WO2013047145A1 - Composition adhésive sensible à la pression conductrice de la chaleur, corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, procédé de fabrication d'une composition adhésive sensible à la pression conductrice de la chaleur, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, et composant électronique - Google Patents

Composition adhésive sensible à la pression conductrice de la chaleur, corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, procédé de fabrication d'une composition adhésive sensible à la pression conductrice de la chaleur, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, et composant électronique 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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English (en)
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 CN201280023461.XA priority Critical patent/CN103562334A/zh
Priority to KR1020137030473A priority patent/KR20140074869A/ko
Publication of WO2013047145A1 publication Critical patent/WO2013047145A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—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.

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Abstract

L'invention concerne une composition adhésive sensible à la pression conductrice de la chaleur qui a des propriétés isolantes et une conductivité thermique d'une manière équilibrée et qui est obtenue en effectuant une réaction de polymérisation d'un mélange de monomère ester d'acide (méth)acrylique et une réaction de réticulation d'un polymère qui comprend une unité structurale issue d'un polymère ester d'acide (méth)acrylique (A1) et/ou d'un monomère ester d'acide (méth)acrylique (α1) dans une composition mixte qui contient : 100 parties en masse d'une composition de résine (méth)acrylique (A) qui contient le polymère ester d'acide (méth)acrylique (A1) et le monomère ester d'acide (méth)acrylique (α1) ; de 0,5 partie en masse à 40 parties en masse (bornes incluses) d'un oxyde de zinc (C) ayant une partie de type aiguille ; de 0,5 partie en masse à 20 parties en masse (bornes incluses) d'une poudre de graphite expansé (D) ; et de 600 parties en masse à 1 400 parties en masse (bornes incluses) d'une charge conductrice de la chaleur isolante (B) qui est autre que l'oxyde de zinc (C) ayant une partie de type aiguille et la poudre de graphite expansé (D). L'invention concerne également un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur ; un procédé de fabrication de la composition adhésive sensible à la pression conductrice de la chaleur ; un procédé de fabrication du corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur ; et un composant électronique qui comporte la composition adhésive sensible à la pression conductrice de la chaleur ou le corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur.
PCT/JP2012/072777 2011-09-28 2012-09-06 Composition adhésive sensible à la pression conductrice de la chaleur, corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, procédé de fabrication d'une composition adhésive sensible à la pression conductrice de la chaleur, procédé de fabrication d'un corps moulé de type feuille adhésive sensible à la pression conducteur de la chaleur, et composant électronique WO2013047145A1 (fr)

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JP2013072020A (ja) * 2011-09-28 2013-04-22 Nippon Zeon Co Ltd 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
WO2015045918A1 (fr) * 2013-09-26 2015-04-02 日本ゼオン株式会社 Composition adhésive autocollante thermoconductrice, article stratiforme adhésif autocollant thermoconducteur, leur procédé de production et matériel électronique
WO2015045919A1 (fr) * 2013-09-26 2015-04-02 日本ゼオン株式会社 Composition adhésive sensible à la pression et thermoconductrice, article stratiforme adhésif sensible à la pression et thermoconducteur, leur procédé de production et équipement électronique
JP2018510937A (ja) * 2015-03-05 2018-04-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ 熱伝導性接着剤
WO2019131415A1 (fr) * 2017-12-28 2019-07-04 北川工業株式会社 Composition élastomère thermoconductrice et article moulé thermoconducteur
WO2020149193A1 (fr) * 2019-01-15 2020-07-23 コスモ石油ルブリカンツ株式会社 Composition durcissable, et produit durci
JPWO2019065514A1 (ja) * 2017-09-26 2020-11-05 国立大学法人北海道大学 高靭性繊維複合エラストマー

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CN112852309A (zh) * 2021-02-24 2021-05-28 东莞市博翔电子材料有限公司 一种用于动力电池铝塑膜的胶粘剂及其加工工艺

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WO2015045918A1 (fr) * 2013-09-26 2015-04-02 日本ゼオン株式会社 Composition adhésive autocollante thermoconductrice, article stratiforme adhésif autocollant thermoconducteur, leur procédé de production et matériel électronique
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WO2019131415A1 (fr) * 2017-12-28 2019-07-04 北川工業株式会社 Composition élastomère thermoconductrice et article moulé thermoconducteur
JP2019119752A (ja) * 2017-12-28 2019-07-22 北川工業株式会社 熱伝導エラストマー組成物、及び熱伝導成形体
WO2020149193A1 (fr) * 2019-01-15 2020-07-23 コスモ石油ルブリカンツ株式会社 Composition durcissable, et produit durci
JPWO2020149193A1 (ja) * 2019-01-15 2021-11-25 コスモ石油ルブリカンツ株式会社 硬化性組成物及び硬化物
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