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WO2013183389A1 - Composition adhésive sensible à la pression, thermiquement conductrice, corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice, procédé de fabrication d'une composition adhésive sensible à la pression, thermiquement conductrice, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice, et dispositif électronique - Google Patents

Composition adhésive sensible à la pression, thermiquement conductrice, corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice, procédé de fabrication d'une composition adhésive sensible à la pression, thermiquement conductrice, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice, et dispositif électronique Download PDF

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Publication number
WO2013183389A1
WO2013183389A1 PCT/JP2013/062625 JP2013062625W WO2013183389A1 WO 2013183389 A1 WO2013183389 A1 WO 2013183389A1 JP 2013062625 W JP2013062625 W JP 2013062625W WO 2013183389 A1 WO2013183389 A1 WO 2013183389A1
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WO
WIPO (PCT)
Prior art keywords
meth
less
heat conductive
acid ester
mass
Prior art date
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Ceased
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PCT/JP2013/062625
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English (en)
Japanese (ja)
Inventor
明子 北川
拓朗 熊本
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Zeon Corp
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Zeon Corp
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Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to CN201380024987.4A priority Critical patent/CN104321400A/zh
Priority to KR1020147030510A priority patent/KR20150016496A/ko
Priority to JP2014519886A priority patent/JPWO2013183389A1/ja
Publication of WO2013183389A1 publication Critical patent/WO2013183389A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H10W40/70—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H10W40/251—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet.
  • the present invention relates to an electronic device provided with a shaped molded body.
  • thermo conductivity feeling a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • a pressure-sensitive adhesive composition ”) and a sheet-like member hereinafter referred to as“ thermally conductive pressure-sensitive adhesive sheet-like molded body ”.
  • the above-mentioned heat conductive pressure-sensitive adhesive composition and heat conductive pressure-sensitive adhesive sheet-like molded body are required to be flexible so as to be in close contact with the heat generator and the heat radiator in order to transmit heat from the heat generator to the heat radiator.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded article having excellent flexibility for example, there are a flame-retardant heat dissipation sheet disclosed in Patent Document 1 and a heat conductive sheet disclosed in Patent Document 2.
  • heat is generated by improving flexibility. It is conceivable to improve the adhesion between the body and the radiator. Further, in order to efficiently transfer heat from the heating element to the heat radiating body using the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded body, for example, these are formed into thin thicknesses. It is conceivable to reduce the thermal resistance in the direction. However, the conventional heat conductive pressure-sensitive adhesive composition or heat conductive pressure-sensitive adhesive sheet-like molded product may be easily broken or may have pinholes when it is thinly formed.
  • the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded product that are difficult to break even when molded thinly, their production methods, and the thermally conductive pressure-sensitive adhesive composition.
  • an object of the present invention is to provide an electronic device including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
  • (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) The heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • a mixed composition containing at least part by mass, and at least a polymerization reaction of the (meth) acrylate monomer ( ⁇ 1), and a (meth) acrylate polymer (A1) and / or (meth) acrylate.
  • Polymer and the crosslinking reaction is taking place, including a structural unit derived from ester monomers ([alpha] 1), a thermally conductive pressure-sensitive adhesive composition (F).
  • (meth) acryl means “acryl and / or methacryl”.
  • the “thermally conductive filler” is added to improve the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) described later. It means a filler having a thermal conductivity of 0.5 W / m ⁇ K or more.
  • the “polymerization reaction of (meth) acrylate monomer ( ⁇ 1)” means a polymerization reaction to obtain a polymer containing a structural unit derived from (meth) acrylate monomer ( ⁇ 1).
  • (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer ( ⁇ 1) -derived polymer cross-linking reaction means (meth) acrylic acid ester Cross-linking reaction between polymers (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylate monomer ( ⁇ 1), and (meth) acrylate polymer (A1) and ( Among crosslinking reactions with a polymer containing a structural unit derived from a (meth) acrylate monomer ( ⁇ 1), it means one or a plurality of crosslinking reactions.
  • (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) The heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1) The heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • a step of preparing a mixed composition comprising: less than or equal to parts by mass; and in the mixed composition, at least a polymerization reaction of the (meth) acrylate monomer ( ⁇ 1) and (meth) acrylate polymerization (A1) and / or the process of performing the crosslinking reaction of the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1), to produce a heat conductive pressure-sensitive adhesive composition (F) Is the method.
  • the 4th aspect of this invention is 100 mass parts of (meth) acrylic resin compositions (A) containing the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1).
  • the heat conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g is 300 to 1000 parts by mass, the average particle diameter is 20 ⁇ m or less, and the BET specific surface area.
  • the polyfunctional epoxy compound (C) having a functional group of 2 to 10000 and 60 parts by mass to 4 parts by mass and a thermal conductive filler (B2) of 1.0 m 2 / g or more and 4 to 900 parts by mass.
  • a step of preparing a mixed composition comprising the mass part or less, and after forming the mixed composition into a sheet or while forming the mixed composition into a sheet, at least a (meth) acrylate ester
  • G heat conductive pressure-sensitive-adhesive sheet-like molded object
  • the heat conductive filler (B1) is a metal oxide having an average particle size of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g
  • the conductive filler (B2) is preferably a metal oxide having an average particle size of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more
  • the thermally conductive filler (B1) has an average particle size of 20 ⁇ m.
  • the (meth) acrylic resin composition (A) is not less than 5% by mass and not more than 25% by mass of the (meth) acrylic acid ester polymer (A1) and not less than 75% by mass of the (meth) acrylic acid ester monomer ( ⁇ 1). It is preferable to contain 95 mass% or less.
  • a radiator and the thermally conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the radiator, or the radiator and the radiator. It is the electronic device provided with the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of the 2nd aspect of the said this invention bonded.
  • a heat-conductive pressure-sensitive adhesive composition and a heat-conductive pressure-sensitive adhesive sheet-shaped molded body that are difficult to break even when molded thinly, their production methods, and the heat-conductive pressure-sensitive adhesive composition Or the electronic device provided with this heat conductive pressure-sensitive-adhesive sheet-like molded object can be provided.
  • the heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition ((meth) acrylic acid ester polymer (A1)) and a (meth) acrylic acid ester monomer ( ⁇ 1) ( A) and a thermally conductive filler (B1) having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g (hereinafter, simply referred to as “thermally conductive filler (B1)”).
  • thermoconductive filler (B2) having an average particle size of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more (hereinafter sometimes simply referred to as “thermal conductive filler (B2)”).
  • a polyfunctional epoxy compound (C) having a functional group of 2 or more and 10,000 or less hereinafter sometimes simply referred to as “polyfunctional epoxy compound (C)”.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is at least (meth) acryl after shape
  • the materials constituting the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) will be described below.
  • the (meth) acrylic resin composition (A) used in the present invention contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1).
  • a polymerization reaction and a crosslinking reaction are performed as mentioned above.
  • the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1) is mixed with the component of the (meth) acrylic acid ester polymer (A1) and / or. Partially join.
  • the amount of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1) used is (mass) acrylic resin composition (A) being 100% by mass
  • the (meth) acrylate polymer (A1) is preferably 5% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 75% by mass or more and 95% by mass or less. More preferably, the acrylic acid ester polymer (A1) is 10% by mass or more and 25% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is 75% by mass or more and 90% by mass or less.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are formed. Easy to do.
  • the components contained in the (meth) acrylic resin composition (A) will be described in more detail below.
  • the (meth) acrylate polymer (A1) that can be used in the present invention is not particularly limited, but a (meth) acrylate monomer unit that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain (a1) and a monomer unit (a2) having an organic acid group.
  • the (meth) acrylate monomer (a1m) that gives the unit (a1) of the (meth) acrylate monomer is not particularly limited.
  • ethyl acrylate the glass transition temperature of the homopolymer is -24 ° C
  • n-propyl acrylate (-37 ° C)
  • n-butyl acrylate (-54 ° C)
  • sec-butyl acrylate (-22 ° C)
  • n-octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), 2-methoxyethyl acrylate (-50 ° C) ), 3-methoxypropyl acrylate (-75 ° C), 3-methoxybutyl acrylate (-56 ° C), ethoxymethyl acrylate (-50
  • n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is more preferable.
  • acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
  • the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1).
  • it is used for polymerization in such an amount that it is more preferably 85% by mass or more and 99.5% by mass or less.
  • the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the viscosity of the polymerization system at the time of polymerization can be easily maintained within an appropriate range.
  • the monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, but representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group.
  • monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used.
  • the monomer having a carboxyl group include, for example, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and ⁇ , ⁇ such as itaconic acid, maleic acid, and fumaric acid.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be exemplified.
  • the monomer having a sulfonic acid group examples include allyl sulfonic acid, methacryl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, ⁇ , ⁇ -unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, and the like. These salts can be mentioned.
  • the monomer (a2m) among the monomers having an organic acid group exemplified above, a monomer having a carboxyl group is more preferable, and a monomer having acrylic acid or methacrylic acid is particularly preferable. . These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.
  • the monomer unit (a2) derived from the monomer unit (a2) is preferably 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1). More preferably, it is used for the polymerization in such an amount that it is 0.5 to 15% by mass.
  • the usage-amount of the monomer (a2m) which has an organic acid group exists in the said range, it will become easy to maintain the viscosity of the polymerization system at the time of superposition
  • the monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer (A1) by polymerization of the monomer (a2m) having an organic acid group as described above.
  • an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer (A1) is produced.
  • the (meth) acrylic acid ester polymer (A1) may contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group.
  • the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.
  • Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.
  • Examples of the monomer having an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
  • Examples of monomers having an amide group include ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.
  • Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
  • the monomer (a3m) having a functional group other than the organic acid group one type may be used alone, or two or more types may be used in combination.
  • the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferable to use it for polymerization in such an amount.
  • the monomer (a3m) of 10% by mass or less it becomes easy to keep the viscosity of the polymerization system during polymerization in an appropriate range.
  • the (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • a monomer derived from the monomer (a4m) copolymerizable with the above-described monomer may be contained.
  • the monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), ⁇ , ⁇ -ethylenic monomers. Saturated polycarboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, etc. Can be mentioned.
  • the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.
  • ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester examples include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
  • alkenyl aromatic monomer examples include styrene, ⁇ -methylstyrene, methyl ⁇ -methylstyrene, vinyl toluene, and divinylbenzene.
  • conjugated diene monomer examples include 1,3-butadiene, 2-methyl-1,3-butadiene (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. 2-chloro-1,3-butadiene, cyclopentadiene and the like.
  • non-conjugated diene monomer examples include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
  • olefin monomer examples include ethylene, propylene, butene, pentene and the like.
  • the monomer (a4m) one type may be used alone, or two or more types may be used in combination.
  • the amount of the monomer unit (a4) derived therefrom is preferably 10% by mass or less, more preferably 5% by mass or less in the (meth) acrylate polymer (A1). It is subjected to polymerization in such an amount.
  • the (meth) acrylic acid ester polymer (A1) has the above-mentioned (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • Monomer (a2m) a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
  • the polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. .
  • solution polymerization is preferable, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferable.
  • the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once.
  • the method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator.
  • the thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
  • Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
  • the amount of the soot polymerization initiator used is not particularly limited, but is preferably in the range of 0.01 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the monomer.
  • polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
  • the obtained polymer is separated from the polymerization medium if necessary.
  • the separation method is not particularly limited.
  • the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is preferably in the range of 100,000 to 1,000,000, more preferably in the range of 200,000 to 900,000.
  • a weight average molecular weight (Mw) means what measured the weight average molecular weight of standard polystyrene conversion by molecular weight measurement gel permeation chromatography (GPC) (hereinafter the same).
  • GPC molecular weight measurement gel permeation chromatography
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet form are used.
  • Appropriate strength can be given to the molded body (G) to make it difficult to break.
  • the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molding are used.
  • the body (G) can have appropriate flexibility. That is, by using both in combination, appropriate strength and flexibility can be achieved.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
  • the (meth) acrylate monomer ( ⁇ 1) is not particularly limited as long as it contains the (meth) acrylate monomer, but forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
  • a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) )
  • a (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer ( ⁇ 1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer ( ⁇ 1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • the (meth) acrylic acid ester monomer ( ⁇ 1) is a (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is good also as a mixture of the monomer (a6m) which has a polymerizable organic acid group.
  • Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to.
  • a monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 30% by mass or less, and more preferably 10% by mass or less.
  • the (meth) acrylic acid ester monomer ( ⁇ 1) in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture containing the monomer (a7m) copolymerizable with these.
  • Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m).
  • the body can be mentioned.
  • a monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 20% by mass or less, and more preferably 15% by mass or less.
  • a polyfunctional monomer can also be used in the (meth) acrylic resin composition (A).
  • the polyfunctional monomer that can be used in the present invention a monomer that is copolymerizable with the monomer contained in the (meth) acrylic acid ester monomer ( ⁇ 1) is used.
  • the polyfunctional monomer has a plurality of polymerizable unsaturated bonds, and preferably has the unsaturated bond at the terminal.
  • intramolecular and / or intermolecular crosslinking is introduced into the copolymer, and the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet are introduced.
  • the cohesive force as a pressure-sensitive adhesive of the shaped molded body (G) can be increased.
  • a certain degree of crosslinking reaction proceeds without using a polyfunctional monomer.
  • a polyfunctional monomer may be used in order to form a desired amount of a crosslinked structure more reliably.
  • polyfunctional monomer examples include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloro Other substituted triazines, such as chill)
  • monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used.
  • pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable.
  • a polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polyfunctional monomer used is preferably 10% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the (meth) acrylic resin composition (A).
  • the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) are suitable as a pressure sensitive adhesive. It becomes easy to give a strong cohesive force.
  • ⁇ Polymerization initiator> When obtaining the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G), the components contained in the (meth) acrylic resin composition (A) are polymerized as described above. . In order to accelerate the polymerization reaction, it is preferable to use a polymerization initiator.
  • the polymerization initiator include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator.
  • an organic peroxide thermal polymerization initiator is used. Is preferably used.
  • acylphosphine oxide compounds are preferred.
  • Preferred examples of the acylphosphine oxide compound that is a photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
  • azo-based thermal polymerization initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.
  • organic peroxide thermal polymerization initiator examples include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone.
  • hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone.
  • organic peroxide thermal polymerization initiators those having a 1-minute half-life temperature of 100 ° C. or more and 170 ° C. or less are preferable.
  • the amount of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin composition (A). More preferably, it is 0.3 to 2 parts by mass.
  • the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is 95% by mass or more, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the monomer odor from remaining on the surface. Moreover, by making the usage-amount of a polymerization initiator into the said range, a polymerization reaction will advance too much and will cause material destruction, without a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) becoming a smooth sheet form. It becomes easy to prevent the situation.
  • the heat conductive filler (B1) used in the present invention is a heat conductive filler having an average particle size of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g.
  • the heat conductive filler with a small BET specific surface area like the heat conductive filler (B1) was used.
  • a thermally conductive filler having a small BET specific surface area it becomes easy to suppress an excessive increase in the viscosity of the mixed composition.
  • BET specific surface area of the thermally conductive filler (B1) is less than 1.0 m 2 / g, preferably not more than 0.05 m 2 / g or more 0.9m 2 / g, 0.08m 2 / g or more 0 More preferably, it is 8 m 2 / g or less.
  • Mixing which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the BET specific surface area of the heat conductive filler (B1) in the above range. Heat of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) molded from the mixed composition while suppressing the viscosity of the composition from becoming excessively high Conductivity can be improved.
  • BET specific surface area means that measured by the following method. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring apparatus, and a sample cell containing a sample (an object to be measured for BET specific surface area) is immersed in liquid nitrogen to adsorb nitrogen gas to the sample surface. After reaching adsorption equilibrium, the sample cell is placed in a water bath and warmed to room temperature, and nitrogen adhering to the sample is desorbed. Since the mixing ratio of the gas before and after passing through the sample cell changes during the adsorption and desorption of nitrogen gas, this change is detected by a thermal conductivity detector (TCD) using a gas with a constant mixing ratio of nitrogen and helium as a control.
  • TCD thermal conductivity detector
  • the adsorption amount and desorption amount of nitrogen gas are obtained.
  • a unit amount of nitrogen gas is introduced into the apparatus for calibration, and the surface area value corresponding to the value detected by TCD is obtained to obtain the surface area of the sample.
  • the BET specific surface area can be obtained by dividing the surface area by the mass of the sample.
  • the average particle size of the heat conductive filler (B1) is 20 ⁇ m or less, preferably 0.05 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average particle size exceeds the above upper limit, when a thin sheet is produced, there is a risk that irregularities due to the filler or pinholes may occur on the surface.
  • the “average particle diameter” means that measured by the method described below. That is, a laser type particle size measuring machine (manufactured by Seishin Enterprise Co., Ltd.) is used, and measurement is performed by a microsorting control method (a method in which the measurement target particles are allowed to pass only in the measurement region and the measurement reliability is improved). According to this measurement method, when the measurement target particles 0.01 g to 0.02 g are flowed into the cell, the measurement target particles flowing in the measurement region are irradiated with the semiconductor laser light having a wavelength of 670 nm. By measuring the scattering and diffraction of laser light with a measuring instrument, the average particle size and particle size distribution are calculated from the diffraction principle of Franhofer.
  • the heat conductive filler (B1) is not particularly limited as long as the average particle diameter and the BET specific surface area satisfy the above ranges.
  • Specific examples of the thermally conductive filler (B1) include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; metal oxides such as aluminum oxide (alumina), magnesium oxide, and zinc oxide; carbonic acid Metal carbonates such as calcium and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate hydrate; silica; Among them, a metal oxide is preferable and aluminum oxide (alumina) is most preferable because it has excellent thermal conductivity and is chemically stable.
  • a heat conductive filler (B1) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the heat conductive filler (B1) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) It is 300 to 1000 mass parts with respect to 100 mass parts, It is preferable that they are 400 to 900 mass parts, More preferably, it is 500 to 800 mass parts. Mixing that is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B1) to the upper limit or less. It becomes easy to suppress that the viscosity of a composition becomes high too much.
  • the heat conductive filler (B2) used in the present invention is a heat conductive filler having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more.
  • the viscosity of the mixed composition which is a precursor of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G) becomes high too much.
  • the BET specific surface area as in the heat conductive filler (B1) is increased. It is conceivable to use a small thermally conductive filler.
  • a filler having a large specific gravity with respect to the (meth) acrylic resin composition (A) is likely to precipitate in the mixed composition.
  • the mixed composition When air is entrained and included during preparation (mixing) of the mixed composition, it is preferable that the mixed composition is allowed to stand in order to remove the air.
  • the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet is formed while gradually discharging the mixed composition as a coating liquid.
  • a part with extremely high filler content may be formed. When this becomes a cause of trouble, it becomes difficult to continuously produce the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) from the mixed composition. was there.
  • a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet are used by using a heat conductive filler having a relatively large BET specific surface area such as the heat conductive filler (B2).
  • the viscosity of the mixed composition of the precursor of the shaped compact (G) is moderately increased. It is thought that precipitation of fillers having a large specific gravity such as the heat conductive filler (B1) can be suppressed by adding an appropriate amount of the heat conductive filler (B2) to moderately increase the viscosity of the mixed composition.
  • BET specific surface area of the thermally conductive filler (B2) is at 1.0 m 2 / g or more, is preferably from 1.0 m 2 / g or more 100m 2 / g, 1.0m 2 / g or more 10 m 2 / More preferably, it is g or less.
  • the mixture is a precursor of the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G). It becomes easy to raise the viscosity of a composition moderately, and it becomes easy to suppress precipitation of a filler with large specific gravity with respect to (meth) acrylic resin composition (A).
  • the average particle size of the heat conductive filler (B2) is 20 ⁇ m or less, preferably 0.05 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average particle size exceeds the above upper limit, when a thin sheet is produced, there is a risk that irregularities due to the filler or pinholes may occur on the surface.
  • the heat conductive filler (B2) is not particularly limited as long as the average particle diameter and the BET specific surface area satisfy the above ranges.
  • Specific examples of the thermally conductive filler (B2) include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; metal oxides such as aluminum oxide (alumina), magnesium oxide, and zinc oxide; carbonic acid Metal carbonates such as calcium and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin clay; calcium aluminate hydrate; silica; Among them, a metal oxide is preferable and aluminum oxide (alumina) is most preferable because it has excellent thermal conductivity and is chemically stable.
  • a heat conductive filler (B2) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the heat conductive filler (B2) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) 60 parts by mass or more and 900 parts by mass or less, preferably 70 parts by mass or more and 700 parts by mass or less, and more preferably 80 parts by mass or more and 600 parts by mass or less with respect to 100 parts by mass.
  • Mixing that is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the content of the heat conductive filler (B2) to the upper limit or less.
  • the content of the heat conductive filler (B2) is not less than the above lower limit, the viscosity of the mixed composition is appropriately increased as described above, and the specific gravity of the (meth) acrylic resin composition (A) is increased. It is believed that large fillers can be prevented from precipitating in the mixed composition.
  • the polyfunctional epoxy compound (C) is a polyfunctional epoxy compound having 2 to 10,000 functional groups.
  • the polyfunctional epoxy compound (C) can react with the organic acid group in the (meth) acrylic acid ester polymer (A1) to form a crosslinked structure.
  • the (meth) acrylate monomer ( ⁇ 1) contains a monomer having an organic acid group, it can react with the organic acid group.
  • a crosslinked structure can be formed in the polymer containing the structural unit derived from the monomer ( ⁇ 1).
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) have a certain amount. Since strength is imparted, it is considered that the strength of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be easily secured. Therefore, by using the polyfunctional epoxy compound (C), it is considered that even if the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are thinly formed, it is difficult to break. It is done.
  • the polyfunctional epoxy compound (C) that can be used in the present invention preferably has a viscosity at 25 ° C. of 600 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, and 400 mPa ⁇ s or less. Further preferred.
  • a mixed composition which is a precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It is considered that the polyfunctional epoxy compound (C) is easily dispersed uniformly therein, and the cross-linked structure by the polyfunctional epoxy compound (C) is easily formed uniformly.
  • the viscosity of a polyfunctional epoxy compound (C) means what was measured as demonstrated below.
  • the polyfunctional epoxy compound (C) which can be used for this invention has 2 or more and 10,000 or less functional groups, and it is preferable that the number of functional groups is 2 or more and 1000 or less, and is 2 or more and 10 or less. More preferably.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) have appropriate strength. It becomes easy to prepare.
  • a tetrafunctional epoxy compound is preferable because a crosslinked structure can be effectively formed even in a small amount, and pentaerythritol tetraglycidyl ether is more preferable.
  • a polyfunctional epoxy compound (C) may be used individually by 1 type, and may use 2 or more types together.
  • the amount of the polyfunctional epoxy compound (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the (meth) acrylic resin composition ( A) is 100 parts by mass, 0.05 parts by mass to 4 parts by mass, preferably 0.07 parts by mass to 3 parts by mass, and 0.09 parts by mass to 2 parts by mass. Is more preferable.
  • ⁇ Other additives> In addition to the above-described substances, the above-described effects due to the addition of the above-described substances are hindered in the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention.
  • Various known additives can be added within the range.
  • Known additives include: foaming agents (including foaming aids); glass fibers; external cross-linking agents; pigments; other fillers such as clay; nanoparticles such as fullerenes and carbon nanotubes; polyphenols, hydroquinones, Antioxidants such as hindered amines; thickeners such as acrylic polymer particles and fine silica; flame retardants such as phosphates;
  • the present invention even if it is thinly formed by using a suitable amount of the polyfunctional epoxy compound (C), the heat conductive filler (B1) and the heat conductive filler (B2), it is It is possible to obtain a heat conductive pressure-sensitive adhesive composition (F) and a heat conductive pressure-sensitive adhesive sheet-like molded body (G) that are difficult to cut.
  • the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 1.0 mm or less. By thinly forming, the thermal resistance in the thickness direction can be lowered.
  • the upper limit of the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.5 mm.
  • the lower limit of the thickness of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.07 mm.
  • the heat conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing the substances described so far to prepare a mixed composition, and then polymerizing the (meth) acrylate monomer ( ⁇ 1). And a cross-linking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1).
  • the manufacturing method of the heat conductive pressure-sensitive adhesive composition (F) of the present invention includes (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1).
  • the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentioned, and detailed description is abbreviate
  • the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is prepared by mixing each of the substances described so far to prepare a mixed composition, and molding the mixed composition into a sheet shape, or While forming the mixed composition into a sheet, the polymerization reaction of the (meth) acrylate monomer ( ⁇ 1) and the (meth) acrylate polymer (A1) and / or (meth) acrylate ester It can be obtained by performing at least a crosslinking reaction of a polymer containing a structural unit derived from the body ( ⁇ 1).
  • the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1)
  • a step of producing a mixed composition comprising a (meth) acrylic resin composition (A), a thermally conductive filler (B1), a thermally conductive filler (B2), and a polyfunctional epoxy compound (C); and The polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1) and the (meth) acrylic acid ester polymer after forming the mixed composition into a sheet or while forming the mixed composition into a sheet
  • the substance which can be used other than that, the preferable content ratio of each substance, etc. are as above-mentione
  • heating is preferably performed when the polymerization and the crosslinking reaction are performed.
  • heating for example, hot air, an electric heater, infrared rays, or the like can be used.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylate monomer ( ⁇ 1) proceeds.
  • the temperature range varies depending on the type of polymerization initiator used, but is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 130 ° C. or higher and 180 ° C. or lower.
  • the method for molding the mixed composition into a sheet shape is not particularly limited. Suitable methods include, for example, a method of forming a sheet by applying the mixed composition onto a process paper such as a polyester film subjected to a release treatment, and the mixed composition between two release-processed papers. There are a method of forming a sheet by pressing between rolls with a sandwich, and a method of forming the sheet by extruding the mixed composition using an extruder and controlling the thickness through a die at that time. Can be mentioned.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate.
  • the material which comprises the said base material is not specifically limited.
  • Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone.
  • Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc.
  • a heat-resistant polymer film can be used.
  • the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention can be used as some electronic components with which an electronic device is equipped. In that case, it can also be directly molded on a base material such as a radiator and provided as a part of the electronic component.
  • the electronic device and electronic component include electroluminescence (EL), a component around a heat generating part in a device having a light emitting diode (LED) light source, a component around a power device such as an automobile, a fuel cell, a solar cell, and a battery.
  • Devices and parts having heat generating parts such as mobile phones, personal digital assistants (PDAs), notebook computers, liquid crystals, surface conduction electron-emitting device displays (SED), plasma display panels (PDP), or integrated circuits (ICs) Can be mentioned.
  • PDAs personal digital assistants
  • SED surface conduction electron-emitting device displays
  • PDP plasma display panels
  • ICs integrated circuits
  • an LED light source is exemplified below. Examples of usage can be mentioned.
  • LED light source is directly attached to the LED light source; sandwiched between the LED light source and the heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.);
  • Examples of LED light source applications include backlight devices for display devices having transmissive liquid crystal panels (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; Lighting; and the like.
  • LED light source examples include the following. That is, PDP panel; IC heating part; Cold cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High luminance light emitting LED light source; High luminance light emitting organic EL light source; And so on.
  • examples of the method of using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention include affixing to the housing of the apparatus.
  • affixing to the housing of the apparatus.
  • a device provided in an automobile or the like it is affixed inside a casing provided in the automobile; affixed outside the casing provided in the automobile; a heat generating part (inside the casing provided in the automobile) Connecting the car navigation / fuel cell / heat exchanger) and the housing; affixing to a heat sink connected to the heat generating part (car navigation / fuel cell / heat exchanger) in the housing of the automobile; Etc.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention can be used in the same manner.
  • personal computers homes; TVs; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Organic EL display; laptop computer; PDA; fuel cell; semiconductor device; rice cooker; washing machine; laundry dryer; optical semiconductor device combining optical semiconductor elements and phosphors; Is mentioned.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention are not limited to the above-described usage methods, and may be used in other methods depending on the application. Is also possible.
  • used for heat uniformity of carpets and warm mats, etc . used as LED light source / heat source sealant; used as solar cell sealant; used as solar cell backsheet Used between the backsheet of the solar cell and the roof; used inside the heat insulating layer inside the vending machine; used inside the housing of the organic EL lighting with a desiccant or a hygroscopic agent; organic EL lighting Use with desiccant and hygroscopic agent on the heat conductive layer inside the housing of the LED; Use with desiccant and hygroscopic agent on the heat conductive layer and heat dissipation layer inside the housing of the organic EL lighting Used for heat conduction layer inside the housing of organic EL lighting, epoxy heat dissipation layer, and on top of it with desiccant and moisture absorbent; cooling equipment, clothing, towels, sheets, etc.
  • the member Used as a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer
  • Pressing member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as it is
  • used as a heat transfer part for heat flow control on which the object to be processed of the film forming apparatus is placed used between the outer layer of the radioactive substance storage container and the interior; a box body with a solar panel that absorbs sunlight Can be used between the reflective sheet of the CCFL backlight and the aluminum chassis.
  • the heat conductive filler (B2) is preferably a metal oxide having an average particle diameter of 20 ⁇ m or less and a BET specific surface area of 1.0 m 2 / g or more, and the heat conductive filler (B1) is The aluminum oxide has an average particle diameter of 20 ⁇ m or less and a BET specific surface area of less than 1.0 m 2 / g, and the thermally conductive filler (B2) has an average particle diameter of 20 ⁇ m or less and a BET specific surface area of 1.0 m. 2 / g or more of aluminum oxide More preferably.
  • the (meth) acrylic resin composition (A) is not less than 5% by mass and not more than 25% by mass of the (meth) acrylic acid ester polymer (A1) and not less than 75% by mass of the (meth) acrylic acid ester monomer ( ⁇ 1). It is preferable to contain 95 mass% or less.
  • ⁇ Manufacturable thickness> When a mixed composition is prepared as described later, and a heat conductive pressure-sensitive adhesive sheet-like molded body is prepared using 100 ml of the mixed composition as described later, it can be manufactured without a pinhole. The thickness was examined. The results are shown in Tables 2 and 3. This measurement was performed in a range up to a sheet thickness of 150 ⁇ m (lower limit). This thickness does not include the thickness of a release PET film (a release-treated polyethylene terephthalate film; the same applies hereinafter).
  • a heat conductive pressure-sensitive adhesive sheet-like molded article having a thickness of 150 ⁇ m (not including the thickness of the release PET film) sandwiched between the release PET films was prepared. Then, it cut
  • Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.015 part 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 800,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 2.5.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
  • a reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was performed at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylate polymer (A1-2).
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-2) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
  • a thermostatic bath (Viscomate 150III, manufactured by Toki Sangyo Co., Ltd.) and a Hobart mixer (ACM-5LVT type, manufactured by Kodaira Seisakusho Co., Ltd., capacity: 5 L) were used.
  • the temperature control of the Hobart container was set to 40 ° C.
  • the rotation speed scale was set to 3
  • stirring was performed for 10 minutes. This process is referred to as a first mixing process.
  • the mixed composition obtained through the first and second mixing steps is hung on a release PET film having a thickness of 75 ⁇ m, and another release PET film having a thickness of 75 ⁇ m is further dropped on the mixed composition. Covered.
  • This laminate in which the mixed composition is sandwiched between the release PET films is passed through a roll whose spacing is adjusted so that a heat-conductive pressure-sensitive adhesive sheet-like molded product having a desired thickness is obtained.
  • the (meth) acrylic acid ester monomer is polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester polymer (A1-2) And a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer is subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). It was. In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet
  • Example 2 to 7 and Comparative Examples 1 to 6 Sheets (G2 to G7) according to Examples 2 to 7 in the same manner as in Example 1 except that the composition of each substance in the first mixing process and the second mixing process was changed as shown in Table 2 and Table 3. And sheets (GC1 to GC6) according to Comparative Examples 1 to 6 were produced.
  • the details of the polyfunctional monomer used in the first mixing step in Comparative Example 1 and the spherical alumina used in the second mixing step in Comparative Example 6 are as follows.
  • Polyfunctional monomer used in Comparative Example 1 Polyfunctional monomer (light acrylate PE-3A) in which pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate were mixed in a ratio of 60: 35: 5 Manufactured by Kyoeisha Chemical Co., Ltd.) -Spherical alumina used in Comparative Example 6 manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “DAM-45”, average particle size: 45 ⁇ m, BET specific surface area: 0.2 m 2 / g

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition adhésive sensible à la pression, thermiquement conductrice, que l'on a obtenue en effectuant au moins une réaction de polymérisation d'un monomère ester d'acide (méth)acrylique (α1) et une réaction de réticulation d'un polymère d'ester d'acide (méth)acrylique (A1) et/ou d'un polymère qui a une unité structurale issue du monomère ester d'acide (méth)acrylique (α1) dans une composition mixte qui contient une quantité prédéterminée d'une composition de résine (méth)acrylique (A) qui contient le polymère d'ester d'acide (méth)acrylique (A1) et le monomère ester d'acide (méth)acrylique (α1), une quantité prédéterminée d'une charge thermiquement conductrice (B1) qui a un diamètre moyen de particule de 20 µm ou moins et une surface spécifique BET inférieure à 1,0 m2/g, une quantité prédéterminée d'une charge thermiquement conductrice (B2) qui a un diamètre moyen de particule de 20 µm ou moins et une surface spécifique BET de 1,0 m2/g ou plus et une quantité prédéterminée d'un composé époxy polyfonctionnel (C) qui a de 2 à 10 000 (bornes incluses) groupes fonctionnels, ladite composition adhésive sensible à la pression, thermiquement conductrice, n'étant pas facilement déchirée même si elle est moulée en un corps fin ; et un corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice.
PCT/JP2013/062625 2012-06-04 2013-04-30 Composition adhésive sensible à la pression, thermiquement conductrice, corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice, procédé de fabrication d'une composition adhésive sensible à la pression, thermiquement conductrice, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression, thermiquement conductrice, et dispositif électronique Ceased WO2013183389A1 (fr)

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KR1020147030510A KR20150016496A (ko) 2012-06-04 2013-04-30 열전도성 감압 접착제 조성물, 열전도성 감압 접착성 시트상 성형체, 이들의 제조 방법, 및 전자 기기
JP2014519886A JPWO2013183389A1 (ja) 2012-06-04 2013-04-30 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート状成形体、これらの製造方法、及び電子機器

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CN110234722B (zh) 2017-05-02 2021-07-16 株式会社Lg化学 双部分粘合剂组合物
KR102617131B1 (ko) * 2020-09-29 2023-12-27 주식회사 엘지화학 경화성 조성물
CN116096765B (zh) * 2020-09-29 2024-12-13 株式会社Lg化学 可固化组合物
KR102719685B1 (ko) * 2021-12-30 2024-10-17 한국세라믹기술원 열전소자용 하이드로겔 히트싱크 및 이를 포함하는 유연열전소자

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