WO2013047145A1 - 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 component - 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 component Download PDF

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Publication number
WO2013047145A1
WO2013047145A1 PCT/JP2012/072777 JP2012072777W WO2013047145A1 WO 2013047145 A1 WO2013047145 A1 WO 2013047145A1 JP 2012072777 W JP2012072777 W JP 2012072777W WO 2013047145 A1 WO2013047145 A1 WO 2013047145A1
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parts
meth
mass
conductive pressure
sensitive adhesive
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PCT/JP2012/072777
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French (fr)
Japanese (ja)
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拓朗 熊本
明子 北川
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日本ゼオン株式会社
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Priority to KR1020137030473A priority Critical patent/KR20140074869A/en
Priority to CN201280023461.XA priority patent/CN103562334A/en
Publication of WO2013047145A1 publication Critical patent/WO2013047145A1/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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • 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-like molding.
  • the present invention relates to an electronic component having a body.
  • thermo conductive pressure-sensitive adhesive composition a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • sheet a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are preferably used for the purpose of transferring heat from the heat generating body to the heat radiating body, and therefore preferably have high heat conductivity.
  • expanded graphite powder has high thermal conductivity and high conductivity. Therefore, the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body, which have improved thermal conductivity by containing a large amount of expanded graphite powder, are used for applications that also require insulation. There were cases where it could not be used.
  • zinc oxide may be used as a filler capable of improving thermal conductivity (Patent Documents 1 to 3).
  • the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article having a good balance between insulation and thermal conductivity, their production methods, and the thermally conductive pressure-sensitive adhesive. It is an object of the present invention to provide an agent composition or an electronic component including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
  • the present inventors have found that the above problems can be solved by using a plurality of fillers having thermal conductivity in combination at an appropriate ratio, and have completed the present invention.
  • 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part In a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating heat conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D), (meth) acrylic Polymerization reaction of acid ester monomer ( ⁇ 1) and crosslinking reaction of polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer ( ⁇ 1) Thermally conductive pressure-sensitive adhesive composition ( ) It is.
  • (Meth) acryl means “acryl and / or methacryl”.
  • Zinc oxide (C) having a needle-like part means zinc oxide having a needle-like part, as will be described in detail later.
  • the “expanded graphite powder (D)” means a powdery body obtained by expanding and pulverizing graphite, as will be described in detail later.
  • “Insulating heat conductive filler (B) excluding zinc oxide (C) having acicular part and expanded graphite powder (D)” means zinc oxide (C) having acicular part and expanded graphite Excluding the powder (D), the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) described later is improved by adding the powder (D).
  • the “polymerization reaction of (meth) acrylate monomer ( ⁇ 1)” means a polymerization reaction for obtaining a polymer that generates a structural unit derived from the (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 polymer Cross-linking reaction between (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylic acid ester monomer ( ⁇ 1), and (meth) acrylic acid ester polymers (A1) and (meth) Among crosslinking reactions with a polymer containing a structural unit derived from an acrylate monomer ( ⁇ 1), it means one or more crosslinking reactions.
  • 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part After forming a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating thermally conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D) having a sheet shape
  • 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part A step of producing a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D), and
  • the polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1), the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1) A cross-linking reaction of a polymer containing a structural unit derived from Extent, including a method for producing a thermally conductive pressure-sensitive adhesive composition (F).
  • the 4th aspect of this invention is 100 masses of (meth) acrylic-ester resin compositions (A) containing the (meth) acrylic-ester polymer (A1) and the (meth) acrylic-ester monomer ((alpha) 1). 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part A step of producing a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D), and After forming the mixed composition into a sheet 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) acrylic acid ester monomer ( A method for producing a heat conductive pressure-sensitive adhesive sheet-like molded article (G), comprising
  • a heat radiator and the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the heat radiator, or the heat radiator and the heat radiator.
  • An electronic component comprising the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) according to the second aspect of the present invention.
  • a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article having a good balance between insulation and thermal conductivity, their production methods, and the thermally conductive pressure-sensitive adhesive It is possible to provide an agent composition or an electronic component provided with the thermally conductive pressure-sensitive adhesive sheet-like molded body.
  • the thermally conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1).
  • a mixed composition containing an insulating thermally conductive filler (B) hereinafter sometimes simply referred to as “thermally conductive filler (B)” excluding zinc (C) and expanded graphite powder (D).
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is (meth) acrylic acid after shape
  • Polymerization reaction for obtaining a polymer that produces a structural unit derived from an ester monomer ( ⁇ 1) a crosslinking reaction between (meth) acrylic acid ester polymers (A1), (meth) acrylic acid ester monomer ( ⁇ 1)
  • 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).
  • (meth) acrylic acid ester monomer ((alpha) 1) origin Polymerization reaction to obtain a polymer that yields a structural unit of the above, 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 ( ⁇ 1) And done.
  • 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 usage-amount of an acrylic ester polymer (A1) and the (meth) acrylic ester monomer ((alpha) 1) is (meth) with respect to 100 mass% of (meth) acrylic resin compositions (A).
  • the acrylate polymer (A1) is preferably 5% by mass or more and 40% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 60% by mass or more and 95% by mass or less.
  • the (meth) acrylic acid ester polymer (A1) that can be used in the present invention is not particularly limited, but the (meth) acrylic acid ester monomer that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the unit (a1) and the 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, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.
  • 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 formed.
  • 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), which forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • Monomer (a2m) a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
  • the polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. .
  • solution polymerization is preferable, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferable.
  • the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once.
  • the method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator.
  • the thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
  • Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
  • the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
  • polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
  • the obtained polymer is separated from the polymerization medium if necessary.
  • the separation method is not particularly limited.
  • the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. It is more preferable that it is in the range of 200,000 or more and 500,000 or less.
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
  • the (meth) acrylate monomer ( ⁇ 1) is not particularly limited as long as it contains a (meth) acrylate monomer, but a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is molded. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
  • the (meth) acrylate monomer (a5m) for forming 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) may be a mixture of a (meth) acrylic acid ester monomer (a5m) and a monomer copolymerizable therewith.
  • the (meth) acrylate monomer ( ⁇ 1) is a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or less, and can be copolymerized with these monomers. It is good also as a mixture of the monomer (a6m) which has an 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 with the monomer (a7m) which can be copolymerized 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.
  • ⁇ Polymerization initiator> When obtaining the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G), the (meth) acrylic acid ester monomer ( ⁇ 1) and a polyfunctional monomer described below are used. The body polymerizes. In order to accelerate the polymerization, 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. From the viewpoint of imparting excellent adhesiveness to the obtained heat conductive pressure-sensitive adhesive composition (F) and heat conductive pressure-sensitive adhesive sheet-like molded body (G), an organic peroxide thermal polymerization initiator is used. It is preferable to use it.
  • 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 mass part or more and 1 mass part or less.
  • 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.
  • ⁇ Multifunctional monomer> It is preferable to use a polyfunctional monomer in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention.
  • the polyfunctional monomer one that can be copolymerized 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 has the unsaturated bond at the terminal.
  • 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 in the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 mass of the (meth) acrylic resin composition (A). It is preferably 0.1 parts by weight or more and 15 parts by weight or less, more preferably 0.2 parts by weight or more and 8 parts by weight or less, and further preferably 0.5 parts by weight or more and 2 parts by weight or less. preferable.
  • 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.
  • Zinc oxide (C) used in the present invention has a needle-like part.
  • the length of the needle-like part is preferably 2 ⁇ m or more and 50 ⁇ m or less.
  • the length of the acicular part of zinc oxide (C) can be measured by observing with a scanning electron microscope, for example.
  • the thermally conductive pressure-sensitive adhesive composition (F) and the combination with other fillers having thermal conductivity are used. It is thought that it becomes easy to make a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) have high heat conductivity.
  • the shape of zinc oxide (C) used in the present invention only needs to have a needle-like part. That is, the zinc oxide (C) may be provided with one or a plurality of needle-like portions around the core portion, or may be composed of only the needle-like portions. However, as will be described later, between the thermally conductive pressure-sensitive adhesive composition (F) and the other thermally conductive filler filled in the thermally conductive pressure-sensitive adhesive sheet-like molded body (G), zinc oxide ( From the viewpoint of facilitating connection by C), a shape in which a plurality of needle-like portions are provided extending in different directions around the core portion is preferable.
  • a more preferable shape is a shape in which there are three or more needle-like portions around the core portion, and at least one of the needle-like portions is not coplanar with the other needle-like portions.
  • the number of needle-like portions existing around one nucleus is preferably 3-6. When the number is within this range, the orientation of the needle-like portion becomes three-dimensional and the connection with other fillers is good.
  • “Panatetra (registered trademark)” manufactured by Amtec Corporation can be exemplified.
  • the amount of zinc oxide (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 parts by weight of the (meth) acrylic resin composition (A). 0.5 parts by mass or more and 40 parts by mass or less, and preferably 0.8 parts by mass or more and 35 parts by mass or less.
  • the insulating property of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) does not fall by making content of zinc oxide (C) into the said range.
  • the effect of improving the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is sufficiently obtained. It is done.
  • the expanded graphite powder (D) is obtained by expanding graphite and then pulverizing it.
  • the acid-treated graphite is heat-treated at 500 ° C. or more and 1200 ° C. or less to expand to 100 ml / g or more and 300 ml / g or less, and then pulverized. What was obtained by the method of containing can be mentioned. More preferably, the graphite is treated with a strong acid, then sintered in an alkali, and then again treated with a strong acid at a temperature of 500 ° C. to 1200 ° C.
  • the temperature of the heat treatment is particularly preferably 800 ° C. or higher and 1000 ° C. or lower.
  • the average particle diameter of the expanded graphite powder (D) used in the present invention is preferably 10 ⁇ m or more and 1000 ⁇ m or less, more preferably 20 ⁇ m or more and 700 ⁇ m or less, and further preferably 30 ⁇ m or more and 500 ⁇ m or less.
  • the average particle size of the expanded graphite powder (D) within the above range, the heat conduction path in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). And the expanded graphite powder (D) is easily prevented from being destroyed.
  • the “average particle diameter” means that measured by the method described below.
  • a laser type particle size measuring machine manufactured by Seishin Enterprise Co., Ltd.
  • 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).
  • 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.
  • the amount of the expanded graphite powder (D) used in the present invention is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts 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 The heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) while suppressing the fluidity of the mixed composition that is the basis of the molded product (G). Can be provided with a good balance between insulation and thermal conductivity.
  • the insulating property of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) can be hold
  • Thermal conductive filler (B)> 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, zinc oxide (C) having an acicular portion and expanded graphite powder (D) are contained. Insulating heat conductive filler (B) is used.
  • the heat conductive filler (B) has insulating properties, and when added, 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 is a filler that can improve.
  • thermally conductive filler (B) examples include calcium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum oxide (alumina), magnesium oxide, silica, glass fiber, boron nitride and aluminum nitride.
  • calcium carbonate, aluminum hydroxide, and aluminum oxide are preferable because they are easily available, chemically stable, and can be added in a large amount, and aluminum hydroxide and aluminum oxide are more preferable.
  • a heat conductive filler (B) may be used individually by 1 type, and may use 2 or more types together.
  • the average particle size of the heat conductive filler (B) used in the present invention is preferably 0.1 ⁇ m or more and 50 ⁇ m or less.
  • the amount of the heat conductive filler (B) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is (meth) acrylic resin composition (A) 100. It is 600 parts by mass or more and 1400 parts by mass or less, preferably 700 parts by mass or more and 1200 parts by mass or less, and more preferably 800 parts by mass or more and 1000 parts by mass or less with respect to parts by mass.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are used. It suppresses the thickening of the mixed composition, prevents the productivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) from decreasing, and increases the hardness. It suppresses that and shape followability falls.
  • the zinc oxide (C) or the expanded graphite powder (D) can be used by combining the thermally conductive filler (B), zinc oxide (C) and the expanded graphite powder (D) in appropriate amounts. Even if the addition amount of the conductive filler such as D) is less than that of the conventional one, it is high in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). Heat conductivity can be provided and it can suppress that the insulation of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) falls.
  • a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) having a good balance between insulation and thermal conductivity. .
  • the following reasons can be considered.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive property.
  • the insulating heat conductive filler (B) mainly forms a heat transfer path inside the sheet-like molded body (G).
  • Zinc oxide (C) and expanded graphite powder (D) complement it.
  • the needle-shaped portion of zinc oxide (C) has the above-mentioned predetermined length.
  • the expanded graphite powder (D) has high thermal conductivity but high conductivity, it is preferable to use the amount within the predetermined range described above.
  • the amount of the expanded graphite powder (D) used is the predetermined amount described above.
  • Phosphate ester can also be used for the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention.
  • phosphate ester it becomes easy to improve the flame retardance of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G).
  • the phosphate ester used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
  • a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
  • the viscosity of the phosphate ester is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to the following procedure.
  • a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
  • (1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
  • (2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
  • the container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the condensed phosphate ester in the container.
  • the rotation speed is selected from 20, 10, 4, and 2.
  • the rotation speed is selected from 20, 10, 4, and 2.
  • the value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa ⁇ s].
  • the coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.
  • the phosphate ester used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester is liquid when mixed, the workability is good, and it is easy to form the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G). become.
  • the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less.
  • the glass transition temperature of the (meth) acrylic resin composition (A) is set to be equal to or higher than the volatilization or polymerization of monomers contained in the (meth) acrylic resin composition (A). Since it becomes easy to prevent the reaction from starting, the environmental performance and workability can be improved.
  • a condensed phosphate ester or a non-condensed phosphate ester can be used as the phosphate ester.
  • condensed phosphate ester means one having a plurality of phosphate ester moieties in one molecule
  • non-condensed phosphate ester means one phosphate ester moiety in one molecule. It means something that exists only. Specific examples of phosphate esters that satisfy the conditions described so far are listed below.
  • condensed phosphate ester examples include aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyalkylene bisdichloroalkyl And halogen-containing condensed phosphates such as phosphates; non-aromatic non-halogen-based condensed phosphates; Of these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no risk of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.
  • aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyal
  • non-condensed phosphate ester examples include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris ( ⁇ -chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.
  • Phosphoric acid ester may be used alone or in combination of two or more.
  • the amount of the phosphoric acid ester used for the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is 100 (meth) acrylic resin composition (A).
  • the mass part is preferably 20 parts by mass or more and 100 parts by mass or less.
  • ⁇ Other additives> In addition to the above-described components, the above-described effects due to the addition of the above-described components 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 assistants); flame retardant thermally conductive inorganic compounds such as metal hydroxides and metal salt hydrates; glass fibers; PITCH-based carbon fibers and the above-described thermal conductivity.
  • the thermally conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing the substances described above, followed by the polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1) and (meth) acrylic. It can obtain by performing the crosslinking reaction of the polymer containing the structural unit derived from the 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 this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1) ( (Meth) acrylic resin composition (A), zinc oxide (C) having an acicular part, expanded graphite powder (D), zinc oxide (C) having an acicular part and expanded graphite powder (D) And a step of preparing a mixed composition comprising an insulating thermally conductive filler (B), and a polymerization reaction of the (meth) acrylate monomer ( ⁇ 1) in the mixed composition, And a crosslinking reaction of a polymer containing a structural unit derived from a (meth) acrylic acid ester polymer (A1) and / or a (meth) acrylic acid ester monomer ( ⁇ 1).
  • the substances that can be used, the preferable content ratio of each substance, the preferable average particle diameter of each substance, and the like are as described above,
  • heat for example, hot air, an electric heater, infrared rays, or the like can be used.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer proceeds.
  • a temperature range changes with kinds of polymerization initiator to be used 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.
  • the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is prepared by mixing the substances described so far into a sheet shape, or while forming into a sheet shape, with a single (meth) acrylate ester.
  • the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention comprises (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1).
  • heat for example, hot air, an electric heater, infrared rays, or the like can be used.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer proceeds.
  • a temperature range changes with kinds of polymerization initiator to be used 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.
  • the method for forming the mixed composition into a sheet is not particularly limited.
  • a suitable method for example, a method of forming the sheet by applying the mixed composition onto a process paper such as a release-treated polyester film, and if necessary, between the two release-processed process papers.
  • a method of forming a sheet by pressing between the rolls with the mixed composition interposed therebetween, and extruding the mixed composition using an extruder, and forming the sheet by controlling the thickness through a die at that time The method etc. are mentioned.
  • the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 5 mm or less. By setting the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) to the upper limit or less, the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be lowered. . By setting the thickness of the heat conductive pressure-sensitive adhesive sheet-shaped molded body (G) to the above lower limit or more, the thermal conductive pressure-sensitive adhesive sheet-shaped molded body (G) is applied to the heating element and the heat radiating body.
  • the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.1 mm or more and 2 mm or less.
  • 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 (PET), polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic A film of a heat-resistant polymer such as an aromatic polyamide 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. 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 component include components around a heat generating part in a device having an electroluminescence (EL) light emitting diode (LED) light source, components around a power device such as an automobile, a fuel cell, a solar cell, a battery, and a mobile phone.
  • EL electroluminescence
  • LED light emitting diode
  • PDA personal digital assistant
  • notebook computer liquid crystal
  • SED surface conduction electron-emitting device display
  • PDP plasma display panel
  • IC integrated circuit
  • the following is an example of the case where it is used for an LED light source.
  • the usage method can be illustrated. That is, it is directly attached to the LED light source; sandwiched between the LED light source and a heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); , Heat pipe, graphite sheet, etc.); used as a casing surrounding the LED light source; affixed to the casing surrounding the LED light source; and filling a gap between the LED light source and the casing.
  • a heat dissipation material heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.
  • a display device having a transmissive liquid crystal panel Backlight devices (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; general residential lighting;
  • examples of the use 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 other than LED light sources 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; Etc., the heat conductive pressure-sensitive adhesive composition (F) of the present invention and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) can be used.
  • the usage method of the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is not limited to the form mentioned above, Other than what was illustrated so far. It can also be used by being attached to a casing or the like of the apparatus. For example, it can be used for an apparatus provided in an automobile or the like.
  • 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 houses; televisions; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Lighting; Organic EL display; Notebook PC; PDA; Fuel cell; Semiconductor device; Rice cooker; Washing machine; Washing and drying machine: Optical semiconductor device combining optical semiconductor elements and phosphors; Etc.
  • 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 equalization 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 hygroscopic agent; cooling equipment, clothing, towels, sheets, etc.
  • the member Used for a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer; Pressurizing a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as a member itself; used as a heat flow control heat transfer part for placing a treatment object of a membrane control device; used as a heat flow control heat transfer part for placing a treatment object of a film control device; outer layer of a radioactive substance storage container It can be used between the interior and interior; used in a box body with a solar panel that absorbs sunlight; used between the reflective sheet of the CCFL backlight and the aluminum chassis.
  • the heat conductive pressure sensitive adhesive composition (F) according to the present invention, the heat conductive pressure sensitive adhesive sheet-like molded product (G), the method for producing the heat conductive pressure sensitive adhesive composition (F), and
  • a preferable heat conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  • the heat conductive pressure-sensitive-adhesive composition (F) which concerns on this invention, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G), the manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F), and heat (Meth) acrylic resin containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) in the method for producing conductive pressure-sensitive adhesive sheet-like molded product (G) 100 parts by mass of composition (A), 0.5 to 40 parts by mass of zinc oxide (C) having acicular parts, and 0.5 to 20 parts by mass of expanded graphite powder (D) Part of the insulating heat conductive filler (B) excluding zinc oxide (C) having the acicular part and the expanded graphite powder (D).
  • the mixed composition preferably further comprises a polymerization initiator, a (meth) acrylic resin.
  • a polymerization initiator e.g., a (meth) acrylic resin.
  • the heat conductive pressure-sensitive-adhesive composition (F) which concerns on this invention, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G), the manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F), and heat
  • the mixed composition preferably further includes a polyfunctional monomer with respect to 100 parts by mass of the (meth) acrylic resin composition (A). 0.1 parts by mass or more and 15 parts by mass or less.
  • the heat conductive pressure-sensitive-adhesive composition (F) which concerns on this invention, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G), the manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F), and heat
  • the mixed composition preferably further contains 20 mass parts of phosphate ester with respect to 100 mass parts of the (meth) acrylic resin composition (A). Part to 100 parts by mass.
  • ⁇ Fluidity> The fluidity of the mixed composition obtained through the first to third mixing steps described later was evaluated. Specifically, the Hobart container in which the mixed composition was put was tilted by 30 ° with respect to the horizontal plane, and the state of the mixed composition after 1 minute was evaluated. The results are shown in Table 2. The case where the mixed composition flowed along the inclination was indicated as “ ⁇ ”, and the case where it did not move was indicated as “X”. The fluidity of the mixed composition makes it easier to form the mixed composition into a sheet. That is, the productivity of the heat conductive pressure-sensitive adhesive sheet-like molded product is increased.
  • a test piece was prepared by cutting a thermally conductive pressure-sensitive adhesive sheet produced by the method described later into a size of 80 mm ⁇ 80 mm.
  • a test piece was set on a digital ultra-high resistance / micro-ammeter (trade name “8340A”, manufactured by ADC Corporation), and a current was passed through both right and left ends of the test piece to measure resistivity.
  • the voltage started from 500 V and gradually decreased to a measurable voltage, and the resistivity at the measurable voltage was measured.
  • the charging time was 1 minute.
  • the measurement was performed three times, and the average value was defined as the volume resistivity (unit: ⁇ ⁇ cm) of the heat conductive pressure-sensitive adhesive sheet.
  • Table 2 If the result of this evaluation is 1.0 ⁇ 10 10 ⁇ ⁇ cm or more, it can be said that the insulation is excellent.
  • a test piece cut to a size of 25 mm ⁇ 25 mm was prepared for a heat-conductive pressure-sensitive adhesive sheet-like molded body produced by the method described later, which was judged to have excellent insulation properties by the above test.
  • the test piece was affixed to an aluminum plate of 150 mm ⁇ 150 mm ⁇ thickness 3 mm, and a micro ceramic heater (manufactured by Sakaguchi Electric Heat Co., Ltd., trade name: MS) ⁇ 5, 25 mm ⁇ 25 mm) was fixed with a vise and the aluminum plate was suspended. Thereafter, a micro ceramic heater was connected to the slidac, and the surface of the micro ceramic heater when heated at 60 W for 60 minutes was photographed by thermography.
  • the maximum temperature at that time is shown in Table 2.
  • the lower the temperature means that more heat is transferred from the micro ceramic heater to the aluminum plate, so the lower the temperature, the lower the thermal resistance of the heat conductive pressure-sensitive adhesive sheet-like molded body. It can be said.
  • This evaluation was performed in an atmosphere at 23 ° C.
  • Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
  • a thermostatic bath manufactured by Toki Sangyo Co., Ltd., trade name “Biscomate Meat 150III”
  • a Hobart mixer manufactured by Kodaira Manufacturing Co., Ltd., trade name “ACM-5LVT type”, capacity: 5 L
  • the temperature control of the Hobart container was set to 60 ° C.
  • the rotation speed scale was set to 3
  • the mixture was stirred for 10 minutes. This process is referred to as a first mixing process.
  • the mixed composition obtained through the first to third mixing steps is hung on a release-treated PET film having a thickness of 75 ⁇ m, and another release mold having a thickness of 75 ⁇ m is further formed on the mixed composition.
  • the treated PET film was covered.
  • the laminate, which was sandwiched between the release films of the mixed composition, was passed through a roll having a distance of 0.65 mm between them to form a sheet. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes. Through this heating step, the (meth) acrylic acid ester monomer was polymerized and crosslinked to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet
  • Example 2 to 5 and Comparative Examples 1 to 3 Sheets (G2 to 5, GC1 to 3) were obtained in the same manner as in Example 1 except that the composition of each substance was changed as shown in Table 2. The evaluation results are shown in Table 2.
  • each of the sheets (G1) to (G5) according to the examples has good fluidity of the mixed composition before forming into a sheet, and after forming into a sheet, the sheet has a high volume resistivity.
  • the cool down effect was excellent. That is, according to this invention, it turned out that the heat conductive pressure-sensitive-adhesive sheet-like molded object provided with insulation and heat conductivity with sufficient balance can be provided.
  • one of the above performances was inferior in the sheets (GC1) to (GC3) according to the comparative examples. Specifically, it was as follows.
  • the sheet (GC1) of Comparative Example 1 having a small content of zinc oxide and expanded graphite was inferior in the cool-down effect.
  • the sheet (GC2) of Comparative Example 2 having a large content of expanded graphite and the sheet (GC3) of Comparative Example 3 having a large content of zinc oxide had low volume resistivity.
  • the test of the cool-down effect was not implemented.

Abstract

Provided is a thermally conductive pressure-sensitive adhesive composition which has insulating properties and thermal conductivity in a balanced manner and is obtained by carrying out a polymerization reaction of a (meth)acrylic acid ester monomer mixture and a crosslinking reaction of a polymer that comprises a structural unit derived from a (meth)acrylic acid ester polymer (A1) and/or a (meth)acrylic acid ester monomer (α1) in a mixed composition that contains: 100 parts by mass of a (meth)acrylic resin composition (A) that contains the (meth)acrylic acid ester polymer (A1) and the (meth)acrylic acid ester monomer (α1); from 0.5 parts by mass to 40 parts by mass (inclusive) of a zinc oxide (C) having a needle-like portion; from 0.5 parts by mass to 20 parts by mass (inclusive) of an expanded graphite powder (D); and from 600 parts by mass to 1,400 parts by mass (inclusive) of an insulating thermally conductive filler (B) that is other than the zinc oxide (C) having a needle-like portion and the expanded graphite powder (D). Also provided are: a thermally conductive pressure-sensitive adhesive sheet-like molded body; a method for producing the thermally conductive pressure-sensitive adhesive composition; a method for producing the thermally conductive pressure-sensitive adhesive sheet-like molded body; and an electronic component which is provided with the thermally conductive pressure-sensitive adhesive composition or the 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、及び電子部品Thermally conductive pressure-sensitive adhesive composition, thermally conductive and pressure-sensitive adhesive sheet-like molded product, production method thereof, and electronic component
　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、これらの製造方法、及び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部品に関する。 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-like molding. The present invention relates to an electronic component having a 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、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。一般的には、金属製のヒートシンク、放熱板、放熱フィン等の放熱体を電子部品等に備えられる発熱体に取り付けることによって放熱させる方法が採られている。発熱体から放熱体への熱伝導を効率よく行うためには、各種熱伝導シートが使用されている。一般的に、発熱体と放熱体とを固定する用途においては、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（以下、「熱伝導性感圧接着性シート状成形体」という。）が必要とされている。 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 general, a method of dissipating heat by attaching a heat sink such as a metal heat sink, a heat radiating plate, or a heat radiating fin to a heat generator provided in an electronic component or the like is employed. In order to efficiently conduct heat conduction from the heat generating body to the heat radiating body, various heat conducting sheets are used. In general, in applications where a heating element and a radiator are fixed, a composition having a pressure-sensitive adhesive property in addition to thermal conductivity (hereinafter referred to as a “thermal conductive pressure-sensitive adhesive composition”) or sheet. (Hereinafter referred to as “thermally conductive pressure-sensitive adhesive sheet-like molded product”).
　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ことを主目的として用いられるため、熱伝導性が高いことが好ましい。熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体の熱抵抗を低くするためには、例えばこれらに膨張化黒鉛粉等を添加することが考えられる。しかしながら、膨張化黒鉛粉は高い熱伝導性を有するとともに、高い導電性も有する。したがって、膨張化黒鉛粉を多量に含有させることによって熱伝導性を向上させた熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体は、絶縁性も要求される用途には使用できない場合があった。一方、熱伝導性を向上させることができるフィラーとしては酸化亜鉛が用いられることもある（特許文献１乃至３）。 The heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are preferably used for the purpose of transferring heat from the heat generating body to the heat radiating body, and therefore preferably have high heat conductivity. In order to reduce the thermal resistance of the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded product, for example, it is conceivable to add expanded graphite powder or the like thereto. However, expanded graphite powder has high thermal conductivity and high conductivity. Therefore, the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body, which have improved thermal conductivity by containing a large amount of expanded graphite powder, are used for applications that also require insulation. There were cases where it could not be used. On the other hand, zinc oxide may be used as a filler capable of improving thermal conductivity (Patent Documents 1 to 3).
特開２００８－１６３１４５号公報JP 2008-163145 A 特開２００８－１２７４８２号公報JP 2008-127482 A 特開２００８－１２７４８１号公報JP 2008-127481 A
　酸化亜鉛は膨張化黒鉛粉よりは導電性が低いため、熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体に酸化亜鉛を添加した場合、膨張化黒鉛粉を添加するよりは導電性の上昇を抑えることができる。 Since zinc oxide has lower conductivity than expanded graphite powder, when zinc oxide is added to the thermally conductive pressure-sensitive adhesive composition and the thermally conductive pressure-sensitive adhesive sheet-like molded product, the expanded graphite powder is added. Can suppress an increase in conductivity.
　しかしながら、酸化亜鉛の導電性が膨張化黒鉛粉より低いとはいえ、酸化亜鉛によって熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体の熱伝導性を向上させるために特許文献１乃至３に記載された技術のように多量の酸化亜鉛を添加すると、熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体の導電性が高くなり、絶縁性が要求される用途では使用できない場合があった。このように、従来の技術では、熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体に絶縁性と熱伝導性とをバランスよく備えさせることが困難であった。 However, although the conductivity of zinc oxide is lower than that of expanded graphite powder, it is patented to improve the thermal conductivity of the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body by zinc oxide. When a large amount of zinc oxide is added as in the techniques described in Documents 1 to 3, the conductivity of the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body is increased, and insulation is required. In some cases, it could not be used. As described above, in the conventional technique, it is difficult to provide the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded article with a good balance between insulation and heat conductivity.
　そこで、本発明は、絶縁性及び熱伝導性をバランスよく備えた熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体と、これらの製造方法と、該熱伝導性感圧接着剤組成物又は該熱伝導性感圧接着性シート状成形体を備えた電子部品とを提供することを課題とする。 Therefore, the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article having a good balance between insulation and thermal conductivity, their production methods, and the thermally conductive pressure-sensitive adhesive. It is an object of the present invention to provide an agent composition or an electronic component including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
　本発明者らは、複数の熱伝導性を有するフィラーを適切な割合で組み合わせて使用することにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have found that the above problems can be solved by using a plurality of fillers having thermal conductivity in combination at an appropriate ratio, and have completed the present invention.
　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、針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、を含む混合組成物中において、（メタ）アクリル酸エステル単量体（α１）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 mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part In a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating heat conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D), (meth) acrylic 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) Thermally conductive pressure-sensitive adhesive composition ( ) It is.
　以下に、本明細書中で用いる文言の定義を記載する。「（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。「針状部を有する酸化亜鉛（Ｃ）」とは、後に詳述するように、針状部を有する酸化亜鉛のことを意味する。「膨張化黒鉛粉（Ｄ）」とは、後に詳述するように、黒鉛を膨張させて粉砕した粉状体を意味する。「針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）」とは、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除くものであって、添加することによって熱伝導性感圧接着剤組成物（Ｆ）又は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、電気抵抗率が１０１２Ωｍ以上であり、熱伝導率が１Ｗ／ｍ・Ｋ以上であるフィラーを意味する。「（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）由来の構造単位を生じる重合体を得る重合反応を意味する。「（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。 The definitions of terms used in this specification are described below. “(Meth) acryl” means “acryl and / or methacryl”. “Zinc oxide (C) having a needle-like part” means zinc oxide having a needle-like part, as will be described in detail later. The “expanded graphite powder (D)” means a powdery body obtained by expanding and pulverizing graphite, as will be described in detail later. “Insulating heat conductive filler (B) excluding zinc oxide (C) having acicular part and expanded graphite powder (D)” means zinc oxide (C) having acicular part and expanded graphite Excluding the powder (D), the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) described later is improved by adding the powder (D). Means a filler having an electrical resistivity of 10 12 Ωm or more and a thermal conductivity of 1 W / m · K or more. The “polymerization reaction of (meth) acrylate monomer (α1)” means a polymerization reaction for obtaining a polymer that generates a structural unit derived from the (meth) acrylate monomer (α1). "(Meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) -derived polymer cross-linking reaction" means (meth) acrylic acid ester polymer Cross-linking reaction between (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylic acid ester monomer (α1), and (meth) acrylic acid ester polymers (A1) and (meth) Among crosslinking reactions with a polymer containing a structural unit derived from an acrylate monomer (α1), it means one or more 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、針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００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、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 mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part After forming a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating thermally conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D) having a sheet shape Alternatively, 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 Polymer frame containing structural unit derived from monomer (α1) Reaction and, it been conducted, is a heat-conductive and pressure-sensitive adhesive sheet-like molded article (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、針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、を含む混合組成物を作製する工程、並びに、該混合組成物中において、（メタ）アクリル酸エステル単量体（α１）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 mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part A step of producing a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D), and In the mixed composition, 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 monomer (α1) A cross-linking reaction of a polymer containing a structural unit derived from Extent, including a method for producing a thermally conductive pressure-sensitive adhesive composition (F).
　本発明の第４の態様は、（メタ）アクリル酸エステル重合体（Ａ１）、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、針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００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、（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 masses of (meth) acrylic-ester resin compositions (A) containing the (meth) acrylic-ester polymer (A1) and the (meth) acrylic-ester monomer ((alpha) 1). 0.5 to 40 parts by mass of zinc oxide (C) having a part and an acicular part, 0.5 to 20 parts by mass of expanded graphite powder (D), and the acicular part A step of producing a mixed composition containing 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) and expanded graphite powder (D), and After forming the mixed composition into a sheet 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) acrylic acid ester monomer ( A method for producing a heat conductive pressure-sensitive adhesive sheet-like molded article (G), comprising a step of performing a crosslinking reaction of a polymer containing a structural unit derived from α1).
　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）、を備えた電子部品である。 According to a fifth aspect of the present invention, there is provided a heat radiator and the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the heat radiator, or the heat radiator and the heat radiator. An electronic component comprising the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) according to the second aspect of the present invention.
　本発明によれば、絶縁性及び熱伝導性をバランスよく備えた熱伝導性感圧接着剤組成物及び熱伝導性感圧接着性シート状成形体と、これらの製造方法と、該熱伝導性感圧接着剤組成物又は該熱伝導性感圧接着性シート状成形体を備えた電子部品とを提供することができる。 According to the present invention, a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article having a good balance between insulation and thermal conductivity, their production methods, and the thermally conductive pressure-sensitive adhesive It is possible to provide an agent composition or an electronic component provided with the thermally conductive pressure-sensitive adhesive sheet-like molded body.
　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、針状部を有する酸化亜鉛（Ｃ）（以下、単に「酸化亜鉛（Ｃ）」という場合がある。）と、膨張化黒鉛粉（Ｄ）と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）（以下、単に「熱伝導性フィラー（Ｂ）」という場合がある。）を含む混合組成物中において、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を生じる重合体を得る重合反応、並びに、（メタ）アクリル酸エステル重合体（Ａ１）同士の架橋反応、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体同士の架橋反応、及び、（メタ）アクリル酸エステル重合体（Ａ１）と（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体との架橋反応のうちいずれかの架橋反応が少なくとも行われてなるものである。 1. Thermally conductive pressure-sensitive adhesive composition (F), thermally conductive pressure-sensitive adhesive sheet-like molded body (G)
The thermally conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (α1). An object (A), zinc oxide (C) having a needle-like part (hereinafter sometimes simply referred to as “zinc oxide (C)”), expanded graphite powder (D), and oxidation having a needle-like part In a mixed composition containing an insulating thermally conductive filler (B) (hereinafter sometimes simply referred to as “thermally conductive filler (B)”) excluding zinc (C) and expanded graphite powder (D). , A polymerization reaction for obtaining a polymer that produces a structural unit derived from the (meth) acrylate monomer (α1), a crosslinking reaction between the (meth) acrylate polymers (A1), (meth) acrylic acid Polymers containing structural units derived from ester monomers (α1) At least one of the crosslinking reaction and the crosslinking reaction of the (meth) acrylic acid ester polymer (A1) and the polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1). It is done.
　また、本発明の熱伝導性感圧接着性シート状成形体（Ｇ）は、上記混合組成物をシート状に成形した後、又は上記混合組成物をシート状に成形しながら、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を生じる重合体を得る重合反応、並びに、（メタ）アクリル酸エステル重合体（Ａ１）同士の架橋反応、（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体同士の架橋反応、及び、（メタ）アクリル酸エステル重合体（Ａ１）と（メタ）アクリル酸エステル単量体（α１）由来の構造単位を含む重合体との架橋反応のうちいずれかの架橋反応が少なくとも行われてなるものである。 Moreover, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is (meth) acrylic acid after shape | molding the said mixed composition in a sheet form, or shape | molding the said mixed composition in a sheet form. Polymerization reaction for obtaining a polymer that produces a structural unit derived from an ester monomer (α1), a crosslinking reaction between (meth) acrylic acid ester polymers (A1), (meth) acrylic acid ester monomer (α1) Crosslinking reaction between polymers containing structural units derived from, and crosslinking with a polymer containing structural units derived from (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) Any cross-linking reaction among the reactions is performed at least.
　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、上述したように、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）を得る際には（メタ）アクリル酸エステル単量体（α１）由来の構造単位を生じる重合体を得る重合反応と、（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, as mentioned above, when obtaining a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G), (meth) acrylic acid ester monomer ((alpha) 1) origin Polymerization reaction to obtain a polymer that yields a structural unit of the above, 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) And done. 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、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）１００質量％に対して、（メタ）アクリル酸エステル重合体（Ａ１）５質量％以上４０質量％以下、（メタ）アクリル酸エステル単量体（α１）６０質量％以上９５質量％以下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）の含有比率を上記範囲とすることによって、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）を成形することが容易になる。 In this invention, the usage-amount of an acrylic ester polymer (A1) and the (meth) acrylic ester monomer ((alpha) 1) is (meth) with respect to 100 mass% of (meth) acrylic resin compositions (A). The acrylate polymer (A1) is preferably 5% by mass or more and 40% by mass or less, and the (meth) acrylic acid ester monomer (α1) is preferably 60% by mass or more and 95% 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.
　（（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の単位（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) acrylic acid ester polymer (A1) that can be used in the present invention is not particularly limited, but the (meth) acrylic acid ester monomer that forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is preferable to contain the unit (a1) and the 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 n-decyl methacrylate (-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, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, α, β-unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, And salts thereof.
　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）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 perform, an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer (A1) is formed.
　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成形する（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), which forms a homopolymer having a glass transition temperature of −20 ° C. or lower, and an organic acid group. Monomer (a2m), a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
　（メタ）アクリル酸エステル重合体（Ａ１）を得る際の重合方法は特に限定されず、溶液重合、乳化重合、懸濁重合、塊状重合などのいずれであってもよく、これら以外の方法でもよい。ただしこれらの重合方法の中で溶液重合が好ましく、中でも重合溶媒として、酢酸エチル、乳酸エチルなどのカルボン酸エステルやベンゼン、トルエン、キシレンなどの芳香族溶媒を用いた溶液重合がより好ましい。重合に際して、単量体は、重合反応容器に分割添加してもよいが、全量を一括添加するのが好ましい。重合開始の方法は、特に限定されないが、重合開始剤として熱重合開始剤を用いるのが好ましい。当該熱重合開始剤
は特に限定されず、例えば過酸化物重合開始剤やアゾ化合物重合開始剤を用いることができる。 The polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. . However, among these polymerization methods, solution polymerization is preferable, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferable. In the polymerization, the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once. The method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator. The thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
　過酸化物重合開始剤としては、ｔ－ブチルヒドロペルオキシドのようなヒドロペルオキシドや、ベンゾイルペルオキシド、シクロヘキサノンペルオキシドのようなペルオキシドの他、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムなどの過硫酸塩などを挙げることができる。これらの過酸化物は、還元剤と適宜組み合わせて、レドックス系触媒として使用することもできる。 Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
　アゾ化合物重合開始剤としては、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）などを挙げることができる。 As azo compound polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) And so on.
　重合開始剤の使用量は特に限定されないが、単量体１００質量部に対して０．０１質量部以上５０質量部以下の範囲であることが好ましい。 Although the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
　これらの単量体のその他の重合条件（重合温度、圧力、撹拌条件など）は、特に制限がない。 Other polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
　重合反応終了後、必要により、得られた重合体を重合媒体から分離する。分離の方法は特に限定されない。例えば、溶液重合の場合、重合溶液を減圧下に置き、重合溶媒を留去することによって、（メタ）アクリル酸エステル重合体（Ａ１）を得ることができる。 After completion of the polymerization reaction, the obtained polymer is separated from the polymerization medium if necessary. The separation method is not particularly limited. For example, in the case of solution polymerization, the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
　（メタ）アクリル酸エステル重合体（Ａ１）の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフ法（ＧＰＣ法）で測定して、標準ポリスチレン換算で１０万以上１００万以下の範囲にあることが好ましく、２０万以上５０万以下の範囲にあることが、より好ましい。（メタ）アクリル酸エステル重合体（Ａ１）の重量平均分子量は、重合の際に使用する重合開始剤の量や、連鎖移動剤の量を適宜調整することによって制御することができる。 The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. It is more preferable that it is in the range of 200,000 or more and 500,000 or less. The weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
　（（メタ）アクリル酸エステル単量体混合物（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成形する（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 mixture (α1))
The (meth) acrylate monomer (α1) is not particularly limited as long as it contains a (meth) acrylate monomer, but a homopolymer having a glass transition temperature of −20 ° C. or lower is molded. 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成形する（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 the (meth) acrylate monomer (a5m) for forming 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、（メタ）アクリル酸エステル単量体（ａ５ｍ）及びそれと共重合可能な単量体の混合物としてもよい。 The (meth) acrylic acid ester monomer (α1) may be a mixture of a (meth) acrylic acid ester monomer (a5m) and a monomer copolymerizable therewith.
　（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成形する（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) acrylate monomer (α1) is a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of −20 ° C. or less, and can be copolymerized with these monomers. It is good also as a mixture of the monomer (a6m) which has an 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）との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 with the monomer (a7m) which can be copolymerized 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.
　＜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）を得る際に、（メタ）アクリル酸エステル単量体（α１）及び後述する多官能性単量体は重合する。その重合を促進するため、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。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）に優れた接着性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 product (G), the (meth) acrylic acid ester monomer (α1) and a polyfunctional monomer described below are used. The body polymerizes. In order to accelerate the polymerization, 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. From the viewpoint of imparting excellent adhesiveness to the obtained heat conductive pressure-sensitive adhesive composition (F) and heat conductive pressure-sensitive adhesive sheet-like molded body (G), an organic peroxide thermal polymerization initiator is used. It is preferable to use it.
　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１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混合物（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、重合開始剤を添加することにより重合反応の進行を過度に誘発し、その結果、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、材料破壊を起こす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 mass part or more and 1 mass part or less. By making the usage-amount of a polymerization initiator into the said range, it becomes easy to make the polymerization conversion rate of (meth) acrylic acid ester monomer mixture ((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 product (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, the progress of polymerization reaction is induced excessively by adding a polymerization initiator, As a result, a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) However, it does not become a smooth sheet, and it is easy to prevent a situation in which material destruction occurs.
　＜多官能性単量体＞
　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）には多官能性単量体も用いることが好ましい。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、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。 <Multifunctional monomer>
It is preferable to use a polyfunctional monomer in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention. As the polyfunctional monomer, one that can be copolymerized with the monomer contained in the (meth) acrylic acid ester monomer (α1) is used. Moreover, it is preferable that the polyfunctional monomer has a plurality of polymerizable unsaturated bonds, and 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ることが好ましい。 Usually, at the time of polymerization such as radical thermal polymerization, a certain degree of crosslinking reaction proceeds without using a polyfunctional monomer. However, it is preferable to use a polyfunctional monomer 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.
　熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）に用いる多官能性単量体の量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量部として０．１質量部以上１５質量部以下であることが好ましく、０．２質量部以上８質量部以下であることがより好ましく、０．５質量部以上２質量部以下であることがさらに好ましい。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 in the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 mass of the (meth) acrylic resin composition (A). It is preferably 0.1 parts by weight or more and 15 parts by weight or less, more preferably 0.2 parts by weight or more and 8 parts by weight or less, and further preferably 0.5 parts by weight or more and 2 parts by weight or less. preferable. 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.
　＜酸化亜鉛（Ｃ）＞
  本発明に用いる酸化亜鉛（Ｃ）は、針状部を有する。該針状部の長さは２μｍ以上５０μｍ以下であることが好ましい。なお、酸化亜鉛（Ｃ）の針状部の長さは、例えば、走査電子顕微鏡で観察して測定することができる。後に説明するように、酸化亜鉛（Ｃ）の針状部の長さを上記範囲とすることによって、その他の熱伝導性を有するフィラーとの組み合わせ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）に高い熱伝導性を備えさせ易くなると考えられる。 <Zinc oxide (C)>
Zinc oxide (C) used in the present invention has a needle-like part. The length of the needle-like part is preferably 2 μm or more and 50 μm or less. In addition, the length of the acicular part of zinc oxide (C) can be measured by observing with a scanning electron microscope, for example. As will be described later, by setting the length of the needle-shaped portion of zinc oxide (C) within the above range, the thermally conductive pressure-sensitive adhesive composition (F) and the combination with other fillers having thermal conductivity are used. It is thought that it becomes easy to make a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) have high heat conductivity.
　本発明で用いる酸化亜鉛（Ｃ）の形状は、針状部を有していればよい。すなわち、酸化亜鉛（Ｃ）は、核となる部分の周囲に１又は複数の針状部が備えられていてもよく、針状部のみで構成されていてもよい。ただし、後述するように、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）内に充填された他の熱伝導性を有するフィラー間を酸化亜鉛（Ｃ）によって繋ぎ易くするという観点からは、核となる部分の周囲に複数の針状部がそれぞれ異なる方向に伸びて備えられている形状が好ましい。より好ましい形状は、核となる部分の周囲に３つ以上の針状部があり、該針状部のうちの少なくとも１つは他の針状部と同一平面上にない形状である。なお、１つの核の周囲に存在する針状部の数は、３～６個が好ましい。この範囲の数であると針状部の配向が３次元的になり、かつ、他のフィラーとの結びつきが良いものとなる。核となる部分の周囲に複数の針状部が備えられている酸化亜鉛の市販品としては、例えば、株式会社アムテック製の「パナテトラ（登録商標）」を挙げることができる。 The shape of zinc oxide (C) used in the present invention only needs to have a needle-like part. That is, the zinc oxide (C) may be provided with one or a plurality of needle-like portions around the core portion, or may be composed of only the needle-like portions. However, as will be described later, between the thermally conductive pressure-sensitive adhesive composition (F) and the other thermally conductive filler filled in the thermally conductive pressure-sensitive adhesive sheet-like molded body (G), zinc oxide ( From the viewpoint of facilitating connection by C), a shape in which a plurality of needle-like portions are provided extending in different directions around the core portion is preferable. A more preferable shape is a shape in which there are three or more needle-like portions around the core portion, and at least one of the needle-like portions is not coplanar with the other needle-like portions. In addition, the number of needle-like portions existing around one nucleus is preferably 3-6. When the number is within this range, the orientation of the needle-like portion becomes three-dimensional and the connection with other fillers is good. As a commercial product of zinc oxide having a plurality of needle-like parts around the core part, for example, “Panatetra (registered trademark)” manufactured by Amtec Corporation can be exemplified.
　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）に使用する酸化亜鉛（Ｃ）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．５質量部以上４０質量部以下であり、０．８質量部以上３５質量部以下であることが好ましい。酸化亜鉛（Ｃ）の含有量を上記範囲とすることによって、他の熱伝導性を有するフィラーとの組み合わせ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）に高い熱伝導性を備えさせ易くなる。また、酸化亜鉛（Ｃ）の含有量を上記範囲とすることによって、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の絶縁性が低下せず、絶縁性を要求される用途に使用できる他、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も十分に得られる。 The amount of zinc oxide (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 parts by weight of the (meth) acrylic resin composition (A). 0.5 parts by mass or more and 40 parts by mass or less, and preferably 0.8 parts by mass or more and 35 parts by mass or less. By setting the content of zinc oxide (C) within the above range, a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body in combination with other heat-conductive fillers. It becomes easy to provide (G) with high thermal conductivity. Moreover, the insulating property of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) does not fall by making content of zinc oxide (C) into the said range. In addition to being able to be used for applications requiring insulating properties, the effect of improving the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is sufficiently obtained. It is done.
　＜膨張化黒鉛粉（Ｄ）＞
  膨張化黒鉛粉（Ｄ）とは、黒鉛を膨張させた後に粉砕して得られものである。本発明に用いる膨張化黒鉛粉（Ｄ）の例としては、酸処理した黒鉛を５００℃以上１２００℃以下にて熱処理して１００ｍｌ／ｇ以上３００ｍｌ／ｇ以下に膨張させ、次いでそれを粉砕する工程を含む方法によって得られたものを挙げることができる。より好ましくは、黒鉛を強酸で処理した後にアルカリ中で焼結し、その後再度強酸で処理したものを５００℃以上１２００℃以下にて熱処理して酸を除去すると共に１００ｍｌ／ｇ以上３００ｍｌ／ｇ以下に膨張させ、次いで粉砕する工程を含む方法によって得られたものを挙げることができる。上記熱処理の温度は、特に好ましくは８００℃以上１０００℃以下である。 <Expanded graphite powder (D)>
The expanded graphite powder (D) is obtained by expanding graphite and then pulverizing it. As an example of the expanded graphite powder (D) used in the present invention, the acid-treated graphite is heat-treated at 500 ° C. or more and 1200 ° C. or less to expand to 100 ml / g or more and 300 ml / g or less, and then pulverized. What was obtained by the method of containing can be mentioned. More preferably, the graphite is treated with a strong acid, then sintered in an alkali, and then again treated with a strong acid at a temperature of 500 ° C. to 1200 ° C. to remove the acid and 100 ml / g to 300 ml / g. And a product obtained by a method including a step of expanding and then crushing. The temperature of the heat treatment is particularly preferably 800 ° C. or higher and 1000 ° C. or lower.
　本発明に用いる膨張化黒鉛粉（Ｄ）の平均粒径は、１０μｍ以上１０００μｍ以下であることが好ましく、２０μｍ以上７００μｍ以下であることがより好ましく、３０μｍ以上５００μｍ以下であることがさらに好ましい。膨張化黒鉛粉（Ｄ）の平均粒径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）内において熱の伝導経路を形成しやすくなり、また膨張化黒鉛粉（Ｄ）が破壊される事態を防止しやすくなる。
  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。 The average particle diameter of the expanded graphite powder (D) used in the present invention is preferably 10 μm or more and 1000 μm or less, more preferably 20 μm or more and 700 μm or less, and further preferably 30 μm or more and 500 μm or less. By setting the average particle size of the expanded graphite powder (D) within the above range, the heat conduction path in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). And the expanded graphite powder (D) is easily prevented from being destroyed.
In the present invention, the “average particle diameter” means that measured by the method described below. That is, a laser type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) is used, and measurement is performed by a microsorting control method (a method in which the measurement target particles are allowed to pass only in the measurement region and the measurement reliability is improved). According to this measurement method, when the measurement target particles 0.01 g to 0.02 g are flowed into the cell, the measurement target particles flowing in the measurement region are irradiated with the semiconductor laser light having a wavelength of 670 nm. By measuring the scattering and diffraction of laser light with a measuring instrument, the average particle size and particle size distribution are calculated from the diffraction principle of Franhofer.
　本発明に用いる膨張化黒鉛粉（Ｄ）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．５質量部以上２０質量部以下である。膨張化黒鉛粉（Ｄ）の量を上記範囲とすることによって、他の熱伝導性を有するフィラーとの組み合わせで、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）のもととなる混合組成物の流動性が低下す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）に絶縁性と熱伝導性とをバランス良く備えさせることができる。膨張化黒鉛粉（Ｄ）の量が上記上限以下であることで、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）の絶縁性が保持できる。 The amount of the expanded graphite powder (D) used in the present invention is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin composition (A). By making the amount of the expanded graphite powder (D) in the above range, in combination with other heat conductive filler, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet The heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) while suppressing the fluidity of the mixed composition that is the basis of the molded product (G). Can be provided with a good balance between insulation and thermal conductivity. The insulating property of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) can be hold | maintained because the quantity of expanded graphite powder (D) is below the said upper limit.
　＜熱伝導性フィラー（Ｂ）＞
  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、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を用いる。熱伝導性フィラー（Ｂ）は、絶縁性を有しており、添加することによって熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の熱伝導性を向上させることができるフィラーである。 <Thermal conductive filler (B)>
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, zinc oxide (C) having an acicular portion and expanded graphite powder (D) are contained. Insulating heat conductive filler (B) is used. The heat conductive filler (B) has insulating properties, and when added, 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 is a filler that can improve.
　熱伝導性フィラー（Ｂ）の具体例としては、炭酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム（アルミナ）、酸化マグネシウム、シリカ、ガラス繊維、窒化ホウ素及び窒化アルミニウム等を挙げることができる。この中でも、炭酸カルシウム、水酸化アルミニウム及び酸化アルミニウムが、入手が容易で、化学的に安定であり、かつ、多量の配合が可能であることから好ましく、水酸化アルミニウム及び酸化アルミニウムがより好ましい。熱伝導性フィラー（Ｂ）は一種を単独で使用してもよく、二種以上を併用してもよい。 Specific examples of the thermally conductive filler (B) include calcium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum oxide (alumina), magnesium oxide, silica, glass fiber, boron nitride and aluminum nitride. Among these, calcium carbonate, aluminum hydroxide, and aluminum oxide are preferable because they are easily available, chemically stable, and can be added in a large amount, and aluminum hydroxide and aluminum oxide are more preferable. A heat conductive filler (B) may be used individually by 1 type, and may use 2 or more types together.
　また、本発明に用いる熱伝導性フィラー（Ｂ）の平均粒径は、０．１μｍ以上５０μｍ以下であることが好ましい。 The average particle size of the heat conductive filler (B) used in the present invention is preferably 0.1 μm or more and 50 μm or less.
　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（Ｂ）の量は、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して、６００質量部以上１４００質量部以下であり、７００質量部以上１２００質量部以下であることが好ましく、８００質量部以上１０００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（Ｂ）の含有量を上記範囲とすることによって、その他のフィラーとの組み合わせ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）に絶縁性と熱伝導性をバランス良く備えさせやすくなる。一方、熱伝導性フィラー（Ｂ）の含有量が上記上限以下であることで、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）の素となる混合組成物の増粘を抑制し、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の生産性が低下することを防ぐとともに、硬度が高くなることを抑制して形状追随性が低下することを防ぐ。形状追随性が低下することを防ぐことにより、発熱体及び放熱体に貼付した際に、発熱体から放熱体へと熱を伝え易くなる。また、熱伝導性フィラー（Ｂ）の含有量が上記下限以上であることで、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）の熱伝導性を向上させる効果が十分に得られる。 The amount of the heat conductive filler (B) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is (meth) acrylic resin composition (A) 100. It is 600 parts by mass or more and 1400 parts by mass or less, preferably 700 parts by mass or more and 1200 parts by mass or less, and more preferably 800 parts by mass or more and 1000 parts by mass or less with respect to parts by mass. By making content of a heat conductive filler (B) into the said range, a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) in combination with another filler. It becomes easy to equip with a good balance between insulation and thermal conductivity. On the other hand, when the content of the heat conductive filler (B) is not more than the above upper limit, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are used. It suppresses the thickening of the mixed composition, prevents the productivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) from decreasing, and increases the hardness. It suppresses that and shape followability falls. By preventing the shape followability from being lowered, heat is easily transferred from the heat generating element to the heat dissipating element when attached to the heat generating element and the heat dissipating element. Moreover, heat conductivity of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) because content of a heat conductive filler (B) is more than the said minimum. The effect of improving is sufficiently obtained.
　＜熱伝導性を有するフィラーの組み合わせによる効果＞
  上述したように、酸化亜鉛（Ｃ）や膨張化黒鉛粉（Ｄ）のような導電性を有するフィラーを添加して樹脂組成物の熱伝導性を向上させる場合、これらのフィラーを多量に添加すると該樹脂組成物の絶縁性を低下させるという問題があった。一方、上記熱伝導性フィラー（Ｂ）のような絶縁性のフィラーのみでは、樹脂組成物の絶縁性の低下を防止することは可能であっても、熱伝導性を十分に向上させることが難しかった。本発明によれば、熱伝導性フィラー（Ｂ）、酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）をそれぞれ適切な量で組み合わせて用いることにより、酸化亜鉛（Ｃ）や膨張化黒鉛粉（Ｄ）のような導電性を有するフィラーの添加量をそれぞれ従来のものより少なく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）に高い熱伝導性を備えさせることができ、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）の絶縁性が低下することを抑制できる。すなわち、本発明によれば、絶縁性及び熱伝導性をバランス良く備え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）を提供することができる。これには以下の理由が考えられる。 <Effects of combination of fillers having thermal conductivity>
As described above, when a filler having conductivity such as zinc oxide (C) or expanded graphite powder (D) is added to improve the thermal conductivity of the resin composition, a large amount of these fillers are added. There has been a problem that the insulating properties of the resin composition are lowered. On the other hand, it is difficult to sufficiently improve the thermal conductivity even though it is possible to prevent a decrease in the insulating properties of the resin composition with only an insulating filler such as the above-mentioned thermal conductive filler (B). It was. According to the present invention, the zinc oxide (C) or the expanded graphite powder (D) can be used by combining the thermally conductive filler (B), zinc oxide (C) and the expanded graphite powder (D) in appropriate amounts. Even if the addition amount of the conductive filler such as D) is less than that of the conventional one, it is high in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). Heat conductivity can be provided and it can suppress that the insulation of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) falls. That is, according to the present invention, it is possible to provide a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) having a good balance between insulation and thermal conductivity. . The following reasons can be considered.
　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）によれば、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）の内部で主に絶縁性の熱伝導性フィラー（Ｂ）が熱の伝達経路を形成する。しかしながら、熱伝導性フィラー（Ｂ）だけでは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が不十分であるため、酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）がそれを補完する。酸化亜鉛（Ｃ）は上述したように針状部を有しているため、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）内において他の熱伝導性を有するフィラー間を該針状部によって繋ぐことで、熱の伝達経路を形成することができると推察される。通常、熱伝導性の向上を図るために熱伝導性を有するフィラーを添加する場合、熱伝導性を向上させ易くする観点からは、該フィラーの粒径は大きい方が良いと考えられる。しかしながら、上述したようにして酸化亜鉛（Ｃ）の針状部によって他の熱伝導性を有するフィラー間を繋ぎ易くするという観点からは、熱伝導性フィラー（Ｂ）及び膨張化黒鉛粉（Ｄ）は上述した所定の大きさとし、酸化亜鉛（Ｃ）の針状部は上述した所定の長さにすることが好ましいと考えられる。また、膨張化黒鉛粉（Ｄ）は熱伝導性が高いが導電性も高いので使用量を上述した所定の範囲とすることが好ましく、膨張化黒鉛粉（Ｄ）の使用量を上述した所定の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）の絶縁性が低下するのを抑制しつつ、熱伝導性を向上させることができる。 According to the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive property. The insulating heat conductive filler (B) mainly forms a heat transfer path inside the sheet-like molded body (G). However, the effect of improving the heat conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is insufficient only with the heat conductive filler (B). Zinc oxide (C) and expanded graphite powder (D) complement it. Since zinc oxide (C) has a needle-like portion as described above, other heat is generated in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It is presumed that a heat transfer path can be formed by connecting the fillers having conductivity with the needle-like portions. Usually, when a filler having thermal conductivity is added in order to improve thermal conductivity, it is considered that the filler should have a larger particle size from the viewpoint of easily improving thermal conductivity. However, from the viewpoint of easily connecting the fillers having other thermal conductivity with the needle-shaped portion of zinc oxide (C) as described above, the thermal conductive filler (B) and the expanded graphite powder (D). Is the above-mentioned predetermined size, and it is considered preferable that the needle-shaped portion of zinc oxide (C) has the above-mentioned predetermined length. Further, since the expanded graphite powder (D) has high thermal conductivity but high conductivity, it is preferable to use the amount within the predetermined range described above. The amount of the expanded graphite powder (D) used is the predetermined amount described above. By making it into the range, the thermal conductivity is improved while suppressing the deterioration of the insulating properties of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G). Can do.
　＜リン酸エステル＞
  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、リン酸エステルを用いることもできる。リン酸エステル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）の難燃性を向上させ易くなる。 <Phosphate ester>
Phosphate ester can also be used for the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention. By using phosphate ester, it becomes easy to improve the flame retardance of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G).
　本発明に用いるリン酸エステルは、２５℃における粘度が３０００ｍＰａ・ｓ以上であることが好ましい。リン酸エステルの粘度を上記範囲とすることで、熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）の成形性が悪くなることを防止し易くなる。なお、本発明においてリン酸エステルの「粘度」とは、以下に説明する方法によって測定した粘度を意味する。 The phosphate ester used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa · s or more. By making the viscosity of the phosphoric ester within the above range, it becomes easy to prevent deterioration of the moldability of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). . In the present invention, the “viscosity” of the phosphate ester means the viscosity measured by the method described below.
　（リン酸エステルの粘度測定方法）
  リン酸エステルの粘度測定には、Ｂ型粘度計（東京計器株式会社製）を用いて、以下に示す手順で行う。
（１）常温の環境でリン酸エステルを３００ｍｌ計量し、５００ｍｌの容器に入れる。
（２）攪拌用ロータＮｏ．１、２、３、４、５、６、７から、いずれかを選択し、粘度計に取り付ける。
（３）リン酸エステルが入った容器を粘度計の上に置き、ロータを該容器内の縮合リン酸エステルに沈める。このとき、ロータの目印となる凹みが丁度、リン酸エステルの液状界面にくるように沈める。
（４）回転数を２０、１０、４、２の中から選択する。
（５）攪拌スイッチを入れ、１分後の数値を読み取る。
（６）読み取った数値に、係数Ａを掛け算した値が粘度［ｍＰａ・ｓ］となる。なお、係数Ａは、下記表１に示すように、選択したロータＮｏ．と回転数とから決まる。 (Method for measuring viscosity of phosphate ester)
The viscosity of the phosphate ester is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to the following procedure.
(1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
(2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
(3) The container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the condensed phosphate ester in the container. At this time, the dent which becomes a mark of a rotor sinks so that it may just come to the liquid interface of phosphate ester.
(4) The rotation speed is selected from 20, 10, 4, and 2.
(5) Turn on the stirring switch and read the value after 1 minute.
(6) The value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa · s]. The coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　また、本発明に用いるリン酸エステルは、大気圧下での１５℃以上１００℃以下の温度領域において常に液体であることが好ましい。リン酸エステルは、混合する際に液体であれば、作業性が良く、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）を成形することが容易になる。リン酸エステルを含んだ熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）を成形する際、１５℃以上１００℃以下の環境で、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）を構成する各物質を混合することが好ましい。混合時の温度を上記範囲とすることによって、（メタ）アクリル樹脂組成物（Ａ）のガラス転移温度以上とし、（メタ）アクリル樹脂組成物（Ａ）に含まれる単量体等の揮発あるいは重合反応が始まってしまうことを防止し易くなるため、環境性及び作業性を良くすることができる。 Moreover, it is preferable that the phosphate ester used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester is liquid when mixed, the workability is good, and it is easy to form the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G). become. When forming a heat conductive pressure-sensitive adhesive composition (F) or a heat conductive pressure-sensitive adhesive sheet-like molded product (G) containing a phosphate ester, the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less. It is preferable to mix each substance which comprises an adhesive composition (F) or a heat conductive pressure-sensitive-adhesive sheet-like molded object (G). By setting the temperature during mixing in the above range, the glass transition temperature of the (meth) acrylic resin composition (A) is set to be equal to or higher than the volatilization or polymerization of monomers contained in the (meth) acrylic resin composition (A). Since it becomes easy to prevent the reaction from starting, the environmental performance and workability can be improved.
　本発明には、リン酸エステルとして、縮合リン酸エステルも非縮合リン酸エステルも用いることができる。ここでいう「縮合リン酸エステル」とは、１分子内にリン酸エステル部位が複数存在するものを意味し、「非縮合リン酸エステル」とは、１分子内にリン酸エステル部位が１つだけ存在するものを意味する。これまでに説明した条件を満たすリン酸エステルの具体例を以下に列記する。 In the present invention, either a condensed phosphate ester or a non-condensed phosphate ester can be used as the phosphate ester. As used herein, “condensed phosphate ester” means one having a plurality of phosphate ester moieties in one molecule, and “non-condensed phosphate ester” means one phosphate ester moiety in one molecule. It means something that exists only. Specific examples of phosphate esters that satisfy the conditions described so far are listed below.
　縮合リン酸エステルの具体例としては、１，３－フェニレンビス（ジフェニルホスフェート）、ビスフェノールＡビス（ジフェニルホスフェート）、レゾルシノールビス（ジフェニルホスフェート）などの芳香族縮合リン酸エステル；ポリオキシアルキレンビスジクロロアルキルホスフェートなどの含ハロゲン系縮合リン酸エステル；非芳香族非ハロゲン系縮合リン酸エステル；などが挙げられる。これらの中でも、比重が比較的小さく、有害物質（ハロゲンなど）の放出の危険がなく、入手も容易であることなどから、芳香族縮合リン酸エステルが好ましく、１，３－フェニレンビス（ジフェニルホスフェート）、ビスフェノールＡビス（ジフェニルホスフェート）がより好ましい。 Specific examples of the condensed phosphate ester include aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyalkylene bisdichloroalkyl And halogen-containing condensed phosphates such as phosphates; non-aromatic non-halogen-based condensed phosphates; Of these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no risk of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.
　非縮合リン酸エステルの具体例としては、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジル－２，６－キシレニルホスフェート、２－エチルヘキシルジフェニルホスフェートなどの芳香族リン酸エステル；トリス（β－クロロプロピル）ホスフェート、トリスジクロロプロピルホスフェート、トリス（トリブロモネオペンチル）ホスフェートなどの含ハロゲン系リン酸エステル；などが挙げられる。この中でも、有害物質（ハロゲンなど）が発生しないことなどから、芳香族リン酸エステルが好ましい。 Specific examples of the non-condensed phosphate ester include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris (β-chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.
　リン酸エステルは、一種を単独で用いてもよく、二種以上を併用してもよい。 Phosphoric acid ester may be used alone or in combination of two or more.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）及び熱伝導性感圧接着性シート状成形体（Ｇ）に使用するリン酸エステルの量は、（メタ）アクリル樹脂組成物（Ａ）を１００質量部として、２０質量部以上１００質量部以下であることが好ましい。リン酸エステルの含有量を上記範囲とすることによって、熱伝導性感圧接着剤組成物（Ｆ）又は熱伝導性感圧接着性シート状成形体（Ｇ）の難燃性を向上させやすくなる。 The amount of the phosphoric acid ester used for the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is 100 (meth) acrylic resin composition (A). The mass part is preferably 20 parts by mass or more and 100 parts by mass or less. By making content of phosphate ester into the said range, it becomes easy to improve the flame retardance of a heat conductive pressure sensitive adhesive composition (F) or a heat conductive pressure sensitive adhesive sheet-like molded object (G).
　＜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、上述した成分以外にも、上述した成分を添加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。）；金属の水酸化物、金属塩水和物等の難燃性熱伝導無機化合物；ガラス繊維；ＰＩＴＣＨ系炭素繊維や上述した熱伝導性フィラー（Ｂ）、酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）とは大きさや形状が異なる熱伝導性無機化合物；外部架橋剤；カーボンブラック、二酸化チタンなど顔料；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、酸化マグネシウムなど増粘剤；等を挙げることができる。 <Other additives>
In addition to the above-described components, the above-described effects due to the addition of the above-described components 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 assistants); flame retardant thermally conductive inorganic compounds such as metal hydroxides and metal salt hydrates; glass fibers; PITCH-based carbon fibers and the above-described thermal conductivity. Conductive inorganic compound with different size and shape from conductive filler (B), zinc oxide (C) and expanded graphite powder (D); external cross-linking agent; pigment such as carbon black and titanium dioxide; other filling such as clay Materials: Nanoparticles such as fullerene and carbon nanotubes; Polyphenol-based, hydroquinone-based, hindered amine-based antioxidants; acrylic polymer particles, fine silica, thickeners such as magnesium oxide; and the like.
　２．製造方法
  本発明の熱伝導性感圧接着剤組成物（Ｆ）は、これまでに説明した物質を混合した後、（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、を行うことにより得ることができる。 2. Manufacturing Method The thermally conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing the substances described above, followed by the polymerization reaction of the (meth) acrylic acid ester monomer (α1) and (meth) acrylic. It can obtain by performing the crosslinking reaction of the polymer containing the structural unit derived from the 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、針状部を有する酸化亜鉛（Ｃ）と、膨張化黒鉛粉（Ｄ）と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）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や、各物質の好ましい平均粒径等は上述した通りであり、ここでは説明を省略する。 That is, the manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1) ( (Meth) acrylic resin composition (A), zinc oxide (C) having an acicular part, expanded graphite powder (D), zinc oxide (C) having an acicular part and expanded graphite powder (D) And a step of preparing a mixed composition comprising an insulating thermally conductive filler (B), and a polymerization reaction of the (meth) acrylate monomer (α1) in the mixed composition, And a crosslinking reaction of a polymer containing a structural unit derived from a (meth) acrylic acid ester polymer (A1) and / or a (meth) acrylic acid ester monomer (α1). In addition, the substances that can be used, the preferable content ratio of each substance, the preferable average particle diameter of each substance, and the like are as described above, and the description thereof is omitted here.
　本発明の熱伝導性感圧接着剤組成物（Ｆ）の製造方法において、（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、を行う際には、加熱することが好ましい。当該加熱には、例えば、熱風、電気ヒーター、赤外線などを用いることができる。このときの加熱温度は、重合開始剤が効率良く分解し、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体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) of the present invention, the polymerization reaction of the (meth) acrylate monomer (α1), the (meth) acrylate polymer (A1) and / or When performing the crosslinking reaction of the polymer containing the structural unit derived from the (meth) acrylate monomer (α1), it is preferable to heat. For the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. The heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer proceeds. Although a temperature range changes with kinds of polymerization initiator to be used, 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.
　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物質を混合してシート状に成形した後、又は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 the substances described so far into a sheet shape, or while forming into a sheet shape, with a single (meth) acrylate ester. A polymerization reaction of the monomer (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). It can be obtained by doing.
　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、針状部を有する酸化亜鉛（Ｃ）と、膨張化黒鉛粉（Ｄ）と、針状部を有する酸化亜鉛（Ｃ）及び膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）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や、各物質の好ましい平均粒径等は上述した通りであり、ここでは説明を省略する。 That is, the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention comprises (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). (Meth) acrylic resin composition (A) containing, zinc oxide (C) having an acicular part, expanded graphite powder (D), zinc oxide (C) having an acicular part and expanded graphite powder ( D), a step of producing a mixed composition containing an insulating thermally conductive filler (B), and after forming the mixed composition into a sheet, or after forming the mixed composition into a sheet The (meth) acrylic acid ester monomer (α1) polymerization reaction and (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) -derived A cross-linking reaction of a polymer containing a structural unit. There. In addition, the substances that can be used, the preferable content ratio of each substance, the preferable average particle diameter of each substance, and the like are as described above, and the description thereof is omitted here.
　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、（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、を行う際には、加熱することが好ましい。当該加熱には、例えば、熱風、電気ヒーター、赤外線などを用いることができる。このときの加熱温度は、重合開始剤が効率良く分解し、（メタ）アクリル酸エステル単量体（α１）及び多官能性単量体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 manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention, the polymerization reaction of the (meth) acrylic acid ester monomer (α1), the (meth) acrylic acid ester polymer (A1) and When performing the crosslinking reaction of the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (α1), it is preferable to heat. For the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. The heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer proceeds. Although a temperature range changes with kinds of polymerization initiator to be used, 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.
　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、必要ならば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。 The method for forming the mixed composition into a sheet is not particularly limited. As a suitable method, for example, a method of forming the sheet by applying the mixed composition onto a process paper such as a release-treated polyester film, and if necessary, between the two release-processed process papers. A method of forming a sheet by pressing between the rolls with the mixed composition interposed therebetween, and extruding the mixed composition using an extruder, and forming the sheet by controlling the thickness through a die at that time The method etc. are mentioned.
　熱伝導性感圧接着性シート状成形体（Ｇ）の厚さは０．０５ｍｍ以上５ｍｍ以下にすることができる。熱伝導性感圧接着性シート状成形体（Ｇ）の厚さを上記上限以下とすることによって、熱伝導性感圧接着性シート状成形体（Ｇ）の厚み方向の熱抵抗を低くすることができる。熱伝導性感圧接着性シート状成形体（Ｇ）の厚さを上記下限以上とすることによって、当該熱伝導性感圧接着性シート状成形体（Ｇ）を発熱体及び放熱体に貼付する際に空気を巻き込むことを防止し易く、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。熱伝導性感圧接着性シート状成形体（Ｇ）の厚さは、好ましくは０．１ｍｍ以上２ｍｍ以下である。 The thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 5 mm or less. By setting the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) to the upper limit or less, the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be lowered. . By setting the thickness of the heat conductive pressure-sensitive adhesive sheet-shaped molded body (G) to the above lower limit or more, the thermal conductive pressure-sensitive adhesive sheet-shaped molded body (G) is applied to the heating element and the heat radiating body. It is easy to prevent entrainment of air, and as a result, it is possible to prevent an increase in thermal resistance and to improve workability in the step of attaching to the adherend. The thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.1 mm or more and 2 mm or less.
　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（ＰＥＴ）、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 (PET), polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic A film of a heat-resistant polymer such as an aromatic polyamide 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. 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 component include components around a heat generating part in a device having an electroluminescence (EL) light emitting diode (LED) light source, components around a power device such as an automobile, a fuel cell, a solar cell, a battery, and a mobile phone. And devices and parts having a heat generating part such as a personal digital assistant (PDA), a notebook computer, a liquid crystal, a surface conduction electron-emitting device display (SED), a plasma display panel (PDP), or an integrated circuit (IC). .
　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としては、ＬＥＤ光源に用いる場合を例にすると以下のような使用方法を例示することができる。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など）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など）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；などの方法である。また、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）を備えた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など）；車両用灯具；工業用照明；商業用照明；一般住宅用照明；などが挙げられる。 In addition, as a method of using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention for an electronic device, the following is an example of the case where it is used for an LED light source. The usage method can be illustrated. That is, it is directly attached to the LED light source; sandwiched between the LED light source and a heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); , Heat pipe, graphite sheet, etc.); used as a casing surrounding the LED light source; affixed to the casing surrounding the LED light source; and filling a gap between the LED light source and the casing. Moreover, as an application example of the LED light source provided with the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention, a display device having a transmissive liquid crystal panel Backlight devices (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; general residential lighting;
　また、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ＬＥＤ光源以外への使用例としては、以下のようなものが挙げられる。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；等にも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）を用いることができる。 Also, examples of the use 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 other than LED light sources 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; Etc., the heat conductive pressure-sensitive adhesive composition (F) of the present invention and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) can be used.
　さらに、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）の使用方法は上述した形態に限定されず、これまでに例示したもの以外の装置の筐体等に貼り付けて使用することもできる。例えば、自動車等に備えられる装置にも使用することができる。すなわち、自動車に備えられる装置の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（カーナビゲーション／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（カーナビゲーション／燃料電池／熱交換器）に接続した放熱板に貼り付ける；ことなどが挙げられる。 Furthermore, the usage method of the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is not limited to the form mentioned above, Other than what was illustrated so far. It can also be used by being attached to a casing or the like of the apparatus. For example, it can be used for an apparatus provided in an automobile or the like. That is, it is affixed inside a casing of a device provided in an automobile; affixed to the outside of a casing provided in an automobile; a heat generating part (car navigation / fuel cell / heat exchanger) inside the casing provided in an automobile ) And the casing; and affixing to a heat radiating plate connected to a heat generating part (car navigation / fuel cell / heat exchanger) inside the casing provided in the automobile.
　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；テレビジョン；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；などが挙げられる。 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; houses; televisions; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Lighting; Organic EL display; Notebook PC; PDA; Fuel cell; Semiconductor device; Rice cooker; Washing machine; Washing and drying machine: Optical semiconductor device combining optical semiconductor elements and phosphors; Etc.
　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など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、シートなどの冷却部材に対し、身体と反対の面に使用する；電子写真複写機、電子写真プリンタなどの画像形成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、電子写真プリンタなどの画像形成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；制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；制膜装置の処理対象体を載せる熱流制御用伝熱部に使用する；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；ことなど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 equalization 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 hygroscopic agent; cooling equipment, clothing, towels, sheets, etc. for cooling humans and animals On the opposite side of the body to the member Used for a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer; Pressurizing a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as a member itself; used as a heat flow control heat transfer part for placing a treatment object of a membrane control device; used as a heat flow control heat transfer part for placing a treatment object of a film control device; outer layer of a radioactive substance storage container It can be used between the interior and interior; used in a box body with a solar panel that absorbs sunlight; used between the reflective sheet of the CCFL backlight and the aluminum chassis.
　最後に、本発明に係る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、および、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、好ましい熱伝導性フィラー（Ｂ）は、水酸化アルミニウム及び／又は酸化アルミニウムである。
  また、本発明に係る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、および、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、（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、針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、前記針状部を有する酸化亜鉛（Ｃ）及び前記膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、を含む混合組成物は、好ましくは、さらに重合開始剤を、（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質量部以下含む。
  また、本発明に係る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、および、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、前記混合組成物は、好ましくは、さらに多官能性単量体を、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．１質量部以上１５質量部以下含む。
  また、本発明に係る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、および、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、前記混合組成物は、好ましくは、さらにリン酸エステルを、（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して２０質量部以上１００質量部以下含む。 Finally, the heat conductive pressure sensitive adhesive composition (F) according to the present invention, 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 manufacturing method of a heat conductive pressure-sensitive-adhesive sheet-like molded object (G), a preferable heat conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
Moreover, the heat conductive pressure-sensitive-adhesive composition (F) which concerns on this invention, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G), the manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F), and heat (Meth) acrylic resin containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1) in the method for producing conductive pressure-sensitive adhesive sheet-like molded product (G) 100 parts by mass of composition (A), 0.5 to 40 parts by mass of zinc oxide (C) having acicular parts, and 0.5 to 20 parts by mass of expanded graphite powder (D) Part of the insulating heat conductive filler (B) excluding zinc oxide (C) having the acicular part and the expanded graphite powder (D). The mixed composition preferably further comprises a polymerization initiator, a (meth) acrylic resin. Comprising composition (A) 0.01 part by mass or more than 10 parts by mass with respect to 100 parts by weight.
Moreover, the heat conductive pressure-sensitive-adhesive composition (F) which concerns on this invention, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G), the manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F), and heat In the method for producing a conductive pressure-sensitive adhesive sheet-like molded body (G), the mixed composition preferably further includes a polyfunctional monomer with respect to 100 parts by mass of the (meth) acrylic resin composition (A). 0.1 parts by mass or more and 15 parts by mass or less.
Moreover, the heat conductive pressure-sensitive-adhesive composition (F) which concerns on this invention, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G), the manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F), and heat In the method for producing a conductive pressure-sensitive adhesive sheet-like molded body (G), the mixed composition preferably further contains 20 mass parts of phosphate ester with respect to 100 mass parts of the (meth) acrylic resin composition (A). Part to 100 parts by mass.
　以下に、実施例にて本発明をさらに詳しく説明するが、本発明は実施例に限定されるものではない。なお、ここで用いる「部」や「％」は、特に断らない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The “parts” and “%” used here are based on mass unless otherwise specified.
　＜流動性＞
  後述する第１乃至第３混合工程を経て得られた混合組成物の流動性を評価した。具体的には、混合組成物が入れられたホバート容器を水平面に対して３０°傾け、１分後の該混合組成物の状態で評価した。その結果を表２に示した。混合組成物が傾斜に沿って流れた場合を「○」、動かなかった場合を「×」とした。混合組成物に流動性がある方が、該混合組成物をシート化し易くなる。すなわち、熱伝導性感圧接着性シート状成形体の生産性が高くなる。 <Fluidity>
The fluidity of the mixed composition obtained through the first to third mixing steps described later was evaluated. Specifically, the Hobart container in which the mixed composition was put was tilted by 30 ° with respect to the horizontal plane, and the state of the mixed composition after 1 minute was evaluated. The results are shown in Table 2. The case where the mixed composition flowed along the inclination was indicated as “◯”, and the case where it did not move was indicated as “X”. The fluidity of the mixed composition makes it easier to form the mixed composition into a sheet. That is, the productivity of the heat conductive pressure-sensitive adhesive sheet-like molded product is increased.
　＜体積抵抗率（絶縁性）＞
  後述する方法で作製した熱伝導性感圧接着性シートを８０ｍｍ×８０ｍｍの大きさに裁断した試験片を用意した。デジタル超高抵抗／微少電流計（商品名「８３４０Ａ」、株式会社エーディーシー製）に試験片をセットして、該試験片の左右両端に電流を流して抵抗率を測定した。電圧は５００Ｖから開始して測定できる電圧まで徐々に下げていき、測定できる電圧での抵抗率を測定した。なお、チャージ時間は１分とした。該測定を３回行い、その平均値を熱伝導性感圧接着性シートの体積抵抗率（単位：Ω・ｃｍ）とした。結果を表２に示した。この評価による結果が１．０×１０１０Ω・ｃｍ以上であれば、絶縁性が優れていると言える。 <Volume resistivity (insulating properties)>
A test piece was prepared by cutting a thermally conductive pressure-sensitive adhesive sheet produced by the method described later into a size of 80 mm × 80 mm. A test piece was set on a digital ultra-high resistance / micro-ammeter (trade name “8340A”, manufactured by ADC Corporation), and a current was passed through both right and left ends of the test piece to measure resistivity. The voltage started from 500 V and gradually decreased to a measurable voltage, and the resistivity at the measurable voltage was measured. The charging time was 1 minute. The measurement was performed three times, and the average value was defined as the volume resistivity (unit: Ω · cm) of the heat conductive pressure-sensitive adhesive sheet. The results are shown in Table 2. If the result of this evaluation is 1.0 × 10 10 Ω · cm or more, it can be said that the insulation is excellent.
　＜クールダウン効果＞
  後述する方法で作製した熱伝導性感圧接着性シート状成形体のうち、上記試験によって絶縁性が優れていると判断されたものについて、２５ｍｍ×２５ｍｍの大きさに裁断した試験片を用意した。試験片を１５０ｍｍ×１５０ｍｍ×厚さ３ｍｍのアルミニウム板に貼り付け、試験片の、アルミニウム板に貼り付けた側とは反対側の面に、マイクロセラミックヒーター（坂口電熱株式会社製、商品名：ＭＳ－５、２５ｍｍ×２５ｍｍ）を万力にて固定し、該アルミニウム板を宙吊りにした。その後、マイクロセラミックヒーターをスライダックに接続し、６０Ｗで６０分間加熱したときのマイクロセラミックヒーターの表面をサーモグラフィーで撮影した。そのときの最高温度を表２に示した。当該温度が低くなった方がマイクロセラミックヒーターからアルミニウム板に多くの熱を伝えられていることを意味するので、当該温度が低い程、熱伝導性感圧接着性シート状成形体の熱抵抗が低いと言える。なお、本評価は２３℃雰囲気下で行った。 <Cooldown effect>
A test piece cut to a size of 25 mm × 25 mm was prepared for a heat-conductive pressure-sensitive adhesive sheet-like molded body produced by the method described later, which was judged to have excellent insulation properties by the above test. The test piece was affixed to an aluminum plate of 150 mm × 150 mm × thickness 3 mm, and a micro ceramic heater (manufactured by Sakaguchi Electric Heat Co., Ltd., trade name: MS) −5, 25 mm × 25 mm) was fixed with a vise and the aluminum plate was suspended. Thereafter, a micro ceramic heater was connected to the slidac, and the surface of the micro ceramic heater when heated at 60 W for 60 minutes was photographed by thermography. The maximum temperature at that time is shown in Table 2. The lower the temperature means that more heat is transferred from the micro ceramic heater to the aluminum plate, so the lower the temperature, the lower the thermal resistance of the heat conductive pressure-sensitive adhesive sheet-like molded body. It can be said. This evaluation was performed in an atmosphere at 23 ° C.
　＜熱伝導性感圧接着性シート状成形体の作製＞
  （実施例１）
  反応器に、アクリル酸２－エチルヘキシル９４％とアクリル酸６％とからなる単量体混合物１００部、２，２’－アゾビスイソブチロニトリル０．０３部及び酢酸エチル７００部を入れて均一に溶解し、窒素置換後、８０℃で６時間重合反応を行った。重合転化率は９７％であった。得られた重合体を減圧乾燥して酢酸エチルを蒸発させ、粘性のある固体状の（メタ）アクリル酸エステル重合体（Ａ１－１）を得た。（メタ）アクリル酸エステル重合体（Ａ１－１）の重量平均分子量（Ｍｗ）は２７０，０００、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）は３．１であった。重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、テトラヒドロフランを溶離液とするゲルパーミエーションクロマトグラフィーにより、標準ポリスチレン換算で求めた。 <Preparation of heat conductive pressure-sensitive adhesive sheet-like molded body>
Example 1
A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
　次に、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート及びペンタエリスリトールジアクリレートを６０：３５：５の割合で混合した多官能性単量体１．０部と、アクリル酸２－エチルヘキシル（表２では、「２ＥＨＡ」と略記している。）８８部と、有機過酸化物熱重合開始剤（１，６－ビス（ｔ－ブチルペルオキシカルボニルオキシ）ヘキサン（１分間半減期温度は１５０℃である。））１．０部と、を電子天秤で計量し、これらを上記（メタ）アクリル酸エステル重合体（Ａ１－１）１３部と混合した。混合には、恒温槽（東機産業株式会社製、商品名「ビスコメイト  １５０ＩＩＩ」）及びホバートミキサー（株式会社小平製作所製、商品名「ＡＣＭ－５ＬＶＴ型」、容量：５Ｌ）を用いた。ホバート容器の温調は６０℃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, 1.0 part of a polyfunctional monomer obtained by mixing pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate in a ratio of 60: 35: 5, and 2-ethylhexyl acrylate (in Table 2, 88 parts of abbreviated as “2EHA”) and organic peroxide thermal polymerization initiator (1,6-bis (t-butylperoxycarbonyloxy) hexane (1 minute half-life temperature is 150 ° C.) ) 1.0 part was weighed with an electronic balance, and these were mixed with 13 parts of the (meth) acrylic acid ester polymer (A1-1). For the mixing, a thermostatic bath (manufactured by Toki Sangyo Co., Ltd., trade name “Biscomate Meat 150III”) and a Hobart mixer (manufactured by Kodaira Manufacturing Co., Ltd., trade name “ACM-5LVT type”, capacity: 5 L) were used. The temperature control of the Hobart container was set to 60 ° C., the rotation speed scale was set to 3, and the mixture was stirred for 10 minutes. This process is referred to as a first mixing process.
　次に、リン酸エステル（味の素ファインテクノ株式会社製、商品名「レオフォス６５」、化合物名「リン酸トリアリールイソプロピル化物」）５０部と、水酸化アルミニウム（日本軽金属株式会社製、商品名「ＢＦ－０８３」、平均粒径：８μｍ、ＢＥＴ比表面積：０．８ｍ２／ｇ）５００部と、アルミナ（昭和電工株式会社製、商品名「ＡＬ－４７－Ｈ」、平均粒径：２μｍ、ＢＥＴ比表面積：１．１ｍ２／ｇ）５００部と、酸化亜鉛（株式会社アムテック製、パナテトラ  ＷＺ－０５１１）２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６０℃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, 50 parts of phosphoric acid ester (Ajinomoto Fine Techno Co., Ltd., trade name “Reophos 65”, compound name “triaryl isopropylate”) and aluminum hydroxide (Nihon Light Metal Co., Ltd., trade name “BF”) -083 ”, average particle size: 8 μm, BET specific surface area: 0.8 m 2 / g) and alumina (made by Showa Denko KK, trade name“ AL-47-H ”, average particle size: 2 μm, BET Specific surface area: 1.1 m 2 / g) 500 parts and zinc oxide (manufactured by Amtec Co., Ltd., Panatetra WZ-0511) are weighed and put into the Hobart container, and the temperature of the Hobart container is adjusted to 60 ° C. The mixture was stirred for 10 minutes at a rotation speed scale of 5. This process is referred to as a second mixing process.
　次に、膨張化黒鉛粉（伊藤黒鉛工業株式会社製、商品名「ＥＣ－５００」、平均粒径：３０μｍ）２部を計量して上記ホバート容器に投入し、ホバート容器内を真空（－０．１ＭＰａ（Ｇ））にして、ホバート容器の温調を６０℃に設定し、回転数目盛を３にして１０分間、真空脱泡しながら攪拌した。この工程を第３混合工程という。 Next, 2 parts of expanded graphite powder (trade name “EC-500” manufactured by Ito Graphite Industries Co., Ltd., average particle size: 30 μm) are weighed and put into the Hobart container, and the inside of the Hobart container is vacuumed (−0 0.1 MPa (G)), the temperature control of the Hobart container was set to 60 ° C., the rotation speed scale was set to 3, and the mixture was stirred for 10 minutes while vacuum degassing. This process is referred to as a third mixing process.
　次に、上記第１乃至第３混合工程を経て得た混合組成物を、厚さ７５μｍの離型処理した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の他の離型処理したＰＥＴフィルムを被せた。混合組成物が離型処理したＰＥＴフィルムに挟持されたこの積層体を、両者の間隔を０．６５ｍｍにしたロールの間を通し、シート状にした。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及び架橋反応させ、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 to third mixing steps is hung on a release-treated PET film having a thickness of 75 μm, and another release mold having a thickness of 75 μm is further formed on the mixed composition. The treated PET film was covered. The laminate, which was sandwiched between the release films of the mixed composition, was passed through a roll having a distance of 0.65 mm between them to form a sheet. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes. Through this heating step, the (meth) acrylic acid ester monomer was polymerized and crosslinked to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet | seat (G1).
　（実施例２乃至５、及び比較例１乃至３）
  各物質の配合を表２に示したように変更した以外は実施例１と同様にして、シート（Ｇ２～５、ＧＣ１～３）を得た。評価結果を表２に示す。 (Examples 2 to 5 and Comparative Examples 1 to 3)
Sheets (G2 to 5, GC1 to 3) were obtained in the same manner as in Example 1 except that the composition of each substance was changed as shown in Table 2. The evaluation results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、実施例にかかるシート（Ｇ１）乃至シート（Ｇ５）は、いずれもシート化する前の混合組成物の流動性が良く、シート化後、該シートは体積抵抗率が高く、クールダウン効果が優れていた。すなわち、本発明によれば、絶縁性及び熱伝導性をバランスよく備えた熱伝導性感圧接着性シート状成形体を提供できることがわかった。一方、比較例にかかるシート（ＧＣ１）乃至シート（ＧＣ３）は上記性能のいずれかが劣っていた。具体的には、以下の通りであった。酸化亜鉛及び膨張化黒鉛の含有量が少ない比較例１のシート（ＧＣ１）は、クールダウン効果が劣っていた。また、膨張化黒鉛の含有量が多い比較例２のシート（ＧＣ２）及び酸化亜鉛の含有量が多い比較例３のシート（ＧＣ３）は、体積抵抗率が低かった。なお、体積抵抗率の低い比較例２及び比較例３については、本発明の課題を解決しうるものではなかったので、クールダウン効果の試験を実施しなかった。 As shown in Table 2, each of the sheets (G1) to (G5) according to the examples has good fluidity of the mixed composition before forming into a sheet, and after forming into a sheet, the sheet has a high volume resistivity. The cool down effect was excellent. That is, according to this invention, it turned out that the heat conductive pressure-sensitive-adhesive sheet-like molded object provided with insulation and heat conductivity with sufficient balance can be provided. On the other hand, one of the above performances was inferior in the sheets (GC1) to (GC3) according to the comparative examples. Specifically, it was as follows. The sheet (GC1) of Comparative Example 1 having a small content of zinc oxide and expanded graphite was inferior in the cool-down effect. Moreover, the sheet (GC2) of Comparative Example 2 having a large content of expanded graphite and the sheet (GC3) of Comparative Example 3 having a large content of zinc oxide had low volume resistivity. In addition, about the comparative example 2 and the comparative example 3 with low volume resistivity, since the subject of this invention was not able to be solved, the test of the cool-down effect was not implemented.

Claims (21)

  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、
    　針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、
    　膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、
    　前記針状部を有する酸化亜鉛（Ｃ）及び前記膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、
    を含む混合組成物中において、前記（メタ）アクリル酸エステル単量体（α１）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 acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
    0.5 to 40 parts by mass of zinc oxide (C) having a needle-like part;
    0.5 parts by mass or more and 20 parts by mass or less of expanded graphite powder (D),
    Insulating thermally conductive filler (B) excluding zinc oxide (C) having the needle-like part and expanded graphite powder (D) is 600 parts by mass or more and 1400 parts by mass or less,
    In the mixed composition containing, the polymerization reaction of the (meth) acrylate monomer (α1), the (meth) acrylate polymer (A1) and / or the (meth) acrylate ester A heat-conductive pressure-sensitive adhesive composition (F) obtained by performing a crosslinking reaction of a polymer containing a structural unit derived from the body (α1).
  2. 　前記熱伝導性フィラー（Ｂ）が、水酸化アルミニウム及び／又は酸化アルミニウムである、請求項１に記載の熱伝導性感圧接着剤組成物（Ｆ）。 The heat conductive pressure-sensitive adhesive composition (F) according to claim 1, wherein the heat conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  3. 　前記混合組成物が、さらに重合開始剤を、前記（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質量部以下含む、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 according to claim 1 or 2, wherein the mixed composition further contains a polymerization initiator in an amount of 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). Conductive pressure sensitive adhesive composition (F).
  4. 　前記混合組成物が、さらに多官能性単量体を、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．１質量部以上１５質量部以下含む、請求項１～３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 mixed composition further comprises a polyfunctional monomer in an amount of 0.1 parts by weight to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin composition (A). The heat conductive pressure-sensitive-adhesive composition (F) of any one of Claims.
  5. 　前記混合組成物が、さらにリン酸エステルを、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して２０質量部以上１００質量部以下含む、請求項１～４のいずれか１項に記載の熱伝導性感圧接着剤組成物（Ｆ）。 The mixed composition according to any one of claims 1 to 4, wherein the mixed composition further contains a phosphate ester in an amount of 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The heat conductive pressure-sensitive adhesive composition (F) described.
  6. 　（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、
    　針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、
    　膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、
    　前記針状部を有する酸化亜鉛（Ｃ）及び前記膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、を含む混合組成物をシート状に成形した後、又は前記混合組成物をシート状に成形しながら、前記（メタ）アクリル酸エステル単量体（α１）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 acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
    0.5 to 40 parts by mass of zinc oxide (C) having a needle-like part;
    0.5 parts by mass or more and 20 parts by mass or less of expanded graphite powder (D),
    A mixed composition comprising 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) having the acicular part and the expanded graphite powder (D). After forming into a sheet shape or while forming the mixed composition into a sheet shape, the polymerization reaction of the (meth) acrylate monomer (α1) and the (meth) acrylate polymer (A1) And / or a cross-linking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1), and a thermally conductive pressure-sensitive adhesive sheet-like molded article (G).
  7. 　前記熱伝導性フィラー（Ｂ）が、水酸化アルミニウム及び／又は酸化アルミニウムである、請求項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 pressure-sensitive adhesive sheet-like molded article (G) according to claim 6, wherein the heat conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  8. 　前記混合組成物が、さらに重合開始剤を、前記（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質量部以下含む、請求項６又は７に記載の熱伝導性感圧接着性シート状成形体（Ｇ）。 The heat according to claim 6 or 7, wherein the mixed composition further contains a polymerization initiator in an amount of 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). Conductive pressure-sensitive adhesive sheet-like molded product (G).
  9. 　前記混合組成物が、さらに多官能性単量体を、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．１質量部以上１５質量部以下含む、請求項６～８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）。 The mixture composition according to any one of claims 6 to 8, wherein the mixed composition further contains a polyfunctional monomer in an amount of 0.1 parts by weight to 15 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin composition (A). The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of any one of Claims.
  10. 　前記混合組成物が、さらにリン酸エステルを、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して２０質量部以上１００質量部以下含む、請求項６～９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）。 10. The mixed composition according to any one of claims 6 to 9, wherein the mixed composition further contains a phosphate ester in an amount of 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The heat-conductive pressure-sensitive-adhesive sheet-like molded object (G) of description.
  11. 　（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、
    　針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、
    　膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、
    　前記針状部を有する酸化亜鉛（Ｃ）及び前記膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、を含む混合組成物を作製する工程、並びに、
    　前記混合組成物中において、前記（メタ）アクリル酸エステル単量体（α１）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 acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
    0.5 to 40 parts by mass of zinc oxide (C) having a needle-like part;
    0.5 parts by mass or more and 20 parts by mass or less of expanded graphite powder (D),
    A mixed composition comprising 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) having the acicular part and the expanded graphite powder (D). Manufacturing process, and
    In the mixed composition, 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 monomer. A step of performing a crosslinking reaction of a polymer containing a structural unit derived from (α1),
    The manufacturing method of a heat conductive pressure sensitive adhesive composition (F) containing this.
  12. 　前記熱伝導性フィラー（Ｂ）が、水酸化アルミニウム及び／又は酸化アルミニウムである、請求項１１に記載の熱伝導性感圧接着剤組成物（Ｆ）の製造方法。 The method for producing a heat conductive pressure-sensitive adhesive composition (F) according to claim 11, wherein the heat conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  13. 　前記混合組成物が、さらに重合開始剤を、前記（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質量部以下含む、請求項１１又は１２に記載の熱伝導性感圧接着剤組成物（Ｆ）の製造方法。 The heat according to claim 11 or 12, wherein the mixed composition further contains a polymerization initiator in an amount of 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin composition (A). A method for producing a conductive pressure-sensitive adhesive composition (F).
  14. 　前記混合組成物が、さらに多官能性単量体を、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．１質量部以上１５質量部以下含む、請求項１１～１３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 mixed composition further comprises 0.1 to 15 parts by mass of a polyfunctional monomer with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of any one.
  15. 　前記混合組成物が、さらにリン酸エステルを、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して２０質量部以上１００質量部以下含む、請求項１１～１４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 mixed composition according to any one of claims 11 to 14, wherein the mixed composition further contains a phosphate ester in an amount of 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of description.
  16. 　（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、
    　針状部を有する酸化亜鉛（Ｃ）を０．５質量部以上４０質量部以下と、
    　膨張化黒鉛粉（Ｄ）を０．５質量部以上２０質量部以下と、
    　前記針状部を有する酸化亜鉛（Ｃ）及び前記膨張化黒鉛粉（Ｄ）を除く、絶縁性の熱伝導性フィラー（Ｂ）を６００質量部以上１４００質量部以下と、を含む混合組成物を作製する工程、並びに、
    　前記混合組成物をシート状に成形した後、又は、前記混合組成物をシート状に成形しながら、前記（メタ）アクリル酸エステル単量体（α１）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 acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
    0.5 to 40 parts by mass of zinc oxide (C) having a needle-like part;
    0.5 parts by mass or more and 20 parts by mass or less of expanded graphite powder (D),
    A mixed composition comprising 600 parts by mass or more and 1400 parts by mass or less of an insulating thermal conductive filler (B) excluding zinc oxide (C) having the acicular part and the expanded graphite powder (D). Manufacturing process, and
    After forming the mixed composition into a sheet shape, or while forming the mixed composition into a sheet shape, a polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the (meth) acrylic acid A step of performing a crosslinking reaction of the ester polymer (A1) and / or a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1),
    The manufacturing method of a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) including this.
  17. 　前記熱伝導性フィラー（Ｂ）が、水酸化アルミニウム及び／又は酸化アルミニウムである、請求項１６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 manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 16 whose said heat conductive filler (B) is aluminum hydroxide and / or aluminum oxide.
  18. 　前記混合組成物が、さらに重合開始剤を、前記（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質量部以下含む、請求項１６又は１７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 according to claim 16 or 17, wherein the mixed composition further contains a polymerization initiator in an amount of 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The manufacturing method of a conductive pressure-sensitive-adhesive sheet-like molded object (G).
  19. 　前記混合組成物が、さらに多官能性単量体を、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して０．１質量部以上１５質量部以下含む、請求項１６～１８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 mixed composition further comprises a polyfunctional monomer in an amount of 0.1 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of any one of Claims.
  20. 　前記混合組成物が、さらにリン酸エステルを、前記（メタ）アクリル樹脂組成物（Ａ）１００質量部に対して２０質量部以上１００質量部以下含む、請求項１６～１９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 mixed composition according to any one of claims 16 to 19, wherein the mixed composition further contains a phosphate ester in an amount of 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object of description (G).
  21. 　放熱体及び該放熱体に貼合された請求項１～５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６～１０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）、を備えた電子部品。 The heat conductive pressure-sensitive adhesive composition (F) according to any one of claims 1 to 5, which is bonded to the heat radiator and the heat radiator, or the heat radiator and the heat bonded to the heat radiator. Item 11. An electronic component comprising the heat conductive pressure-sensitive adhesive sheet-like molded body (G) according to any one of Items 6 to 10.
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