WO2015060091A1 - Procédé pour la production de composition adhésive autocollante thermoconductrice, procédé pour la production d'article de type feuille adhésive autocollante thermoconductrice et dispositif électronique - Google Patents

Procédé pour la production de composition adhésive autocollante thermoconductrice, procédé pour la production d'article de type feuille adhésive autocollante thermoconductrice et dispositif électronique Download PDF

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WO2015060091A1
WO2015060091A1 PCT/JP2014/076443 JP2014076443W WO2015060091A1 WO 2015060091 A1 WO2015060091 A1 WO 2015060091A1 JP 2014076443 W JP2014076443 W JP 2014076443W WO 2015060091 A1 WO2015060091 A1 WO 2015060091A1
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meth
sensitive adhesive
conductive pressure
parts
mass
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PCT/JP2014/076443
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English (en)
Japanese (ja)
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明子 北川
拓朗 熊本
豊和 武藤
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日本ゼオン株式会社
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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a method for producing a thermally conductive pressure-sensitive adhesive composition, a method for producing a thermally conductive pressure-sensitive adhesive sheet-like molded article, and a thermally conductive pressure-sensitive adhesive composition or a thermally conductive pressure-sensitive adhesive sheet-like molded article.
  • the present invention relates to an electronic device 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
  • 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 expanded graphite powder, polar group-modified halogenated hydrocarbon fiber, or the like is added.
  • a thermally conductive pressure-sensitive adhesive sheet-like molded body having a good balance of thermal conductivity, flame retardancy, insulation and flexibility can be obtained.
  • a polar group-modified halogenated hydrocarbon fiber by adding a polar group-modified halogenated hydrocarbon fiber, functions such as flame retardancy of a heat conductive pressure-sensitive adhesive sheet-like molded body are improved.
  • an object of the present invention is to provide a heat conductive pressure-sensitive adhesive composition having improved flame retardancy and good productivity and a method for producing a heat conductive pressure-sensitive adhesive sheet-like molded product. Moreover, the electronic device provided with the heat conductive pressure-sensitive-adhesive composition obtained by these manufacturing methods or a heat conductive pressure-sensitive-adhesive sheet-like molded object is provided.
  • the polar group-modified halogenated hydrocarbon fiber (C) is 0.3 parts by mass or more and 3.5 parts by mass or less
  • the polyhydric alcohol polymer fatty acid ester (D) is 2 parts by mass.
  • 1st mixing process which produces the 1st mixed composition containing 13 mass parts or less above, (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (alpha) are included.
  • a second mixed composition containing 100 parts by weight of the (meth) acrylic resin composition (A), 50 parts by weight or more and 1000 parts by weight or less of the thermally conductive filler (B), and the first mixed composition.
  • a heat-sensitive pressure-sensitive adhesive comprising: a second mixing step for producing a polymer; and a polymerization step for performing a polymerization reaction of at least the (meth) acrylic acid ester monomer ( ⁇ 1) in the second mixed composition. It is a manufacturing method of a composition (F).
  • the “polar group-modified halogenated hydrocarbon fiber” means a fiber made of a halogenated hydrocarbon having a polar group in the structure. Specific examples of the polar group-modified halogenated hydrocarbon fiber (C) will be described later.
  • “(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 “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 polar group-modified halogenated hydrocarbon fiber (C) is 0.3 parts by mass or more and 3.5 parts by mass or less
  • the polyhydric alcohol polymer fatty acid ester (D) is 2 parts by mass.
  • 1st mixing process which produces the 1st mixed composition containing 13 mass parts or less above, (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (alpha) are included.
  • a second mixed composition containing 100 parts by weight of the (meth) acrylic resin composition (A), 50 parts by weight or more and 1000 parts by weight or less of the thermally conductive filler (B), and the first mixed composition.
  • the second mixing step for preparing the resin composition, and after forming the second mixed composition into a sheet shape, or while forming the second mixed composition into a sheet shape, at least a (meth) acrylate monomer ( ⁇ 1) polymerization reaction, molding process and weight at least a (meth) acrylate monomer ( ⁇ 1) polymerization reaction, molding process and weight
  • the third aspect of the present invention is the heat conduction obtained by the method for producing the heat generating element and the heat conductive pressure-sensitive adhesive composition (F) according to the first aspect of the present invention bonded to the heat generating element.
  • the manufacturing method of the heat-sensitive pressure-sensitive adhesive composition (F) or the heat-generating pressure-sensitive adhesive sheet-like molded body (G) according to the second aspect of the present invention bonded to the heat-generating body. It is an electronic device provided with the obtained heat conductive pressure-sensitive-adhesive sheet-like molded object (G).
  • the viscosity of the heat conductive pressure-sensitive adhesive composition and the composition that is a precursor of the heat conductive pressure-sensitive adhesive sheet-like molded product May increase excessively, resulting in decreased productivity or difficulty in production.
  • the present inventors do not mix all the substances constituting the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded article at the same time, but by preparing the composition through a predetermined stage. It has been found that an excessive increase in the viscosity of the composition can be suppressed even when the amount of the polar group-modified halogenated hydrocarbon fiber is increased. The present invention is based on this finding. This will be described in detail below.
  • the method for producing the thermally conductive pressure sensitive adhesive composition (F) of the present invention comprises a polar group-modified halogenated hydrocarbon fiber (C), polyhydric alcohol heavy 1st mixing process which produces the 1st mixed composition containing fatty acid ester (D) of a coalescence, (meth) acrylic acid ester polymer (A1), and (meth) acrylic acid ester monomer ( ⁇ 1)
  • a second mixing step of producing a second mixed composition comprising a (meth) acrylic resin composition (A) containing a thermal conductive filler (B) and a first mixed composition;
  • the second mixed composition includes at least a polymerization step for performing a polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1).
  • the polar group-modified halogenated hydrocarbon fiber (C) that can be used in the present invention is a fiber in which a polar group-modified halogenated hydrocarbon is in the form of a fiber. Since it is a halogenated hydrocarbon having a polar group and needs to be fibrous, it is usually a solid, preferably a polymer compound.
  • the polar group may be only one kind or a plurality of different polar groups.
  • polar group examples include (meth) acryl group, hydroxyl group, carbonyl group, carboxyl group, epoxy group, glycidyl group, amino group, amide group, imide group, cyano group, and the like. (Meth) acrylic groups are preferred.
  • halogen atom contained in the structure of the polar group-modified halogenated hydrocarbon constituting the polar group-modified halogenated hydrocarbon fiber (C) include a fluorine atom, a chlorine atom, and a bromine atom. Of these, a fluorine atom is preferred.
  • the halogenated hydrocarbons excluding the polar group part constituting the polar group-modified halogenated hydrocarbon fiber (C) are bonded to all the carbon atoms constituting the halogenated hydrocarbon excluding the polar group part.
  • the halogen atoms are preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more. 100 mol% is particularly preferable.
  • polar group-modified halogenated hydrocarbon fiber (C) (meth) acryl group-modified halogenated hydrocarbon fiber
  • polar group-modified polytetrafluoroethylene fiber hereinafter referred to as polytetrafluoroethylene, (May be abbreviated as “PTFE”)
  • acrylic group-modified PTFE fibers for example, “methabrene A-3000” manufactured by Mitsubishi Rayon Co., Ltd.
  • the amount of the polar group-modified halogenated hydrocarbon fiber (C) used in the first mixing step is 0.3 parts by mass with 100 parts by mass of the (meth) acrylic resin composition (A) used in the second mixing step. It is preferably 3.5 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass or less, and more preferably 0.5 parts by mass or more and 2 parts by mass or less.
  • the amount of the polar group-modified halogenated hydrocarbon fiber (C) is not less than the lower limit of the above range, the heat conductive pressure-sensitive adhesive composition (F) can be provided with sufficient flame retardancy.
  • the amount of the polar group-modified halogenated hydrocarbon fiber (C) is not more than the upper limit of the above range, it is possible to suppress an excessive increase in the viscosity of the second mixed composition described in detail later.
  • the inventors previously prepared a first mixed composition containing the polar group-modified halogenated hydrocarbon fiber (C) and the fatty acid ester (D) of a polyhydric alcohol polymer in the first mixing step. Later, a polar group-modified halogen functioning as a flame retardant is produced by preparing a second mixed composition comprising the first mixed composition with another substance contained in the heat conductive pressure-sensitive adhesive composition (F). Even if the use amount of the activated hydrocarbon fiber (C) is increased from the conventional amount, an excessive increase in the viscosity of the second mixed composition is suppressed, and the productivity of the heat conductive pressure-sensitive adhesive composition (F) is improved. I found out that That is, it has been found that the productivity of the heat conductive pressure-sensitive adhesive composition (F) having high flame retardancy can be improved.
  • fatty acid ester (D) of the polyhydric alcohol polymer used in the present invention examples include polyglycerin fatty acid ester, polysorbitan fatty acid ester, and polypropylene glycol fatty acid ester. Of these, polyglycerol fatty acid esters are more preferable.
  • polyglycerin fatty acid ester examples include polyglycerin condensed ricinoleic acid ester, polyglycerin ricinoleic acid ester, polyglycerin oleic acid ester, polyglycerin stearic acid ester, and the like. Among them, polyglycerin condensed ricinoleic acid ester is particularly preferable.
  • polysorbitan fatty acid ester include polysorbitan condensed ricinoleic acid ester, polysorbitan ricinoleic acid ester, polysorbitan oleic acid ester, polysorbitan stearic acid ester, and the like.
  • polypropylene glycol fatty acid ester examples include polypropylene glycol condensed ricinoleic acid ester, polypropylene glycol ricinoleic acid ester, polypropylene glycol oleic acid ester, and polypropylene glycol stearic acid ester.
  • ricinoleic acid is a compound having both a carboxyl group and a hydroxyl group
  • a compound obtained by the esterification reaction between the carboxyl group possessed by ricinoleic acid and the hydroxyl group possessed by ricinoleic acid, which is a separate molecule is referred to as “condensed ricinolein”.
  • acid a compound obtained by the esterification reaction between the carboxyl group possessed by ricinoleic acid and the hydroxyl group possessed by ricinoleic acid, which is a separate molecule
  • the polyglycerin condensed ricinoleic acid ester is obtained by an esterification reaction between a carboxyl group in condensed ricinoleic acid and a hydroxyl group in a compound having a hydroxyl group.
  • fatty acid ester (D) of the polyhydric alcohol polymer those having a number average molecular weight of 1,000 or more and 10,000 or less are preferable.
  • the fatty acid ester (D) of the polyhydric alcohol polymer is preferably liquid at a temperature of 10 ° C. or higher and 40 ° C. or lower.
  • the amount of the fatty acid ester (D) of the polyhydric alcohol polymer used in the first mixing step is 2 parts by mass or more and 13 parts by mass with the (meth) acrylic resin composition (A) used in the second mixing step being 100 parts by mass. 3 parts by mass or more, preferably 10 parts by mass or less, and more preferably 4 parts by mass or more and 10 parts by mass or less.
  • the amount of the fatty acid ester (D) of the polyhydric alcohol polymer is set to be equal to or less than the upper limit of the above range, the cohesive force of the second mixed composition is lowered and the heat conductive pressure-sensitive adhesive composition (F). It is possible to prevent the molding of the material from becoming difficult.
  • a 2nd mixing process is a process of producing the 2nd mixed composition containing a (meth) acrylic resin composition (A), a heat conductive filler (B), and the said 1st mixed composition. is there.
  • the (meth) acrylic resin composition (A) and the heat conductive filler (B) used in the second mixing step will be described below.
  • the (meth) acrylic resin composition (A) used in the second mixing step contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1), which will be described later. It may contain a multifunctional monomer.
  • the polymerization reaction of a (meth) acrylic acid ester monomer ((alpha) 1) is performed at least. By performing the polymerization reaction, 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 mixing ratio of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ( ⁇ 1) is (meth) acrylic acid with the (meth) acrylic resin composition (A) being 100% by mass.
  • the ester polymer (A1) is preferably 20% by mass or more and 80% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 20% by mass or more and 80% by mass or less. More preferably, the coalescence (A1) is 30% by mass or more and 69.5% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is 30% by mass or more and 69.5% by mass or less. 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. It is convenient and preferable. However, after producing the (meth) acrylic acid ester polymer (A1), an organic acid group may be introduced by a known polymer reaction.
  • 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.
  • the agent composition (F) can be easily obtained.
  • 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 is introduced into the copolymer, and the heat conductive pressure sensitive adhesive composition (F) is aggregated as a pressure sensitive adhesive. You can increase your power.
  • 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 Multifunctional (meth) acrylates such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trick Other substituted triazines, such as Romechiru) -6
  • 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 0.5% by mass or more and 5% by mass or less. Is more preferable.
  • ⁇ Polymerization initiator> When obtaining the heat conductive pressure sensitive adhesive composition (F), 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. However, it is preferable to use an organic peroxide thermal polymerization initiator from the viewpoint of imparting strong adhesive force to the obtained heat conductive pressure-sensitive adhesive composition (F).
  • 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, it becomes easy to prevent the monomer odor from remaining in the heat conductive pressure-sensitive adhesive composition (F). Moreover, by making the usage-amount of a polymerization initiator into the said range, superposition
  • the thermally conductive filler (B) the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) can be improved by adding it, and its own thermal conductivity is 0.3 W / m ⁇ K or more.
  • thermally conductive filler (B) examples include aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and other metal hydroxides; aluminum oxide ( Alumina), magnesium oxide, silica (silicon oxide), metal oxides such as zinc oxide; metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate; kaolin Clay; calcium aluminate hydrate; dosonite; carbon-containing conductive fillers such as expanded graphite powder, artificial graphite, carbon black, and carbon fiber; Among these, metal hydroxides, metal oxides, and carbon-containing conductive fillers are preferable, metal hydroxides and carbon-containing conductive fillers are more preferable, and aluminum hydroxide and expanded graphite powder are more preferable.
  • a heat conductive filler (B) may be used individually by 1 type, and may use 2 or more
  • the expanded graphite powder that can be used as the thermally conductive filler (B) will be described.
  • the expanded graphite powder has high thermal conductivity, and by adding the expanded graphite powder, the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G).
  • the thermal conductivity of can be improved.
  • by adding the expanded graphite powder it is possible to suppress melting even when the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are heated. Flammability can be improved.
  • the expanded graphite powder is preferably added in the second mixing step.
  • Expanded graphite powder is obtained by expanding and then pulverizing graphite.
  • a method comprising a step of heat-treating acid-treated graphite at 500 ° C. or more and 1200 ° C. or less to expand it to 100 ml / g or more and 300 ml / g or less and then crushing it.
  • 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.
  • a product obtained by a method including a step of expanding and then crushing is particularly preferably 800 ° C. or higher and 1000 ° C. or lower.
  • the amount of the thermally conductive filler (B) used in the second mixing step is 50 parts by mass or more and 1000 parts by mass or less, and 100 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic resin composition (A). It is preferably 900 parts by mass or less, more preferably 150 parts by mass or more and 800 parts by mass or less, and further preferably 150 parts by mass or more and 300 parts by mass or less.
  • the heat conductive pressure-sensitive adhesive composition (F) it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (F), or even if it can be molded, the hardness of the heat conductive pressure-sensitive adhesive composition (F) increases and the shape followability (to the adherend) ) Can be prevented.
  • the effect of improving the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) is easily exhibited by setting the content of the heat conductive filler (B) to the above lower limit or more.
  • the amount of the carbon-containing conductive filler used in the second mixing step is based on 100 parts by mass of the (meth) acrylic resin composition (A). 50 parts by mass or less, preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less, and further preferably 3 parts by mass or more and 10 parts by mass or less. .
  • the average particle diameter of the whole filler used as the thermally conductive filler (B) is preferably 0.5 ⁇ m or more and 15 ⁇ m or less, and more preferably 0.8 ⁇ m or more and 12 ⁇ m or less. Further, BET specific surface area of the entire filler used as the thermally conductive filler (B) is preferably from 0.3 m 2 / g or more 10m 2 / g, 0.5m 2 / g or more 5 m 2 / g or less It is more preferable that Even if the content of the heat conductive filler (B) is increased by adjusting the average particle diameter and BET specific surface area of the whole filler used as the heat conductive filler (B) within the above range, the viscosity of the mixed composition is appropriate.
  • 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, and the strength can be further suppressed from decreasing. .
  • 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.
  • the polymerization step is a step of performing a polymerization reaction of at least the (meth) acrylic acid ester monomer ( ⁇ 1) in the second mixed composition.
  • heat for the heating, for example, hot air, an electric heater, infrared rays, or the like can be used.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylate monomer ( ⁇ 1) proceeds.
  • the specific preferable 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 first mixing step and the second mixing step are performed separately, whereby the polar group-modified halogenated hydrocarbon fiber ( Even if the addition amount of C) is slightly increased from the conventional amount, the viscosity of the second mixed composition can be suppressed from excessively increasing, and therefore the productivity of the heat conductive pressure-sensitive adhesive composition (F) is improved. It can suppress that it falls. Therefore, the productivity of the heat conductive pressure-sensitive adhesive composition (F) having high flame retardancy can be improved.
  • the thermally conductive pressure-sensitive adhesive composition (F) of the present invention includes the above-described method for producing the thermally conductive pressure-sensitive adhesive composition (F) of the present invention in addition to the substances described above.
  • Various known additives can be added as long as the effect of is improved or not hindered.
  • Known additives include, for example, flame retardants such as phosphate esters; foaming agents (including foaming aids); glass fibers; external crosslinking agents; pigments; other fillers other than thermally conductive fillers; , Hydroquinone-based and hindered amine-based antioxidants; acrylic polymer particle-based thickeners; and the like.
  • the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention contains the fatty acid ester (C) of a polyhydric alcohol polymer, and a polar group modified
  • molding step and the polymerization step in the method for producing the heat conductive pressure-sensitive adhesive sheet-shaped body (G) of the present invention will be described.
  • at least the (meth) acrylic acid ester monomer ( ⁇ 1) is formed after the second mixed composition is molded into a sheet shape or while the second mixed composition is molded into a sheet shape.
  • This is a step of performing a polymerization reaction.
  • heating is preferably performed when the polymerization reaction is performed.
  • heating for example, hot air, an electric heater, infrared rays, or the like can be used.
  • the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylate monomer ( ⁇ 1) proceeds.
  • the specific preferable 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 second mixed composition into a sheet is not particularly limited.
  • a suitable method for example, a method in which the second mixed composition is applied on a process paper such as a release-treated polyester film and formed into a sheet shape, or between two process papers subjected to a release process A method of forming a sheet by pressing between the rolls with the second mixed composition in between, and extruding the second mixed composition using an extruder, and controlling the thickness through a die at that time The method etc. which shape
  • 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 2 mm.
  • the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (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 first mixing step and the second mixing step are performed separately, whereby the polar group-modified halogenated hydrocarbon is obtained. Even if the addition amount of the fiber (C) is slightly increased from the conventional amount, the viscosity of the second mixed composition can be suppressed from being excessively increased, so that the thermally conductive pressure-sensitive adhesive sheet-like molded product (G) It can suppress that productivity of this falls. Therefore, the productivity of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) having high flame retardancy can be improved.
  • the heat-conductive pressure-sensitive adhesive sheet-like molded product (G) obtained by the production method (2) has high heat conductivity and pressure-sensitive adhesive properties, and therefore is interposed between the heating element and the heat radiating body. Therefore, it can be used for applications such as efficiently conducting heat conduction from the heat generating element to the heat radiating element.
  • the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) are attached to an electronic component that is a heating element provided in an electronic device, and are part of the electronic component. Can be used.
  • the usage example of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) is demonstrated, referring FIG.
  • 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.
  • Viscosity measurement using a B-type viscometer is performed 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.
  • (5) Turn on the stirring switch and read the value after 1 minute.
  • 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 first mixing step was performed as follows. That is, 1 part of acrylic modified PTFE fiber (trade name “Membrane A-3000”, manufactured by Mitsubishi Rayon Co., Ltd.) and a fatty acid ester of a polyhydric alcohol polymer (Tirabazole H-818, manufactured by Taiyo Chemical Co., Ltd., number average molecular weight: 4000) 5 parts were weighed with an electronic balance, and these were mixed with a spatula for 1 minute while stirring to obtain a first mixed composition.
  • acrylic modified PTFE fiber trade name “Membrane A-3000”, manufactured by Mitsubishi Rayon Co., Ltd.
  • a fatty acid ester of a polyhydric alcohol polymer Teirabazole H-818, manufactured by Taiyo Chemical Co., Ltd., number average molecular weight: 4000
  • 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 at 23 ° C.
  • the rotation speed scale was set to 5, and the mixture was stirred for 10 minutes.
  • the second mixed composition was hung on a release PET film having a thickness of 75 ⁇ m, and another release PET film having a thickness of 75 ⁇ m was further covered on the second mixed composition.
  • the laminate, in which the second mixed composition was sandwiched between the release PET films, was passed between two rolls adjusted to a distance of 650 ⁇ m, and the second mixed composition was formed into a sheet. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes to perform a polymerization step.
  • the (meth) acrylic acid ester monomer and the polyfunctional monomer are polymerized, and at the same time, the polyfunctional monomer as a cross-linking 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%.
  • Examples 2 to 5 and Comparative Examples 1 to 6 The sheets (G2 to G5) according to Examples 2 to 5 and the sheets according to Comparative Examples 1 to 6 (Similar to Example 1) except that the composition of each substance was changed as shown in Tables 2 and 3. GC1 to GC6) were produced. Tables 2 and 3 show the amount of each substance in parts by mass. In Comparative Example 3, a titanate coupling agent (manufactured by Ajinomoto Finetech Co., Ltd., Preneact TTS, isopropyl triisostearoyl titanate) was used instead of the fatty acid ester of the polyhydric alcohol polymer. Tables 2 and 3 show the presence or absence of the first mixing step.
  • a titanate coupling agent manufactured by Ajinomoto Finetech Co., Ltd., Preneact TTS, isopropyl triisostearoyl titanate
  • the first mixing step is performed in the same manner as in Example 1.
  • the first mixing step is not performed, and the polar group is formed in a step corresponding to the second mixing step.
  • the mixed composition obtained by mixing the modified halogenated hydrocarbon fiber and the fatty acid ester of the polyhydric alcohol polymer was formed into a sheet and subjected to the polymerization step.
  • the sheets (G1 to G5) according to the examples all had low viscosity of the second mixed composition and high flame retardancy. That is, productivity was good and flame retardancy was high.
  • the sheet (GC1) according to Comparative Example 1 in which the addition amount of the polar group-modified halogenated hydrocarbon fiber exceeded the range specified in the present invention the viscosity of the second mixed composition was high and the productivity was poor. It was.
  • regulated by this invention has the high viscosity of 2nd mixed composition (productivity is bad).
  • the sheet (GC3) according to Comparative Example 3 using a titanate coupling agent in place of the fatty acid ester of the polyhydric alcohol polymer also has a high viscosity of the second mixed composition (productivity is poor), and flame retardancy. The sex was inferior.
  • the sheet (GC4) according to Comparative Example 4 in which the first mixing step was not performed has a high viscosity of the second mixed composition despite the fact that the amount of each substance is the same as Example 1. (Productivity was bad) and flame retardancy was poor.
  • the sheet (GC5) according to Comparative Example 5 in which the addition amount of the polar group-modified halogenated hydrocarbon fiber was less than the range specified in the present invention was inferior in flame retardancy.
  • the sheet (GC6) according to Comparative Example 6 in which the addition amount of the fatty acid ester of the polyhydric alcohol polymer exceeded the range defined in the present invention was inferior in flame retardancy.

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Abstract

L'invention porte sur un procédé pour la production d'une composition adhésive autocollante thermoconductrice (F), qui comprend : une première étape de mélange consistant à produire une première composition mélangée qui comprend 0,3 à 3,5 parties en masse d'une fibre d'hydrocarbure halogéné modifié par un groupe polaire (C) et 2 à 13 parties en masse d'un ester (D) d'acide gras et d'un copolymère de polyalcool ; une seconde étape de mélange consistant à produire une seconde composition mélangée qui comprend 100 parties en masse d'une composition de résine (méth)acrylique (A) comprenant un polymère d'ester d'acide (méth)acrylique (A1) et un monomère ester d'acide (méth)acrylique (α1), 50 à 1000 parties en masse d'une charge thermoconductrice (B) et la première composition mélangée ; et une étape de polymérisation consistant à effectuer une réaction de polymérisation au moins du comonomère ester d'acide (méth)acrylique (α1) dans la seconde composition mélangée.
PCT/JP2014/076443 2013-10-24 2014-10-02 Procédé pour la production de composition adhésive autocollante thermoconductrice, procédé pour la production d'article de type feuille adhésive autocollante thermoconductrice et dispositif électronique WO2015060091A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032454A (ja) * 2009-07-07 2011-02-17 Mitsubishi Rayon Co Ltd 分散性向上剤、熱可塑性樹脂組成物及び成形体
JP2011246590A (ja) * 2010-05-26 2011-12-08 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、及び電子部品
JP2013129814A (ja) * 2011-11-25 2013-07-04 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、及び電子機器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011032454A (ja) * 2009-07-07 2011-02-17 Mitsubishi Rayon Co Ltd 分散性向上剤、熱可塑性樹脂組成物及び成形体
JP2011246590A (ja) * 2010-05-26 2011-12-08 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、及び電子部品
JP2013129814A (ja) * 2011-11-25 2013-07-04 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、及び電子機器

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