reaction proceeds without using a polyfunctional monomer. However, a polyfunctional monomer may be used in order to form a desired amount of a crosslinked structure more reliably.
　多官能性単量体としては、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 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, ditrimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloro Other substituted triazines, such as chill) -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 may be used individually by 1 type, and may use 2 or more types together.
　多官能性単量体の使用量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量％として、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。多官能性単量体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。 The amount of the polyfunctional monomer used is preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the (meth) acrylic resin composition (A). By setting the amount of the polyfunctional monomer used in the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) are suitable as a pressure sensitive adhesive. It becomes easy to give a strong cohesive force.
　＜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、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラーである。 <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 having an average particle size of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g.
　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）の熱伝導性を向上させるには、熱伝導性フィラーを添加することが考えられる。このとき、熱伝導性フィラーのＢＥＴ比表面積が大きい場合、多量に添加しようとすると、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高くなりやすい。当該混合組成物の粘度が過度に高くなると、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）を成形することが困難になる。よって、本発明では、熱伝導性フィラー（Ｂ１）のようにＢＥＴ比表面積が小さな熱伝導性フィラーを用いた。ＢＥＴ比表面積が小さな熱伝導性フィラーを用いることによって、上記混合組成物の粘度が過度に高くなることを抑制しやすくなる。 In order to improve the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), it is conceivable to add a heat conductive filler. At this time, when the BET specific surface area of the heat conductive filler is large, if a large amount is added, the precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). The viscosity of the mixed composition is likely to be excessively high. When the viscosity of the mixed composition is excessively high, 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). Therefore, in this invention, the heat conductive filler with a small BET specific surface area like the heat conductive filler (B1) was used. By using a thermally conductive filler having a small BET specific surface area, it becomes easy to suppress an excessive increase in the viscosity of the mixed composition.
　熱伝導性フィラー（Ｂ１）のＢＥＴ比表面積は１．０ｍ２／ｇ未満であり、０．０５ｍ２／ｇ以上０．９ｍ２／ｇ以下であることが好ましく、０．０８ｍ２／ｇ以上０．８ｍ２／ｇ以下であることがより好ましい。熱伝導性フィラー（Ｂ１）のＢＥＴ比表面積を上記範囲にすることによって、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）の前駆体である混合組成物の粘度が過度に高くなるのを抑制しつつ、該混合組成物から成形さ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）の熱伝導率を向上させることができる。 BET specific surface area of the thermally conductive filler (B1) is less than 1.0 m 2 / g, preferably not more than 0.05 m 2 / g or more 0.9m 2 / g, 0.08m 2 / g or more 0 More preferably, it is 8 m 2 / g or less. Mixing which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the BET specific surface area of the heat conductive filler (B1) in the above range. Heat of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) molded from the mixed composition while suppressing the viscosity of the composition from becoming excessively high Conductivity can be improved.
　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.
　また、熱伝導性フィラー（Ｂ１）の平均粒径は２０μｍ以下であり、０．０５μｍ以上１５μｍ以下であることが好ましく、０．１μｍ以上１０μｍ以下であることがより好ましい。平均粒径が上記上限を超えると、薄いシートを作製した場合、表面にフィラーによる凹凸や、ピンホールが発生する虞がある。 The average particle size of the heat conductive filler (B1) is 20 μm or less, preferably 0.05 μm or more and 15 μm or less, and more preferably 0.1 μm or more and 10 μm or less. When the average particle size exceeds the above upper limit, when a thin sheet is produced, there is a risk that irregularities due to the filler or pinholes may occur on the surface.
　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.
　熱伝導性フィラー（Ｂ１）は、平均粒径及びＢＥＴ比表面積が上記範囲を満たす熱伝導性フィラーであれば特に限定されない。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。その中でも特に、熱伝導率に優れ、かつ、化学的に安定していることから、金属酸化物が好ましく、酸化アルミニウム（アルミナ）が最も好ましい。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。 The heat conductive filler (B1) is not particularly limited as long as the average particle diameter and the BET specific surface area satisfy the above ranges. 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 them, a metal oxide is preferable and aluminum oxide (alumina) is most preferable because it has excellent thermal conductivity and is chemically stable. A heat conductive filler (B1) 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（Ｂ１）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、３００質量部以上１０００質量部以下であり、４００質量部以上９００質量部以下であることが好ましく、５００質量部以上８００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）の含有量が上記上限以下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）の前駆体である混合組成物の粘度が過度に高くなることを抑制しやすくなる。そのため、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）が低下したりする事態を防ぐことができる。一方、熱伝導性フィラー（Ｂ１）の含有量が上記下限以上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）の熱伝導性を向上させる効果を発揮しやすくなる。 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) It is 300 to 1000 mass parts with respect to 100 mass parts, It is preferable that they are 400 to 900 mass parts, More preferably, it is 500 to 800 mass parts. Mixing that is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B1) to the upper limit or less. It becomes easy to suppress that the viscosity of a composition becomes high too much. Therefore, even if it becomes difficult to shape | mold a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G), and it can shape | mold, a heat conductive pressure sensitive adhesive composition (F). In addition, it is possible to prevent a situation in which the hardness of 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 not less than the above lower limit, the heat conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It becomes easy to demonstrate the effect of improving.
　＜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、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラーである。 <Thermal conductive filler (B2)>
Next, the heat conductive filler (B2) will be described. The heat conductive filler (B2) used in the present invention is a heat conductive filler having an average particle diameter of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more.
　上記のように、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高くなることを抑制しつつ、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）の熱伝導性を向上させるには、熱伝導性フィラー（Ｂ１）のようにＢＥＴ比表面積が小さな熱伝導性フィラーを用いることが考えられる。しかしながら、混合組成物の粘度が低い場合、（メタ）アクリル樹脂組成物（Ａ）に対して比重の大きなフィラーは混合組成物中において沈殿しやすくなる。混合組成物を作成時（混合時）に空気を巻き込んで包含すると、この空気を抜くために混合組成物を静置することが好ましい。このように静置する際に上記のようにフィラーが沈殿すると、混合組成物を塗工液として徐々に排出しつつ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）を連続して作製する際に、フィラーの含有量が極度に多い部分ができることがある。これがトラブルの原因となって、混合組成物から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）を連続的に生産し続けることが困難になる場合があった。よって、本発明では、熱伝導性フィラー（Ｂ２）のようにＢＥＴ比表面積が比較的大きな熱伝導性フィラーを用いて、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）の前駆体の混合組成物の粘度を適度に高めている。熱伝導性フィラー（Ｂ２）を適量添加して混合組成物の粘度を適度に高めることによって、熱伝導性フィラー（Ｂ１）などの比重が大きなフィラーが沈殿することを抑制できると考えられる。 As mentioned above, while suppressing that the viscosity of the mixed composition which is a precursor of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G) becomes high too much. In order to improve the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), the BET specific surface area as in the heat conductive filler (B1) is increased. It is conceivable to use a small thermally conductive filler. However, when the viscosity of the mixed composition is low, a filler having a large specific gravity with respect to the (meth) acrylic resin composition (A) is likely to precipitate in the mixed composition. When air is entrained and included during preparation (mixing) of the mixed composition, it is preferable that the mixed composition is allowed to stand in order to remove the air. When the filler is precipitated as described above when allowed to stand as described above, the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet is formed while gradually discharging the mixed composition as a coating liquid. When producing a molded object (G) continuously, a part with extremely high filler content may be formed. When this becomes a cause of trouble, it becomes difficult to continuously produce the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) from the mixed composition. was there. Therefore, in the present invention, a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet are used by using a heat conductive filler having a relatively large BET specific surface area such as the heat conductive filler (B2). The viscosity of the mixed composition of the precursor of the shaped compact (G) is moderately increased. It is thought that precipitation of fillers having a large specific gravity such as the heat conductive filler (B1) can be suppressed by adding an appropriate amount of the heat conductive filler (B2) to moderately increase the viscosity of the mixed composition.
　熱伝導性フィラー（Ｂ２）のＢＥＴ比表面積は１．０ｍ２／ｇ以上であり、１．０ｍ２／ｇ以上１００ｍ２／ｇ以下であることが好ましく、１．０ｍ２／ｇ以上１０ｍ２／ｇ以下であることがより好ましい。熱伝導性フィラー（Ｂ２）のＢＥＴ比表面積を上記範囲にすることによって、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）の前駆体である混合組成物の粘度を適度に高めやすく、（メタ）アクリル樹脂組成物（Ａ）に対して比重の大きなフィラーの沈殿を抑制しやすくなる。 BET specific surface area of the thermally conductive filler (B2) is at 1.0 m 2 / g or more, is preferably from 1.0 m 2 / g or more 100m 2 / g, 1.0m 2 / g or more 10 m 2 / More preferably, it is g or less. By mixing the BET specific surface area of the heat conductive filler (B2) within the above range, 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). It becomes easy to raise the viscosity of a composition moderately, and it becomes easy to suppress precipitation of a filler with large specific gravity with respect to (meth) acrylic resin composition (A).
　また、熱伝導性フィラー（Ｂ２）の平均粒径は２０μｍ以下であり、０．０５μｍ以上１５μｍ以下であることが好ましく、０．１μｍ以上１０μｍ以下であることがより好ましい。平均粒径が上記上限を超えると、薄いシートを作製した場合、表面にフィラーによる凹凸や、ピンホールが発生する虞がある。 The average particle size of the heat conductive filler (B2) is 20 μm or less, preferably 0.05 μm or more and 15 μm or less, and more preferably 0.1 μm or more and 10 μm or less. When the average particle size exceeds the above upper limit, when a thin sheet is produced, there is a risk that irregularities due to the filler or pinholes may occur on the surface.
　熱伝導性フィラー（Ｂ２）は、平均粒径及びＢＥＴ比表面積が上記範囲を満たす熱伝導性フィラーであれば特に限定されない。熱伝導性フィラー（Ｂ２）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。その中でも特に、熱伝導率に優れ、かつ、化学的に安定していることから、金属酸化物が好ましく、酸化アルミニウム（アルミナ）が最も好ましい。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。 The heat conductive filler (B2) is not particularly limited as long as the average particle diameter and the BET specific surface area satisfy the above ranges. Specific examples of the thermally conductive filler (B2) 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 them, a metal oxide is preferable and aluminum oxide (alumina) is most preferable because it has excellent thermal conductivity and is chemically stable. A heat conductive filler (B2) 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（Ｂ２）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、６０質量部以上９００質量部以下であり、７０質量部以上７００質量部以下であることが好ましく、８０質量部以上６００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）の含有量を上記上限以下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）の前駆体である混合組成物の粘度が過度に高くなることを抑制できる。そのため、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）が低下したりする事態を防ぐことができる。一方、熱伝導性フィラー（Ｂ２）の含有量が上記下限以上とすることによって、上記のように混合組成物の粘度を適度に高め、（メタ）アクリル樹脂組成物（Ａ）に対して比重の大きなフィラーが混合組成物中において沈殿することを防止できると考えられる。 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) 60 parts by mass or more and 900 parts by mass or less, preferably 70 parts by mass or more and 700 parts by mass or less, and more preferably 80 parts by mass or more and 600 parts by mass or less with respect to 100 parts by mass. Mixing that is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B2) to the upper limit or less. It can suppress that the viscosity of a composition becomes high too much. Therefore, even if it becomes difficult to shape | mold a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G), and it can shape | mold, a heat conductive pressure sensitive adhesive composition (F). In addition, it is possible to prevent a situation in which the hardness of 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 not less than the above lower limit, the viscosity of the mixed composition is appropriately increased as described above, and the specific gravity of the (meth) acrylic resin composition (A) is increased. It is believed that large fillers can be prevented from precipitating in the mixed composition.
　＜多官能エポキシ化合物（Ｃ）＞
  次に、多官能エポキシ化合物（Ｃ）について説明する。多官能エポキシ化合物（Ｃ）は、官能基を２以上１００００以下有する多官能エポキシ化合物である。多官能エポキシ化合物（Ｃ）は、（メタ）アクリル酸エステル重合体（Ａ１）中の有機酸基と反応して架橋構造を形成し得る。また、同様に、（メタ）アクリル酸エステル単量体（α１）が有機酸基を有する単量体を含有している場合、該有機酸基と反応し得るため、（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に架橋構造を形成し得る。 <Polyfunctional epoxy compound (C)>
Next, the polyfunctional epoxy compound (C) will be described. The polyfunctional epoxy compound (C) is a polyfunctional epoxy compound having 2 to 10,000 functional groups. The polyfunctional epoxy compound (C) can react with the organic acid group in the (meth) acrylic acid ester polymer (A1) to form a crosslinked structure. Similarly, when the (meth) acrylate monomer (α1) contains a monomer having an organic acid group, it can react with the organic acid group. A crosslinked structure can be formed in the polymer containing the structural unit derived from the monomer (α1).
　多官能エポキシ化合物（Ｃ）を用いることによって上記のように架橋構造を形成すれば、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）にある程度の強度を持たせられるので、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）の強度を確保し易くなると考えられる。したがって、多官能エポキシ化合物（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）を薄く成形しても千切れ難くなると考えられる。 If a cross-linked structure is formed as described above by using the polyfunctional epoxy compound (C), the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) have a certain amount. Since strength is imparted, it is considered that the strength of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be easily secured. Therefore, by using the polyfunctional epoxy compound (C), it is considered that even if the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are thinly formed, it is difficult to break. It is done.
　本発明に用いることができる多官能エポキシ化合物（Ｃ）は、２５℃における粘度が６００ｍＰａ・ｓ以下であることが好ましく、５００ｍＰａ・ｓ以下であることがより好ましく、４００ｍＰａ・ｓ以下であることがさらに好ましい。多官能エポキシ化合物（Ｃ）の粘度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）の前駆体である混合組成物中に多官能エポキシ化合物（Ｃ）が均一に分散されやすくなり、多官能エポキシ化合物（Ｃ）による上記架橋構造が均一に形成されやすくなると考えられる。なお、多官能エポキシ化合物（Ｃ）の粘度は、以下に説明するようにして測定したものを意味する。 The polyfunctional epoxy compound (C) that can be used in the present invention preferably has a viscosity at 25 ° C. of 600 mPa · s or less, more preferably 500 mPa · s or less, and 400 mPa · s or less. Further preferred. By setting the viscosity of the polyfunctional epoxy compound (C) within the above range, a mixed composition which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It is considered that the polyfunctional epoxy compound (C) is easily dispersed uniformly therein, and the cross-linked structure by the polyfunctional epoxy compound (C) is easily formed uniformly. In addition, the viscosity of a polyfunctional epoxy compound (C) means what was measured as demonstrated below.
　（粘度測定方法）
  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）常温の環境で測定対象を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）測定対象が入った容器を粘度計の上に置き、ロータを該容器内の測定対象に沈める。このとき、ロータの目印となる凹みが丁度、測定対象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。 (Viscosity measurement method)
Using a B-type viscometer (Tokyo Keiki Co., Ltd.), the following procedure is performed.
(1) Weigh 300 ml of the measurement object in a room 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 measurement object is placed on the viscometer, and the rotor is submerged in the measurement object in the container. At this time, the dent which becomes the mark of the rotor is submerged so as to be exactly at the liquid interface to be measured.
(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、本発明に用いることができる多官能エポキシ化合物（Ｃ）は、官能基を２以上１００００以下有しており、官能基の数は２以上１０００以下であることが好ましく、２以上１０以下であることがより好ましい。多官能エポキシ化合物（Ｃ）の官能基の数が上記範囲であることで、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）に適切な強度を備えさせ易くなる。 Moreover, the polyfunctional epoxy compound (C) which can be used for this invention has 2 or more and 10,000 or less functional groups, and it is preferable that the number of functional groups is 2 or more and 1000 or less, and is 2 or more and 10 or less. More preferably. When the number of functional groups of the polyfunctional epoxy compound (C) is in the above range, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) have appropriate strength. It becomes easy to prepare.
　本発明に用いることができる多官能エポキシ化合物（Ｃ）の具体例としては、レゾルシノールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、水素化ビスフェノールＡジグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールジグリシジルエーテル、ペンタエリスリトールトリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、ジグリセロールテトラグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテルなどが挙げられる。中でも、少量でも効果的に架橋構造ができることから、４官能エポキシ化合物が好ましく、ペンタエリスリトールテトラグリシジルエーテルがより好ましい。多官能エポキシ化合物（Ｃ）は、１種を単独で使用してもよく、２種以上を併用してもよい。 Specific examples of the polyfunctional epoxy compound (C) that can be used in the present invention include resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenation Bisphenol A diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycerol tetraglycidyl ether, polyglycerol polyglycidyl ether, sorbitol poly Examples thereof include glycidyl ether. Among them, a tetrafunctional epoxy compound is preferable because a crosslinked structure can be effectively formed even in a small amount, and pentaerythritol tetraglycidyl ether is more preferable. A polyfunctional epoxy compound (C) 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）に使用する多官能エポキシ化合物（Ｃ）の量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量部として、０．０５質量部以上４質量部以下であり、０．０７質量部以上３質量部以下であることが好ましく、０．０９質量部以上２質量部以下であることがより好ましい。多官能エポキシ化合物（Ｃ）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）の強度を確保し易くなり、薄く成形しても千切れ難くなる。 The amount of the polyfunctional epoxy compound (C) 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) is 100 parts by mass, 0.05 parts by mass to 4 parts by mass, preferably 0.07 parts by mass to 3 parts by mass, and 0.09 parts by mass to 2 parts by mass. Is more preferable. By making the usage-amount of a polyfunctional epoxy compound (C) into the said range, it becomes easy to ensure the intensity | strength of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G). Even if it is thinly molded, it becomes difficult to break.
　＜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；リン酸エステルなどの難燃剤；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; flame retardants such as phosphates;
　これまでに説明したように、本発明によれば、多官能エポキシ化合物（Ｃ）、熱伝導性フィラー（Ｂ１）及び熱伝導性フィラー（Ｂ２）を適量併用することによって、薄く成形しても千切れ難い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。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）の厚さは０．０５ｍｍ以上１．０ｍｍ以下にすることができる。薄く成形することによって、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）の厚さの上限は、好ましくは０．５ｍｍである。一方、ある程度の厚さをもたせることによって、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。かかる観点から、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）の厚さの下限は、好ましくは０．０７ｍｍである。 As explained so far, according to the present invention, even if it is thinly formed by using a suitable amount of the polyfunctional epoxy compound (C), the heat conductive filler (B1) and the heat conductive filler (B2), it is It is possible to obtain a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) that are difficult to cut. The thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 1.0 mm or less. By thinly forming, the thermal resistance in the thickness direction can be lowered. From such a viewpoint, the upper limit of the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.5 mm. On the other hand, by giving a certain thickness, it becomes easy to prevent air from being involved when sticking to the heating element and the radiator, and as a result, the increase in thermal resistance is prevented, and the sticking process to the adherend is performed. It becomes easy to improve workability. From such a viewpoint, the lower limit of the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.07 mm.
　２．製造方法
  次に、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。 2. Manufacturing method Next, the manufacturing method of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G) is demonstrated.
　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）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 composition (F) of the present invention is prepared by mixing the substances described so far to prepare a mixed composition, and then polymerizing the (meth) acrylate monomer (α1). And a cross-linking 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).
　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）及び（メタ）アクリル酸エステル単量体（α１）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、多官能エポキシ化合物（Ｃ）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）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 composition (F) of the present invention includes (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). The process of producing the mixed composition containing an acrylic resin composition (A), a heat conductive filler (B1), a heat conductive filler (B2), and a polyfunctional epoxy compound (C), and this mixed composition In the product, the polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the structure derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1) And a step of performing at least a crosslinking reaction of the polymer containing the unit. 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）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 (meth) acrylate polymer (A1) and / or (meth) acrylate ester It can be obtained by performing at least a crosslinking reaction of a polymer containing a structural unit derived from the body (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）及び（メタ）アクリル酸エステル単量体（α１）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、多官能エポキシ化合物（Ｃ）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）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 object (G) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1) ( A step of producing a mixed composition comprising a (meth) acrylic resin composition (A), a thermally conductive filler (B1), a thermally conductive filler (B2), and a polyfunctional epoxy compound (C); and The polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the (meth) acrylic acid ester polymer after forming the mixed composition into a sheet or while forming the mixed composition into a sheet A step of performing at least a crosslinking reaction of a polymer containing a structural unit derived from (A1) and / or a (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）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) acrylate monomer (α1) 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.
　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、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の金属酸化物であり、熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の金属酸化物であることが好ましく、熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の酸化アルミニウムであり、熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の酸化アルミニウム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％以下及び（メタ）アクリル酸エステル単量体（α１）７５質量％以上９５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 product (G), the heat conductive filler (B1) has a mean particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g. The heat conductive filler (B2) is preferably a metal oxide having an average particle diameter of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more, and the heat conductive filler (B1) is The aluminum oxide has an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermally conductive filler (B2) has an average particle diameter of 20 μm or less and a BET specific surface area of 1.0 m. 2 / g or more of aluminum oxide More preferably. The (meth) acrylic resin composition (A) is not less than 5% by mass and not more than 25% by mass of the (meth) acrylic acid ester polymer (A1) and not less than 75% by mass of the (meth) acrylic acid ester monomer (α1). It is preferable to contain 95 mass% or less.
　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.
　＜作製可能厚さ＞
  後に説明するようにして混合組成物を作製し、当該混合組成物を１００ｍｌ用いて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する際に、ピンホールができることなく作製できる厚みを調べた。その結果を表２及び表３に示した。なお、本測定はシート厚１５０μｍ（下限）までの範囲で行った。なお、この厚さには、後述する離型ＰＥＴフィルム（離型処理されたポリエチレンテレフタレートフィルム。以下同じ。）の厚みは含まない。 <Manufacturable thickness>
When a mixed composition is prepared as described later, and a heat conductive pressure-sensitive adhesive sheet-like molded body is prepared using 100 ml of the mixed composition as described later, it can be manufactured without a pinhole. The thickness was examined. The results are shown in Tables 2 and 3. This measurement was performed in a range up to a sheet thickness of 150 μm (lower limit). This thickness does not include the thickness of a release PET film (a release-treated polyethylene terephthalate film; the same applies hereinafter).
　＜連続生産性＞
  後に説明するようにして混合組成物を作製し、当該混合組成物１００ｍｌを用いて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する際に、当該混合組成物を通すロールの間隔を３００μｍにして連続で生産できるか否かを調べた。その結果を表２及び表３に示した。表２及び表３において、最後までシートにピンホールができることなく生産できた場合を「○」とし、ピンホールができた場合を「×」とした。なお、作製可能厚さが１５０μｍより厚いものについては、連続生産性及び下記千切れ性の評価を行っていない。 <Continuous productivity>
A roll through which the mixed composition is prepared when a mixed composition is prepared as described later and a heat conductive pressure-sensitive adhesive sheet-like molded body is prepared using 100 ml of the mixed composition as described later It was investigated whether continuous production was possible with an interval of 300 μm. The results are shown in Tables 2 and 3. In Table 2 and Table 3, the case where the sheet could be produced without making a pinhole until the end was “◯”, and the case where the pinhole was made was “x”. In addition, about the thing whose thickness which can be produced is thicker than 150 micrometers, continuous productivity and the following tearability are not evaluated.
　＜千切れ性＞
  後に説明するようにして離型ＰＥＴフィルムに挟持された厚さ１５０μｍ（離型ＰＥＴフィルムの厚さは含まない。）の熱伝導性感圧接着性シート状成形体を作製した。その後、５ｍｍ×１００ｍｍの大きさに裁断し、離型ＰＥＴフィルムから熱伝導性感圧接着性シート状成形体を剥がしてアルミニウム板に貼り付けた。その状態で３時間放置した後、アルミニウム板から熱伝導性感圧接着性シート状成形体を剥がした。このとき、熱伝導性感圧接着性シート状成形体が千切れるか否かを調べた。その結果を表２及び表３に示した。表２及び表３において、千切れなかった場合を「○」とし、千切れた場合を「×」とした。なお、上記連続生産性の評価において結果が悪かったものについては、千切れ性の評価を行っていない。 <Clearance>
As described later, a heat conductive pressure-sensitive adhesive sheet-like molded article having a thickness of 150 μm (not including the thickness of the release PET film) sandwiched between the release PET films was prepared. Then, it cut | judged to the magnitude | size of 5 mm x 100 mm, peeled off the heat conductive pressure-sensitive-adhesive sheet-like molded object from the mold release PET film, and affixed on the aluminum plate. After leaving it in that state for 3 hours, the heat conductive pressure-sensitive adhesive sheet-like molded product was peeled off from the aluminum plate. At this time, it was investigated whether or not the heat conductive pressure-sensitive adhesive sheet-like molded product was broken. The results are shown in Tables 2 and 3. In Table 2 and Table 3, the case where it was not broken was designated as “◯”, and the case where it was broken was designated as “X”. In addition, about the thing with a bad result in the evaluation of the above-mentioned continuous productivity, evaluation of tearing property is 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０．０１５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８００，０００、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）は２．５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, 0.015 part 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 800,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.5. 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.
　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（Ａ１－２）を得た。（メタ）アクリル酸エステル重合体（Ａ１－２）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。 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 performed 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) acrylate polymer (A1-2). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-2) 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、アクリル酸２－エチルヘキシル（２ＥＨＡ）７９．１部と、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、多官能エポキシ化合物（ナガセケムテックス株式会社製、商品名「ＥＸ－１４１０」、ペンタエリスリトールテトラグリシジルエーテル、官能基数：４、粘度：３２０ｍＰａ・ｓ、全塩素：０．５％未満、エポキシ当量：１６０）０．１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）０．９部、及び上記（メタ）アクリル酸エステル重合体（Ａ１－２）２０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, 79.1 parts of 2-ethylhexyl acrylate (2EHA) and a polymerization initiator (1,6-bis (t-butylperoxycarbonyloxy) hexane (1 minute half-life temperature is 150 ° C.)) 1 0.0 part and a polyfunctional epoxy compound (manufactured by Nagase ChemteX Corporation, trade name “EX-1410”, pentaerythritol tetraglycidyl ether, functional group number: 4, viscosity: 320 mPa · s, total chlorine: less than 0.5% , Epoxy equivalent: 160) 0.1 parts, weighed with an electronic balance, 0.9 parts of the (meth) acrylate polymer (A1-1) and the (meth) acrylate polymer (A1-2) 20 parts was mixed. 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、球状アルミナ（電気化学工業株式会社製、商品名「ＤＡＭ－０３」、平均粒径：３μｍ、ＢＥＴ比表面積：０．６ｍ２／ｇ）６００部と、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：１．１μｍ、ＢＥＴ比表面積：２ｍ２／ｇ）１２０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, 600 parts of spherical alumina (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DAM-03”, average particle diameter: 3 μm, BET specific surface area: 0.6 m 2 / g) and fine alumina (manufactured by Showa Denko KK) , 120 parts of a product name “AL-47-H”, average particle diameter: 1.1 μm, BET specific surface area: 2 m 2 / g) are weighed and put into the Hobart container, and the temperature control of the Hobart container is adjusted to 40. The temperature was set to 0 ° C., the rotation speed scale was set to 5, and the mixture was stirred for 10 minutes. 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、所望の厚さの熱伝導性感圧接着性シート状成形体が得られるように間隔を調整したロールの間に通し、混合組成物を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）、（メタ）アクリル酸エステル重合体（Ａ１－２）及び（メタ）アクリル酸エステル単量体由来の構造単位を含む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。 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 is sandwiched between the release PET films is passed through a roll whose spacing is adjusted so that a heat-conductive pressure-sensitive adhesive sheet-like molded product having a desired thickness is obtained. Was 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 is polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester polymer (A1-2) And a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer is subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). It was. 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).
　（実施例２～７、及び比較例１～６）
  第１混合工程及び第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。なお、比較例１において第１混合工程で用いた多官能性単量体、及び比較例６において第２混合工程で用いた球状アルミナの詳細は下記の通りである。
・比較例１で用いた多官能性単量体
  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）
・比較例６で用いた球状アルミナ
  電気化学工業株式会社製、商品名「ＤＡＭ－４５」、平均粒径：４５μｍ、ＢＥＴ比表面積：０．２ｍ２／ｇ (Examples 2 to 7 and Comparative Examples 1 to 6)
Sheets (G2 to G7) according to Examples 2 to 7 in the same manner as in Example 1 except that the composition of each substance in the first mixing process and the second mixing process was changed as shown in Table 2 and Table 3. And sheets (GC1 to GC6) according to Comparative Examples 1 to 6 were produced. The details of the polyfunctional monomer used in the first mixing step in Comparative Example 1 and the spherical alumina used in the second mixing step in Comparative Example 6 are as follows.
Polyfunctional monomer used in Comparative Example 1 Polyfunctional monomer (light acrylate PE-3A) in which pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate were mixed in a ratio of 60: 35: 5 Manufactured by Kyoeisha Chemical Co., Ltd.)
-Spherical alumina used in Comparative Example 6 manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DAM-45”, average particle size: 45 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）はいずれも薄く成形可能であり、薄く成形する場合でも連続生産が可能で千切れ難かった。一方、比較例１にかかるシート（ＧＣ１）は千切れやすかった。これは、多官能エポキシ化合物を含有していなことによって架橋が不十分になったためであると考えられる。また、比較例２にかかるシート（ＧＣ２）も千切れやすかった。これは、多官能エポキシ化合物の含有量が多すぎたことによって、シートが硬くなりすぎたためと考えられる。また、比較例３にかかるシート（ＧＣ３）は薄く成形することができなかった。これは、熱伝導性フィラー（Ｂ１）の添加量が多すぎたことによって、混合組成物の粘度が過度に高くなったためであると考えられる。また、比較例４にかかるシート（ＧＣ４）は、シートを連続生産している際に徐々にピンホールができてきた。これは、熱伝導性フィラー（Ｂ２）の含有量が少なかったため、混合組成物の粘度が低くなり、シート作製中に、混合組成物中で熱伝導性フィラー（Ｂ１）が沈殿したためであると考えられる。また、比較例５にかかるシート（ＧＣ５）は薄く成形することができなかった。これは、熱伝導性フィラー（Ｂ２）の添加量が多すぎたことによって、混合組成物の粘度が過度に高くなったためであると考えられる。また、比較例６にかかるシート（ＧＣ６）は、粒径の大きな球状アルミナが沈降しやすいため、シートを連続生産している際に徐々にピンホールができてきた。 As shown in Table 2, all the sheets (G1 to G7) according to the examples can be formed thinly, and even when thinly formed, continuous production is possible and it is difficult to cut them. On the other hand, the sheet (GC1) according to Comparative Example 1 was easily cut off. This is considered to be due to insufficient crosslinking due to the absence of the polyfunctional epoxy compound. Further, the sheet (GC2) according to Comparative Example 2 was easily cut off. This is presumably because the sheet became too hard due to the excessive content of the polyfunctional epoxy compound. Moreover, the sheet | seat (GC3) concerning the comparative example 3 was not able to be shape | molded thinly. This is considered to be because the viscosity of the mixed composition became excessively high due to the addition amount of the heat conductive filler (B1) being too large. In addition, the sheet (GC4) according to Comparative Example 4 gradually formed pinholes during continuous production of the sheet. This is probably because the content of the heat conductive filler (B2) was small, so that the viscosity of the mixed composition was lowered, and the heat conductive filler (B1) was precipitated in the mixed composition during sheet production. It is done. Moreover, the sheet | seat (GC5) concerning the comparative example 5 was not able to be shape | molded thinly. This is considered to be because the viscosity of the mixed composition became excessively high due to the excessive amount of the thermally conductive filler (B2) added. Further, in the sheet (GC6) according to Comparative Example 6, since spherical alumina having a large particle size easily settles, pinholes are gradually formed during continuous production of the sheet.

Claims (17)

  1. 　（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）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、
    　官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４質量部以下と、
    を含む混合組成物中において、少なくとも前記（メタ）アクリル酸エステル単量体（α１）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）。     100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
    300 parts by mass or more and 1000 parts by mass or less of a heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g;
    The heat conductive filler (B2) having an average particle size of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more is from 60 parts by weight to 900 parts by weight;
    0.05 to 4 parts by mass of a polyfunctional epoxy compound (C) having a functional group of 2 to 10000,
    In the mixed composition containing at least the polymerization reaction of the (meth) acrylic acid ester monomer (α1), the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester alone. A heat conductive pressure-sensitive adhesive composition (F) obtained by performing a crosslinking reaction of a polymer containing a structural unit derived from a monomer (α1).
  2. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の金属酸化物であり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の金属酸化物である、請求項１に記載の熱伝導性感圧接着剤組成物（Ｆ）。 The thermal conductive filler (B1) is a metal oxide having an average particle size of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermal conductive filler (B2) has an average particle size. The heat conductive pressure-sensitive-adhesive composition (F) of Claim 1 which is a metal oxide of 20 micrometers or less and a BET specific surface area of 1.0 m < 2 > / g or more.
  3. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の酸化アルミニウムであり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の酸化アルミニウムである、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 heat conductive filler (B1) is an aluminum oxide having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the heat conductive filler (B2) has an average particle diameter of 20 μm. The heat conductive pressure-sensitive adhesive composition (F) according to claim 1 or 2, which is aluminum oxide having a BET specific surface area of 1.0 m 2 / g or more.
  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％以下及び前記（メタ）アクリル酸エステル単量体（α１）７５質量％以上９５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 75% by mass of the (meth) acrylic acid ester monomer (α1). The heat conductive pressure-sensitive adhesive composition (F) according to any one of claims 1 to 3, comprising 95% by mass or less.
  5. 　（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）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、
    　官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４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、少なくとも前記（メタ）アクリル酸エステル単量体（α１）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）。     100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
    300 parts by mass or more and 1000 parts by mass or less of a heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g;
    The heat conductive filler (B2) having an average particle size of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more is from 60 parts by weight to 900 parts by weight;
    0.05 to 4 parts by mass of a polyfunctional epoxy compound (C) having a functional group of 2 to 10000,
    And after forming the mixed composition into a sheet, or while forming the mixed composition into a sheet, at least the polymerization reaction of the (meth) acrylate monomer (α1) and the (meth) acrylic Thermally conductive pressure-sensitive adhesive sheet-like molding, wherein the acid ester polymer (A1) and / or a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1) is crosslinked. Body (G).
  6. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の金属酸化物であり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の金属酸化物である、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 thermal conductive filler (B1) is a metal oxide having an average particle size of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermal conductive filler (B2) has an average particle size. The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 5 which is a metal oxide of 20 micrometers or less and a BET specific surface area of 1.0 m < 2 > / g or more.
  7. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の酸化アルミニウムであり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の酸化アルミニウムである、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 heat conductive filler (B1) is an aluminum oxide having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the heat conductive filler (B2) has an average particle diameter of 20 μm. The thermally conductive pressure-sensitive adhesive sheet-like molded product (G) according to claim 5 or 6, which is aluminum oxide having a BET specific surface area of 1.0 m 2 / g or more.
  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％以下及び前記（メタ）アクリル酸エステル単量体（α１）７５質量％以上９５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 75% by mass of the (meth) acrylic acid ester monomer (α1). The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of any one of Claims 5 thru | or 7 containing 95 mass% or less.
  9. 　（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）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、
    　官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４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、少なくとも前記（メタ）アクリル酸エステル単量体（α１）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。     100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
    300 parts by mass or more and 1000 parts by mass or less of a heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g;
    The heat conductive filler (B2) having an average particle size of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more is from 60 parts by weight to 900 parts by weight;
    0.05 to 4 parts by mass of a polyfunctional epoxy compound (C) having a functional group of 2 to 10000,
    Producing a mixed composition comprising:
    In the mixed composition, at least the polymerization reaction of the (meth) acrylic acid ester monomer (α1), the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester single amount. A step of performing a crosslinking reaction of a polymer containing a structural unit derived from the body (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、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の金属酸化物であり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の金属酸化物である、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 thermal conductive filler (B1) is a metal oxide having an average particle size of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermal conductive filler (B2) has an average particle size. The manufacturing method of the heat conductive pressure sensitive adhesive composition (F) of Claim 9 which is a metal oxide of 20 micrometers or less and a BET specific surface area of 1.0 m < 2 > / g or more.
  11. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の酸化アルミニウムであり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の酸化アルミニウムである、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 heat conductive filler (B1) is an aluminum oxide having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the heat conductive filler (B2) has an average particle diameter of 20 μm. The method for producing a thermally conductive pressure-sensitive adhesive composition (F) according to claim 9 or 10, which is aluminum oxide having a BET specific surface area of 1.0 m 2 / g or more.
  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％以下及び前記（メタ）アクリル酸エステル単量体（α１）７５質量％以上９５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 75% by mass of the (meth) acrylic acid ester monomer (α1). The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of any one of Claims 9 thru | or 11 containing 95 mass% or less.
  13. 　（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）を含む（メタ）アクリル樹脂組成物（Ａ）を１００質量部と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の熱伝導性フィラー（Ｂ１）を３００質量部以上１０００質量部以下と、
    　平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の熱伝導性フィラー（Ｂ２）を６０質量部以上９００質量部以下と、
    　官能基を２以上１００００以下有する多官能エポキシ化合物（Ｃ）を０．０５質量部以上４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、少なくとも前記（メタ）アクリル酸エステル単量体（α１）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。     100 parts by weight of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1),
    300 parts by mass or more and 1000 parts by mass or less of a heat conductive filler (B1) having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g;
    The heat conductive filler (B2) having an average particle size of 20 μm or less and a BET specific surface area of 1.0 m 2 / g or more is from 60 parts by weight to 900 parts by weight;
    0.05 to 4 parts by mass of a polyfunctional epoxy compound (C) having a functional group of 2 to 10000,
    Producing a mixed composition comprising:
    After forming the mixed composition into a sheet shape or while forming the mixed composition into a sheet shape, at least a polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the (meth) acrylic A step of performing a crosslinking reaction of the acid 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 sheet-like molded object (G) including this.
  14. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の金属酸化物であり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の金属酸化物である、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 thermal conductive filler (B1) is a metal oxide having an average particle size of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermal conductive filler (B2) has an average particle size. The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 13 which is a metal oxide of 20 micrometers or less and a BET specific surface area of 1.0 m < 2 > / g or more.
  15. 　前記熱伝導性フィラー（Ｂ１）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ未満の酸化アルミニウムであり、前記熱伝導性フィラー（Ｂ２）が、平均粒径が２０μｍ以下、且つＢＥＴ比表面積が１．０ｍ２／ｇ以上の酸化アルミニウムである、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 heat conductive filler (B1) is an aluminum oxide having an average particle diameter of 20 μm or less and a BET specific surface area of less than 1.0 m 2 / g, and the heat conductive filler (B2) has an average particle diameter of 20 μm. The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 13 or 14 which is aluminum oxide whose BET specific surface area is 1.0 m < 2 > / g or more below.
  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％以下及び前記（メタ）アクリル酸エステル単量体（α１）７５質量％以上９５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 75% by mass of the (meth) acrylic acid ester monomer (α1). The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of any one of Claims 13 thru | or 15 containing the above 95 mass% or less.
  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.
PCT/JP2013/062625 2012-06-04 2013-04-30 Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded body, method for producing thermally conductive pressure-sensitive adhesive composition, method for producing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic device WO2013183389A1 (en)

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