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WO2015060092A1 - Composition adhésive sensible à la pression, thermiquement conductrice, article en forme de feuille adhésive sensible à la pression et thermiquement conductrice, son procédé de production, et dispositif électronique - Google Patents

Composition adhésive sensible à la pression, thermiquement conductrice, article en forme de feuille adhésive sensible à la pression et thermiquement conductrice, son procédé de production, et dispositif électronique Download PDF

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WO2015060092A1
WO2015060092A1 PCT/JP2014/076444 JP2014076444W WO2015060092A1 WO 2015060092 A1 WO2015060092 A1 WO 2015060092A1 JP 2014076444 W JP2014076444 W JP 2014076444W WO 2015060092 A1 WO2015060092 A1 WO 2015060092A1
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meth
mass
sensitive adhesive
parts
conductive pressure
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English (en)
Japanese (ja)
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拓朗 熊本
明子 北川
正文 水島
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Zeon Corp
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Zeon Corp
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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
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H10W40/251—

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 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
  • thermo conductive pressure-sensitive adhesive sheet a composition having a pressure-sensitive adhesive property in addition to thermal conductivity
  • thermoally conductive pressure-sensitive adhesive sheet-like molded product 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 mainly intended to transfer heat from the heat generating body to the heat radiating body, and therefore it is preferable to improve the heat conductivity.
  • the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded article have fillers corresponding to the functions to be provided in order to provide other functions other than the heat conductivity depending on the use. May be added.
  • Patent Document 1 below discloses a heat conductive pressure-sensitive adhesive sheet-like molded body to which a predetermined expanded graphite powder, phosphate ester, alumina, and a flame retardant heat conductive inorganic compound are added.
  • an object of the present invention is to provide a heat conductive pressure-sensitive adhesive composition and a heat conductive pressure-sensitive adhesive sheet-like molded article having flame retardancy and improved thermal conductivity. Moreover, these manufacturing methods and the electronic device provided with this heat conductive pressure-sensitive-adhesive composition or this heat conductive pressure-sensitive-adhesive sheet-like molded object are provided.
  • (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 whose own thermal conductivity is 0.3 W / m ⁇ K or more.
  • the term “flame retardant thermally conductive inorganic compound” means an inorganic compound that can be added to improve flame retardancy and thermal conductivity and has a thermal conductivity of 0.3 W / m ⁇ K or more. To do.
  • the “polymerization reaction of (meth) acrylate monomer ( ⁇ 1)” means a polymerization reaction for obtaining a polymer containing a structural unit derived from (meth) acrylate monomer ( ⁇ 1).
  • 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 “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 determined by dividing the determined surface area by the mass of the sample.
  • a step of producing a mixed composition comprising 300 parts by mass or more and 700 parts by mass or less of the heat conductive filler (C), and in the mixed composition, at least a (meth) acrylate monomer ( ⁇ 1) Carrying out the poly
  • 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). 6 parts by mass or more and 45 parts by mass or less of expanded graphite powder (B) having an average particle size of 50 ⁇ m or more, and 150 parts by mass of a flame-retardant thermally conductive inorganic compound (D) other than the expanded graphite powder (B) 450 parts by mass or less, an average particle diameter of 50 ⁇ m or more, and a BET specific surface area of 0.4 m 2 / g or less, other than the expanded graphite powder (B) and the flame-retardant thermally conductive inorganic compound (D)
  • a thermally conductive pressure-sensitive adhesive composition having flame retardancy and improved thermal conductivity, a thermally conductive pressure-sensitive adhesive sheet-like molded article, and the thermally conductive pressure-sensitive adhesive composition Or the electronic device provided with this heat conductive pressure-sensitive-adhesive sheet-like molded object can be obtained.
  • the present inventors have adjusted the particle size and the like of the thermally conductive filler to be added, thereby improving the thermal conductivity of the conventional thermal conductive pressure-sensitive adhesive composition and the thermal conductive pressure-sensitive adhesive sheet. It was found that a shaped molded body can be obtained. The present invention is based on this finding. This will be described in detail below.
  • 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), an expanded graphite powder (B) having an average particle diameter of 50 ⁇ m or more, a flame-retardant thermally conductive inorganic compound (D) other than the expanded graphite powder (B), an average particle diameter of 50 ⁇ m or more, and a BET A mixed composition containing a specific amount of a thermally conductive filler (C) other than the expanded graphite powder (B) and the flame-retardant thermally conductive inorganic compound (D), each having a specific surface area of 0.4 m 2 / g or less.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is at least (meth) acryl after shape
  • the polymerization reaction of the acid ester monomer ( ⁇ 1) is performed.
  • 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). May contain a functional monomer.
  • the polymerization reaction of at least (meth) acrylic acid ester monomer ((alpha) 1) is carried out. Done.
  • the polymer containing the structural unit derived from the (meth) acrylate monomer ( ⁇ 1) is mixed and / or partially bonded to the component of the (meth) acrylate polymer (A1). .
  • the proportion 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 50% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 50% by mass or more and 95% by mass or less. More preferably, the acrylic acid ester polymer (A1) is 15% by mass or more and 50% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is 50% by mass or more and 84.9% by mass or less.
  • the acrylic ester polymer (A1) is 25% by mass or more and 45% by mass or less, and the (meth) acrylic ester monomer ( ⁇ 1) is 55% by mass or more and 74.7% by mass or less.
  • Arbitrariness. By making the use ratio of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1) in the above range, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive feeling. It becomes easy to shape
  • 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
  • n-octyl methacrylate (-25 ° C)
  • a (meth) acrylic acid alkyl ester that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C.
  • n-decyl methacrylate (-49 ° C.); 2-methoxyethyl acrylate
  • the glass transition temperature is ⁇ 50 ° C.), 3-methoxypropyl acrylate (-75 ° C.), 3-methoxybutyl acrylate (-56 ° C.), ethoxymethyl acrylate ( ⁇ 50 ° C.), etc.
  • (meth) acrylic acid alkoxyalkyl esters that form a homopolymer of 20 ° C. or lower. Among them, (meth) acrylic acid alkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C.
  • (meth) acrylic acid alkoxyalkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower (meth) acrylic acid alkyl ester forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is 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 mass% or more and 99.5 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 an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid is more preferable. (Meth) acrylic acid is particularly preferred. 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 polyvalent carboxylic acid complete ester, alkenyl aromatic monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer and the like 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, vinyltoluene and the like.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
  • olefin monomer examples include ethylene, propylene, butene, pentene and the like.
  • the monomer (a4m) one type may be used alone, or two or more types may be used in combination.
  • the amount of the monomer unit (a4) derived therefrom is preferably 10% by mass or less, more preferably 5% by mass or less in the (meth) acrylate polymer (A1). It is subjected to polymerization in such an amount.
  • the (meth) acrylic acid ester polymer (A1) has the above-mentioned (meth) acrylic acid ester monomer (a1m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, and an organic acid group.
  • Monomer (a2m) a monomer containing a functional group other than an organic acid group (a3m) used as necessary, and a monomer copolymerizable with these monomers used as needed It can be particularly suitably obtained by copolymerizing the monomer (a4m).
  • the polymerization method for obtaining the (meth) acrylic acid ester polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, or any other method. .
  • solution polymerization is preferable, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferable.
  • the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once.
  • the method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator.
  • the thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.
  • Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
  • the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.
  • polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.
  • the obtained polymer is separated from the polymerization medium if necessary.
  • the separation method is not particularly limited.
  • the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.
  • the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and may be in the range of 1,000 to 1,000,000 in terms of standard polystyrene. Preferably, it is in the range of 100,000 or more and 500,000 or less.
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
  • the (meth) acrylate monomer ( ⁇ 1) is not particularly limited as long as it contains the (meth) acrylate monomer, but forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
  • a (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower, it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) )
  • a (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer ( ⁇ 1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer ( ⁇ 1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • the (meth) acrylic acid ester monomer ( ⁇ 1) is a (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is good also as a mixture of the monomer (a6m) which has a polymerizable organic acid group.
  • Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to.
  • a monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 30% by mass or less, and more preferably 10% by mass or less.
  • the (meth) acrylic acid ester monomer ( ⁇ 1) in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture containing the monomer (a7m) copolymerizable with these.
  • Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m).
  • the body can be mentioned.
  • a monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 20% by mass or less, and more preferably 15% by mass or less.
  • a polyfunctional monomer in the present invention, can also be used in the (meth) acrylic resin composition (A). Usually, at the time of polymerization such as radical thermal polymerization, a certain degree of crosslinking reaction proceeds without using a polyfunctional monomer. However, a polyfunctional monomer may be used in order to form a desired amount of a crosslinked structure more reliably.
  • the polyfunctional monomer that can be used in the present invention 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 preferably has the unsaturated bond at the terminal.
  • intramolecular and / or intermolecular crosslinking can be introduced into the copolymer to increase the cohesive force as a pressure-sensitive adhesive.
  • 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.
  • polyfunctional (meth) acrylate is preferable, and pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are more 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, based on the (meth) acrylic resin composition (A) as 100% by mass, and is 0.1% by mass or more and 5% by mass or less. Is more preferable, and it is still more preferable that it is 0.3 mass% or more and 2 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 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, superposition
  • the expanded graphite powder (B) used in the present invention is an expanded graphite powder having an average particle size of 50 ⁇ m or more.
  • the expanded graphite powder (B) has high thermal conductivity, and when added, the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G). Can be improved.
  • the inventors of the present invention used a thermally conductive pressure-sensitive adhesive composition by using the expanded graphite powder (B) having a large particle size as described above and the thermally conductive filler (C) having a large particle size described later.
  • Heat-sensitive pressure-sensitive adhesive composition while suppressing a decrease in productivity by suppressing an increase in viscosity of the mixed composition which is a precursor of the product (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) It has been found that the thermal conductivity of (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be improved.
  • the expanded graphite powder (B) is added to the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), whereby the heat conductive pressure-sensitive adhesive composition.
  • the product (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can function to suppress melting when heated. Therefore, by adding the expanded graphite powder (B), the flame resistance of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can also be improved. .
  • the expanded graphite powder 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. to remove the acid and 100 ml / g to 300 ml / g. And a product obtained by a method including a step of expanding and then crushing.
  • the temperature of the heat treatment is particularly preferably 800 ° C. or higher and 1000 ° C. or lower.
  • the average particle diameter of the expanded graphite powder (B) is 50 ⁇ m or more, preferably 100 ⁇ m or more and 500 ⁇ m or less, and more preferably 150 ⁇ m or more and 350 ⁇ m or less.
  • the precursor of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) It is possible to suppress an increase in the viscosity of the mixed composition, and to suppress a decrease in the productivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • the thermal conductivity can be effectively increased.
  • the amount of the expanded graphite powder (B) added to the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is the (meth) acrylic resin composition (A) 100. It is 6 parts by mass or more and 45 parts by mass or less, preferably 8 parts by mass or more and 45 parts by mass or less, and more preferably 10 parts by mass or more and 45 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) it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), and even if it can be molded, the hardness increases and the shape followability (adhesion) It is possible to prevent a situation where the adhesion to the body is reduced.
  • the addition amount of the expanded graphite powder (B) more than the lower limit of the above range, the heat 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 improve conductivity and flame retardancy.
  • the flame-retardant heat conductive inorganic compound (D) used in the present invention is an inorganic compound other than the expanded graphite powder (B), and when added, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive feeling. It is an inorganic compound that can improve the flame retardancy and thermal conductivity of the pressure-adhesive sheet-like molded body (G) and has a thermal conductivity of 0.3 W / m ⁇ K or more.
  • the flame retardant thermally conductive inorganic compound (D) include metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide; Metal salt hydrates such as dihydrate gypsum, zinc borate hydrate, calcium aluminate hydrate; metal carbonates such as calcium carbonate and aluminum carbonate; and the like. Of these, metal hydroxides are preferred, and aluminum hydroxide is particularly preferred. By using aluminum hydroxide, it becomes easy to improve the flame retardance and thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • a flame-retardant heat conductive inorganic compound (D) may be used individually by 1 type, and may use 2 or more types together.
  • the average particle size of the flame retardant thermally conductive inorganic compound (D) is preferably 0.5 ⁇ m or more and 15 ⁇ m or less, and more preferably 5 ⁇ m or more and 12 ⁇ m or less. Further, the BET specific surface area of the flame retardant thermally conductive inorganic compound (D) is preferably 0.3 m 2 / g or more and 10 m 2 / g or less, and is 0.5 m 2 / g or more and 2 m 2 / g or less. It is more preferable.
  • the flame-retardant heat conductive inorganic compound (D) is more familiar to 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 less likely to become brittle even if the content of the flame retardant heat conductive inorganic compound (D) is increased. be able to.
  • the amount of the flame-retardant heat-conductive inorganic compound (D) added to the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) is determined by the (meth) acrylic resin composition ( A) It is 150 mass parts or more and 450 mass parts or less with respect to 100 mass parts, It is preferable that they are 180 mass parts or more and 420 mass parts or less, More preferably, they are 200 mass parts or more and 400 mass parts or less.
  • the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) It is easy to suppress the viscosity of the mixed composition that is a precursor of ()) from becoming excessively high. Therefore, even if it becomes difficult to shape
  • the thermally conductive filler (C) used in the present invention is added to the thermally conductive pressure-sensitive adhesive composition (F) by adding other than the expanded graphite powder (B) and the flame retardant thermally conductive inorganic compound (D). It is a filler that can improve thermal conductivity and has a thermal conductivity of 0.3 W / m ⁇ K or more.
  • the heat conductive filler (C) used in the present invention has an average particle diameter of 50 ⁇ m or more and a BET specific surface area of 0.4 m 2 / g or less.
  • thermally conductive filler (C) examples include metal oxides such as aluminum oxide (alumina), magnesium oxide, silica, and zinc oxide; metal nitrides such as boron nitride and aluminum nitride; artificial graphite and carbon Examples thereof include carbon-containing conductive fillers other than the expanded graphite powder (B), such as black and carbon fibers. Of these, metal oxides are preferred, and aluminum oxide (alumina) is particularly preferred.
  • a heat conductive filler (C) may be used individually by 1 type, and may use 2 or more types together.
  • the average particle diameter of the heat conductive filler (C) is 50 ⁇ m or more, preferably 55 ⁇ m or more and 200 ⁇ m or less, and more preferably 60 ⁇ m or more and 100 ⁇ m or less.
  • Precursor of heat conductive pressure-sensitive adhesive composition (F) and heat conductive pressure-sensitive adhesive sheet-like molded body (G) by setting the average particle size of the heat conductive filler (C) to be not less than the lower limit of the above range. It is possible to suppress an excessive increase in viscosity of the mixed composition, and to suppress a decrease in productivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). .
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are formed by setting the average particle size of the heat conductive filler (C) to be equal to or lower than the upper limit of the above range. It becomes easy to increase the strength.
  • the BET specific surface area of the thermally conductive filler (C) is 0.4 m 2 / g or less, preferably 0.01 m 2 / g or more and 0.3 m 2 / g or less, preferably 0.02 m 2 / g or more. More preferably, it is 0.2 m 2 / g or less.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are less likely to be brittle, and the tensile strength can be prevented from decreasing. .
  • the amount of the heat conductive filler (C) added to 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 300 to 700 parts by mass, preferably 350 to 700 parts by mass, and more preferably 400 to 700 parts by mass with respect to parts by mass. By making the quantity of a heat conductive filler (C) below the upper limit of the said range, it becomes easy to suppress that the viscosity of a mixed composition becomes high too much.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), and even if it can be molded, the hardness increases and the shape followability (adhesion) It is possible to prevent a situation where the adhesion to the body is reduced.
  • the addition amount of the heat conductive filler (C) more than the lower limit of the above range, the heat 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 improve conductivity.
  • the heat conductive pressure-sensitive adhesive composition (F) From the viewpoint of further improving the flame retardancy of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G), the heat conductive pressure-sensitive adhesive composition (F).
  • a phosphate ester By using a phosphate ester, it becomes easy to improve the flame retardance of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (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.
  • Viscosity measurement method Viscosity is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to the following procedure.
  • (1) Weigh 300 ml of the measurement object in a room temperature environment and place it in a 500 ml container.
  • Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
  • (3) The container containing the measurement object is placed on the viscometer, and the rotor is submerged in the measurement object in the container. At this time, the dent which becomes the mark of the rotor is submerged so as to be exactly at the liquid interface to be measured.
  • 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 mixed, it is liquid and the workability is good, and it is easy to mold the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). Become.
  • the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded product (G) containing a phosphate ester the thermally conductive pressure-sensitive adhesive is used in an environment of 15 ° C to 100 ° C.
  • 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 quantity is 100 mass of (meth) acrylic resin compositions (A). As a part, it is preferable that it is 100 mass parts or less, and it is more preferable that they are 20 mass parts or more and 80 mass parts or less.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention comprise a predetermined expanded graphite powder (B) and a heat conductive filler (C). )
  • a predetermined amount in the acrylic resin composition (A) it has high thermal conductivity while suppressing a decrease in productivity as described above. It also has flame resistance.
  • the thermally conductive pressure-sensitive adhesive composition (F) and thermally conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention include, in addition to the materials described above, the above-described thermally conductive pressure-sensitive adhesive of the present invention.
  • Various known additives can be added within a range in which the performance of the adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be satisfied.
  • Known additives include: foaming agents (including foaming aids); glass fibers; external cross-linking agents; pigments; antioxidants such as polyphenols, hydroquinones, hindered amines; thickeners such as acrylic polymer particles And the like.
  • the heat conductive pressure-sensitive adhesive composition (F) is prepared by mixing the substances contained in the heat conductive pressure-sensitive adhesive composition (F) described so far to prepare a mixed composition, and then in the mixed composition.
  • (meth) acrylic acid ester monomer ( ⁇ 1) polymerization reaction that is, the manufacturing method of the heat conductive pressure-sensitive adhesive composition (F) of the present invention includes (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1).
  • Other substances that can be used and preferable content ratios of the respective substances are as described above, and a detailed description thereof is omitted here.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention mixes the substance contained in the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) demonstrated so far, and mixes a composition. It can be obtained by forming and then forming the mixed composition into a sheet or by performing a polymerization reaction of at least a (meth) acrylate monomer ( ⁇ 1) while forming the mixed composition into a sheet. it can.
  • 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) ( (Meth) acrylic resin composition (A), expanded graphite powder (B) having an average particle size of 50 ⁇ m or more, flame retardant thermally conductive inorganic compound (D) other than expanded graphite powder (B), and average particles A thermally conductive filler (C) other than the expanded graphite powder (B) and the flame retardant thermally conductive inorganic compound (D) having a diameter of 50 ⁇ m or more and a BET specific surface area of 0.4 m 2 / g or less; A step of preparing a mixed composition containing the mixture, and after forming the mixed composition into a sheet or while forming the mixed composition into a sheet, at least a (meth) acrylate monomer ( ⁇ 1) Performing a polymerization reaction.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention it is preferable to heat the polymerization reaction.
  • 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 120 ° 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 in which the mixed composition is applied onto a process paper such as a polyester film that has been subjected to a mold release treatment, and the sheet is formed into a sheet, or the process paper that has been subjected to a mold release process between the two process papers.
  • a method of forming a sheet by pressing between the rolls with the mixed composition sandwiched, and extruding the mixed composition using an extruder, and controlling the thickness through a die at that time to form a sheet Examples of the method include molding.
  • the process paper is not particularly limited, for example, a release-treated polyethylene terephthalate film or a release-treated polyethylene naphthalate film can be used. Among these, a polyethylene terephthalate film subjected to a release treatment is preferable.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can reduce the thermal resistance in the thickness direction by reducing the thickness.
  • the upper limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably about 6 mm.
  • the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 0.1 mm.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate.
  • the material which comprises the said base material is not specifically limited.
  • Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone.
  • polyimide As a plastic film, polyimide; polyester such as polyethylene terephthalate and polyethylene naphthalate; fluorine resin such as polytetrafluoroethylene; polyetherketone; polyethersulfone; polymethylpentene; polyetherimide; polysulfone; polyphenylene sulfide; Polyesterimide; polyamide; and 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 have high heat conductivity and pressure-sensitive adhesiveness, By interposing between a heat generating body and a heat radiating body, it can be used for applications such as efficiently conducting heat conduction from the heat generating body to the heat radiating body.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention are attached to an electronic component which is a heating element provided in an electronic device, and the electronic component Can be used as part.
  • FIG. 1 is a diagram for explaining an example of use of a heat conductive pressure-sensitive adhesive sheet-like molded body (G).
  • FIG. 1A is a perspective view schematically showing a part of an electronic device such as a personal computer.
  • FIG. 1A shows a substrate 1, an electronic component 2 that is a heating element installed on the substrate 1, a heat sink 3 that is a radiator, and a thermally conductive pressure-sensitive adhesive disposed between the electronic component 2 and the heat sink 3.
  • the sheet-like molded article (G) 4 is shown.
  • a heat conductive pressure-sensitive adhesive sheet-like molded body (G) 4 is sandwiched and fixed between the electronic component 2 and the heat sink 3, thereby forming a heat conductive pressure-sensitive adhesive sheet-like mold.
  • the heat conductive pressure-sensitive adhesive sheet-like molded body (G) 4 is bonded to the electronic component 2 and the heat sink 3. And since the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) 4 has high heat conductivity, the heat
  • FIG. 1B schematically shows a state in which the NPN transistor 12a and the PNP transistor 12b, which are heating elements, are attached to the heat sink 13, which is a radiator, through the heat conductive pressure-sensitive adhesive sheet-like molded bodies (G) 14, 14.
  • FIG. 1B by attaching the NPN transistor 12a and the PNP transistor 12b to the heat sink 13 via the heat conductive pressure-sensitive adhesive sheet-like molded bodies (G) 14 and 14, the heat conductive feeling is obtained.
  • one heat conductive pressure-sensitive adhesive sheet-like molded body (G) 14 is bonded to the NPN transistor 12a and the heat sink 13, and the other heat
  • the conductive pressure-sensitive adhesive sheet-like molded body (G) 14 is bonded to the PNP transistor 12 b and the heat sink 13.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) 14 has high heat conductivity, the heat
  • both the NPN transistor 12a and the PNP transistor 12b are attached to one heat sink 13 via the heat conductive pressure-sensitive adhesive sheet-like molded bodies (G) 14 and 14 having high heat conductivity.
  • the temperature difference between the NPN transistor 12a and the PNP transistor 12b can be suppressed.
  • FIG. 1C is a cross-sectional view schematically showing a state in which two transistors 22 and 22 that are heating elements are fixed via a heat conductive pressure-sensitive adhesive sheet-like molded body (G) 24.
  • two heat generating elements 22 and 22 are fixed via a heat conductive pressure-sensitive adhesive sheet-like molded body (G) 24, thereby forming a heat conductive pressure-sensitive adhesive sheet. Due to the pressure-sensitive adhesive property of the molded body (G) 24, the thermally conductive pressure-sensitive adhesive sheet-shaped molded body (G) 24 is bonded to the two heating elements 22 and 22.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) 24 has high heat conductivity, if one temperature of two heat generating bodies 22 and 22 becomes high compared with the other, from one side. Since heat can be quickly transmitted to the other side, it is possible to suppress the occurrence of a temperature difference between the two heating elements 22 and 22.
  • the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) was used in the example shown in FIG. 1, it replaces with a heat conductive pressure-sensitive-adhesive sheet-like molded object (G), and a heat conductive pressure-sensitive-adhesive composition.
  • a thing (F) can also be used similarly.
  • the heat sink is used as the heat radiating body.
  • a housing of an electronic component or the like can be used as the heat radiating body.
  • other usage examples 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 will be described.
  • 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 as a part of an electronic component provided in an electronic device.
  • 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.
  • EL electroluminescence
  • LED light emitting diode
  • Devices and parts having heat generating parts such as mobile phones, personal digital assistants (PDAs), notebook computers, liquid crystal panels, 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 a heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); , Heat pipe, graphite sheet, etc.); used as a housing surrounding the LED light source; pasted on a housing surrounding the LED light source; filling a gap between the LED light source and the housing;
  • 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.
  • a heat conductive pressure-sensitive adhesive sheet-like molded product was produced using a mixed composition that gave good results in the evaluation of the productivity as described later, and this was formed into a strip shape having a width of 10 mm and a length of 150 mm.
  • Five test pieces cut into pieces were prepared.
  • a blue flame with a height of about 20 mm was created by adjusting the air and gas flow rate of the Bunsen burner, and the flame of the burner was applied to the lower end of the vertically supported test piece (so that it crossed the flame for about 10 mm) and held for 10 seconds. After that, the test piece and the burner flame were released.
  • the flame- and flame-free combustion durations after the first and second flame contact and the presence / absence of combustion drops (drip) were evaluated, and UL-94 (flame retardant standard) was determined. That is, the flaming combustion duration after the end of the first and second flame contact, the total of the flammable combustion duration and the flameless combustion duration after the end of the second flame contact, The determination was made based on the total flame-free combustion time and the presence or absence of combustion drops (drip).
  • a heat conductive pressure-sensitive adhesive sheet-like molded article produced in the same manner as the heat-conductive pressure-sensitive adhesive sheet-like molded article obtained with good results in the above-mentioned flame retardancy evaluation was obtained in a size of 25 mm ⁇ 25 mm.
  • a cut specimen was prepared.
  • a micro ceramic heater (trade name: MS-5, 25 mm ⁇ 25 mm) manufactured by Sakaguchi Electric Heat Co., Ltd. is attached to one side of the test piece, and an aluminum plate (150 mm ⁇ 50 mm ⁇ thickness 2 mm) is attached to the other side. ) was attached to produce a laminate.
  • 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., Viscomate 150III
  • a Hobart mixer manufactured by Kodaira Manufacturing Co., Ltd., ACM-5LVT type, capacity: 5 L
  • the temperature control of the Hobart container was set to 50 ° C.
  • the vacuum ⁇ 0.1 MPaG
  • the rotation speed scale was set to 3
  • the mixture was stirred for 30 minutes. This process is referred to as a first mixing process.
  • the mixed composition obtained through the first mixing step and the second mixing step is hung on a release PET film having a thickness of 75 ⁇ m, and another release agent having a thickness of 75 ⁇ m is further applied on the mixed composition. Covered with PET film.
  • This laminate in which the mixed composition was sandwiched between the release PET films was passed between two rolls adjusted to a distance of 1600 ⁇ m to form the mixed composition into a sheet. Thereafter, the laminate was put into an oven, heated at 120 ° C. for 15 minutes, and then heated at 150 ° C. for 15 minutes.
  • the (meth) acrylic acid ester monomer and the polyfunctional monomer are polymerized, and at the same time, the polyfunctional monomer as a crosslinking agent allows the (meth) acrylic acid ester polymer ( A1-1) and a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer are crosslinked to form a thermally conductive pressure-sensitive adhesive sheet-like molded product (hereinafter simply referred to as “sheet”) (G1). )
  • sheet thermally conductive pressure-sensitive adhesive sheet-like molded product
  • the polymerization conversion rate of all monomers was calculated from the amount of residual monomers in the sheet (G1) and found to be 99.9%.
  • Example 2 to 7 and Comparative Examples 1 to 9 Sheets (G2 to G7) according to Examples 2 to 7 and sheets according to Comparative Examples 1 to 9 in the same manner as Example 1 except that the composition of each substance was changed as shown in Tables 2 and 3 ( GC1 to GC9) were produced.
  • Tables 2 and 3 show the amount of each substance in parts by mass.
  • other alumina DAM-45, manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size: 45 ⁇ m, BET specific surface area: 0.3 m 2 / g
  • Comparative Example 3 other alumina (manufactured by Showa Denko KK, A12C, average particle size: 85 ⁇ m, BET specific surface area: 0.6 m 2 / g) was used in place of DAM-70.
  • the sheets (G1 to G7) according to the examples were all excellent in productivity, flame retardancy, and thermal conductivity.
  • the sheet (GC1) according to Comparative Example 1 using alumina with a small particle size was inferior in thermal conductivity although the same amount of alumina as in Example 1 was added.
  • the sheet (GC2) according to Comparative Example 2 in which the expanded graphite powder was not used was inferior in flame retardancy.
  • the viscosity of the mixed composition was high, and a sheet could not be produced.
  • the sheet (GC4) according to Comparative Example 4 in which the added amount of alumina was small was inferior in thermal conductivity.

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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)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Composition adhésive (F) sensible à la pression, thermiquement conductrice, qui est produite par mise en œuvre d'une réaction de polymérisation d'au moins un ester de l'acide (méth)acrylique monomère (α1) dans une composition mélangée qui comprend : 100 parties en masse d'une composition de résine (méth)acrylique (A) qui comprend un polymère (A1) d'un ester de l'acide (méth)acrylique et l'ester de l'acide (méth)acrylique monomère (α1) ; 6 à 45 parties en masse d'une poudre de graphite expansée (B) ayant une granulométrie moyenne de 50 µm ou plus ; 150 à 450 parties en masse d'un composé inorganique (D) thermiquement conducteur, ignifuge, autre que la poudre de graphite expansée (B) ; et 300 à 700 parties en masse d'une charge thermiquement conductrice (C) ayant une granulométrie moyenne de 50 µm ou plus et une aire spécifique BET de 0,4 m2/g ou moins, autre que la poudre de graphite expansée (B) et le composé inorganique (D) thermiquement conducteur et ignifuge.
PCT/JP2014/076444 2013-10-24 2014-10-02 Composition adhésive sensible à la pression, thermiquement conductrice, article en forme de feuille adhésive sensible à la pression et thermiquement conductrice, son procédé de production, et dispositif électronique Ceased WO2015060092A1 (fr)

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JP2017147260A (ja) * 2016-02-15 2017-08-24 パナソニックＩｐマネジメント株式会社 ヒートシンク
TWI657591B (zh) * 2017-11-29 2019-04-21 住華科技股份有限公司 太陽能光學膜疊層及其製造方法
CN116135942A (zh) * 2021-11-16 2023-05-19 亨玖科技股份有限公司 耐高温防漏胶及其制备方法及具有耐高温防漏胶的紧固件

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0688061A (ja) * 1992-04-15 1994-03-29 Minnesota Mining & Mfg Co <3M> 熱伝導電気絶縁テープ
WO1998024860A1 (fr) * 1996-12-04 1998-06-11 Nitto Denko Corporation Adhesif autocollant conducteur thermique, feuille adhesive contenant cet adhesif, et procede de fixation d'une piece electronique a un element emettant un rayonnement thermique au moyen de cet adhesif
WO2007116686A1 (fr) * 2006-03-28 2007-10-18 Zeon Corporation Composition d'adhesif sensible a la pression a conductivite thermique et corps moule en forme de feuille adhesive sensible a la pression a conductivite thermique
WO2011102170A1 (fr) * 2010-02-19 2011-08-25 日本ゼオン株式会社 Composition d'adhésif autocollant thermiquement conducteur, feuille adhésive autocollante thermiquement conductrice et composant électronique
JP2012007090A (ja) * 2010-06-25 2012-01-12 Nippon Zeon Co Ltd 熱伝導性感圧接着剤組成物、熱伝導性感圧接着剤組成物の製造方法、熱伝導性感圧接着性シート、及び電子部品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0688061A (ja) * 1992-04-15 1994-03-29 Minnesota Mining & Mfg Co <3M> 熱伝導電気絶縁テープ
WO1998024860A1 (fr) * 1996-12-04 1998-06-11 Nitto Denko Corporation Adhesif autocollant conducteur thermique, feuille adhesive contenant cet adhesif, et procede de fixation d'une piece electronique a un element emettant un rayonnement thermique au moyen de cet adhesif
WO2007116686A1 (fr) * 2006-03-28 2007-10-18 Zeon Corporation Composition d'adhesif sensible a la pression a conductivite thermique et corps moule en forme de feuille adhesive sensible a la pression a conductivite thermique
WO2011102170A1 (fr) * 2010-02-19 2011-08-25 日本ゼオン株式会社 Composition d'adhésif autocollant thermiquement conducteur, feuille adhésive autocollante thermiquement conductrice et composant électronique
JP2012007090A (ja) * 2010-06-25 2012-01-12 Nippon Zeon Co Ltd 熱伝導性感圧接着剤組成物、熱伝導性感圧接着剤組成物の製造方法、熱伝導性感圧接着性シート、及び電子部品

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