CN103221501B - Heat-conductive, pressure-sensitive adhesive composition, heat-conductive, pressure-sensitive adhesive sheet formed body, method for producing each, and electronic component - Google Patents

Heat-conductive, pressure-sensitive adhesive composition, heat-conductive, pressure-sensitive adhesive sheet formed body, method for producing each, and electronic component Download PDF

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Publication number
CN103221501B
CN103221501B CN201280003973.XA CN201280003973A CN103221501B CN 103221501 B CN103221501 B CN 103221501B CN 201280003973 A CN201280003973 A CN 201280003973A CN 103221501 B CN103221501 B CN 103221501B
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methyl
sensitive adhesive
thermal conductivity
mass parts
conductivity pressure
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CN103221501A (en
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熊本拓朗
川村明子
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—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
    • 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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    • 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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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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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    • H01—ELECTRIC ELEMENTS
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    • 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
    • H01L24/80—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
    • 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
    • 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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    • 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
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    • C09J2433/00—Presence of (meth)acrylic polymer
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
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    • 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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    • H01L2224/29198—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
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    • H01—ELECTRIC ELEMENTS
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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
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    • 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
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Abstract

Provided are: a heat-conductive, pressure-sensitive adhesive composition provided in a balanced fashion with heat conductivity and insulating properties and characterized by, in a mixed composition containing a predetermined quantity of each of a (meth)acrylic resin composition containing a (meth)acrylic ester polymer (A1) and a (meth)acrylic ester monomer (a1), a heat-conductive filler (B) having an average particle size of no greater than 50 [mu]m, and zinc oxide (C) having an acicular section, the length of the acicular section being 2-50 [mu]m inclusive, the adhesive composition resulting from performing a polymerization reaction of the (meth)acrylic ester monomer mixture, and a cross-linking reaction of a polymer containing a structural unit derived from the (meth)acrylic ester monomer (a1) and/or the (meth)acrylic ester polymer (A1); a heat-conductive, pressure-sensitive adhesive sheet formed body; a method for producing the composition and the body; and an electronic component provided with the heat-conductive, pressure-sensitive adhesive composition and the heat-conductive, pressure-sensitive adhesive sheet formed body.

Description

Thermal conductivity pressure-sensitive adhesive composite, thermal conductivity pressure-sensitive adhesive sheet-like formed body, their manufacture method and electronic unit
Technical field
The present invention relates to thermal conductivity pressure-sensitive adhesive composite, thermal conductivity pressure-sensitive adhesive sheet-like formed body, they manufacture method and possess the electronic unit of this thermal conductivity pressure-sensitive adhesive composite or this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
Background technology
In recent years, such electronic unit such as plasma display (PDP), unicircuit (IC) chip is along with its high performance, and thermal value increases.Its result, creates and needs to rise to Yin Wendu and the function of generation damages the necessity pair taken some countermeasures.Usually, the method taked is: be arranged on by the radiators such as metal scatterer, heating panel, radiator element on heating element that electronic unit etc. possesses, thus make it dispel the heat.In order to make the heat conduction from heating element to radiator effectively carry out, use various thermally-conductive sheet.Usually, in the purposes of fixing heating element and radiator, need the composition also possessing pressure-sensitive adhesive on the basis of thermal conductivity (hereinafter referred to as " thermal conductivity pressure-sensitive adhesive composite ".) or need the sheet material also possessing pressure-sensitive adhesive on the basis of thermal conductivity (hereinafter referred to as " thermal conductivity pressure-sensitive adhesive sheet-like formed body ".）。
One of object of above-mentioned thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body is for heat is delivered to radiator from heating element, therefore preferably makes thermal resistance reduce.In order to reduce the thermal resistance of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, such as, can consider to add expanded graphite powder etc. in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body.But expanded graphite powder has high thermal conductivity and has high conductivity.Therefore, when also requiring the purposes of insulativity, the thermal conductivity pressure-sensitive adhesive composite and the thermal conductivity pressure-sensitive adhesive sheet-like formed body that are improved thermal conductivity by expanded graphite powder sometimes can not be used.
In addition, as recorded in patent documentation 1 ~ 3, except expanded graphite powder, as the filler of thermal conductivity that can improve thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, zinc oxide can also be used.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2008-163145 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-127482 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2008-127481 publication.
Summary of the invention
Because zinc oxide is lower than the electroconductibility of expanded graphite powder, therefore think, when adding zinc oxide in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, compared with interpolation expanded graphite powder, the rising of the electroconductibility of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body can be suppressed.
But, although the electroconductibility of zinc oxide is lower than expanded graphite powder, but as the technology recorded in patent documentation 1 ~ 3, add a large amount of zinc oxide in order to utilizing zinc oxide to make the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body improve, then the electroconductibility of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body uprises, and sometimes can not be used in the purposes of requirement insulativity.Like this, existing technology is difficult to balance and possesses in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body required many performances well.
Herein, problem of the present invention is to provide: balance possesses the thermal conductivity pressure-sensitive adhesive composite of thermal conductivity and insulativity and thermal conductivity pressure-sensitive adhesive sheet-like formed body and their manufacture method well and possesses the electronic unit of this thermal conductivity pressure-sensitive adhesive composite or this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
The present inventor etc. find the conducting filler by combinationally using the regulation beyond the zinc oxide of regulation and zinc oxide, can solve the problem, thus complete the present invention.
First embodiment of the present invention is thermal conductivity pressure-sensitive adhesive composite (F), it in following blend compositions, carry out polyreaction and crosslinking reaction forms, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); Be below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts with median size; With there is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts, wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is the crosslinking reaction of described (methyl) acrylic ester polymer (A1) and/or the polymkeric substance comprising the structural unit being derived from described (methyl) acrylate monomer (α 1).
Below the definition of the wording used in this specification sheets is recorded." (methyl) vinylformic acid " refers to " vinylformic acid and/or methacrylic acid ".In addition, " median size " refers to the particle diameter measured with following illustration method.That is, laser granulometry (セ イ シ Application enterprise of Co., Ltd. system) is used to utilize micro-sequence control mode (make determination object particle by means of only in mensuration region, improve the mode of the reliability measured) to measure.According to this measuring method, determination object particle 0.01g ~ 0.02g is flowed in unit (セ Le), thus to the semiconductor laser flowing into the determination object particle-irradiation wavelength 670nm measured in region, measure by utilizing determinator and now swash scattering of light and diffraction, calculate median size and size distribution by the diffraction principle of Fraunhofer.In addition, " conducting filler " refers to, by adding, can make the filler that thermal conductivity pressure-sensitive adhesive composite (F) or the thermal conductivity of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) that is described after a while improve.In addition, " length of needle-like portion " of zinc oxide (C) refers to, is undertaken observing and the length measured by scanning electronic microscope.In addition, " polyreaction of (methyl) acrylate monomer (α 1) " refers to, obtains the polyreaction that generation is derived from the polymkeric substance of the structural unit of (methyl) acrylate monomer (α 1).In addition, " (methyl) acrylic ester polymer (A1) and/or comprise the crosslinking reaction of polymkeric substance of the structural unit being derived from (methyl) acrylate monomer (α 1) " refers to, crosslinking reaction between (methyl) acrylic ester polymer (A1), crosslinking reaction between the polymkeric substance comprising the structural unit being derived from (methyl) acrylate monomer (α 1), and (methyl) acrylic ester polymer (A1) with comprise the structural unit being derived from (methyl) acrylate monomer (α 1) polymkeric substance crosslinking reaction among one or more crosslinking reactions.
In the thermal conductivity pressure-sensitive adhesive composite (F) of the first embodiment of the present invention, preferred blend compositions also comprises below more than phosphoric acid ester 20 mass parts 100 mass parts.In addition, median size be the conducting filler (B) of less than 50 μm be preferably median size be less than 50 μm, aluminum oxide and/or aluminium hydroxide.
Second embodiment of the present invention is thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), its be following blend compositions is shaped to sheet after, or while being shaped to sheet, carry out polyreaction and crosslinking reaction, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); Be below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts with median size; With there is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts, wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is the crosslinking reaction of described (methyl) acrylic ester polymer (A1) and/or the polymkeric substance comprising the structural unit being derived from (methyl) acrylate monomer (α 1).
In the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the second embodiment of the present invention, preferred blend compositions also comprises below more than phosphoric acid ester 20 mass parts 100 mass parts.In addition, median size be the conducting filler (B) of less than 50 μm be preferably median size be less than 50 μm, aluminum oxide and/or aluminium hydroxide.
3rd embodiment of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), and the method comprises: the operation making following blend compositions; And in described blend compositions, carry out the polyreaction of described (methyl) acrylate monomer (α 1) and described (methyl) acrylic ester polymer (A1) and/or comprise the operation of crosslinking reaction of polymkeric substance of the structural unit being derived from (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); Be below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts with median size; With there is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts.
In the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) of the 3rd embodiment of the present invention, preferred blend compositions also comprises below more than phosphoric acid ester 20 mass parts 100 mass parts.In addition, median size be the conducting filler (B) of less than 50 μm be preferably median size be less than 50 μm, aluminum oxide and/or aluminium hydroxide.
4th embodiment of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), and the method comprises: the operation making following blend compositions, and after described blend compositions is shaped to sheet, or while described blend compositions is shaped to sheet, carry out the polyreaction of described (methyl) acrylate monomer (α 1), the operation of the crosslinking reaction of the polymkeric substance of the structural unit of described (methyl) acrylate monomer (α 1) is derived from described (methyl) acrylic ester polymer (A1) and/or comprise, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), be below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts with median size, with there is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts.
In the manufacture method of the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the 4th embodiment of the present invention, blend compositions preferably also comprises below more than phosphoric acid ester 20 mass parts 100 mass parts.In addition, median size be less than 50 μm conducting filler (B) preferably median size be less than 50 μm, aluminum oxide and/or aluminium hydroxide.
5th embodiment of the present invention is a kind of electronic unit, and it possesses: radiator and be fitted in the first embodiment of the present invention on this radiator thermal conductivity pressure-sensitive adhesive composite (F) or, radiator and be fitted in the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the second embodiment of the present invention on this radiator.
The thermal conductivity pressure-sensitive adhesive composite that balance can be provided to possess thermal conductivity and insulativity well according to the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body; With their manufacture method; With the electronic unit possessing this thermal conductivity pressure-sensitive adhesive composite or this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
Embodiment
1. thermal conductivity pressure-sensitive adhesive composite (F), thermal conductivity pressure-sensitive adhesive sheet-like formed body (G)
Thermal conductivity pressure-sensitive adhesive composite (F) of the present invention, it in following blend compositions, at least carry out polyreaction and crosslinking reaction forms, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), with the conducting filler (B) (below sometimes referred to as " conducting filler (B) ") that median size is less than 50 μm, with there is needle-like portion and the length of this needle-like portion is the zinc oxide (C) (below sometimes referred to as " zinc oxide (C) ") of more than 2 μm less than 50 μm, wherein, described polyreaction is derived from the polyreaction of the polymkeric substance of the structural unit of (methyl) acrylate monomer (α 1) for obtaining generation, described crosslinking reaction is the crosslinking reaction between described (methyl) acrylic ester polymer (A1), crosslinking reaction between the polymkeric substance comprising the structural unit being derived from (methyl) acrylate monomer (α 1), and (methyl) acrylic ester polymer (A1) with comprise the structural unit being derived from (methyl) acrylate monomer (α 1) polymkeric substance crosslinking reaction in any one crosslinking reaction.
In addition, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the present invention, its be above-mentioned blend compositions is shaped to sheet after, or while above-mentioned blend compositions is shaped to sheet, at least carry out polyreaction and crosslinking reaction, wherein, described polyreaction is derived from the polyreaction of the polymkeric substance of the structural unit of (methyl) acrylate monomer (α 1) for obtaining generation, described crosslinking reaction is the crosslinking reaction between described (methyl) acrylic ester polymer (A1), crosslinking reaction between the polymkeric substance comprising the structural unit being derived from (methyl) acrylate monomer (α 1), and (methyl) acrylic ester polymer (A1) with comprise the structural unit being derived from (methyl) acrylate monomer (α 1) polymkeric substance crosslinking reaction among any one crosslinking reaction.
Below the material forming such thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is described.
< (methyl) acrylic acid resin composition (A) >
(methyl) acrylic acid resin composition (A) used in the present invention comprises (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1).In addition, as mentioned above, when obtaining thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), carry out obtaining the crosslinking reaction of polymkeric substance that generation is derived from the polyreaction of the polymkeric substance of the structural unit of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or comprises the structural unit being derived from (methyl) acrylate monomer (α 1).By carrying out this polyreaction and crosslinking reaction, the polymkeric substance comprising the structural unit being derived from (methyl) acrylate monomer (α 1) mix with the composition of (methyl) acrylic ester polymer (A1) and/or with one moiety.
In the present invention, the consumption of acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) is preferably relative to (methyl) acrylic acid resin composition (A) 100 quality %, and (methyl) acrylic ester polymer (A1) is below more than 5 quality % 40 quality %, (methyl) acrylate monomer (α 1) is below more than 60 quality % 95 quality %.Be in above-mentioned scope by what make (methyl) acrylate monomer (α 1) containing ratio, can be easy to by thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) shaping.
((methyl) acrylic ester polymer (A1))
Spendable in the present invention (methyl) acrylic ester polymer (A1) there is no particular limitation, preferably containing forming unit (a1) that second-order transition temperature is (methyl) acrylate monomer of the homopolymer of less than-20 DEG C and having the monomeric unit (a2) of organic acidic group.
For (methyl) acrylate monomer (a1m) of unit (a1) obtaining above-mentioned (methyl) acrylate monomer, there is no particular limitation, such as, ethyl propenoate (second-order transition temperature of homopolymer is-24 DEG C) can be listed, n-propyl (second-order transition temperature of homopolymer is-37 DEG C), n-butyl acrylate (second-order transition temperature of homopolymer is-54 DEG C), sec-butyl acrylate (second-order transition temperature of homopolymer is-22 DEG C), vinylformic acid n-pentyl ester (second-order transition temperature of homopolymer is-60 DEG C), the just own ester of vinylformic acid (second-order transition temperature of homopolymer is-61 DEG C), n-octyl (second-order transition temperature of homopolymer is-65 DEG C), 2-EHA (second-order transition temperature of homopolymer is-50 DEG C), vinylformic acid 2-methoxy acrylate (second-order transition temperature of homopolymer is-50 DEG C), vinylformic acid 3-methoxyl group propyl ester (second-order transition temperature of homopolymer is-75 DEG C), vinylformic acid 3-methoxybutyl (second-order transition temperature of homopolymer is-56 DEG C), ethioxy methyl esters (second-order transition temperature of homopolymer is-50 DEG C), n octyl methacrylate (second-order transition temperature of homopolymer is-25 DEG C), methacrylic acid ester in the positive last of the ten Heavenly stems (second-order transition temperature of homopolymer is-49 DEG C) etc.Wherein, preferred n-butyl acrylate, 2-EHA, vinylformic acid 2-methoxy acrylate, more preferably n-butyl acrylate, 2-EHA, further preferred 2-EHA.
These (methyl) acrylate monomers (a1m) can be used alone one, also can be used in combination of two or more.
About the amount of (methyl) acrylate monomer (a1m), preferably with make by its derivative monomeric unit (a1) in (methyl) acrylic ester polymer (A1) for preferred below more than 80 quality % 99.9 quality %, the amount that is more preferably below more than 85 quality % 99.5 quality % are come for polymerization.If the consumption of (methyl) acrylate monomer (a1m) is in above-mentioned scope, be then easy to the viscosity of polymerization system during polymerization to remain on suitable scope.
Then, the monomeric unit (a2) with organic acidic group is described.For obtaining the monomer (a2m) with the monomeric unit (a2) of organic acidic group, there is no particular limitation, and can list as its representational monomer, carboxyl, anhydride group, sulfonic group etc. have the monomer of organic acidic group.In addition, in addition, the monomer containing sulfeno, sulfino, phosphate etc. can also be used.
As the concrete example of monomer with carboxyl, include, for example out: α, the β-olefinic unsaturated monocarboxylics such as vinylformic acid, methacrylic acid, β-crotonic acid; The unsaturated polycarboxylic acids of α, β-olefinic such as methylene-succinic acid, toxilic acid, fumaric acid; And α, the β-unsaturated partial esters of polycarboxylic acids of olefinic etc. such as monomethyl itaconate, butyl maleate, fumaric acid list propyl ester.In addition, the hydrolysis etc. had by maleic anhydride, itaconic anhydride etc. can be similarly used to derive the monomer of the group of carboxyl.
As the concrete example with sulfonic monomer, can list, α, β-unsaturated sulfonic acid and their salt such as allyl sulphonic acid, methacrylic sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide-2-methyl propane sulfonic.
As monomer (a2m), have in the monomer of organic acidic group illustrative above, preferably there is the monomer of carboxyl, wherein particularly preferably there is the monomer of vinylformic acid or methacrylic acid.These monomers are industrially cheap and can easily obtain, with the copolymerizable of other monomer components also good, be also preferred in productivity.In addition, monomer (a2m) can be used alone one, also can combinationally use two or more.
About the monomer (a2m) with organic acidic group, preferably to make, the monomeric unit (a2) derived by it is below more than 0.1 quality % 20 quality % in (methyl) acrylic ester polymer (A1), the amount being preferably below more than 0.5 quality % 15 quality % is come for polymerization.If the consumption with the monomer (a2m) of organic acidic group is in above-mentioned scope, be then easy to the viscosity of polymerization system during polymerization to remain on suitable scope.
In addition, the monomeric unit (a2) with organic acidic group as described previously by have organic acidic group monomer (a2m) polymerization and to import in (methyl) acrylic ester polymer (A1) be easy and preferred, but also after (methyl) acrylic ester polymer (A1) generates, organic acidic group can be imported by known high molecular weight reactive.
In addition, (methyl) acrylic ester polymer (A1) can also containing the monomeric unit (a3) derived by the monomer (a3m) of the functional group had beyond organic acidic group.
As the functional group beyond above-mentioned organic acidic group, hydroxyl, amino, amide group, epoxy group(ing), sulfydryl etc. can be listed.
As the monomer with hydroxyl, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester etc., (methyl) hydroxyalkyl acrylates etc. can be listed.
As having amino monomer, (methyl) vinylformic acid N can be listed, N-dimethylamino methyl esters, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, aminostyryl etc.
As the monomer with amide group, the unsaturated carboxylic acid amides monomers of α, β-olefinic etc. such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA can be listed.
As the monomer with epoxy group(ing), (methyl) glycidyl acrylate, glycidyl allyl ether etc. can be listed.
The monomer (a3m) with the functional group beyond organic acidic group can be used alone one, also can combinationally use two or more.
There is about these monomer (a3m) of the functional group beyond organic acidic group, come for polymerization with the amount that to make by its derivative monomeric unit (a3) be below 10 quality % in (methyl) acrylic ester polymer (A1).By using the monomer (a3m) of below 10 quality %, be easy to the viscosity of polymerization system during polymerization to remain on suitable scope.
(methyl) acrylic ester polymer (A1), except containing being formed beyond (methyl) acrylate monomeric units (a1) that above-mentioned second-order transition temperature is the homopolymer of less than-20 DEG C, the monomeric unit (a2) with organic acidic group and the monomeric unit (a3) with the functional group except organic acidic group, can also contain by the monomeric unit (a4) that can be derived with the monomer of above-mentioned monomer copolymerization (a4m).Monomer (a4m) can be used alone one, also can combinationally use two or more.
By the amount of the derivative monomeric unit (a4) of monomer (a4m) be preferably acrylic ester polymer (A1) below 10 quality %, be more preferably below 5 quality %.
To monomer (a4m), there is no particular limitation, as its concrete example, (methyl) acrylate monomer beyond above-mentioned (methyl) acrylate monomer (a1m), the full ester of the unsaturated polycarboxylic acid of α, β-olefinic, alkenyl aromatic monomers can be listed, use as a servant diene monomer, non-co-labour diene monomer, cyanided vinyl monomer, the unsaturated alcohol ester of carboxylic acid, olefinic monomers etc. altogether.
As the concrete example of (methyl) acrylate monomer beyond above-mentioned (methyl) acrylate monomer (a1m), methyl acrylate (second-order transition temperature of homopolymer is 10 DEG C), methyl methacrylate (second-order transition temperature of homopolymer is 105 DEG C), β-dimethyl-aminoethylmethacrylate (second-order transition temperature of homopolymer is 63 DEG C), n propyl methacrylate (second-order transition temperature of homopolymer is 25 DEG C), n-BMA (second-order transition temperature of homopolymer is 20 DEG C) etc. can be listed.
As the concrete example of the full ester of the unsaturated polycarboxylic acid of α, β-olefinic, dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate etc. can be listed.
As the concrete example of alkenyl aromatic monomers, vinylbenzene, alpha-methyl styrene, methyl alpha-methyl styrene, Vinyl toluene and Vinylstyrene etc. can be listed.
As the concrete example of common labour diene monomer, can list, 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (with isoprene synonym), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, chlorbutadiene, cyclopentadiene etc.
As the concrete example of non-co-labour diene monomer, Isosorbide-5-Nitrae-hexadiene, Dicyclopentadiene (DCPD), ethylidene norbornene (Ethylidene norbornene) etc. can be listed.
As the concrete example of cyanided vinyl monomer, vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, α-ethyl acrylonitrile etc. can be listed.
As the concrete example of the unsaturated ester monomer of carboxylic acid, vinyl-acetic ester etc. can be listed.
As the concrete example of olefinic monomers, ethene, propylene, butylene, amylene etc. can be listed.
The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (A1) is measured by gel permeation chromatography (GPC method), convert in polystyrene standard, be preferably the scope of less than more than 100,000 100 ten thousand, be more preferably less than more than 200,000 50 ten thousand scope.
(methyl) acrylic ester polymer (A1) suitably obtains especially by the following monomer of copolymerization: formed (methyl) acrylate monomer (a1m) that second-order transition temperature is the homopolymer of less than-20 DEG C, the monomer (a2m) with organic acidic group, the monomer (a3m) containing the functional group beyond organic acidic group used as required and use as required can with the monomer of these monomer copolymerizations (a4m).
There is no particular limitation for the method for polymerization, and can use any one method such as solution polymerization, letex polymerization, suspension polymerization, mass polymerization, also can be the method beyond these.Be preferably solution polymerization, be wherein more preferably the solution polymerization using the aromatic solvent such as the carboxylicesters such as ethyl acetate, ethyl lactate or benzene,toluene,xylene as polymer solvent.During polymerization, monomer can portion-wise addition in polymerization container, preferably once all add.There is no particular limitation for the method for initiated polymerization, preferably uses thermal polymerization as polymerization starter.There is no particular limitation for thermal polymerization, can be any one in superoxide and azo-compound.
As peroxidic polymerization initiators, can list: the persulphate etc. such as superoxide and Potassium Persulphate, Sodium Persulfate, ammonium persulphate that the such hydroperoxide of tertbutyl peroxide, benzoyl peroxide, cyclohexanone peroxide are such.These superoxide can also use as redox series catalysts with reductive agent is appropriately combined.
As azo-compound polymerization starter, can 2 be listed, 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
There is no particular limitation for the consumption of polymerization starter, relative to monomer 100 mass parts, is preferably the scope of below more than 0.01 mass parts 50 mass parts.
Other polymerizing conditions (polymerization temperature, pressure, agitation condition etc.) of these monomers have no particular limits.
After polyreaction terminates, as required the polymkeric substance of gained is separated from polymerisation medium.There is no particular limitation for the method be separated.Such as, in the case of a solution polymerization, under polymeric solution is placed in decompression, heat up in a steamer polymer solvent, thus (methyl) acrylic ester polymer (A1) can be obtained.
The amount of the polymerization starter used when the weight-average molecular weight of (methyl) acrylic ester polymer (A1) is by suitably adjusting polymerization, the amount of chain-transfer agent control.
((methyl) acrylate monomer blend (α 1))
(methyl) acrylate monomer (α 1), as long as just there is no particular limitation for the material containing (methyl) acrylate monomer, is preferably (methyl) acrylate monomer (a5m) of the homopolymer of less than-20 DEG C containing formation second-order transition temperature.
As forming the example that second-order transition temperature is (methyl) acrylate monomer (a5m) of the homopolymer of less than-20 DEG C, (methyl) acrylate monomer identical with (methyl) acrylate monomer (a1m) for the synthesis of (methyl) acrylic ester polymer (A1) can be listed.(methyl) acrylate monomer (a5m) can be used alone one, also can combinationally use two or more.
The ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) is preferably below more than 50 quality % 100 quality %, is more preferably below more than 75 quality % 100 quality %.By making the ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) be in above-mentioned scope, be easy to obtain pressure-sensitive adhesive, the thermal conductivity pressure-sensitive adhesive composite (F) of flexibility excellence and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
In addition, (methyl) acrylate monomer (α 1) can also be with (methyl) acrylate monomer (a5m) and can with the mixture of the monomer of its copolymerization.
Particularly preferred (methyl) acrylate monomer (α 1) be comprise formed second-order transition temperature be the homopolymer of less than-20 DEG C (methyl) acrylate monomer (a5m) and can with the material of the monomer (a6m) with organic acidic group of their copolymerization.
As the example of above-mentioned monomer (a6m), the monomer with organic acidic group same with the illustrative monomer as the monomer (a2m) used in the synthesis of (methyl) acrylic ester polymer (A1) can be listed.Monomer (a6m) can be used alone one, also can combinationally use two or more.
The ratio of the monomer (a6m) in (methyl) acrylate monomer (α 1) is preferably below 30 quality %, is more preferably below 10 quality %.Above-mentioned scope is in by making the ratio of the monomer (a6m) in (methyl) acrylate monomer (α 1), can be easy to obtain pressure-sensitive adhesive, the thermal conductivity pressure-sensitive adhesive composite (F) of flexibility excellence and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
(methyl) acrylate monomer (α 1) can also be (methyl) acrylate monomer (a5m) and the monomer (a6m) with organic acidic group that can carry out copolymerization as required and can with the mixture of the monomer of their copolymerization (a7m).The ratio of the monomer (a7m) in (methyl) acrylate monomer (α 1) is preferably below 20 quality %, is more preferably below 15 quality %.
As the example of above-mentioned monomer (a7m), the monomer (a3m) for the synthesis of (methyl) acrylic ester polymer (A1) and the monomer identical with the monomer exemplified as monomer (a4m) can be listed.Monomer (a7m) can be used alone one, also can combinationally use two or more.
< polymerization starter >
When obtaining thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), polymerization (methyl) acrylate monomer (α 1) and multi-functional monomer described later.In order to promote that it is polymerized, preferably use polymerization starter.
As polymerization starter used in the present invention, Photoepolymerizationinitiater initiater, azo system thermal polymerization, organo-peroxide thermal polymerization etc. can be listed.From the viewpoint of the cementability etc. that the thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of giving gained are excellent, preferably use organo-peroxide thermal polymerization.
As Photoepolymerizationinitiater initiater, known various Photoepolymerizationinitiater initiater can be used.Wherein, acylphosphine oxide based compound is preferably.As the acylphosphine oxide based compound of preferred Photoepolymerizationinitiater initiater, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, TMDPO etc. can be listed.
As azo system thermal polymerization, can 2 be listed, 2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
As organo-peroxide thermal polymerization, can list: hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1 that tertbutyl peroxide is such, two (the t-butylperoxycarbonyl oxygen base) hexane, 1 of 6-, two (t-butyl peroxy)-3 of 1-, the superoxide etc. that 3,5-trimethylcyclohexanone is such.Wherein, the initiator of the volatile matter of the reason becoming foul smell is not released during preferred thermolysis.In addition, among organo-peroxide thermal polymerization, preferably 1 minute half life temperature is more than 100 DEG C and the initiator of less than 170 DEG C.
The consumption of polymerization starter, relative to (methyl) acrylic acid resin composition (A) 100 mass parts, is preferably below more than 0.01 mass parts 10 mass parts, is more preferably below more than below more than 0.1 mass parts 5 mass parts, more preferably 0.3 mass parts 1 mass parts.Above-mentioned scope is in by making the consumption of polymerization starter, can be easy to make the polymerisation conversion of (methyl) acrylate monomer blend (α 1) be in suitable scope, be easy to prevent residual monomer in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) smelly.In addition, the polymerisation conversion of (methyl) acrylate monomer (α 1) is preferably more than 95 quality %.If the polymerisation conversion of (methyl) acrylate monomer (α 1) is more than 95 quality %, be then easy to prevent residual monomer in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) smelly.In addition, above-mentioned scope is in by making the consumption of polymerization starter, can prevent owing to adding polymerization starter and bring out polyreaction and excessively carry out, the sheet that result causes thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) not become level and smooth, causing material damage.
The multi-functional monomer > of <
Preferably in thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), also use multi-functional monomer.As multi-functional monomer, use can carry out the monomer of copolymerization with the monomer be included in (methyl) acrylate monomer (α 1).In addition, preferred multi-functional monomer has multiple polymerizability unsaturated link(age), has this unsaturated link(age) at end.By using so multi-functional monomer, importing in molecule in co-polymer and/or intermolecular cross-linking, the cohesive force as pressure adhesive of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be improved.
Usually, even if do not use multi-functional monomer when polymerizations such as free radical thermopolymerizations, crosslinking reaction also can be carried out to a certain degree.But, in order to more definitely and make it form the crosslinking structure of desired amount, preferably use multi-functional monomer.
As multi-functional monomer, can use such as, 1, 6-hexylene glycol two (methyl) acrylate, 1, 2-ethylene glycol bisthioglycolate (methyl) acrylate, 1, 12-dodecanediol two (methyl) acrylate, many ethylene glycol bisthioglycolates (methyl) acrylate, many propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, two trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, multi-functional (methyl) acrylate such as Dipentaerythritol six (methyl) acrylate, two (the trichloromethyl)-6-of 2,4-replaces triazine and the such unsaturated aromatic ketone of monoene key system etc. of 4-acryloxybenzophenone to methoxy styrene-5-triazine etc.Wherein, preferred tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate.Multi-functional monomer can be used alone one, also can combinationally use two or more.
The amount of the multi-functional monomer used in thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), relative to acrylic acid resin composition (A) 100 mass parts, is preferably below more than 0.1 mass parts 15 mass parts, is more preferably below more than below more than 0.2 mass parts 8 mass parts, more preferably 0.5 mass parts 2 mass parts.By making the consumption of multi-functional monomer be in above-mentioned scope, be easy to give thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) as the suitable cohesive force of pressure adhesive.
< conducting filler (B) >
Conducting filler (B) is used in thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Conducting filler (B) is the filler by adding the thermal conductivity improving thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), and median size is less than 50 μm.Wherein, from the viewpoint of being easy to make thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) possess insulativity, preferably lower than aftermentioned zinc oxide (C) electroconductibility filler.
As the object lesson of conducting filler (B), calcium carbonate, aluminium hydroxide, magnesium hydroxide, aluminum oxide (alumina), magnesium oxide, silicon oxide, glass fibre, boron nitride and aluminium nitride etc. can be listed.Wherein, due to calcium carbonate, aluminium hydroxide and aluminum oxide can easily obtain, chemical stabilization and can be a large amount of compounding, be therefore preferred, particularly preferably aluminum oxide and aluminium hydroxide.Conducting filler (B) can be used alone one, also can combinationally use two or more.
In addition, the median size of the conducting filler (B) used in the present invention is less than 50 μm.The preferred scope of the median size of conducting filler (B) infers that it is also relevant with the size of zinc oxide (C) as described below, but be preferably such as less than 30 μm, be more preferably less than 10 μm, more preferably more than 0.5 μm less than 10 μm.As described below, above-mentioned scope is in by making the median size of conducting filler (B), combine with aftermentioned zinc oxide (C), thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity can be given.
The amount of thermal conductivity pressure-sensitive adhesive composite (F) and the middle conducting filler (B) used of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), relative to (methyl) acrylic acid resin composition (A) 100 mass parts, is below more than 600 mass parts 1400 mass parts.The upper limit of the content of conducting filler (B) is preferably 1300 mass parts, is more preferably 1200 mass parts.On the other hand, the lower limit of the content of conducting filler (B) is preferably 700 mass parts, is more preferably 800 mass parts.By making the content of conducting filler (B) be in above-mentioned scope, combining with aftermentioned zinc oxide (C), thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity can be given.On the other hand, when the content of conducting filler (B) is more than 1400 mass parts, the viscosity becoming the blend compositions of the material of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) increases, the productivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) reduces, and hardness increases, and has the tendency that shape trackability reduces.If shape trackability reduces, then become and be difficult to conduct heat to radiator from heating element.In addition, if conducting filler (B) containing quantity not sufficient 600 mass parts, then there is the worry that effect that the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is improved is insufficient.
< zinc oxide (C) >
The zinc oxide (C) used in the present invention has needle-like portion and the length of this needle-like portion is more than 2 μm less than 50 μm.As described below, above-mentioned scope is in by the length of the needle-like portion making zinc oxide (C), combine with conducting filler (B), thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity can be given.
The zinc oxide (C) used in the present invention has needle-like portion, can possess one or more needle-like portion around core part, also can forming only by needle-like portion.But, some conducting filler (B) of filling in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) are as described later connected easily through zinc oxide (C) with between other conducting filler (B), the surrounding of preferred core part possesses multiple needle-like portion, and these needle-like portion extend to each different direction.It is further preferred that there is core part and be present in the needle-like portion of more than three around it, to it is desirable among described needle-like portion at least one and other needle-like portion not at grade.In addition, the quantity of the needle-like portion existed around a core is preferably 3 ~ 6.If quantity is in this scope, then needle-like portion be oriented to three-dimensional, and, also can become good with the connection of other fillers.Surrounding as core part possesses the commercially available product of the zinc oxide of multiple needle-like portion, can list such as, " パ Na テ ト ラ (registered trademark) " of Co., Ltd. ア system テ ッ Network.
The amount of thermal conductivity pressure-sensitive adhesive composite (F) and the middle zinc oxide (C) used of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), relative to (methyl) acrylic acid resin composition (A) 100 mass parts, is below more than 0.5 mass parts 40 mass parts, is preferably below more than 0.5 mass parts 10 mass parts, is more preferably below more than 0.5 mass parts 5 mass parts.By making the content of zinc oxide (C) be in above-mentioned scope, combining with conducting filler (B), thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity can be given.On the other hand, if the content of zinc oxide (C) is more than 40 mass parts, then the insulativity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) reduces, and there is the worry that cannot use in the purposes requiring insulativity.In addition, if zinc oxide (C) containing quantity not sufficient 0.5 mass parts, then there is the worry that effect that the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is improved is insufficient.
According to the present invention, by conducting filler (B) and zinc oxide (C) are combinationally used with specified amount, even if the consumption of conducting filler (B) and zinc oxide (C) is more less than thermal conductivity pressure-sensitive adhesive sheet-like formed body in the past respectively, also can being balanced property possess thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of thermal conductivity and insulativity well.
By combinationally using conducting filler (B) and zinc oxide (C), the reason that the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) improves is presumed as follows: some conducting filler (B) be filled in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) are connected by zinc oxide (C) with between other conducting filler (B), thus, heat is easy to conduct in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Usually, in order to improve thermal conductivity add conducting filler when, from the view point of be easy to improve thermal conductivity, think that the particle diameter of this conducting filler is better greatly.But, as mentioned above, the discoveries such as the present inventor, by the conducting filler (B) below the median size that combinationally uses regulation and the zinc oxide (C) of needle-like portion with specified length, the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be improved.Infer this be due to: by making the median size of conducting filler (B) be in below the value of regulation, some conducting filler (B) be filled in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) become with between other conducting filler (B) cause be connected easily through zinc oxide (C).Therefore, infer in the present invention, the thermal conductivity of the relation between the length of the particle diameter of conducting filler (B) and the needle-like portion of zinc oxide (C) on thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) has impact.
In addition, the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be improved by combinationally using conducting filler (B) and zinc oxide (C), suppress insulativity to reduce simultaneously, infer that this is not because only zinc oxide (C) connects and improves the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), but because between some zinc oxide (C) and other zinc oxide (C), there is the conducting filler (B) lower than zinc oxide (C) electroconductibility with being mingled with.
< phosphoric acid ester >
Phosphoric acid ester can also be used in thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).By using phosphoric acid ester, be easy to the flame retardant resistance improving thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
The viscosity of the phosphoric acid ester used in the present invention preferably at 25 DEG C is more than 3000mPa s.By making the viscosity of phosphoric acid ester be in above-mentioned scope, be easy to the formability deteriorates preventing thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).In addition, in the present invention, " viscosity " of phosphoric acid ester refers to, the viscosity measured by the method for following explanation.
(viscosity measurement of phosphoric acid ester)
The viscosimetric analysis of phosphoric acid ester uses Brookfield viscometer (Tokyo Keiki Inc.'s system) to carry out in accordance with the following steps.
(1), under the environment of normal temperature, measure phosphoric acid ester 300ml and load in the container of 500ml.
(2) from stirring rotor No.1,2,3,4,5,6,7, any one is selected to be arranged on viscometer.
(3) by being equipped with the container of phosphoric acid ester as above viscometer, rotor is sunken in the condensed phosphoric acid esters in this container.Now, just in time it is made to sink in the mode at the aqueous interface of phosphoric acid ester with the indenture becoming mark of rotor.
(4) rotating speed is selected among 20,10,4,2.
(5) open stirring switch, read the numerical value after 1 minute.
(6) numerical value read is multiplied by coefficient A, using the value that calculates as viscosity ［ mPa s ］.
In addition, coefficient A is as shown in table 1 below, is determined by the rotor No. selected and rotating speed.
[table 1]
In addition, be liquid in the preferred temperature province of more than 15 DEG C less than 100 DEG C under atmospheric pressure of the phosphoric acid ester used in the present invention always.If phosphoric acid ester is liquid when mixing, then operability is good, easy shaping thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Shaping when comprising thermal conductivity pressure-sensitive adhesive composite (F) or the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of phosphoric acid ester, preferably under the environment of less than 100 DEG C, each material forming thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is mixed more than 15 DEG C.Above-mentioned scope is in by temperature when making mixing, be more than the second-order transition temperature of acrylic acid resin composition (A), be easy to prevent the volatilization of monomer contained in acrylic acid resin composition (A) etc. or careless polymerization reaction take place, therefore can make Environmental and operability is good.
In the present invention, as phosphoric acid ester, can condensed phosphoric acid esters be used, also can use non-condensed phosphoric acid esters.So-called " condensed phosphoric acid esters " refers to herein, and 1 molecular memory is at multiple phosphoric acid ester position, and " non-condensed phosphoric acid esters " refers to, only there is a phosphoric acid ester position in 1 molecule.The object lesson meeting the phosphoric acid ester of thus much illustrated condition is as follows.
As the object lesson of condensed phosphoric acid esters, can list: the aromatic condensation phosphoric acid ester such as 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester), Resorcinol two (diphenyl phosphoester); The Halogen system condensed phosphoric acid esters such as the two dichloro alkyl phosphates of polyoxy alkylidene; Non-aromatic non-halogen system condensed phosphoric acid esters; Deng.In the middle of these, the releasing of, unharmful substance (halogen etc.) less from the viewpoint of proportion is dangerous, easily obtain, and optimization aromatic condensed phosphoric acid esters, is more preferably 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane pair (diphenyl phosphoester).
As the object lesson of non-condensed phosphoric acid esters, can list: the aromatic phosphoric esters such as triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, tricresyl phosphate base diphenyl, tricresyl phosphate base-2,6-diformazan phenyl ester, phosphoric acid 2-ethylhexyl diphenyl phosphate; The Halogen system phosphoric acid ester such as three (β-chloropropyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, three (tribromo neo-pentyl) phosphoric acid ester; Deng.Wherein, never produce the aspects such as objectionable impurities (halogen etc.) and consider, optimization aromatic phosphoric acid ester.
Phosphoric acid ester can be used alone one, also can combinationally use two or more.
The amount of thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and the middle phosphoric acid ester used of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), relative to (methyl) acrylic acid resin composition (A) 100 mass parts, is preferably below more than 20 mass parts 100 mass parts.By making the content of phosphoric acid ester be in above-mentioned scope, be easy to the flame retardant resistance improving thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
Other additives of < >
In thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) except mentioned component, not hindering by adding in the scope of the above-mentioned effect that mentioned component plays, known various additive can also be added.As known additive, can list: whipping agent (comprises frothing aid.); The flame retardant resistance heat conduction mineral compound such as oxyhydroxide, metal salt hydrates of metal; Glass fibre; The thermal conductivity mineral compound such as expanded graphite powder, aluminum oxide, PITCH based carbon fiber; External crosslinker; The face such as carbon black, titanium dioxide material; Other packing materials such as clay; The nanoparticle such as soccerballene, carbon nanotube; The antioxidants such as polyphenol system, quinhydrones system, hindered amine system; The thickening materials such as acrylic acid polymer particle, particulate oxide silicon, magnesium oxide; Deng.
2. manufacture method
Thermal conductivity pressure-sensitive adhesive composite (F) of the present invention by after the material mixing that will thus much be described, carry out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or comprise the structural unit being derived from (methyl) acrylate monomer (α 1) polymkeric substance crosslinking reaction and obtain.
That is, the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) of the present invention comprising: the operation making following blend compositions; And in this blend compositions, carry out the polyreaction of described (methyl) acrylate monomer (α 1) and described (methyl) acrylic ester polymer (A1) and/or comprise the operation of crosslinking reaction of polymkeric substance of the structural unit being derived from (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With the conducting filler (B) that median size is less than 50 μm; With there is needle-like portion and the length of this needle-like portion is the zinc oxide (C) of more than 2 μm less than 50 μm.In addition, the preferred preferred median size containing ratio, each material of other spendable materials, each material etc. as mentioned above, omit its description.
In the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) of the present invention, when carrying out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or comprise the crosslinking reaction of polymkeric substance of the structural unit being derived from (methyl) acrylate monomer (α 1), preferably heat.This heating can use such as, hot blast, electric heater, infrared rays etc.Heating temperature now preferably makes polymerization starter efficiency decompose well, carries out the temperature of the polymerization of (methyl) acrylate monomer (α 1) and multi-functional monomer.Temperature range is different according to the kind of the polymerization starter used, and is preferably more than 100 DEG C less than 200 DEG C, is more preferably more than 130 DEG C less than 180 DEG C.
Thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the present invention is undertaken after mixing moulding is sheet or while being shaped to sheet by the material that will be thus much illustrated, carry out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or comprise the structural unit being derived from (methyl) acrylate monomer (α 1) polymkeric substance crosslinking reaction and obtain.
That is, the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the present invention comprising: the operation making blend compositions, and after blend compositions is shaped to sheet, or while blend compositions is shaped to sheet, carry out the polyreaction of (methyl) acrylate monomer (α 1), (methyl) acrylic ester polymer (A1) and/or comprise the operation of crosslinking reaction of polymkeric substance of the structural unit being derived from (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) comprising (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), with the conducting filler (B) that median size is less than 50 μm, with there is needle-like portion and the length of this needle-like portion is the zinc oxide (C) of more than 2 μm less than 50 μm.In addition, the preferred preferred median size containing ratio, each material of other spendable materials, each material etc. as mentioned above, omit its description.
In the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the present invention, when carrying out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or comprise the crosslinking reaction of polymkeric substance of the structural unit being derived from (methyl) acrylate monomer (α 1), preferably heat.This heating can use such as, hot blast, electric heater, infrared rays etc.Heating temperature now preferably makes polymerization starter efficiency decompose well, carries out the temperature of the polymerization of (methyl) acrylate monomer (α 1) and multi-functional monomer.Temperature range is different according to the kind of the polymerization starter used, and is preferably more than 100 DEG C less than 200 DEG C, is more preferably more than 130 DEG C less than 180 DEG C.
There is no particular limitation above-mentioned blend compositions to be shaped to the method for sheet.As preferred method, include, for example out the casting method (キ ャ ス ト method) be coated on by blend compositions on the operation paper such as polyester film of lift-off processing, blend compositions is clipped in if required two chien shihs through the operation paper of lift-off processing its by the method between roller and use forcing machine, controlled the method etc. of thickness when extruding blend compositions by mould (ダ イ ス).
The thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be made to be more than 0.05mm below 5mm.By making the lower thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), the thermal resistance of the thickness direction of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be made to reduce.Consider from this viewpoint, the upper limit of the thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is preferably 2mm.On the other hand, the lower limit of the thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is preferably 0.1mm.Be more than 0.05mm by making thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), be easy to prevent from being involved in air when being attached on heating element and radiator by this thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), its result, be easy to the increase preventing thermal resistance, easily make the operability attached in operation to adherend become good.
In addition, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can also at the one side of base material or double-faced forming.To the material forming this base material, there is no particular limitation.As the object lesson of this base material, can list: the metal of the excellent thermal conductivity such as aluminium, copper, stainless steel, beryllium copper and the foil-like thing, heat-conductive silicone etc. of alloy himself comprise the flap, the thermal conductivity plastic film containing thermal conductivity additive, various non-woven fabrics, woven fiber glass, honeycomb structured body etc. of the polymkeric substance of excellent thermal conductivity.As plastic film, the thermally stable polymer films such as polyimide, polyethylene terephthalate, PEN, tetrafluoroethylene, polyetherketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfones, polyphenylene sulfide, polyamidoimide, polyester-imide, aromatic polyamide can be used.
3. example
The part that thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be used as electronic unit uses.Now, also can be directly shaping on the such base material of radiator, the part as electronic unit provides.As the object lesson of this electronic unit, parts, fuel cell, solar cell, battery, mobile phone, handheld terminal (PDA), notebook computer, liquid crystal, surface-conduction-electron emission display (SED), plasma display (PDP) or unicircuit (IC) etc. around the power device that can list the parts, automobile etc. in the equipment with electroluminescent (EL), photodiode (LED) light source around heating part have equipment, the parts of heating part.
In addition, routine as of thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) using method in the electronic device, can list: using LED light source as concrete example, using method as described below.That is, be directly attached on LED light source; Be clipped between LED light source and heat sink material (scatterer, fan, peltier-element, heat pipe, graphite sheet etc.); Be attached on the heat sink material (scatterer, fan, peltier-element, heat pipe, graphite sheet etc.) that is connected with LED light source; Use as the casing around LED light source; Be attached on the casing around LED light source; Imbed in the gap of LED light source and casing; Etc. method.As the purposes example of LED light source, can list: the back lighting device (TV, mobile phone, PC, notebook PC, PDA etc.) with the display unit of permeation type liquid crystal panel; Lamps apparatus for vehicle; Industrial illumination; Business is thrown light on; General house illumination; Deng.
In addition, can be listed below as the object lesson beyond LED light source.That is, PDP panel; IC heating part; Cold-cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High brightness luminescent LED light source; The organic EL light source of high brightness luminescent; The inorganic EL light source of high brightness luminescent; CPU; MPU; Semiconductor element; Deng.
And then it is first-class to list as the using method of thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) casing being attached to device.Such as, at middle devices used such as automobiles, the inside of the casing that automobile possesses is attached to; Be attached to the outside of the casing that automobile possesses; Connect the heating part (auto-navigation system/fuel cell/heat exchanger) of the inside of the casing that automobile possesses and this casing; On the heating panel that the heating part (auto-navigation system/fuel cell/heat exchanger) attaching the inside of the casing possessed with automobile is connected; Deng.
In addition, in addition to automobiles, also can use the same method use thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).As its object, include, for example out: PC; House; TV; Mobile phone; Vending machine; Refrigerator; Solar cell; Surface-conduction-electron emission display (SED); OLED display; Inorganic EL indicating meter; Organic EL illuminating; Inorganic EL illumination; OLED display; Notebook computer; PDA; Fuel cell; Semiconductor device; Electric cooker; Washing machine; Scrubbing-and-drying unit; Be combined with the optical semiconductor device of optical semiconductor and fluor; Various power device; Game machine; Electrical condenser; Deng.
And then thermal conductivity pressure-sensitive adhesive composite (F) of the present invention and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) are not limited only to above-mentioned using method, can also use according to purposes in other method.Such as, can list: use in order to the homogenizing of the heat of carpet, warm pad etc.; Sealing agent as LED light source/thermal source uses; Sealing agent as solar battery cell uses; Back seat (バ ッ Network シ-ト) as solar cell uses; Use between the back seat and top of solar cell; The inner side of the thermofin in vending machine inside uses; In the casing internal of organic EL illuminating, use together with siccative, moisture adsorbent; Above the heat-conducting layer of the casing internal of organic EL illuminating and its, use together with siccative, moisture adsorbent; The heat-conducting layer of the casing internal of organic EL illuminating, heat dissipating layer and its above, use together with siccative, moisture adsorbent; The heat-conducting layer of the casing internal of organic EL illuminating, the heat dissipating layer of epoxy and its above, use together with siccative, moisture adsorbent; For the cooling-part such as device, clothing, towel, sheet material in order to make people, animal cooling, the face contrary with health uses; On the pressure-producing part of the stationary installation that the image processing systems such as electronic photo duplicating machine, electrophotographic printer carry; Pressure-producing part as the stationary installation of carrying on the image processing systems such as electronic photo duplicating machine, electrophotographic printer uses; Hot-fluid control heat-conducting part as the handling object of carrying film forming apparatus uses; The hot-fluid control heat-conducting part of the handling object of carrying film forming apparatus uses; Use between the skin and inside of radioactive substance storing container; Use in the casing being provided with the solar panel absorbing sunlight; Use between the reflective sheet and aluminium cabinet of CCFL backlight; Deng.
Embodiment
The present invention will be described in more detail below to utilize embodiment, but the present invention is not by the restriction of embodiment.In addition, " portion " used herein, " % " represent quality criteria when not having specified otherwise.
< mobility >
Evaluate the mobility through the blend compositions of the aftermentioned 1st and the 2nd mixed processes gained.Specifically, Hobart's container (ホ バ ー ト container of blend compositions will be housed) be inclined relative to horizontal 30 °, evaluate with the state of this blend compositions after 1 minute.The results are shown in table 2 and table 3.Blend compositions is set to "○" along the situation of oblique flow, motionless situation is set to "×".Blend compositions has being easy to this blend compositions sheet material of mobility.That is, be easy to manufacture thermal conductivity pressure-sensitive adhesive sheet-like formed body.
< volume specific resistance (insulativity) >
Prepare the test film thermal conductivity pressure-sensitive adhesive sheet material made by aftermentioned method being cut into the size of 80mm × 80mm.Test film is placed on digital ultra-high resistance/pettiness rheometer (trade(brand)name " 8340A ", Co., Ltd. エ ー デ ィ ー シ ー system), passes into electric current at the two ends, left and right of this test film, measure resistivity.Voltage is slowly down to measurable voltage from 500V, determines the resistivity that can measure under voltage.In addition, the duration of charging is set to 1 minute.Carry out 3 these mensuration, using the volume specific resistance (unit: Ω cm) of its mean value as thermal conductivity pressure-sensitive adhesive sheet material.Result is shown in table 2 and table 3.If the result obtained by this evaluation is 1.0 × 10 10more than Ω cm, then can say that insulativity is excellent.
< cooling performance >
Prepare the test film being cut into the size of 25mm × 25mm with the thermal conductivity pressure-sensitive adhesive sheet-like formed body of aftermentioned making.Test film is attached on the aluminium sheet of 150mm × 150mm × thickness 3mm, miniature ceramic heater (Sakaguchi Dennetsu Kabushiki Kaisha's system, trade(brand)name: MS-5,25mm × 25mm) is fixed on test film with double faced adhesive tape be attached at aluminium sheet side and be on the face of opposition side, this aluminium sheet is suspended in mid air.Then, miniature ceramic heater is connected on contact type voltage regulator, the surface of miniature ceramic heater when heating 60 minutes with thermal imager shooting under 60W.Top temperature is now shown in table 2 and table 3.More heat has been conducted in the explanation of this temperature step-down from miniature ceramic heater to aluminium sheet, therefore can say that this temperature is lower, and the thermal resistance of thermal conductivity pressure-sensitive adhesive sheet-like formed body is lower.In addition, this evaluation is carried out under 23 DEG C of atmosphere.
(embodiment 1)
Add the monomer mixture 100 parts, 2 be made up of 2-EHA 94% and vinylformic acid 6% in the reactor, 2 '-Diisopropyl azodicarboxylate 0.03 part and ethyl acetate 700 parts, make its uniform dissolution, at 80 DEG C, after nitrogen replacement, carry out the polyreaction of 6 hours.Polymerisation conversion is 97%.The polymkeric substance of gained is carried out drying under reduced pressure makes ethyl acetate evaporate, and obtains (methyl) acrylic ester polymer (A1-1) of sticking solid state.The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (A1-1) is 270000, weight-average molecular weight (Mw)/number-average molecular weight (Mn) is 3.1.Weight-average molecular weight (Mw) and number-average molecular weight (Mn) are by obtaining the gel permeation chromatography of tetrahydrofuran (THF) as elutriant with polystyrene standard conversion.
Then, the multi-functional monomer 1.0 parts and 2-EHA that pentaerythritol triacrylate, tetramethylol methane tetraacrylate and pentaerythritol diacrylate are mixed with the ratio of 60:35:5 is weighed (referred to as " 2EHA " in table 2 and table 3 with electronics Libra.) ((within 1 minute, half life temperature is 150 DEG C to two (the t-butylperoxycarbonyl oxygen base) hexane of 1,6-for 88 parts and organo-peroxide thermal polymerization.)) 1.0 parts, these are mixed with above-mentioned (methyl) acrylic ester polymer (A1-1) 13 parts.Thermostatic bath (Toki Sangyo Co., Ltd.'s system, trade(brand)name " PVC ス コ メ イ ト 150III ") and Hobart's mixing tank (the little flat making of Co., Ltd. made, trade(brand)name " ACM-5LVT type ", capacity: 5L) is used during mixing.The temperature control of Hobart's container is set as 60 DEG C, rotating speed scale is set to 3 and stirs 10 minutes.This operation is called the 1st mixed processes.
Then, phosphoric acid ester (aginomoto Off ァ イ Application テ Network ノ Co., Ltd. system, trade(brand)name " レ オ Off ォ ス 65 ", compound name " tricresyl phosphate aryl sec.-propyl compound ") 50 parts and aluminum oxide (Showa Denko K. K's system, trade(brand)name " AL-47-H ", median size: 2 μm, BET specific surface area: 1.1m is weighed 2/ g) 1000 parts and 2 parts, zinc oxide (Co., Ltd. ア system テ ッ Network system, パ Na テ ト ラ WZ-0511), drop in above-mentioned Hobart's container, the temperature control of Hobart's container is set as 60 DEG C, rotating speed scale is set to 5 and stirs 10 minutes.This operation is called the 2nd mixed processes.
Then, the blend compositions through the above-mentioned 1st and the 2nd mixed processes gained is dropped in demoulding PET film, this blend compositions covers demoulding PET film further.Make blend compositions be held on this duplexer of demoulding PET film, by spacing be 0.3mm two rollers between, formed sheet.Then, this duplexer is put in baking oven, heat 15 minutes at 150 DEG C.By this heating process, make acrylate monomer that polymerization and crosslinking reaction occur, obtain thermal conductivity pressure-sensitive adhesive sheet-like formed body and (be only denoted as below " sheet material ".）（G1）。In addition, calculate the polymerisation conversion of (methyl) acrylate monomer from the levels of residual monomers sheet material (G1), result is 99.9%.
(embodiment 2 ~ 6 and comparative example 1 ~ 6)
By the formula change of each material for shown in table 2 and table 3, operate similarly to Example 1 in addition, obtain sheet material (G2 ~ 6, GC1 ~ 6).
The additive be illustrated so far used in embodiment 2 ~ 6 and comparative example 1 ~ 6 is as follows.
Aluminium hydroxide (Nippon Light Metal Co., Ltd's system, trade(brand)name " BF-083 ", median size: 8 μm, BET specific surface area: 0.8m 2/ g)
Aluminum oxide: Showa Denko K. K's system, trade(brand)name " A-13-H ", median size: 57 μm, BET specific surface area: 0.8m 2/ g
[table 2]
[table 3]
As shown in table 2, sheet material (G1) ~ (G6) in embodiment, the mobility of the blend compositions before sheet material is all good, and after sheet material, the volume specific resistance of this sheet material is high, and cooling performance is excellent.On the other hand, as shown in table 3, the above-mentioned performance inequality of sheet material (GC1) ~ (GC6) in comparative example.Specifically, as follows.
Comparative example 1: the sheet material (GC1) of the comparative example 1 of oxygen-freeization zinc, cooling performance is poor.
Comparative example 2: the sheet material (GC2) of the comparative example 2 containing the scope specified in quantity not sufficient the present invention of zinc oxide, cooling performance is poor.
Comparative example 3: the content of zinc oxide exceedes the sheet material (GC3) of the comparative example 3 of the scope specified in the present invention, volume specific resistance reduces.
Comparative example 4: the sheet material (GC4) of the comparative example 4 containing the scope specified in quantity not sufficient the present invention of conducting filler, cooling performance is poor.
Comparative example 5: the content of conducting filler exceedes the sheet material (GC5) of the comparative example 5 of the scope specified in the present invention, the blend compositions before sheet material, without mobility, cannot carry out sheet material.
Comparative example 6: the sheet material (GC6) employing the comparative example 6 of the conducting filler of the particle diameter larger than the scope specified in the present invention, cooling performance is poor.

Claims (13)

1. thermal conductivity pressure-sensitive adhesive composite (F), it in following blend compositions, carry out polyreaction and crosslinking reaction forms, and wherein, described blend compositions comprises:
Comprise (methyl) acrylic acid resin composition (A) 100 mass parts of (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts; With
There is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts,
Wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is the crosslinking reaction of described (methyl) acrylic ester polymer (A1) and/or the polymkeric substance comprising the structural unit being derived from described (methyl) acrylate monomer (α 1).
2. the thermal conductivity pressure-sensitive adhesive composite (F) according to right 1, wherein, described blend compositions also comprises the phosphoric acid ester of below more than 20 mass parts 100 mass parts.
3. thermal conductivity pressure-sensitive adhesive composite (F) according to claim 1 and 2, wherein, median size is the described conducting filler (B) of less than 50 μm to be median size be aluminum oxide and/or the aluminium hydroxide of less than 50 μm.
4. thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), its be following blend compositions is shaped to sheet after, or while described blend compositions is shaped to sheet, carry out polymer reaction and crosslinking reaction, wherein, described blend compositions comprises:
Comprise (methyl) acrylic acid resin composition (A) 100 mass parts of (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts; With
There is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts,
Wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is the crosslinking reaction of described (methyl) acrylic ester polymer (A1) and/or the polymkeric substance comprising the structural unit being derived from described (methyl) acrylate monomer (α 1).
5. thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) according to claim 4, wherein, described blend compositions also comprises the phosphoric acid ester of below more than 20 mass parts 100 mass parts.
6. the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) according to claim 4 or 5, wherein, median size is the described conducting filler (B) of less than 50 μm to be median size be aluminum oxide and/or the aluminium hydroxide of less than 50 μm.
7. the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), the method comprises:
Make the operation of following blend compositions; And
In described blend compositions, carry out the polyreaction of described (methyl) acrylate monomer (α 1) and described (methyl) acrylic ester polymer (A1) and/or comprise the operation of crosslinking reaction of polymkeric substance of the structural unit being derived from described (methyl) acrylate monomer (α 1)
Wherein, described blend compositions comprises:
Comprise (methyl) acrylic acid resin composition (A) 100 mass parts of (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts; With
There is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts.
8. the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) according to claim 7, wherein, described blend compositions also comprises the phosphoric acid ester of below more than 20 mass parts 100 mass parts.
9. the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) according to right 7 or 8, wherein, median size is the described conducting filler (B) of less than 50 μm to be median size be aluminum oxide and/or the aluminium hydroxide of less than 50 μm.
10. the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), the method comprises:
Make the operation of following blend compositions; And
After described blend compositions is shaped to sheet, or while described blend compositions is shaped to sheet, carry out the polyreaction of described (methyl) acrylate monomer (α 1) and described (methyl) acrylic ester polymer (A1) and/or comprise the operation of crosslinking reaction of polymkeric substance of the structural unit being derived from described (methyl) acrylate monomer (α 1)
Wherein, described blend compositions comprises:
Comprise (methyl) acrylic acid resin composition (A) 100 mass parts of (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below more than conducting filler (B) 600 mass parts of less than 50 μm 1400 mass parts; With
There is needle-like portion and the length of this needle-like portion is below more than zinc oxide (C) 0.5 mass parts of more than 2 μm less than 50 μm 40 mass parts.
The manufacture method of 11. thermal conductivity pressure-sensitive adhesive sheet-like formed bodies (G) according to claim 10, wherein, described blend compositions also comprises the phosphoric acid ester of below more than 20 mass parts 100 mass parts.
12. the manufacture method of the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) according to claim 10 or 11, wherein, median size is the described conducting filler (B) of less than 50 μm to be median size be aluminum oxide and/or the aluminium hydroxide of less than 50 μm.
13. electronic unit, it possesses: radiator and the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 1 or 2 be fitted on this radiator or, radiator and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 4 or 5 that is fitted on this radiator.
CN201280003973.XA 2011-03-29 2012-02-22 Heat-conductive, pressure-sensitive adhesive composition, heat-conductive, pressure-sensitive adhesive sheet formed body, method for producing each, and electronic component Expired - Fee Related CN103221501B (en)

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