WO2012132657A1 - 熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート状成形体、これらの製造方法、及び電子部品 - Google Patents
熱伝導性感圧接着剤組成物、熱伝導性感圧接着性シート状成形体、これらの製造方法、及び電子部品 Download PDFInfo
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- sensitive adhesive
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
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- 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
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- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
- 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
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29099—Material
- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29199—Material of the matrix
- H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
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- H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
- H01L2224/29298—Fillers
- H01L2224/29299—Base material
- H01L2224/29386—Base material with a principal constituent of the material being a non metallic, non metalloid inorganic material
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
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- H01L2924/0543—13th Group
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- H01L2924/12—Passive devices, e.g. 2 terminal devices
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- H01L2924/12041—LED
Definitions
- the present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molding.
- the present invention relates to an electronic component having a body.
- thermoally conductive pressure-sensitive adhesive composition a composition having pressure-sensitive adhesiveness in addition to thermal conductivity
- thermally conductive pressure-sensitive adhesive sheet-like molded product A sheet having pressure-sensitive adhesiveness in addition to thermal conductivity
- the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are used as one of the purposes for transferring heat from the heat generating body to the heat radiating body. preferable.
- the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded article it is conceivable to add expanded graphite powder or the like.
- expanded graphite powder has high thermal conductivity and high conductivity. Therefore, there is a case where the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body whose thermal conductivity is improved by the expanded graphite powder cannot be used for applications that also require insulation. .
- the thermal conductivity of the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body can be improved.
- Zinc oxide is also used as a filler.
- the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article having a good balance between thermal conductivity and insulation, their production methods, and the thermally conductive pressure-sensitive adhesive. It is an object of the present invention to provide an agent composition or an electronic component including the thermally conductive pressure-sensitive adhesive sheet-like molded body.
- the present inventors have found that the above problem can be solved by using a predetermined zinc oxide and a predetermined heat conductive filler other than zinc oxide in combination, and have completed the present invention.
- a mixed composition containing 0.5 parts by mass or more and 40 parts by mass or less of zinc (C) a polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1), and a (meth) acrylic acid ester polymer
- (Meth) acryl means “acryl and / or methacryl”.
- the “average particle size” 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 to improve measurement reliability). 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.
- the average particle size and particle size distribution are calculated from the diffraction principle of Franhofer.
- the “thermally conductive filler” is added to improve the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) or the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) described later. Means a filler that can.
- the length of the needle-like portion” of zinc oxide (C) means a length measured by observation with a scanning electron microscope.
- the “polymerization reaction of (meth) acrylate monomer ( ⁇ 1)” means a polymerization reaction to obtain a polymer that generates a structural unit derived from the (meth) acrylate monomer ( ⁇ 1).
- “(meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer ( ⁇ 1) -derived polymer cross-linking reaction” means (meth) acrylic acid ester Cross-linking reaction between polymers (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylate monomer ( ⁇ 1), and (meth) acrylate polymer (A1) and ( Among crosslinking reactions with a polymer containing a structural unit derived from a (meth) acrylate monomer ( ⁇ 1), it means one or a plurality of crosslinking reactions.
- the mixed composition preferably further contains 20 parts by mass or more and 100 parts by mass or less of a phosphate ester.
- the heat conductive filler (B) whose average particle diameter is 50 micrometers or less is an aluminum oxide and / or aluminum hydroxide whose average particle diameter is 50 micrometers or less.
- a mixed composition containing zinc (C) in an amount of 0.5 to 40 parts by mass into a sheet, or while forming the mixed composition into a sheet.
- the polymerization reaction of the monomer ( ⁇ 1) and the crosslinking reaction of the polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1) are performed.
- the mixed composition further contains 20 parts by mass or more and 100 parts by mass or less of a phosphate ester.
- the heat conductive filler (B) whose average particle diameter is 50 micrometers or less is an aluminum oxide and / or aluminum hydroxide whose average particle diameter is 50 micrometers or less.
- pressure sensitive adhesive composition (F) That.
- the mixed composition preferably further contains 20 parts by mass or more and 100 parts by mass or less of a phosphate ester.
- the heat conductive filler (B) whose average particle diameter is 50 micrometers or less is an aluminum oxide and / or aluminum hydroxide whose average particle diameter is 50 micrometers or less.
- the 4th aspect of this invention is 100 masses of (meth) acrylic-ester resin compositions (A) containing the (meth) acrylic-ester polymer (A1) and the (meth) acrylic-ester monomer ((alpha) 1). And a heat conductive filler (B) having an average particle diameter of 50 ⁇ m or less, 600 parts by mass to 1400 parts by mass and an acicular part, and the length of the acicular part is 2 ⁇ m to 50 ⁇ m
- the (meth) acrylic acid ester monomer ( ⁇ 1) polymerization reaction and (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer ( ⁇ 1) -derived Performs crosslinking reaction of polymers containing structural units Extent, including a method for producing a heat
- the mixed composition preferably further contains 20 parts by mass or more and 100 parts by mass or less of a phosphate ester.
- the heat conductive filler (B) whose average particle diameter is 50 micrometers or less is an aluminum oxide and / or aluminum hydroxide whose average particle diameter is 50 micrometers or less.
- a heat radiator and the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the heat radiator, or the heat radiator and the heat radiator.
- An electronic component comprising the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) according to the second aspect of the present invention.
- a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded article having a good balance between thermal conductivity and insulation, their production methods, and the thermally conductive pressure-sensitive adhesive It is possible to provide an agent composition or an electronic component provided with the thermally conductive pressure-sensitive adhesive sheet-like molded body.
- the thermally conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin composition containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1).
- thermoly conductive filler (B) having an average particle size of 50 ⁇ m or less
- thermally conductive filler (B) a thermally conductive filler having an average particle size of 50 ⁇ m or less
- a needle-like part a needle-like part
- Z oxide (C) Zinc oxide
- the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is (meth) acrylic acid after shape
- Polymerization reaction for obtaining a polymer that produces a structural unit derived from an ester monomer ( ⁇ 1) a crosslinking reaction between (meth) acrylic acid ester polymers (A1), (meth) acrylic acid ester monomer ( ⁇ 1)
- the materials constituting the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) will be described below.
- the (meth) acrylic resin composition (A) used in the present invention contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer ( ⁇ 1).
- (meth) acrylic acid ester monomer ((alpha) 1) origin Polymerization reaction to obtain a polymer that yields a structural unit of the above, and a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1) And done.
- the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1) is mixed with the component of the (meth) acrylic acid ester polymer (A1) and / or. Join some.
- the usage-amount of an acrylic ester polymer (A1) and the (meth) acrylic ester monomer ((alpha) 1) is (meth) with respect to 100 mass% of (meth) acrylic resin compositions (A).
- the acrylate polymer (A1) is preferably 5% by mass or more and 40% by mass or less, and the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 60% by mass or more and 95% by mass or less.
- the (meth) acrylic acid ester polymer (A1) that can be used in the present invention is not particularly limited, but the (meth) acrylic acid ester monomer that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower. It is preferable to contain the unit (a1) and the monomer unit (a2) having an organic acid group.
- the (meth) acrylic acid ester monomer (a1m) which gives the unit (a1) of the (meth) acrylic acid ester 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-heptyl acrylate - 60 ° C
- n-octyl acrylate -65 ° C
- 2-ethylhexyl acrylate -50 ° C
- 2-methoxyethyl acrylate (-50) ° C)
- 3-methoxypropyl acrylate (-75 ° C)
- 3-methoxybutyl acrylate (-56 ° C)
- n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is more preferable.
- acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
- the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1). In the following, it is preferable to use it in the polymerization in such an amount that it is 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 a monomer having acrylic acid or methacrylic acid is particularly preferable. . These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.
- the monomer unit (a2) derived therefrom is 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1), preferably It is preferable to use it 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.
- Examples of the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.
- 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.
- a monomer (a4m) may be used individually by 1 type, and may use 2 or more types together.
- the amount of the monomer unit (a4) derived from the monomer (a4m) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the acrylate polymer (A1).
- the monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), ⁇ , ⁇ -ethylenic monomers. Saturated polycarboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, etc. Can be mentioned.
- the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.
- ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid complete ester examples include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.
- alkenyl aromatic monomer examples include styrene, ⁇ -methylstyrene, methyl ⁇ -methylstyrene, vinyl toluene, and divinylbenzene.
- conjugated diene monomer examples include 1,3-butadiene, 2-methyl-1,3-butadiene (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. 2-chloro-1,3-butadiene, cyclopentadiene and the like.
- non-conjugated diene monomer examples include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.
- vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
- carboxylic acid unsaturated alcohol ester monomer examples include vinyl acetate.
- olefin monomer examples include ethylene, propylene, butene, pentene and the like.
- the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. It is more preferable that it is in the range of 200,000 or more and 500,000 or less.
- the (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer (a1m), a monomer having an organic acid group, which forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower.
- (A2m) a monomer containing a functional group other than an organic acid group (a3m) used as required, and a monomer copolymerizable with these monomers used as needed ( a4m) can be obtained particularly preferably by copolymerization.
- the polymerization method is not particularly limited, and any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like may be used.
- Solution polymerization is preferred, 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 as the polymerization solvent is more preferred.
- 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 may be either a peroxide or an azo compound.
- 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 of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.
- the (meth) acrylate monomer ( ⁇ 1) is not particularly limited as long as it contains a (meth) acrylate monomer, but a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower is molded. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).
- the (meth) acrylate monomer (a5m) for forming a homopolymer having a glass transition temperature of ⁇ 20 ° C. or lower it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) )
- a (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.
- the ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer ( ⁇ 1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer ( ⁇ 1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
- the (meth) acrylic acid ester monomer ( ⁇ 1) may be a mixture of a (meth) acrylic acid ester monomer (a5m) and a monomer copolymerizable therewith.
- Particularly preferred (meth) acrylate monomer ( ⁇ 1) is (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of ⁇ 20 ° C. or less, and a copolymer thereof. It contains a monomer (a6m) having 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 with the monomer (a7m) which can be copolymerized with these.
- 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.
- 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.
- Examples of the polymerization initiator that can be used in the present invention include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator. From the viewpoint of imparting excellent adhesiveness to the obtained heat conductive pressure-sensitive adhesive composition (F) and heat conductive pressure-sensitive adhesive sheet-like molded body (G), an organic peroxide thermal polymerization initiator is used. It is preferable to use it.
- acylphosphine oxide compounds are preferred.
- Preferred examples of the acylphosphine oxide compound that is a photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
- azo-based thermal polymerization initiator 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.
- Organic peroxide thermal polymerization initiators 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 or less with respect to 100 parts by mass of the (meth) acrylic resin composition (A). It is more preferable that it is 0.3 mass part or more and 1 mass part or less.
- the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer ( ⁇ 1) is 95% by mass or more, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the monomer odor from remaining on the surface.
- ⁇ Multifunctional monomer> In the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention, it is preferable to use a polyfunctional monomer.
- the polyfunctional monomer one that can be copolymerized with the monomer contained in the (meth) acrylic acid ester monomer ( ⁇ 1) is used.
- the polyfunctional monomer has a plurality of polymerizable unsaturated bonds, and has the unsaturated bond at the terminal.
- polyfunctional monomer examples include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane Multifunctional (meth) acrylates such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (trichloro) Other substituted triazines, such as methyl)
- monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used.
- pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable.
- a polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
- the amount of the polyfunctional monomer used in the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 parts by mass of the acrylic resin composition (A). It is preferably from 0.1 parts by weight to 15 parts by weight, more preferably from 0.2 parts by weight to 8 parts by weight, and even more preferably from 0.5 parts by weight to 2 parts by weight.
- the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) are suitable as a pressure sensitive adhesive. It becomes easy to give a strong cohesive force.
- a heat conductive filler (B) is used for the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) of the present invention.
- a heat conductive filler (B) is a filler which can improve the heat conductivity of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) by adding.
- the average particle size is 50 ⁇ m or less.
- the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) easy to be provided with insulation it is more conductive than zinc oxide (C) described later. A low one is preferred.
- thermally conductive filler (B) examples include calcium carbonate, aluminum hydroxide, magnesium hydroxide, aluminum oxide (alumina), magnesium oxide, silica, glass fiber, boron nitride and aluminum nitride.
- calcium carbonate, aluminum hydroxide, and aluminum oxide are preferable because they are easily available, chemically stable, and can be blended in a large amount, and aluminum oxide and aluminum hydroxide are particularly preferable.
- a heat conductive filler (B) may be used individually by 1 type, and may use 2 or more types together.
- the average particle size of the thermally conductive filler (B) used in the present invention is 50 ⁇ m or less.
- the preferable range of the average particle diameter of the thermally conductive filler (B) is presumed to depend on the size of the zinc oxide (C) as will be described later. For example, it is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less. And more preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
- the heat conductive pressure-sensitive adhesive composition (F) and heat conduction in combination with zinc oxide (C) described later are used. High thermal conductivity can be imparted to the pressure-sensitive adhesive sheet-like molded body (G).
- the amount of the heat conductive filler (B) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is (meth) acrylic resin composition (A) 100. It is 600 mass parts or more and 1400 mass parts or less with respect to a mass part.
- the upper limit of the content of the heat conductive filler (B) is preferably 1300 parts by mass, and more preferably 1200 parts by mass.
- the lower limit of the content of the heat conductive filler (B) is preferably 700 parts by mass, more preferably 800 parts by mass.
- High thermal conductivity can be imparted to the body (G).
- the content of the heat conductive filler (B) exceeds 1400 parts by mass, the mixture becomes a base of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
- the viscosity of the composition increases, the productivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) decreases, and the hardness increases and the shape following property decreases. Tend to. When shape followability is lowered, it becomes difficult to transfer heat from the heating element to the radiator. Further, when the content of the heat conductive filler (B) is less than 600 parts by mass, the heat conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). There is a possibility that the effect of improving the resistance becomes insufficient.
- Zinc oxide (C) used in the present invention has a needle-like portion, and the length of the needle-like portion is 2 ⁇ m or more and 50 ⁇ m or less.
- the heat conductive pressure-sensitive adhesive composition (F) and the heat are combined with the heat conductive filler (B).
- High thermal conductivity can be imparted to the conductive pressure-sensitive adhesive sheet-like molded body (G).
- Zinc oxide (C) used in the present invention only needs to have a needle-like part, and one or a plurality of needle-like parts may be provided around the core part, and is constituted only by the needle-like part. May be.
- a certain heat conductive filler (B) filled in the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) and other heat it is preferable that a plurality of needle-like portions are provided extending in different directions around the core portion.
- the core portion and three or more needle-like portions present around the core portion there are a core portion and three or more needle-like portions present around the core portion, and at least one of the needle-like portions is not coplanar with other needle-like portions. It is desirable to be.
- the number of needle-like portions existing around one nucleus is preferably 3-6. When the number is within this range, the orientation of the needle-like portion becomes three-dimensional and the connection with other fillers is good.
- “Panatetra (registered trademark)” manufactured by Amtec Corporation can be exemplified.
- the amount of zinc oxide (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 parts by weight of the (meth) acrylic resin composition (A). On the other hand, it is 0.5 to 40 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass.
- content of zinc oxide (C) into the said range, a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molding (in combination with a heat conductive filler (B) ( High thermal conductivity can be imparted to G).
- the heat conductive filler (B) and the zinc oxide (C) are used in combination with a predetermined amount, so that the amounts of the heat conductive filler (B) and the zinc oxide (C) used can be reduced by the conventional heat.
- the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-shaped product (G) having a good balance between thermal conductivity and insulation, even if less than the conductive pressure-sensitive adhesive sheet-shaped product (G) ) Can be obtained.
- the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) and the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) is improved by using a combination of the thermally conductive filler (B) and zinc oxide (C).
- the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) are filled with a certain heat conductive filler (B) and other heat conductive materials.
- thermally conductive filler when added in order to improve thermal conductivity, it is considered that a larger particle size of the thermally conductive filler is better from the viewpoint of easily improving thermal conductivity.
- the present inventors use a combination of a thermally conductive filler (B) having a predetermined average particle size or less and zinc oxide (C) having a needle-shaped portion having a predetermined length. It has been found that the thermal conductivity of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be improved.
- 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 (B) to a predetermined value or less. This is presumed to be because it is easier to connect a certain thermally conductive filler (B) filled in the plate with another thermally conductive filler (B) with zinc oxide (C). Therefore, in the present invention, the relationship between the particle size of the heat conductive filler (B) and the length of the needle-shaped portion of zinc oxide (C) is determined by the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive. It is presumed that the thermal conductivity of the conductive sheet-like molded body (G) is affected.
- the heat conductivity of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) is used by combining a heat conductive filler (B) and zinc oxide (C). It is possible to suppress the decrease in insulation while improving the heat resistance, and only the zinc oxide (C) is continuously connected to the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).
- the thermal conductivity filler (B) which is less conductive than zinc oxide (C), is present between certain zinc oxide (C) and other zinc oxide (C). It is presumed that this is due to interposition.
- Phosphate ester can also be used for the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention.
- phosphate ester it becomes easy to improve the flame retardance of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G).
- the phosphate ester used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
- a viscosity at 25 ° C. of 3000 mPa ⁇ s or more.
- the viscosity of the phosphate ester is measured by the procedure shown below using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).
- a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
- (1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
- (2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
- the container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the condensed phosphate ester in the container.
- the rotation speed is selected from 20, 10, 4, and 2.
- the rotation speed is selected from 20, 10, 4, and 2.
- the value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa ⁇ s].
- the coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.
- the phosphate ester used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester is liquid when mixed, the workability is good, and it is easy to form the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G). become.
- the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less the heat conductive pressure sensitive in an environment of 15 ° C. or more and 100 ° C. or less.
- the glass transition temperature of the acrylic resin composition (A) is set to be higher than that, and the volatilization or polymerization reaction of the monomers and the like contained in the acrylic resin composition (A) starts. Therefore, 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; Among these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no danger of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.
- non-condensed phosphate ester examples include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris ( ⁇ -chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.
- Phosphoric acid ester may be used alone or in combination of two or more.
- the amount of the phosphoric acid ester used for the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention is 100 (meth) acrylic resin composition (A).
- the mass part is preferably 20 parts by mass or more and 100 parts by mass or less.
- foaming agents include foaming aids; flame retardant thermally conductive inorganic compounds such as metal hydroxides and metal salt hydrates; glass fibers; expanded graphite powder, alumina, PITCH series Thermally conductive inorganic compounds such as carbon fibers; external cross-linking agents; pigments such as carbon black and titanium dioxide; other fillers such as clay; nanoparticles such as fullerenes and carbon nanotubes; oxidations such as polyphenols, hydroquinones, and hindered amines Inhibitors; thickeners such as acrylic polymer particles, fine silica, and magnesium oxide;
- the thermally conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing the materials described so far, followed by the polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1) and (meth) acrylic. It can obtain by performing the crosslinking reaction of the polymer containing the structural unit derived from the acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1).
- the manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1) ( Zinc oxide having a (meth) acrylic resin composition (A), a thermally conductive filler (B) having an average particle diameter of 50 ⁇ m or less, and a needle-like part, the length of the needle-like part being 2 ⁇ m or more and 50 ⁇ m or less (C) and a step of producing a mixed composition containing the same, and in the mixed composition, a polymerization reaction of the (meth) acrylic acid ester monomer ( ⁇ 1) and a (meth) acrylic acid ester polymer ( A1) and / or a step of performing a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer ( ⁇ 1).
- the substance which can be used the preferable content ratio of each substance, the preferable content ratio
- heat for example, hot air, an electric heater, infrared rays, or the like can be used.
- the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer proceeds.
- a temperature range changes with kinds of polymerization initiator to be used 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.
- the heat conductive pressure-sensitive adhesive sheet-shaped molded product (G) of the present invention is obtained by mixing the materials described above into a sheet shape, or while forming into a sheet shape.
- the polymerization reaction of the monomer ( ⁇ 1) and the crosslinking reaction of the polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1) are performed. Can be obtained.
- the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention comprises (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer ( ⁇ 1).
- a step of preparing a mixed composition containing zinc oxide (C), and after forming the mixed composition into a sheet or while forming the mixed composition into a sheet The polymerization reaction of the monomer ( ⁇ 1) and the crosslinking reaction of the polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer ( ⁇ 1) are performed. It includes a process.
- heat for example, hot air, an electric heater, infrared rays, or the like can be used.
- the heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer ( ⁇ 1) and the polyfunctional monomer proceeds.
- a temperature range changes with kinds of polymerization initiator to be used 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.
- the method for forming the mixed composition into a sheet is not particularly limited. Suitable methods include, for example, a casting method in which the mixed composition is applied onto process paper such as a peeled polyester film, and the mixed composition is sandwiched between two peeled process papers if necessary. , A method of passing between rolls, and a method of controlling the thickness through a die when the mixed composition is extruded using an extruder.
- the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be 0.05 mm or more and 5 mm or less. By reducing the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded article (G), the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded article (G) can be reduced. From this viewpoint, the upper limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 2 mm. On the other hand, the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (G) is preferably 0.1 mm.
- the conductive pressure-sensitive adhesive sheet-like molded body (G) By setting the conductive pressure-sensitive adhesive sheet-like molded body (G) to 0.05 mm or more, air is entrained when the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) is attached to the heating element and the heat radiating body. It is easy to prevent this, and as a result, it is possible to prevent an increase in thermal resistance and to improve the workability in the step of attaching to the adherend.
- the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate.
- the material which comprises the said base material is not specifically limited.
- Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone.
- Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc.
- a heat-resistant polymer film can be used.
- the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention can be used as some electronic components. At that time, it can be directly molded on a base material such as a radiator and provided as a part of the electronic component.
- the electronic component include components around a heat generating part in a device having an electroluminescence (EL) light emitting diode (LED) light source, components around a power device such as an automobile, a fuel cell, a solar cell, a battery, and a mobile phone.
- EL electroluminescence
- LED light emitting diode
- PDA personal digital assistant
- notebook computer liquid crystal
- SED surface conduction electron-emitting device display
- PDP plasma display panel
- IC integrated circuit
- an LED light source is described below as a specific example. The usage method to do can be mentioned.
- LED light sources Attaching directly to the LED light source; sandwiching between the LED light source and heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); Heat dissipation material connected to the LED light source (heat sink, fan, Peltier element) , Heat pipe, graphite sheet, etc.); used as a casing surrounding the LED light source; affixed to the casing surrounding the LED light source; and filling a gap between the LED light source and the casing.
- LED light sources include backlight devices for display devices having a transmissive liquid crystal panel (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 body (G) of the present invention include affixing to the housing of the apparatus.
- affixing to the housing of the apparatus.
- it is attached inside a casing provided in the automobile; it is attached outside the casing provided in the automobile; a heat generating part (car navigation / A fuel cell / heat exchanger) and the casing; and affixing to a heat sink connected to a heat generating part (car navigation / fuel cell / heat exchanger) in the casing of the automobile; Can be mentioned.
- the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-shaped product (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; washing dryer; optical semiconductor device combining optical semiconductor elements and phosphors; various power devices; 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. It is also possible to use it.
- used for heat equalization of carpets and warm mats, etc . used as LED light source / heat source sealant; used as solar cell sealant; used as solar cell backsheet Used between the backsheet of the solar cell and the roof; used inside the heat insulating layer inside the vending machine; used inside the housing of the organic EL lighting with a desiccant or a hygroscopic agent; organic EL lighting Use with desiccant and hygroscopic agent on the heat conductive layer inside the housing of the LED; Use with desiccant and hygroscopic agent on the heat conductive layer and heat dissipation layer inside the housing of the organic EL lighting Used for heat conduction layer inside the housing of organic EL lighting, epoxy heat dissipation layer, and on top of it with desiccant and hygroscopic agent; cooling equipment, clothing, towels, sheets, etc.
- the member Used for a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer; Pressurizing a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as a member itself; used as a heat flow control heat transfer part for placing a treatment object of a membrane control device; used as a heat flow control heat transfer part for placing a treatment object of a film control device; outer layer of a radioactive substance storage container It can be used between the interior and interior; used in a box body with a solar panel that absorbs sunlight; used between the reflective sheet of the CCFL backlight and the aluminum chassis.
- a test piece was prepared by cutting a thermally conductive pressure-sensitive adhesive sheet produced by the method described later into a size of 80 mm ⁇ 80 mm.
- a test piece was set on a digital ultra-high resistance / micro-ammeter (trade name “8340A”, manufactured by ADC Corporation), and a current was passed through both right and left ends of the test piece to measure resistivity.
- the voltage started from 500 V and gradually decreased to a measurable voltage, and the resistivity at the measurable voltage was measured.
- the charging time was 1 minute.
- the measurement was performed three times, and the average value was defined as the volume resistivity (unit: ⁇ ⁇ cm) of the heat conductive pressure-sensitive adhesive sheet.
- Tables 2 and 3 If the result of this evaluation is 1.0 ⁇ 10 10 ⁇ ⁇ cm or more, it can be said that the insulation is excellent.
- a test piece was prepared by cutting a thermally conductive pressure-sensitive adhesive sheet-like molded body produced by the method described later into a size of 25 mm ⁇ 25 mm.
- the test piece was affixed to an aluminum plate of 150 mm ⁇ 150 mm ⁇ thickness 3 mm, and a micro ceramic heater (manufactured by Sakaguchi Electric Heat Co., Ltd., trade name: MS) ⁇ 5, 25 mm ⁇ 25 mm) was fixed with double-sided tape, and the aluminum plate was suspended. Thereafter, a micro ceramic heater was connected to the slidac, and the surface of the micro ceramic heater when heated at 60 W for 60 minutes was photographed by thermography. The maximum temperatures at that time are shown in Tables 2 and 3.
- the lower the temperature means that more heat is transferred from the micro ceramic heater to the aluminum plate, so the lower the temperature, the lower the thermal resistance of the heat conductive pressure-sensitive adhesive sheet-like molded body. It can be said.
- This evaluation was performed in an atmosphere at 23 ° C.
- Example 1 A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1-1).
- the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.
- a thermostatic bath manufactured by Toki Sangyo Co., Ltd., trade name “Viscomate 150III”
- a Hobart mixer manufactured by Kodaira Manufacturing Co., Ltd., trade name “ACM-5LVT type”, capacity: 5 L
- the temperature control of the Hobart container was set to 60 ° C.
- the rotation speed scale was set to 3
- the mixture was stirred for 10 minutes. This process is referred to as a first mixing process.
- the mixed composition obtained through the first and second mixing steps was hung on the release PET film, and the release PET film was further covered on the mixture composition.
- This laminate in which the mixed composition was sandwiched between the release PET films was passed through a roll having a distance of 0.3 mm between them to form a sheet. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes. Through this heating step, the acrylate monomer was polymerized and subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet
- Examples 2 to 6 and Comparative Examples 1 to 6 Sheets (G2 to 6, GC1 to 6) were obtained in the same manner as in Example 1 except that the composition of each material was changed as shown in Tables 2 and 3.
- the additives which have not been described so far and used in Examples 2 to 6 and Comparative Examples 1 to 6 are as follows.
- Aluminum hydroxide (trade name “BF-083” manufactured by Nippon Light Metal Co., Ltd., average particle size: 8 ⁇ m, BET specific surface area: 0.8 m 2 / g)
- Alumina Showa Denko Co., Ltd., trade name “A-13-H”, average particle size: 57 ⁇ m, BET specific surface area: 0.8 m 2 / g
- the sheets (G1) to (G8) according to the examples all have good fluidity of the mixed composition before being formed into a sheet, and after forming into a sheet, the sheet has a high volume resistivity, The cool-down effect was excellent.
- any of the above performances of the sheets (GC1) to (GC8) according to the comparative examples was inferior. Specifically, it was as follows.
- -Comparative example 1 The sheet
- -Comparative example 2 The sheet
- -Comparative example 3 The sheet
- -Comparative example 4 The sheet
- -Comparative example 5 The sheet
- -Comparative example 6 The sheet
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Abstract
Description
本発明の熱伝導性感圧接着剤組成物(F)は、(メタ)アクリル酸エステル重合体(A1)、及び、(メタ)アクリル酸エステル単量体(α1)を含む(メタ)アクリル樹脂組成物(A)と、平均粒径が50μm以下の熱伝導性フィラー(B)(以下、単に「熱伝導性フィラー(B)」という場合がある。)と、針状部を有し、該針状部の長さが2μm以上50μm以下である酸化亜鉛(C)(以下、単に「酸化亜鉛(C)」という場合がある。)と、を含む混合組成物中において、(メタ)アクリル酸エステル単量体(α1)由来の構造単位を生じる重合体を得る重合反応、並びに、(メタ)アクリル酸エステル重合体(A1)同士の架橋反応、(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体同士の架橋反応、及び、(メタ)アクリル酸エステル重合体(A1)と(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体との架橋反応のうちいずれかの架橋反応が、少なくとも行われてなるものである。
本発明に用いる(メタ)アクリル樹脂組成物(A)は、(メタ)アクリル酸エステル重合体(A1)、及び、(メタ)アクリル酸エステル単量体(α1)を含んでいる。なお、上述したように、熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)を得る際には(メタ)アクリル酸エステル単量体(α1)由来の構造単位を生じる重合体を得る重合反応と、(メタ)アクリル酸エステル重合体(A1)及び/又は(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体の架橋反応とが行われる。当該重合反応及び架橋反応を行うことによって(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体は、(メタ)アクリル酸エステル重合体(A1)の成分と混合及び/又は一部結合する。
本発明に用いることができる(メタ)アクリル酸エステル重合体(A1)は特に限定されないが、ガラス転移温度が-20℃以下となる単独重合体を形成する(メタ)アクリル酸エステル単量体の単位(a1)、及び、有機酸基を有する単量体単位(a2)を含有することが好ましい。
(メタ)アクリル酸エステル単量体(α1)は、(メタ)アクリル酸エステル単量体を含有するものであれば特に限定されないが、ガラス転移温度が-20℃以下となる単独重合体を成形する(メタ)アクリル酸エステル単量体(a5m)を含有するものであることが好ましい。
熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)を得る際に、(メタ)アクリル酸エステル単量体(α1)及び後述する多官能性単量体は重合する。その重合を促進するため、重合開始剤を用いることが好ましい。
本発明の熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)には、多官能性単量体も用いることが好ましい。多官能性単量体としては、(メタ)アクリル酸エステル単量体(α1)に含まれる単量体と共重合可能なものを用いる。また、多官能性単量体は重合性不飽和結合を複数有しており、該不飽和結合を末端に有することが好ましい。このような多官能性単量体を用いることによって、共重合体に分子内及び/又は分子間架橋を導入して、熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)の感圧接着剤としての凝集力を高めることができる。
本発明の熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)には、熱伝導性フィラー(B)を用いる。熱伝導性フィラー(B)は、添加することによって熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)の熱伝導性を向上させることができるフィラーであり、平均粒径が50μm以下である。ただし、熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)に絶縁性を備えさせ易くする観点からは、後述する酸化亜鉛(C)より導電性の低いものが好ましい。
本発明に用いる酸化亜鉛(C)は、針状部を有し、該針状部の長さが2μm以上50μm以下である。後に説明するように、酸化亜鉛(C)の針状部の長さを上記範囲とすることによって、熱伝導性フィラー(B)との組み合わせで熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)に高い熱伝導性を付与することができる。
本発明の熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)には、リン酸エステルを用いることもできる。リン酸エステルを用いることによって、熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)の難燃性を向上させ易くなる。
リン酸エステルの粘度測定には、B型粘度計(東京計器株式会社製)を用いて、以下に示す手順で行う。
(1)常温の環境でリン酸エステルを300ml計量し、500mlの容器に入れる。
(2)攪拌用ロータNo.1、2、3、4、5、6、7から、いずれかを選択し、粘度計に取り付ける。
(3)リン酸エステルが入った容器を粘度計の上に置き、ロータを該容器内の縮合リン酸エステルに沈める。このとき、ロータの目印となる凹みが丁度、リン酸エステルの液状界面にくるように沈める。
(4)回転数を20、10、4、2の中から選択する。
(5)攪拌スイッチを入れ、1分後の数値を読み取る。
(6)読み取った数値に、係数Aを掛け算した値が粘度[mPa・s]となる。
なお、係数Aは、下記表1に示すように、選択したロータNo.と回転数とから決まる。
本発明の熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)には、上述した成分以外にも、上述した成分を添加することによる上記効果を妨げない範囲で公知の各種添加剤を添加することもできる。公知の添加剤としては、発泡剤(発泡助剤を含む。);金属の水酸化物、金属塩水和物等の難燃性熱伝導無機化合物;ガラス繊維;膨張化黒鉛粉、アルミナ、PITCH系炭素繊維等の熱伝導性無機化合物;外部架橋剤;カーボンブラック、二酸化チタンなど顔料;クレーなどのその他の充填材;フラーレン、カーボンナノチューブなどのナノ粒子;ポリフェノール系、ハイドロキノン系、ヒンダードアミン系などの酸化防止剤;アクリル系ポリマー粒子、微粒シリカ、酸化マグネシウムなど増粘剤;等を挙げることができる。
本発明の熱伝導性感圧接着剤組成物(F)は、これまでに説明した材料を混合した後、(メタ)アクリル酸エステル単量体(α1)の重合反応と、(メタ)アクリル酸エステル重合体(A1)及び/又は(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体の架橋反応とを行うことにより得ることができる。
本発明の熱伝導性感圧接着剤組成物(F)及び熱伝導性感圧接着性シート状成形体(G)は、電子部品の一部として用いることができる。その際、放熱体のような基材上に直接的に成形して、電子部品の一部として提供することもできる。当該電子部品の具体例としては、エレクトロルミネッセンス(EL)、発光ダイオード(LED)光源を有する機器における発熱部周囲の部品、自動車等のパワーデバイス周囲の部品、燃料電池、太陽電池、バッテリー、携帯電話、携帯情報端末(PDA)、ノートパソコン、液晶、表面伝導型電子放出素子ディスプレイ(SED)、プラズマディスプレイパネル(PDP)、又は集積回路(IC)など発熱部を有する機器や部品を挙げることができる。
後述する第1及び第2混合工程を経て得られた混合組成物の流動性を評価した。具体的には、混合組成物が入れられたホバート容器を水平面に対して30°傾け、1分後の該混合組成物の状態で評価した。その結果を表2及び表3に示した。混合組成物が傾斜に沿って流れた場合を「○」、動かなかった場合を「×」とした。混合組成物に流動性がある方が、該混合組成物をシート化し易くなる。すなわち、熱伝導性感圧接着性シート状成形体を製造し易くなる。
後述する方法で作製した熱伝導性感圧接着性シートを80mm×80mmの大きさに裁断した試験片を用意した。デジタル超高抵抗/微少電流計(商品名「8340A」、株式会社エーディーシー製)に試験片をセットして、該試験片の左右両端に電流を流して抵抗率を測定した。電圧は500Vから開始して測定できる電圧まで徐々に下げていき、測定できる電圧での抵抗率を測定した。なお、チャージ時間は1分とした。該測定を3回行い、その平均値を熱伝導性感圧接着性シートの体積抵抗率(単位:Ω・cm)とした。結果を表2及び表3に示した。この評価による結果が1.0×1010Ω・cm以上であれば、絶縁性が優れていると言える。
後述する方法で作製した熱伝導性感圧接着性シート状成形体を25mm×25mmの大きさに裁断した試験片を用意した。試験片を150mm×150mm×厚さ3mmのアルミニウム板に貼り付け、試験片の、アルミニウム板に貼り付けた側とは反対側の面に、マイクロセラミックヒーター(坂口電熱株式会社製、商品名:MS-5、25mm×25mm)を両面テープで固定し、該アルミニウム板を宙吊りにした。その後、マイクロセラミックヒーターをスライダックに接続し、60Wで60分間加熱したときのマイクロセラミックヒーターの表面をサーモグラフィーで撮影した。そのときの最高温度を表2及び表3に示した。当該温度が低くなった方がマイクロセラミックヒーターからアルミニウム板に多くの熱を伝えられていることを意味するので、当該温度が低い程、熱伝導性感圧接着性シート状成形体の熱抵抗が低いと言える。なお、本評価は23℃雰囲気下で行った。
反応器に、アクリル酸2-エチルヘキシル94%とアクリル酸6%とからなる単量体混合物100部、2,2’-アゾビスイソブチロニトリル0.03部及び酢酸エチル700部を入れて均一に溶解し、窒素置換後、80℃で6時間重合反応を行った。重合転化率は97%であった。得られた重合体を減圧乾燥して酢酸エチルを蒸発させ、粘性のある固体状の(メタ)アクリル酸エステル重合体(A1-1)を得た。(メタ)アクリル酸エステル重合体(A1-1)の重量平均分子量(Mw)は270,000、重量平均分子量(Mw)/数平均分子量(Mn)は3.1であった。重量平均分子量(Mw)及び数平均分子量(Mn)は、テトラヒドロフランを溶離液とするゲルパーミエーションクロマトグラフィーにより、標準ポリスチレン換算で求めた。
各材料の配合を表2及び表3に示すように変更した以外は実施例1と同様にして、シート(G2~6、GC1~6)を得た。
・水酸化アルミニウム(日本軽金属株式会社製、商品名「BF-083」、平均粒径:8μm、BET比表面積:0.8m2/g)
・アルミナ:昭和電工株式会社製、商品名「A-13-H」、平均粒径:57μm、BET比表面積:0.8m2/g
・比較例1:酸化亜鉛を含まない比較例1のシート(GC1)は、クールダウン効果が劣っていた。
・比較例2:酸化亜鉛の含有量が本発明で規定する範囲に満たない比較例2のシート(GC2)も、クールダウン効果が劣っていた。
・比較例3:酸化亜鉛の含有量が本発明で規定する範囲を超えた比較例3のシート(GC3)は、体積抵抗率が低くなった。
・比較例4:熱伝導性フィラーの含有量が本発明で規定する範囲に満たない比較例4のシート(GC4)は、クールダウン効果が劣っていた。
・比較例5:熱伝導性フィラーの含有量が本発明で規定する範囲を超えた比較例5のシート(GC5)は、シート化する前の混合組成物に流動性がなく、シート化できなかった。
・比較例6:本発明で規定する範囲より大きな粒径の熱伝導性フィラーを用いた比較例6のシート(GC6)は、クールダウン効果が劣っていた。
Claims (13)
- (メタ)アクリル酸エステル重合体(A1)、及び、(メタ)アクリル酸エステル単量体(α1)を含む(メタ)アクリル樹脂組成物(A)を100質量部と、
平均粒径が50μm以下の熱伝導性フィラー(B)を600質量部以上1400質量部以下と、
針状部を有し、該針状部の長さが2μm以上50μm以下である酸化亜鉛(C)を0.5質量部以上40質量部以下と、
を含む混合組成物中において、前記(メタ)アクリル酸エステル単量体(α1)の重合反応と、前記(メタ)アクリル酸エステル重合体(A1)及び/又は前記(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体の架橋反応とが行われてなる、熱伝導性感圧接着剤組成物(F)。 - 前記混合組成物が、さらにリン酸エステルを20質量部以上100質量部以下含む、請求項1に記載の熱伝導性感圧接着剤組成物(F)。
- 平均粒径が50μm以下の前記熱伝導性フィラー(B)が、平均粒径が50μm以下の、酸化アルミニウム及び/又は水酸化アルミニウムである、請求項1又は2に記載の熱伝導性感圧接着剤組成物(F)。
- (メタ)アクリル酸エステル重合体(A1)、及び、(メタ)アクリル酸エステル単量体(α1)を含む(メタ)アクリル樹脂組成物(A)を100質量部と、
平均粒径が50μm以下の熱伝導性フィラー(B)を600質量部以上1400質量部以下と、
針状部を有し、該針状部の長さが2μm以上50μm以下である酸化亜鉛(C)を0.5質量部以上40質量部以下と、
を含む混合組成物をシート状に成形した後、又は前記混合組成物をシート状に成形しながら、前記(メタ)アクリル酸エステル単量体(α1)の重合反応と、前記(メタ)アクリル酸エステル重合体(A1)及び/又は前記(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体の架橋反応とが行われてなる、熱伝導性感圧接着性シート状成形体(G)。 - 前記混合組成物が、さらにリン酸エステルを20質量部以上100質量部以下含む、請求項4に記載の熱伝導性感圧接着性シート状成形体(G)。
- 平均粒径が50μm以下の前記熱伝導性フィラー(B)が、平均粒径が50μm以下の、酸化アルミニウム及び/又は水酸化アルミニウムである、請求項4又は5に記載の熱伝導性感圧接着性シート状成形体(G)。
- (メタ)アクリル酸エステル重合体(A1)、及び、(メタ)アクリル酸エステル単量体(α1)を含む(メタ)アクリル樹脂組成物(A)を100質量部と、
平均粒径が50μm以下の熱伝導性フィラー(B)を600質量部以上1400質量部以下と、
針状部を有し、該針状部の長さが2μm以上50μm以下である酸化亜鉛(C)を0.5質量部以上40質量部以下と、
を含む混合組成物を作製する工程、並びに、
前記混合組成物中において、前記(メタ)アクリル酸エステル単量体(α1)の重合反応と、前記(メタ)アクリル酸エステル重合体(A1)及び/又は前記(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体の架橋反応とを行う工程、
を含む、熱伝導性感圧接着剤組成物(F)の製造方法。 - 前記混合組成物が、さらにリン酸エステルを20質量部以上100質量部以下含む、請求項7に記載の熱伝導性感圧接着剤組成物(F)の製造方法。
- 平均粒径が50μm以下の前記熱伝導性フィラー(B)が、平均粒径が50μm以下の、酸化アルミニウム及び/又は水酸化アルミニウムである、請求項7又は8に記載の熱伝導性感圧接着剤組成物(F)の製造方法。
- (メタ)アクリル酸エステル重合体(A1)、及び、(メタ)アクリル酸エステル単量体(α1)を含む(メタ)アクリル樹脂組成物(A)を100質量部と、
平均粒径が50μm以下の熱伝導性フィラー(B)を600質量部以上1400質量部以下と、
針状部を有し、該針状部の長さが2μm以上50μm以下である酸化亜鉛(C)を0.5質量部以上40質量部以下と、
を含む混合組成物を作製する工程、並びに、
前記混合組成物をシート状に成形した後、又は、前記混合組成物をシート状に成形しながら、前記(メタ)アクリル酸エステル単量体(α1)の重合反応と、前記(メタ)アクリル酸エステル重合体(A1)及び/又は前記(メタ)アクリル酸エステル単量体(α1)由来の構造単位を含む重合体の架橋反応とを行う工程、
を含む、熱伝導性感圧接着性シート状成形体(G)の製造方法。 - 前記混合組成物が、さらにリン酸エステルを20質量部以上100質量部以下含む、請求項10に記載の熱伝導性感圧接着性シート状成形体(G)の製造方法。
- 平均粒径が50μm以下の前記熱伝導性フィラー(B)が、平均粒径が50μm以下の、酸化アルミニウム及び/又は水酸化アルミニウムである、請求項10又は11に記載の熱伝導性感圧接着性シート状成形体(G)の製造方法。
- 放熱体及び該放熱体に貼合された請求項1~3のいずれか1項に記載の熱伝導性感圧接着剤組成物(F)、又は、放熱体及び該放熱体に貼合された請求項4~6のいずれか1項に記載の熱伝導性感圧接着性シート状成形体(G)、を備えた電子部品。
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