CN103221501A - 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
CN103221501A
CN103221501A CN201280003973XA CN201280003973A CN103221501A CN 103221501 A CN103221501 A CN 103221501A CN 201280003973X A CN201280003973X A CN 201280003973XA CN 201280003973 A CN201280003973 A CN 201280003973A CN 103221501 A CN103221501 A CN 103221501A
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thermal conductivity
methyl
sensitive adhesive
mass parts
pressure
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CN201280003973XA
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CN103221501B (en
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熊本拓朗
川村明子
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Zeon Corp
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Nippon Zeon Co Ltd
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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
    • 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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    • 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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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • 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
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
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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
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/29386—Base material with a principal constituent of the material being a non metallic, non metalloid inorganic material
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    • H01L2224/26—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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    • H01L2224/29198—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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    • 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
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    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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    • H01L2924/11—Device type
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Computer Hardware Design (AREA)
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  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

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 this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of 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, produced need to Yin Wendu rise and the function that produces to damage the necessity that takes some countermeasures right.Usually, the method for taking is: radiators such as metal system scatterer, heating panel, radiator element are installed on the heating element that electronic unit etc. possessed, thereby make its heat radiation.For the heat conduction from the heating element to the radiator is effectively carried out, use various thermally-conductive sheet.Usually, in the purposes of fixedly heating element and radiator, need the composition that also possesses pressure-sensitive adhesive on the basis of thermal conductivity (below be called " thermal conductivity pressure-sensitive adhesive composite ".) or need the sheet material that also possesses pressure-sensitive adhesive on the basis of thermal conductivity (below be called " thermal conductivity pressure-sensitive adhesive sheet-like formed body ".）。
One of purpose of above-mentioned thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body is to be used for heat is delivered to radiator from heating element, and thermal resistance is reduced.In order to reduce the thermal resistance of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, for example, can consider in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, to add expanded graphite powder etc.Yet the expanded graphite powder has high thermal conductivity and has high conductivity.Therefore, when also requiring the purposes of insulativity, can not use the thermal conductivity pressure-sensitive adhesive composite and the thermal conductivity pressure-sensitive adhesive sheet-like formed body that improve thermal conductivity by the expanded graphite powder sometimes.
In addition, as record in the patent documentation 1 ~ 3, except the expanded graphite powder, the filler as the thermal conductivity that can improve thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body can also use zinc oxide.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-163145 communique
Patent documentation 2: TOHKEMY 2008-127482 communique
Patent documentation 3: TOHKEMY 2008-127481 communique.
Summary of the invention
Because zinc oxide is lower than the electroconductibility of expanded graphite powder, therefore think, when in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, adding zinc oxide, compare with adding the expanded graphite powder, can suppress the rising of the electroconductibility of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body.
Yet, though the electroconductibility of zinc oxide is lower than expanded graphite powder, but in order to utilize zinc oxide that the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body is improved and as the technology of record in the patent documentation 1 ~ 3, to add a large amount of zinc oxide, then the electroconductibility of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body uprises, and can not be used for the purposes of requirement insulativity sometimes.Like this, existing technology is difficult to balance and possesses desired many performances in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body well.
Herein, problem of the present invention is to provide: balance possesses thermal conductivity pressure-sensitive adhesive composite and the thermal conductivity pressure-sensitive adhesive sheet-like formed body and their manufacture method of thermal conductivity and insulativity well and possesses this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
The zinc oxide of discoveries such as the inventor by being used in combination regulation and the thermal conductivity filler of the regulation beyond the zinc oxide can address the above problem, thereby finish the present invention.
First embodiment of the present invention is thermal conductivity pressure-sensitive adhesive composite (F), it carries out polyreaction in following blend compositions and crosslinking reaction forms, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be below above 1400 mass parts of thermal conductivity filler (B) 600 mass parts below the 50 μ m; With the length with needle-like portion and this needle-like portion be more than the 2 μ m below above 40 mass parts of zinc oxide (C) 0.5 mass parts below the 50 μ m, wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is described (methyl) acrylic ester polymer (A1) and/or the crosslinking reaction that comprises the polymkeric substance of the structural unit that is derived from described (methyl) acrylate monomer (α 1).
Below the definition of the wording used in this specification sheets is put down in writing." (methyl) vinylformic acid " is meant " vinylformic acid and/or methacrylic acid ".In addition, " median size " is meant the particle diameter of measuring with following illustration method.That is, use laser granulometry (セ イ シ Application enterprise of Co., Ltd. system) to utilize little ordering control mode (make the determination object particle only by measuring in the zone, improve the mode of the reliability of measuring) to measure.According to this measuring method, in unit (セ Le), flow into determination object particle 0.01g ~ 0.02g, thus to flowing into the semiconductor laser of measuring the determination object particle-irradiation wavelength 670nm in the zone, by utilizing determinator to measure the scattering and the diffraction of laser this moment, calculate median size and size distribution by the diffraction principle of Fraunhofer.In addition, " thermal conductivity filler " be meant, by adding, can make thermal conductivity pressure-sensitive adhesive composite (F) or filler that the thermal conductivity of the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) that describes after a while improves.In addition, " length of needle-like portion " of zinc oxide (C) be meant, observes and the length measured with scanning electronic microscope.In addition, " polyreaction of (methyl) acrylate monomer (α 1) " be meant, obtains producing the polyreaction of the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1).In addition, " (methyl) acrylic ester polymer (A1) and/or comprise the crosslinking reaction of the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1) " is meant, the crosslinking reaction between (methyl) acrylic ester polymer (A1), comprises the one or more crosslinking reactions among the crosslinking reaction of crosslinking reaction between the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and the polymkeric substance that comprises the structural unit that is derived from (methyl) acrylate monomer (α 1).
In the thermal conductivity pressure-sensitive adhesive composite (F) of first embodiment of the present invention, preferred blend compositions also comprises below above 100 mass parts of phosphoric acid ester 20 mass parts.In addition, median size be the following thermal conductivity filler (B) of 50 μ m be preferably median size be 50 μ m following, aluminum oxide and/or aluminium hydroxide.
Second embodiment of the present invention is a thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), it is that following blend compositions is shaped to after the sheet, perhaps be shaped to the flaky while, carry out that polyreaction and crosslinking reaction form, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be below above 1400 mass parts of thermal conductivity filler (B) 600 mass parts below the 50 μ m; With the length with needle-like portion and this needle-like portion be more than the 2 μ m below above 40 mass parts of zinc oxide (C) 0.5 mass parts below the 50 μ m, wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is described (methyl) acrylic ester polymer (A1) and/or the crosslinking reaction that comprises the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1).
In the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of second embodiment of the present invention, preferred blend compositions also comprises below above 100 mass parts of phosphoric acid ester 20 mass parts.In addition, median size be the following thermal conductivity filler (B) of 50 μ m be preferably median size be 50 μ m following, aluminum oxide and/or aluminium hydroxide.
The 3rd embodiment of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), and this method comprises: the operation of making following blend compositions; And in described blend compositions, carry out the polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and/or comprise the operation of crosslinking reaction of the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be below above 1400 mass parts of thermal conductivity filler (B) 600 mass parts below the 50 μ m; With the length with needle-like portion and this needle-like portion be more than the 2 μ m below above 40 mass parts of zinc oxide (C) 0.5 mass parts below the 50 μ m.
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 above 100 mass parts of phosphoric acid ester 20 mass parts.In addition, median size be the following thermal conductivity filler (B) of 50 μ m be preferably median size be 50 μ m following, aluminum oxide and/or aluminium hydroxide.
The 4th embodiment of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), and this method comprises: the operation of making following blend compositions; And described blend compositions is shaped to after the sheet, perhaps described blend compositions is being shaped to the flaky while, carry out the polyreaction of described (methyl) acrylate monomer (α 1), with described (methyl) acrylic ester polymer (A1) and/or comprise the operation of crosslinking reaction of the polymkeric substance of the structural unit that is derived from described (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be below above 1400 mass parts of thermal conductivity filler (B) 600 mass parts below the 50 μ m; With the length with needle-like portion and this needle-like portion be more than the 2 μ m below above 40 mass parts of zinc oxide (C) 0.5 mass parts below the 50 μ m.
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 above 100 mass parts of phosphoric acid ester 20 mass parts.In addition, median size be the preferred median size of the following thermal conductivity filler (B) of 50 μ m be 50 μ m following, aluminum oxide and/or aluminium hydroxide.
The 5th embodiment of the present invention is a kind of electronic unit, and it possesses: radiator and be fitted in first embodiment of the present invention on this radiator thermal conductivity pressure-sensitive adhesive composite (F) or, radiator and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) that is fitted in second embodiment of the present invention on this radiator.
The thermal conductivity pressure-sensitive adhesive composite and the thermal conductivity pressure-sensitive adhesive sheet-like formed body that can provide balance to possess thermal conductivity and insulativity well according to the present invention; With their manufacture method; With the electronic unit that possesses 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 of the present invention (F), it carries out polyreaction and crosslinking reaction at least and forms in following blend compositions, wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) that comprises (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be thermal conductivity filler (B) (following abbreviate as sometimes " thermal conductivity filler (B) ") below the 50 μ m; With the length with needle-like portion and this needle-like portion be the zinc oxide (C) below the 50 μ m more than the 2 μ m (following abbreviate as sometimes " zinc oxide (C) "), wherein, described polyreaction is the polyreaction of the polymkeric substance that obtains producing the structural unit be derived from (methyl) acrylate monomer (α 1), and described crosslinking reaction is the crosslinking reaction between described (methyl) acrylic ester polymer (A1), comprise the crosslinking reaction between the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), and any crosslinking reaction in (methyl) acrylic ester polymer (A1) and the crosslinking reaction of polymkeric substance that comprises the structural unit that is derived from (methyl) acrylate monomer (α 1).
In addition, thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G), it is that above-mentioned blend compositions is shaped to after the sheet, perhaps above-mentioned blend compositions is being shaped to the flaky while, at least carry out that polyreaction and crosslinking reaction form, wherein, described polyreaction is the polyreaction of the polymkeric substance that obtains producing the structural unit be derived from (methyl) acrylate monomer (α 1), and described crosslinking reaction is the crosslinking reaction between described (methyl) acrylic ester polymer (A1), comprise the crosslinking reaction between the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), and any crosslinking reaction among (methyl) acrylic ester polymer (A1) and the crosslinking reaction of polymkeric substance that comprises the structural unit that is derived from (methyl) acrylate monomer (α 1).
Below the material that constitutes 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) that uses among 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), obtain producing the structural unit be derived from (methyl) acrylate monomer (α 1) polymkeric substance polyreaction and (methyl) acrylic ester polymer (A1) and/or comprise the crosslinking reaction of the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1).The polymkeric substance of the structural unit by carrying out this polyreaction and crosslinking reaction, comprise being derived from (methyl) acrylate monomer (α 1) mixes and/or bonding a part of with it with the composition of (methyl) acrylic ester polymer (A1).
Among the present invention, the consumption of acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) is preferably with respect to (methyl) acrylic acid resin composition (A) 100 quality %, and (methyl) acrylic ester polymer (A1) is that the above 40 quality % of 5 quality % are following, (methyl) acrylate monomer (α 1) is below the above 95 quality % of 60 quality %.Be in above-mentioned scope by the ratio that contains that makes (methyl) acrylate monomer (α 1), can be easy to thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) moulding.
((methyl) acrylic ester polymer (A1))
There is no particular limitation for spendable among the present invention (methyl) acrylic ester polymer (A1), preferably contains the formation second-order transition temperature and be unit (a1) of (methyl) acrylate monomer of the homopolymer below-20 ℃ and the monomeric unit (a2) with organic acidic group.
There is no particular limitation for (methyl) acrylate monomer (a1m) of the unit (a1) that obtains above-mentioned (methyl) acrylate monomer, for example, can list ethyl propenoate (second-order transition temperature of homopolymer is-24 ℃), vinylformic acid n-propyl (second-order transition temperature of homopolymer is-37 ℃), n-butyl acrylate (second-order transition temperature of homopolymer is-54 ℃), sec-butyl acrylate (second-order transition temperature of homopolymer is-22 ℃), vinylformic acid n-pentyl ester (second-order transition temperature of homopolymer is-60 ℃), the just own ester of vinylformic acid (second-order transition temperature of homopolymer is-61 ℃), vinylformic acid n-octyl (second-order transition temperature of homopolymer is-65 ℃), 2-EHA (second-order transition temperature of homopolymer is-50 ℃), vinylformic acid 2-methoxyl group ethyl ester (second-order transition temperature of homopolymer is-50 ℃), vinylformic acid 3-methoxyl group propyl ester (second-order transition temperature of homopolymer is-75 ℃), vinylformic acid 3-methoxyl group butyl ester (second-order transition temperature of homopolymer is-56 ℃), vinylformic acid oxyethyl group methyl esters (second-order transition temperature of homopolymer is-50 ℃), n octyl methacrylate (second-order transition temperature of homopolymer is-25 ℃), methacrylic acid ester in the positive last of the ten Heavenly stems (second-order transition temperature of homopolymer is-49 ℃) etc.Wherein, preferred n-butyl acrylate, 2-EHA, vinylformic acid 2-methoxyl group ethyl ester, more preferably n-butyl acrylate, 2-EHA, further preferred 2-EHA.
These (methyl) acrylate monomers (a1m) can be used alone, and also can make up two or more uses.
About the amount of (methyl) acrylate monomer (a1m), preferred so that by its deutero-monomeric unit (a1) in (methyl) acrylic ester polymer (A1) for more than the preferred 80 quality % below the 99.9 quality %, more preferably the amount below the 99.5 quality % is used for polymerization more than the 85 quality %.If the consumption of (methyl) acrylate monomer (a1m) is in the above-mentioned scope, the viscosity of the polymerization system when then being easy to polymerization remains on suitable scope.
Then, the monomeric unit (a2) with organic acidic group is described.There is no particular limitation for the monomer (a2m) of the monomeric unit (a2) that obtains to have organic acidic group, can list as its representational monomer, and carboxyl, anhydride group, sulfonic group etc. have the monomer of organic acidic group.In addition, in addition, can also use the monomer that contains sulfeno, sulfino, phosphate etc.
Monomeric concrete example as having carboxyl for example can list: α such as vinylformic acid, methacrylic acid, Ba Dousuan, β-olefinic unsaturated monocarboxylic; α such as methylene-succinic acid, toxilic acid, fumaric acid, the unsaturated polycarboxylic acid of β-olefinic; And α such as monomethyl itaconate, butyl maleate, fumaric acid list propyl ester, the unsaturated partial esters of polycarboxylic acids of β-olefinic etc.In addition, can similarly use have can be by maleic anhydride, itaconic anhydride etc. hydrolysis etc. derive the monomer of the group of carboxyl.
As having sulfonic monomeric concrete example, can list allyl sulphonic acid, methacrylic sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide-α such as 2-methyl propane sulfonic acid, β-unsaturated sulfonic acid and their salt.
As monomer (a2m), in above illustrative monomer with organic acidic group, preferably have the monomer of carboxyl, wherein especially preferably have a monomer of vinylformic acid or methacrylic acid.These monomers are in industrial cheapness and can obtain easily, and are also good with the copolymerization of other monomer components, also be preferred aspect the productivity.In addition, monomer (a2m) can be used alone, and also can be used in combination two or more.
About monomer (a2m), preferred so that in (methyl) acrylic ester polymer (A1) be more than the 0.1 quality % below the 20 quality %, be preferably that the amount below the 15 quality % is used for polymerization more than the 0.5 quality % by its deutero-monomeric unit (a2) with organic acidic group.Be in the above-mentioned scope if having the consumption of the monomer (a2m) of organic acidic group, the viscosity of the polymerization system when then being easy to polymerization remains on suitable scope.
In addition, monomeric unit (a2) with organic acidic group as previously mentioned the polymerization of the monomer (a2m) by having organic acidic group to import in (methyl) acrylic ester polymer (A1) be easy and preferred, but also can after generating, (methyl) acrylic ester polymer (A1) import organic acidic group by known high molecular weight reactive.
In addition, (methyl) acrylic ester polymer (A1) can also contain the monomeric unit (a3) that is derived by the monomer (a3m) with organic acidic group functional group in addition.
Functional group as beyond above-mentioned organic acidic group can list hydroxyl, amino, amide group, epoxy group(ing), sulfydryl etc.
As monomer, can list (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester etc., (methyl) vinylformic acid hydroxyalkyl acrylate etc. with hydroxyl.
As having amino monomer, can list (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, amino-benzene ethene etc.
As monomer, can list α such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA, the unsaturated carboxylic acid amides monomer of β-olefinic etc. with amide group.
As monomer, can list (methyl) glycidyl acrylate, glycidyl allyl ether etc. with epoxy group(ing).
Monomer (a3m) with organic acidic group functional group in addition can be used alone, and also can be used in combination two or more.
Has the monomer (a3m) of the functional group beyond organic acidic group about these, so that be that amount below the 10 quality % is used for polymerization in (methyl) acrylic ester polymer (A1) by its deutero-monomeric unit (a3).By using the monomer (a3m) below the 10 quality %, the viscosity of the polymerization system when being easy to polymerization remains on suitable scope.
(methyl) acrylic ester polymer (A1) except contain form above-mentioned second-order transition temperature for (methyl) acrylate monomeric units (a1) of the homopolymer below-20 ℃, the monomeric unit (a3) that has the monomeric unit (a2) of organic acidic group and have a functional group organic acidic group in addition, can also contain by the monomeric unit (a4) that can derive out with the monomer (a4m) of above-mentioned monomer copolymerization.Monomer (a4m) can be used alone, and also can be used in combination two or more.
By the amount of monomer (a4m) deutero-monomeric unit (a4) be preferably 10 quality % of acrylic ester polymer (A1) following, more preferably below the 5 quality %.
There is no particular limitation to monomer (a4m), as its concrete example, above-mentioned (methyl) acrylate monomer (a1m) (methyl) acrylate monomer, α in addition be can list, the full ester of the unsaturated polycarboxylic acid of β-olefinic, alkenyl aromatic monomer, diene monomer, non-diene monomer, vinyl cyanide base monomer, the unsaturated alcohol ester of carboxylic acid, the ethylene series monomer etc. of using as a servant altogether used as a servant altogether.
As the concrete example of above-mentioned (methyl) acrylate monomer (a1m) (methyl) acrylate monomer in addition, can list methyl acrylate (second-order transition temperature of homopolymer is 10 ℃), methyl methacrylate (second-order transition temperature of homopolymer is 105 ℃), Jia Jibingxisuanyizhi (second-order transition temperature of homopolymer is 63 ℃), n propyl methacrylate (second-order transition temperature of homopolymer is 25 ℃), n-BMA (second-order transition temperature of homopolymer is 20 ℃) etc.
As α, the concrete example of the full ester of the unsaturated polycarboxylic acid of β-olefinic can list dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate etc.
As the monomeric concrete example of alkenyl aromatic, can list vinylbenzene, alpha-methyl styrene, methyl alpha-methyl styrene, Vinyl toluene and Vinylstyrene etc.
As the concrete example of using as a servant diene monomer altogether, can list 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (with the isoprene synonym), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, chlorbutadiene, cyclopentadiene etc.
As non-concrete example of using as a servant diene monomer altogether, can list 1,4-hexadiene, Dicyclopentadiene (DCPD), ethylidene norbornene (Ethylidene norbornene) etc.
As the monomeric concrete example of vinyl cyanide base, can list vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, α-ethyl acrylonitrile etc.
As the monomeric concrete example of the unsaturated alcohol ester of carboxylic acid, can list vinyl-acetic ester etc.
As the monomeric concrete example of ethylene series, can list ethene, propylene, butylene, amylene etc.
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 below 1,000,000 more than 100,000, the scope below 500,000 more than 200,000 more preferably.
(methyl) acrylic ester polymer (A1) can especially suitably obtain by the following monomer of copolymerization: form second-order transition temperature for (methyl) acrylate monomer (a1m) of the homopolymer below-20 ℃, have the monomer (a2m) of organic acidic group, the monomer (a3m) that contains the functional group beyond organic acidic group that uses as required and use as required can with the monomer (a4m) of these monomer copolymerizations.
There is no particular limitation for the polymeric method, can use any methods such as solution polymerization, letex polymerization, suspension polymerization, mass polymerization, also can be the method beyond these.Be preferably solution polymerization, wherein more preferably use of the solution polymerization of aromatic solvents such as carboxylicesterss 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 in superoxide and the azo-compound any.
As peroxidic polymerization initiators, can list: persulphate such as superoxide that such hydroperoxide, benzoyl peroxide, the cyclohexanone peroxide of tertbutyl peroxide is such and Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.These superoxide can also use as the redox series catalysts with the reductive agent appropriate combination.
As the azo-compound polymerization starter, can list 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
There is no particular limitation for the consumption of polymerization starter, with respect to monomer 100 mass parts, is preferably the following scope of above 50 mass parts of 0.01 mass parts.
These monomeric other polymerizing conditions (polymerization temperature, pressure, agitation condition etc.) have no particular limits.
After polyreaction finished, the polymkeric substance with gained separated from polymerisation medium as required.There is no particular limitation for isolating method.For example, under the situation of solution polymerization,, heat up in a steamer polymer solvent, thereby can obtain (methyl) acrylic ester polymer (A1) by polymeric solution being placed decompression down.
The amount of the polymerization starter that uses when the weight-average molecular weight of (methyl) acrylic ester polymer (A1) can be by suitable adjustment polymerization, the amount of chain-transfer agent are controlled.
((methyl) acrylate monomer blend (α 1))
(methyl) acrylate monomer (α 1) forms second-order transition temperature (methyl) acrylate monomer (a5m) for the homopolymer below-20 ℃ so long as the material that contains (methyl) acrylate monomer with regard to there is no particular limitation, preferably contains.
As forming second-order transition temperature is the example of (methyl) acrylate monomer (a5m) of the homopolymer below-20 ℃, can list and identical (methyl) acrylate monomer of (methyl) acrylate monomer (a1m) that is used to synthesize (methyl) acrylic ester polymer (A1).(methyl) acrylate monomer (a5m) can be used alone, and also can be used in combination two or more.
The ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) be preferably the above 100 quality % of 50 quality % following, more preferably below the above 100 quality % of 75 quality %.Be in above-mentioned scope by the ratio that makes (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1), be easy to obtain the thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of pressure-sensitive adhesive, flexibility excellence.
In addition, (methyl) acrylate monomer (α 1) can also be with (methyl) acrylate monomer (a5m) and can with the monomeric mixture of its copolymerization.
Particularly preferred (methyl) acrylate monomer (α 1) be comprise form second-order transition temperature for (methyl) acrylate monomer (a5m) of the homopolymer below-20 ℃ and can with the material of the monomer with organic acidic group (a6m) of their copolymerization.
As the example of above-mentioned monomer (a6m), can list with as the monomer (a2m) of use in (methyl) acrylic ester polymer (A1) synthetic and the same monomer of illustrative monomer with organic acidic group.Monomer (a6m) can be used alone, and also can be used in combination two or more.
The ratio of the monomer (a6m) in (methyl) acrylate monomer (α 1) is preferably below the 30 quality %, more preferably below the 10 quality %.Be in above-mentioned scope by the ratio that makes 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 with organic acidic group (a6m) that can carry out copolymerization as required and can with the mixture of the monomer (a7m) of their copolymerization.The ratio of the monomer (a7m) in (methyl) acrylate monomer (α 1) is preferably below the 20 quality %, more preferably below the 15 quality %.
As the example of above-mentioned monomer (a7m), can list the monomer (a3m) that is used to synthesize (methyl) acrylic ester polymer (A1) and with as monomer (a4m) and the identical monomer of monomer shown in the example.Monomer (a7m) can be used alone, and also can be used in combination 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 its polymerization, preferably use polymerization starter.
As can be used for polymerization starter of the present invention, can list Photoepolymerizationinitiater initiater, azo is thermal polymerization, organo-peroxide thermal polymerization etc.Consider from the viewpoint of the excellent cementability of the thermal conductivity pressure-sensitive adhesive composite (F) of giving gained and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) etc., preferably use the organo-peroxide thermal polymerization.
As Photoepolymerizationinitiater initiater, can use known various Photoepolymerizationinitiater initiater.Wherein, be preferably the acylphosphine oxide based compound.As the acylphosphine oxide based compound of preferred Photoepolymerizationinitiater initiater, can list two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxides, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.
As azo is thermal polymerization, can list 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
As the organo-peroxide thermal polymerization, can list: hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1 that tertbutyl peroxide is such, two (the t-butylperoxy ketonic oxygen base) hexanes, 1 of 6-, two (t-butyl peroxy)-3 of 1-, 3, the superoxide that the 5-trimethylcyclohexanone is such etc.Wherein, do not emit the initiator of the volatile matter of the reason that becomes foul smell during preferred thermolysis.In addition, preferred 1 minute half life temperature is more than 100 ℃ and the initiator below 170 ℃ among the organo-peroxide thermal polymerization.
The consumption of polymerization starter is with respect to (methyl) acrylic acid resin composition (A) 100 mass parts, be preferably above 10 mass parts of 0.01 mass parts following, more preferably above 5 mass parts of 0.1 mass parts following, more preferably below above 1 mass parts of 0.3 mass parts.Be in above-mentioned scope by the consumption that makes polymerization starter, can be easy to make the polymerisation conversion of (methyl) acrylate monomer blend (α 1) to be in suitable scope, be easy to prevent that residual monomer is smelly in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).In addition, the polymerisation conversion of (methyl) acrylate monomer (α 1) is preferably more than the 95 quality %.If the polymerisation conversion of (methyl) acrylate monomer (α 1) is more than the 95 quality %, be easy to then prevent that residual monomer is smelly in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).In addition, be in above-mentioned scope by the consumption that makes polymerization starter, can prevent from excessively to carry out owing to the interpolation polymerization starter brings out polyreaction, the result causes thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) not become level and smooth sheet, cause material damage.
＜multi-functional monomer＞
Preferably in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), also use multi-functional monomer.As multi-functional monomer, the monomer that use can be carried out copolymerization with the monomer that is included in (methyl) acrylate monomer (α 1).In addition, preferred multi-functional monomer has a plurality of polymerizability unsaturated link(age)s, has this unsaturated link(age) endways.By using so multi-functional monomer, in co-polymer, import intramolecularly and/or intermolecular cross-linking, can improve 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).
Usually, even do not use multi-functional monomer when polymerizations such as free radical thermopolymerization, crosslinking reaction also can be carried out to a certain degree.Yet,, preferably use multi-functional monomer for more definitely and make its crosslinking structure that forms desirable amount.
As multi-functional monomer, for example can use, 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; 2, two (the trichloromethyl)-6-of 4-are unsaturated aromatic ketone etc. to replacement triazine such as methoxy styrene-5-triazine and the such monoene key of 4-acryloxy benzophenone.Wherein, preferred tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate.Multi-functional monomer can be used alone, and also can be used in combination two or more.
The multi-functional monomeric amount of using in thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is with respect to acrylic acid resin composition (A) 100 mass parts, be preferably above 15 mass parts of 0.1 mass parts following, more preferably above 8 mass parts of 0.2 mass parts following, more preferably below above 2 mass parts of 0.5 mass parts.By making multi-functional monomeric consumption 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) suitable cohesive force as pressure adhesive.
＜thermal conductivity filler (B)＞
Use thermal conductivity filler (B) in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Thermal conductivity filler (B) is can be by adding the filler of the thermal conductivity that improves thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), and median size is below the 50 μ m.Wherein, consider from the viewpoint that is easy to make thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) possess insulativity, preferably than the lower filler of aftermentioned zinc oxide (C) electroconductibility.
As the object lesson of thermal conductivity filler (B), can list lime carbonate, aluminium hydroxide, magnesium hydroxide, aluminum oxide (alumina), magnesium oxide, silicon oxide, glass fibre, boron nitride and aluminium nitride etc.Wherein, because therefore lime carbonate, aluminium hydroxide and aluminum oxide acquisition easily, chemical stabilization and compounding that can be a large amount of are preferred, preferred especially aluminum oxide and aluminium hydroxide.Thermal conductivity filler (B) can be used alone, and also can be used in combination two or more.
The median size of the thermal conductivity filler (B) that uses among the present invention in addition, is below the 50 μ m.The preferred range of the median size of thermal conductivity filler (B) infers that as described below its size with zinc oxide (C) is also relevant, but for example be preferably 30 μ m following, more preferably 10 μ m following, more preferably below the above 10 μ m of 0.5 μ m.As described below, be in above-mentioned scope by the median size that makes thermal conductivity filler (B), with aftermentioned zinc oxide (C) combination, can give thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity.
The amount of the thermal conductivity filler (B) that uses in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is below above 1400 mass parts of 600 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.The upper limit of the content of thermal conductivity filler (B) is preferably 1300 mass parts, 1200 mass parts more preferably.On the other hand, the lower limit of the content of thermal conductivity filler (B) is preferably 700 mass parts, 800 mass parts more preferably.Be in above-mentioned scope by the content that makes thermal conductivity filler (B),, can give thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity with aftermentioned zinc oxide (C) combination.On the other hand, when the content of thermal conductivity filler (B) surpasses 1400 mass parts, the viscosity of blend compositions that becomes 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 the tendency of shape servo-actuated reduction is arranged.If shape servo-actuated reduction, then becoming is difficult to conduct heat to radiator from heating element.In addition, if thermal conductivity filler (B) contain quantity not sufficient 600 mass parts, the inadequate worry of effect that then exists the thermal conductivity that makes thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) to improve.
＜zinc oxide (C)＞
The length that the zinc oxide that uses among the present invention (C) has needle-like portion and this needle-like portion is below the above 50 μ m of 2 μ m.As described below, the length of the needle-like portion by making zinc oxide (C) is in above-mentioned scope, with thermal conductivity filler (B) combination, can give thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity.
The zinc oxide that uses among the present invention (C) has needle-like portion and gets final product, and can possess one or more needle-like portion around nuclear part, also constituting by needle-like portion only.But, be easy to the viewpoint consideration that is connected by zinc oxide (C) as described later between some thermal conductivity fillers (B) of filling in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) and other the thermal conductivity filler (B), the preferred a plurality of needle-like of possessing on every side of the part portion of examining, these needle-like portions extend to each different direction.More preferably, have nuclear part and be present in the needle-like portion more than three around it, it is desirable among the described needle-like portion at least one and other needle-like portions not at grade.In addition, the quantity of the needle-like portion that exists around a nuclear 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 being connected of other fillers.Commercially available product as the zinc oxide of examining a plurality of needle-like of possessing of part portion on every side for example can list " the パ Na テ ト ラ (registered trademark) " of the ア of Co., Ltd. system テ ッ Network system.
The amount of the zinc oxide (C) that uses in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is with respect to (methyl) acrylic acid resin composition (A) 100 mass parts, be above 40 mass parts of 0.5 mass parts following, be preferably above 10 mass parts of 0.5 mass parts following, more preferably below above 5 mass parts of 0.5 mass parts.Be in above-mentioned scope by the content that makes zinc oxide (C),, can give thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) high thermal conductivity with thermal conductivity filler (B) combination.On the other hand, if the content of zinc oxide (C) surpasses 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 exists in the worry that can't use in the purposes that requires insulativity.In addition, if zinc oxide (C) contain quantity not sufficient 0.5 mass parts, the inadequate worry of effect that then exists the thermal conductivity that makes thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) to improve.
According to the present invention, by thermal conductivity filler (B) and zinc oxide (C) are used in combination with specified amount, even the consumption of thermal conductivity filler (B) and zinc oxide (C) than in the past thermal conductivity pressure-sensitive adhesive sheet-like formed body still less, also can access thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) that balance possesses thermal conductivity and insulativity well respectively.
By being used in combination thermal conductivity 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: be filled between some thermal conductivity fillers (B) and other thermal conductivity fillers (B) in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) and be connected by zinc oxide (C), thus, heat is easy to conduction in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Usually, add in order to improve thermal conductivity under the situation of thermal conductivity filler,, think that the particle diameter of this thermal conductivity filler is better greatly from being easy to improve the viewpoint of thermal conductivity.Yet, as mentioned above, discoveries such as the inventor, by the thermal conductivity filler (B) below the median size that is used in combination regulation with have the zinc oxide (C) of the needle-like portion of specified length, can improve the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Infer this be because: be in below the value of regulation by the median size that makes thermal conductivity filler (B), being filled in becomes between some thermal conductivity fillers (B) and other thermal conductivity fillers (B) in thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is easy to the cause that is connected by zinc oxide (C).Therefore, infer that in the present invention the relation between the length of the needle-like portion of the particle diameter of thermal conductivity filler (B) and zinc oxide (C) is influential to the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
In addition, by being used in combination the thermal conductivity that thermal conductivity filler (B) and zinc oxide (C) can improve thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), suppressing insulativity simultaneously reduces, infer that this is not because only zinc oxide (C) connects and the thermal conductivity of raising thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), but because have the thermal conductivity filler (B) lower between some zinc oxide (C) and other zinc oxide (C) with being mingled with than zinc oxide (C) electroconductibility.
＜phosphoric acid ester＞
Can also use phosphoric acid ester in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).By using phosphoric acid ester, be easy to improve the flame retardant resistance of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
Viscosity under preferred 25 ℃ of the phosphoric acid ester of using among the present invention is as more than the 3000mPa s.Be in above-mentioned scope by the viscosity that makes phosphoric acid ester, be easy to prevent the formability variation of thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).In addition, " viscosity " of phosphoric acid ester is meant among the present invention, the viscosity that the method by following explanation is measured.
(viscosity measurement of phosphoric acid ester)
The viscosimetric analysis of phosphoric acid ester uses Brookfield viscometer (Tokyo Keiki Inc.'s system) to carry out according to following steps.
(1) under the environment of normal temperature, measures phosphoric acid ester 300ml and pack in the container of 500ml.
(2) from stirring, select any to be installed on the viscometer with the rotor No.1,2,3,4,5,6,7.
(3) container that phosphoric acid ester will be housed is as for the viscometer top, and rotor is sunken in the condensed phosphoric acid esters in this container.At this moment, just in time make its sinking with the indenture that becomes mark of rotor in the mode at the aqueous interface of phosphoric acid ester.
(4) rotating speed is selected among 20,10,4,2.
(5) open the stirring switch, read the numerical value after 1 minute.
(6) numerical value that reads multiply by coefficient A, with the value calculated as viscosity ［ mPa s ］.
In addition, coefficient A is as shown in table 1 below, by rotor No. that selects and rotating speed decision.
[table 1]
Figure 760876DEST_PATH_IMAGE001
In addition, the phosphoric acid ester of using among the present invention preferred under atmospheric pressure be liquid more than 15 ℃ in the temperature province below 100 ℃ always.If phosphoric acid ester is a liquid when mixing, then operability is good, easily moulding thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).When moulding comprised the thermal conductivity pressure-sensitive adhesive composite (F) of phosphoric acid ester or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), each material that preferably will constitute thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) under the environment below 100 ℃ more than 15 ℃ mixed.Temperature when mixing by making is in above-mentioned scope, be more than the second-order transition temperature of acrylic acid resin composition (A), be easy to prevent the volatilization or the careless polymerization reaction take place of monomer contained in the acrylic acid resin composition (A) etc., therefore can make environment and operability good.
Among the present invention,, condensed phosphoric acid esters can be used, also non-condensed phosphoric acid esters can be used as phosphoric acid ester.So-called " condensed phosphoric acid esters " is meant that 1 molecular memory is at a plurality of phosphoric acid ester position herein, and " non-condensed phosphoric acid esters " is meant, only there is a phosphoric acid ester position in 1 intramolecularly.The object lesson of phosphoric acid ester that satisfies thus much illustrated condition is as follows.
As the object lesson of condensed phosphoric acid esters, can list: 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester), the two aromatic condensation phosphoric acid ester such as (diphenyl phosphoesters) of Resorcinol; Halogens such as the two dichloro alkyl phosphates of polyoxy alkylidene are condensed phosphoric acid esters; The non-halogen of non-aromatic is condensed phosphoric acid esters; Deng.In the middle of these,, unharmful substance (halogen etc.) less from proportion emit danger, aspects such as acquisitions are considered easily, optimization aromatic condensed phosphoric acid esters, more preferably 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane pair (diphenyl phosphoester).
Object lesson as non-condensed phosphoric acid esters, can list: triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, tricresyl phosphate base diphenyl, tricresyl phosphate base-2, aromatic phosphoric esters such as 6-diformazan phenyl ester, phosphoric acid 2-ethylhexyl diphenyl; Halogens such as three (β-chloropropyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, three (tribromo neo-pentyl) phosphoric acid ester are phosphoric acid ester; Deng.Wherein, never produce objectionable impurities aspects such as (halogens etc.) and consider the optimization aromatic phosphoric acid ester.
Phosphoric acid ester can be used alone, and also can be used in combination two or more.
The amount of the phosphoric acid ester of using in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is preferably below above 100 mass parts of 20 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.Be in above-mentioned scope by the content that makes phosphoric acid ester, be easy to improve the flame retardant resistance of thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
＜other additives＞
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) except mentioned component, in the scope that does not hinder the above-mentioned effect that plays by the interpolation mentioned component, can also add known various additive.As known additive, can list: whipping agent (comprises frothing aid.); Flame retardant resistance heat conduction mineral compound such as the oxyhydroxide of metal, metal salt hydrates; Glass fibre; Thermal conductivity mineral compound such as expanded graphite powder, aluminum oxide, PITCH based carbon fiber; Outside linking agent; Face such as carbon black, titanium dioxide material; Other packing materials such as clay; Nanoparticle such as soccerballene, carbon nanotube; Antioxidants such as polyphenol system, quinhydrones system, hindered amine system; Thickening materials such as acrylic acid polymer particle, particulate oxide silicon, magnesium oxide; Deng.
2. manufacture method
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) can be by after the material mixing that will thus much describe, carry out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and/or comprise the structural unit that is 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 of the present invention (F) comprising: the operation of making following blend compositions; And in this blend compositions, carry out the polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and/or comprise the operation of crosslinking reaction of the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) that comprises (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be thermal conductivity filler (B) below the 50 μ m; With the length with needle-like portion and this needle-like portion be the zinc oxide (C) below the 50 μ m more than the 2 μ m.In addition, the preferred median size that preferably contains ratio, each material of other spendable materials, each material etc. are omitted the explanation to it as mentioned above.
In the manufacture method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F), when carrying out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and/or comprising the crosslinking reaction of polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), preferably heat.This heating for example can be used, hot blast, electric heater, infrared rays etc.The Heating temperature of this moment is preferably and makes polymerization starter efficient decompose well, carries out (methyl) acrylate monomer (α 1) and multi-functional monomeric polymeric temperature.Temperature range is according to the kind of the polymerization starter that uses and difference, is preferably more than 100 ℃ below 200 ℃, more preferably more than 130 ℃ below 180 ℃.
Thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G) can carry out mixing moulding by the material that will thus much be illustrated to be after the sheet or to be shaped to the flaky while, Yi Bian carry out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and/or comprise the structural unit that is 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 of the present invention (G) comprising: the operation of making blend compositions; And blend compositions is shaped to after the sheet, perhaps blend compositions is being shaped to the flaky while, carry out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and/or comprise the operation of crosslinking reaction of the polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), wherein, described blend compositions comprises: (methyl) acrylic acid resin composition (A) that comprises (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With median size be thermal conductivity filler (B) below the 50 μ m; With the length with needle-like portion and this needle-like portion be the zinc oxide (C) below the 50 μ m more than the 2 μ m.In addition, the preferred median size that preferably contains ratio, each material of other spendable materials, each material etc. are omitted the explanation to it as mentioned above.
In the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G), when carrying out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and/or comprising the crosslinking reaction of polymkeric substance of the structural unit that is derived from (methyl) acrylate monomer (α 1), preferably heat.This heating for example can be used, hot blast, electric heater, infrared rays etc.The Heating temperature of this moment is preferably and makes polymerization starter efficient decompose well, carries out (methyl) acrylate monomer (α 1) and multi-functional monomeric polymeric temperature.Temperature range is according to the kind of the polymerization starter that uses and difference, is preferably more than 100 ℃ below 200 ℃, more preferably more than 130 ℃ below 180 ℃.
Above-mentioned blend compositions is shaped to flaky method, and there is no particular limitation.As preferable methods, for example can list blend compositions is coated on through the casting method (キ ャ ス ト method) on the operation paper such as polyester film of lift-off processing, blend compositions is clipped in two if required through making it pass through the method between the roller between the operation paper of lift-off processing and use forcing machine, come the method etc. of control thickness when extruding blend compositions by mould (ダ イ ス).
The thickness that can make thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is below the above 5mm of 0.05mm.By making the thickness attenuation 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) is reduced.Consider that 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.By making thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) for more than the 0.05mm, be involved in air when being easy to prevent be attached to this thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) on heating element and the radiator, its result, be easy to prevent the increase of thermal resistance, make the operability that attaches in the operation to adherend become good easily.
In addition, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can also be at the single face or the double-faced forming of base material.There is no particular limitation to the material that constitutes this base material.As the object lesson of this base material, can list: the paper tinsel shape thing of the metal of excellent thermal conductivity such as aluminium, copper, stainless steel, beryllium copper and alloy, heat-conductive silicone etc. himself comprise the flap of the polymkeric substance of excellent thermal conductivity, the thermal conductivity plastic film that contains the thermal conductivity additive, various non-woven fabrics, woven fiber glass, honeycomb structured body etc.As plastic film, can use thermally stable polymer films such as polyimide, polyethylene terephthalate, PEN, tetrafluoroethylene, polyetherketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfones, polyphenylene sulfide, polyamidoimide, polyester-imide, aromatic polyamide.
3. make use-case
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be used as the part of electronic unit and use.At this moment, also can be directly moulding on the such base material of radiator, provide as the part of electronic unit.As the object lesson of this electronic unit, can list have electroluminescent (EL), equipment, parts that 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 of the parts in the equipment of photodiode (LED) light source around the heating portion, automobile etc. have heating portion.
In addition, the example of the using method in electronics as thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can list: with led light source as concrete example, using method as described below.That is, directly be attached on the led light source; Be clipped between led light source and the 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 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.Purposes example as led light source can list: the back lighting device (TV, mobile phone, PC, notebook PC, PDA etc.) with display unit of permeation type liquid crystal panel; Lamps apparatus for vehicle; Industrial illumination; Commercial with illumination; General dwelling house is with throwing light on; Deng.
In addition, can be listed below as the object lesson beyond the led light source.That is PDP panel; IC heating portion; Cold-cathode tube (CCFL); Organic EL light source; Inorganic EL light source; The 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 the casing that is attached to device as the using method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).For example, for the device that in automobile etc., uses, be attached to the inside of the casing that automobile possesses; Be attached to the outside of the casing that automobile possesses; The heating portion (auto-navigation system/fuel cell/heat exchanger) and this casing that connect the inside of the casing that automobile possessed; Attach on the heating panel that the heating portion (auto-navigation system/fuel cell/heat exchanger) of the inside of the casing that is possessed with automobile is connected; Deng.
In addition, except automobile, also can use the same method and use thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).As its object, for example can list: PC; Dwelling house; TV; Mobile phone; Vending machine; Refrigerator; Solar cell; Surface-conduction-electron emission display (SED); OLED display; Inorganic EL indicating meter; Organic EL illumination; Inorganic EL illumination; OLED display; Notebook computer; PDA; Fuel cell; Semiconductor device; Electric cooker; Washing machine; Scrubbing-and-drying unit; Made up the optical semiconductor device of optical semiconductor and fluor; Various power devices; Game machine; Electrical condenser; Deng.
And then thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) are not limited only to above-mentioned using method, can also use in other method according to purposes.For example, can list: use for 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) use as solar cell; Between the back seat of solar cell and top, use; Use inboard at the thermofin of vending machine inside; In the casing inside of organic EL illumination, use with siccative, moisture adsorbent; The heat-conducting layer of the casing inside of organic EL illumination with and above, use with siccative, moisture adsorbent; The heat-conducting layer of the casing inside of organic EL illumination, heat dissipating layer, with and above, use with siccative, moisture adsorbent; The heat dissipating layer of the heat-conducting layer of the casing inside of organic EL illumination, epoxy system, with and above, use with siccative, moisture adsorbent; For for cooling-parts such as the device that makes the cooling of people, animal, clothing, towel, sheet materials, on the face opposite, use with health; On the pressure-producing part of the stationary installation of carrying on the image processing systems such as electronic photo duplicating machine, electrophotographic printer; Pressure-producing part as the stationary installation of carrying on image processing systems such as electronic photo duplicating machine, electrophotographic printer uses; Hot-fluid control as the process object of carrying film forming apparatus is used with heat-conducting part; On controlling with heat-conducting part, uses the hot-fluid of the process object of carrying film forming apparatus; Between the skin of radioactive substance storing container and inside, use; In the casing that is provided with the solar panel that absorbs sunlight, use; Between CCFL reflective sheet backlight and aluminium cabinet, use; Deng.
Embodiment
The present invention will be described in more detail below to utilize embodiment, but the present invention is not subjected to the qualification of embodiment.In addition, " portion ", " % " that herein uses do not having to represent quality criteria under the situation of specified otherwise.
＜mobile＞
Estimate flowability through the blend compositions of aftermentioned the 1st and the 2nd mixed processes gained.Particularly, will Hobart's container (ホ バ ー ト container of blend compositions be housed) be inclined relative to horizontal 30 °, estimate with the state of this blend compositions after 1 minute.It the results are shown in table 2 and table 3.Blend compositions along the situation of oblique flow be made as " zero ", motionless situation is made as " * ".Blend compositions has mobile being easy to this blend compositions sheet materialization.That is, be easy to make thermal conductivity pressure-sensitive adhesive sheet-like formed body.
＜volume specific resistance (insulativity)＞
The test film that preparation will become the size of 80mm * 80mm to form with the thermal conductivity pressure-sensitive adhesive sheet material severing that the aftermentioned method is made.Test film is placed on digital ultra-high resistance/pettiness rheometer (trade(brand)name " 8340A ", the エ ー デ ィ ー シ ー of Co., Ltd. system), feeds electric current, measure resistivity at the two ends, the left and right sides of this test film.Voltage begins slowly to reduce to the voltage that can measure from 500V, determines the resistivity that can measure under the voltage.In addition, the duration of charging was made as 1 minute.Carry out this mensuration 3 times, with the volume specific resistance (unit: Ω cm) of its mean value as thermal conductivity pressure-sensitive adhesive sheet material.The results are shown in table 2 and table 3.If the result who obtains by this evaluation is 1.0 * 10 10More than the Ω cm, then we can say the insulativity excellence.
＜cooling performance＞
The test film that preparation will become the size of 25mm * 25mm to form with the thermal conductivity pressure-sensitive adhesive sheet-like formed body severing that aftermentioned is made.Test film is attached on the aluminium sheet of 150mm * 150mm * thickness 3mm, with double faced adhesive tape with miniature ceramic heater (Sakaguchi Dennetsu Kabushiki Kaisha's system, trade(brand)name: MS-5,25mm * 25mm) be fixed on test film be attached at the 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 the contact type voltage regulator, takes the surface of the miniature ceramic heater of heating in the time of 60 minutes under 60W with thermal imager.The top temperature of this moment is shown in table 2 and table 3.The explanation of this temperature step-down has been conducted more heat from miniature ceramic heater to aluminium sheet, therefore we can say that this temperature is low more, and the thermal resistance of thermal conductivity pressure-sensitive adhesive sheet-like formed body is low more.In addition, this evaluation is carried out under 23 ℃ of atmosphere.
(embodiment 1)
In reactor, add 100 parts of the monomer mixtures formed by 2-EHA 94% and vinylformic acid 6%, 2,700 parts of 0.03 part of 2 '-Diisopropyl azodicarboxylate and ethyl acetate, make its uniform dissolution, under 80 ℃, carry out 6 hours polyreaction behind the nitrogen replacement.Polymerisation conversion is 97%.The polymkeric substance of gained is carried out drying under reduced pressure make the ethyl acetate evaporation, obtain (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 as the gel permeation chromatography of elutriant tetrahydrofuran (THF) with the polystyrene standard conversion.
Then, (brief note is " 2EHA " in table 2 and table 3 for 1.0 parts of multi-functional monomers that pentaerythritol triacrylate, tetramethylol methane tetraacrylate and pentaerythritol diacrylate formed with the mixed of 60:35:5 with the weighing of electronics Libra and 2-EHA.) (1, (half life temperature was 150 ℃ to two (the t-butylperoxy ketonic oxygen base) hexanes of 6-in 1 minute for 88 parts and organo-peroxide thermal polymerization.)) 1.0 parts, these are mixed for 13 parts with above-mentioned (methyl) acrylic ester polymer (A1-1).(the little flat making of Co., Ltd. is made, trade(brand)name " ACM-5LVT type ", capacity: 5L) to use thermostatic bath (Toki Sangyo Co., Ltd.'s system, trade(brand)name " PVC ス コ メ イ ト 150III ") and Hobart's mixing tank during mixing.The temperature control of Hobart's container is set at 60 ℃, rotating speed scale and is made as 3 and stirred 10 minutes.This operation is called the 1st mixed processes.
Then, 50 parts of weighing 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 isopropylation thing ") and aluminum oxide (Showa Denko K. K's system, trade(brand)name " AL-47-H ", median size: 2 μ m, BET specific surface area: 1.1m 2/ g) 2 parts in 1000 parts and zinc oxide (ア of Co., Ltd. system テ ッ Network system, パ Na テ ト ラ WZ-0511) drops in above-mentioned Hobart's container, and the temperature control of Hobart's container is set at 60 ℃, and the rotating speed scale is made as 5 and stirred 10 minutes.This operation is called the 2nd mixed processes.
Then, will through the above-mentioned the 1st and the blend compositions of the 2nd mixed processes gained drop on the demoulding PET film, on this blend compositions, further cover demoulding PET film.Making blend compositions be held on this duplexer that demoulding PET film forms, is between two rollers of 0.3mm by spacing, forms sheet.Then, this duplexer is put in the baking oven, 150 ℃ were heated 15 minutes down.By this heating process, make acrylate monomer generation polymerization and crosslinking reaction, (following only note is made " sheet material " to obtain thermal conductivity pressure-sensitive adhesive sheet-like formed body.）（G1）。In addition, the levels of residual monomers from sheet material (G1) calculates the polymerisation conversion of (methyl) acrylate monomer, and the result is 99.9%.
(embodiment 2 ~ 6 and comparative example 1 ~ 6)
With the formula change of each material is shown in table 2 and the table 3, and operation similarly to Example 1 obtains sheet material (G2 ~ 6, GC1 ~ 6) in addition.
The additive that is illustrated so far that uses in embodiment 2 ~ 6 and the comparative example 1 ~ 6 is as follows.
Aluminium hydroxide (Nippon Light Metal Co., Ltd's system, trade(brand)name " BF-083 ", median size: 8 μ m, 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 μ m, BET specific surface area: 0.8m 2/ g
[table 2]
[table 3]
As shown in table 2, the sheet material among the embodiment (G1) ~ (G6), the flowability of the blend compositions before the sheet materialization is all good, the volume specific resistance height of this sheet material after the sheet materialization, cooling performance excellence.On the other hand, as shown in table 3, the above-mentioned performance inequality of the sheet material in the comparative example (GC1) ~ (GC6).Particularly, as follows.
Comparative example 1: the sheet material (GC1) of the comparative example 1 of oxygen-free zinc, cooling performance is poor.
Comparative example 2: the sheet material (GC2) of the comparative example that contains the scope of stipulating among quantity not sufficient the present invention 2 of zinc oxide, cooling performance is poor.
Comparative example 3: the content of zinc oxide surpasses the sheet material (GC3) of the comparative example 3 of the scope of stipulating among the present invention, and volume specific resistance reduces.
Comparative example 4: the sheet material (GC4) of the comparative example that contains the scope of stipulating among quantity not sufficient the present invention 4 of thermal conductivity filler, cooling performance is poor.
Comparative example 5: the content of thermal conductivity filler surpasses the sheet material (GC5) of the comparative example 5 of the scope of stipulating among the present invention, and the blend compositions before the sheet materialization does not have flowability, can't carry out sheet materialization.
Comparative example 6: used the sheet material (GC6) of comparative example 6 of the thermal conductivity filler of the particle diameter bigger than the scope of stipulating among the present invention, cooling performance is poor.

Claims (13)

1. thermal conductivity pressure-sensitive adhesive composite (F), it carries out polyreaction in following blend compositions and crosslinking reaction forms, and wherein, described blend compositions comprises:
(methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below above 1400 mass parts of following thermal conductivity filler (B) 600 mass parts of 50 μ m; With
Length with needle-like portion and this needle-like portion is below following above 40 mass parts of zinc oxide (C) 0.5 mass parts of the above 50 μ m of 2 μ m,
Wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is described (methyl) acrylic ester polymer (A1) and/or the crosslinking reaction that comprises the polymkeric substance of the structural unit that is derived from described (methyl) acrylate monomer (α 1).
2. according to right 1 described thermal conductivity pressure-sensitive adhesive composite (F), wherein, described blend compositions also comprises the following phosphoric acid ester of above 100 mass parts of 20 mass parts.
3. thermal conductivity pressure-sensitive adhesive composite according to claim 1 and 2 (F), wherein, median size is that the following described thermal conductivity filler (B) of 50 μ m is that median size is following aluminum oxide and/or aluminium hydroxides of 50 μ m.
4. thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), it is that following blend compositions is shaped to after the sheet, perhaps described blend compositions is being shaped to the flaky while, carries out that polymer reaction and crosslinking reaction form, wherein, described blend compositions comprises:
(methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below above 1400 mass parts of following thermal conductivity filler (B) 600 mass parts of 50 μ m; With
Length with needle-like portion and this needle-like portion is below following above 40 mass parts of zinc oxide (C) 0.5 mass parts of the above 50 μ m of 2 μ m,
Wherein, described polyreaction is the polyreaction of described (methyl) acrylate monomer (α 1), and described crosslinking reaction is described (methyl) acrylic ester polymer (A1) and/or the crosslinking reaction that comprises the polymkeric substance of the structural unit that is derived from described (methyl) acrylate monomer (α 1).
5. thermal conductivity pressure-sensitive adhesive sheet-like formed body according to claim 4 (G), wherein, described blend compositions also comprises the following phosphoric acid ester of above 100 mass parts of 20 mass parts.
6. according to claim 4 or 5 described thermal conductivity pressure-sensitive adhesive sheet-like formed bodies (G), wherein, median size is that the following described thermal conductivity filler (B) of 50 μ m is that median size is following aluminum oxide and/or aluminium hydroxides of 50 μ m.
7. the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), this method comprises:
Make the operation of following blend compositions; And
In described blend compositions, carry out the polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and/or comprise the operation of crosslinking reaction of the polymkeric substance of the structural unit that is derived from described (methyl) acrylate monomer (α 1)
Wherein, described blend compositions comprises:
(methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below above 1400 mass parts of following thermal conductivity filler (B) 600 mass parts of 50 μ m; With
Length with needle-like portion and this needle-like portion is below following above 40 mass parts of zinc oxide (C) 0.5 mass parts of the above 50 μ m of 2 μ m.
8. the manufacture method of thermal conductivity pressure-sensitive adhesive composite according to claim 7 (F), wherein, described blend compositions also comprises the following phosphoric acid ester of above 100 mass parts of 20 mass parts.
9. according to the manufacture method of right 7 or 8 described thermal conductivity pressure-sensitive adhesive composites (F), wherein, median size is that the following described thermal conductivity filler (B) of 50 μ m is that median size is following aluminum oxide and/or aluminium hydroxides of 50 μ m.
10. the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), this method comprises:
Make the operation of following blend compositions; And
Described blend compositions is shaped to after the sheet, perhaps described blend compositions is being shaped to the flaky while, carry out the polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and/or comprise the operation of crosslinking reaction of the polymkeric substance of the structural unit that is derived from described (methyl) acrylate monomer (α 1)
Wherein, described blend compositions comprises:
(methyl) acrylic acid resin composition (A) 100 mass parts that comprise (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); With
Median size is below above 1400 mass parts of following thermal conductivity filler (B) 600 mass parts of 50 μ m; With
Length with needle-like portion and this needle-like portion is below following above 40 mass parts of zinc oxide (C) 0.5 mass parts of the above 50 μ m of 2 μ m.
11. the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body according to claim 10 (G), wherein, described blend compositions also comprises the following phosphoric acid ester of above 100 mass parts of 20 mass parts.
12. according to the manufacture method of claim 10 or 11 described thermal conductivity pressure-sensitive adhesive sheet-like formed bodies (G), wherein, median size is that the following described thermal conductivity filler (B) of 50 μ m is that median size is following aluminum oxide and/or aluminium hydroxides of 50 μ m.
13. electronic unit, it possesses: radiator and be fitted in each described thermal conductivity pressure-sensitive adhesive composite (F) in the claim 1 ~ 3 on this radiator or, radiator and be fitted in each described thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) in the claim 4 ~ 6 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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