CN102741372A - Thermally conductive pressure-sensitive adhesive composition,thermally conductive pressure-sensitive adhesive sheet,and electronic component - Google Patents

Thermally conductive pressure-sensitive adhesive composition,thermally conductive pressure-sensitive adhesive sheet,and electronic component Download PDF

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Publication number
CN102741372A
CN102741372A CN2011800090271A CN201180009027A CN102741372A CN 102741372 A CN102741372 A CN 102741372A CN 2011800090271 A CN2011800090271 A CN 2011800090271A CN 201180009027 A CN201180009027 A CN 201180009027A CN 102741372 A CN102741372 A CN 102741372A
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China
Prior art keywords
thermal conductivity
mass parts
pressure sensitive
methyl
sheet
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CN2011800090271A
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Inventor
熊本拓朗
西冈亮子
川村明子
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Zeon Corp
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Nippon Zeon Co Ltd
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Publication of CN102741372A publication Critical patent/CN102741372A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—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
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Materials Engineering (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Wood Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
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  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

Disclosed are a thermally conductive pressure-sensitive adhesive sheet which has a high thermal conductivity,a good flame retardancy and a high electric breakdown strength in a well-balanced manner,a thermally conductive pressure-sensitive adhesive composition to be used as a base of said sheet,and an electronic component provided with said sheet. Specifically disclosed are:a thermally conductive pressure-sensitive adhesive composition (F) which comprises 100 parts by mass of at least one kind of a polymer (S),1.8-18 parts by mass inclusive of an expanded graphite powder (B),20-130 parts by mass inclusive of a phosphoric acid ester (C) which has a viscosity at 25oC of 3000 mPa.s or above and exists as a liquid within a temperature range of 15-100oC inclusive under atmospheric pressure,100-1000 parts by mass inclusive of alumina (E) having a BET specific surface area of 1 m2/g or above, and 160-600 parts by mass inclusive of flame-retardant thermally conductive inorganic compound(s) (D) excluding the expanded graphite powder (B) and the alumina (E) having a BET specific surface area of 1 m2/g or above;a thermally conductive pressure-sensitive adhesive sheet (G) comprising said thermally conductive pressure-sensitive adhesive composition (F);and an electronic component provided with said sheet.

Description

Thermal conductivity pressure sensitive adhesive compositions, thermal conductivity pressure sensitive glueyness sheet and electron device
Technical field
Thermal conductivity pressure sensitive glueyness sheet that the present invention relates to the thermal conductivity pressure sensitive adhesive compositions, is shaped by this thermal conductivity pressure sensitive adhesive compositions and electron device with this sheet material.
Background technology
In recent years, these electron-like devices such as plasma display panel (PDP), unicircuit (IC) chip are along with its high performance, and thermal value is also increasing.Consequently, must seek measure and deal with the dysfunction that rises and caused by temperature.Usually the method for taking is to dispel the heat through radiators such as metal scatterer, heating panel, radiator element are installed on heating elements such as electron device.In order to carry out using various conducting strips from the heat conduction of heating element to radiator effectively, and generally speaking, thermal conductivity pressure sensitive glueyness sheet is necessary in the purposes of fixedly heating element and radiator.
For this thermal conductivity pressure sensitive glueyness sheet, except requiring adhesivity, the thermal conductivity, but also requiring other performance (flame retardant resistance, dielectric breakdown strength, flexibility etc.) of adapting with purposes.Known to seek to improve the performance of the such flat member of thermal conductivity pressure sensitive glueyness sheet, and in the raw material combination thing that forms this sheet material, add various fillers.For example in patent documentation 1, disclose the resin combination that in thermoplastic resin, contains graphite particle and carbon fiber structure, put down in writing the intention that obtains excellent molding such as thermal diffusivity, processibility by this resin combination.
Patent documentation
Patent documentation 1: TOHKEMY 2008-150595 communique.
Summary of the invention
As stated, thermal conductivity pressure sensitive glueyness sheet also is asked to have except that adhesivity, performance the thermal conductivity according to purposes.Specifically, for electrical condenser that directly is attached to led light source, automobile etc. on purposes corresponding, and require the raising of dielectric breakdown strength.Further, flame retardant resistance also is asked to.But,, be difficult to provide the sheet of the thermal conductivity pressure sensitive glueyness with thermal conductivity, flame retardant resistance and dielectric breakdown strength for the prior art that comprises disclosed technology in the above-mentioned patent documentation 1.For example in order to seek the raising of thermal conductivity, flame retardant resistance, and considered to increase the addition of expanded graphite powder, but the problem that the thermal conductivity pressure sensitive glueyness sheet that contains the expanded graphite powder in a large number exists dielectric breakdown strength significantly to reduce etc.
Therefore, the object of the present invention is to provide the harmonious thermal conductivity pressure sensitive glueyness sheet that has thermal conductivity, flame retardant resistance and dielectric breakdown strength well, form thermal conductivity pressure sensitive adhesive compositions and the electron device of the raw material of this sheet material with this sheet material.
The inventor etc. make great efforts research for thermal conductivity pressure sensitive glueyness sheet; The result finds; Utilization contains sheet-like formed body aluminum oxide, thermal conductivity pressure sensitive adhesive compositions and this thermal conductivity pressure sensitive adhesive compositions of SULPHOSUCCINIC ACID ESTER and the regulation of expanded graphite powder, flame retardant resistance heat conduction mineral compound, regulation with specified amount; Can solve above-mentioned problem, thereby accomplish the present invention.
The 1st the present invention is thermal conductivity pressure sensitive adhesive compositions (F), and it contains at least a polymkeric substance (S) 100 mass parts, expanded graphite powder (B) 1.8 mass parts～18 mass parts, viscosity is that above and 15 ℃～100 ℃ the temperature province under atmospheric pressure of 3000mPa s is that SULPHOSUCCINIC ACID ESTER (C) 20 mass parts～130 mass parts, the BET specific surface area of liquid is 1m 25 ℃ the time 2Aluminum oxide (E) (following be recited as simply sometimes " aluminum oxide (E) ") 100 mass parts～1000 mass parts and flame retardant resistance heat conduction mineral compound (D) 160 mass parts～600 mass parts except that expanded graphite powder (B) and above-mentioned aluminum oxide (E) that/g is above.
In the 1st thermal conductivity pressure sensitive adhesive compositions of the present invention (F), preferred aluminum oxide (E) has a plurality of peaks in size-grade distribution, and the peak particle diameter of maximum particle diameter side is more than 10 with the ratio of the peak particle diameter of minimum grain size side.For the aluminum oxide (E) that obtains having in the size-grade distribution a plurality of peaks, having considered for example to make size-grade distribution is that normal distribution and median size different oxidation aluminium mix.Particle diameter in a plurality of peaks that particle diameter in a plurality of peaks that " the peak particle diameter of maximum particle diameter side " is meant in size-grade distribution to be had, in the maximum peak of particle diameter, " the peak particle diameter of minimum grain size side " are meant in size-grade distribution to be had, in the minimum peak of particle diameter.Like this, contain the aluminum oxide (E) that particle diameter has the particle of big difference, be easy to improve the dielectric breakdown strength and the thermal conductivity of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G) through use.
In the 1st thermal conductivity pressure sensitive adhesive compositions of the present invention (F), SULPHOSUCCINIC ACID ESTER (C) is preferably with forming the material that the SULPHOSUCCINIC ACID ESTER different with molecular weight mixes more than 2 kinds.Form the SULPHOSUCCINIC ACID ESTER different through using, be easy to improve the dielectric breakdown strength of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G) with molecular weight.
In the 1st thermal conductivity pressure sensitive adhesive compositions of the present invention (F), polymkeric substance (S) is (methyl) acrylic ester polymer (A1) preferably.In the present invention, " (methyl) vinylformic acid " is meant " vinylformic acid and/or methylacrylic acid ".Through making polymkeric substance (S) is (methyl) acrylic ester polymer (A1), when thermal conductivity pressure sensitive adhesive compositions (F) is formed thermal conductivity pressure sensitive glueyness sheet (G), is easy to give this thermal conductivity pressure sensitive glueyness sheet (G) tackiness flexibility.In addition, the monomer of (methyl) acrylic ester polymer is a liquid, therefore considers it also is preferred from the angle or the low-cost angle of easy handling.
In the 1st thermal conductivity pressure sensitive adhesive compositions of the present invention (F), (methyl) acrylic ester polymer (A1) preferably through other (methyl) acrylic ester polymer (AP1) in the presence of polymkeric substance that (methyl) acrylate monomer (α 1) polymerization is obtained.Through being aforesaid way, when following mixture (M) is formed thermal conductivity pressure sensitive glueyness sheet (G), can improve the plasticity of this thermal conductivity pressure sensitive glueyness sheet (G).
The 2nd the present invention is configured as the thermal conductivity pressure sensitive glueyness sheet (G) that sheet forms with the 1st thermal conductivity pressure sensitive adhesive compositions of the present invention (F).
The 2nd thermal conductivity pressure sensitive glueyness sheet of the present invention (G) preferably obtains as following: the two adds up to 100 mass parts, expanded graphite powder (B) 1.8 mass parts～18 mass parts, SULPHOSUCCINIC ACID ESTER (C) 20 mass parts～130 mass parts, aluminum oxide (E) 100 mass parts～1000 mass parts and is configured as sheet except that the mixture (M) of expanded graphite powder (B) and flame retardant resistance heat conduction mineral compound (D) 160 mass parts～600 mass parts the aluminum oxide (E) with (methyl) acrylic ester polymer (AP1) and (methyl) acrylate monomer (α 1); Meanwhile or after being configured as sheet, in the presence of (methyl) acrylic ester polymer (AP1) in mixture (M) (methyl) acrylate monomer (α 1) in the mixture (M) is carried out polymerization.
The 3rd the present invention is the electron device with the 2nd thermal conductivity pressure sensitive glueyness sheet of the present invention (G).
As the 3rd electron device of the present invention, can enumerate have electroluminescent cell (EL), power-equipment, fuel cell, solar cell, store battery, portable phone, PDA(Personal Digital Assistant), notebook computer, liquid crystal, surface-conduction-electron emission display (SED), plasma display panel (PDP) or the unicircuit (IC) etc. of instrument of photodiode (LED) light source, automobile etc.
According to the present invention, the harmonious thermal conductivity pressure sensitive glueyness sheet that has thermal conductivity, flame retardant resistance and dielectric breakdown strength well can be provided, form thermal conductivity pressure sensitive adhesive compositions and the electron device of the raw material of this sheet material with this sheet material.
Embodiment
1. thermal conductivity pressure sensitive adhesive compositions (F)
It is 1m that thermal conductivity pressure sensitive adhesive compositions of the present invention (F) contains at least a polymkeric substance (S), expanded graphite powder (B), SULPHOSUCCINIC ACID ESTER (C), BET specific surface area with specified amount 2The aluminum oxide (E) that/g is above and remove expanded graphite powder (B) and the BET specific surface area is 1m 2Flame retardant resistance heat conduction mineral compound (D) (following be expressed as simply sometimes " flame retardant resistance heat conduction mineral compound (D) ") outside the aluminum oxide (E) more than/g.Below describe for the essential substance that in thermal conductivity pressure sensitive adhesive compositions (F), contains or form.
＜polymkeric substance (S)＞
The material that constitutes polymkeric substance (S) does not have special qualification.In addition, in order thermal conductivity pressure sensitive adhesive compositions of the present invention (F) to be configured as sheet and to use as thermal conductivity pressure sensitive glueyness sheet (G), preferred polymers (S) has tackiness and/or adhesivity.In order to make polymkeric substance (S) have tackiness and/or adhesivity, polymkeric substance (S) is preferably selected from have tackiness and/or adhering material.But, also can in not having tackiness and/or adhering polymkeric substance (S), make up adhesion-tackiness additives and use.
Below enumerated the object lesson of the polymkeric substance (S) that uses among the present invention.
Can enumerate the conjugated diolefin polymer of tree elastomer, polybutadiene rubber, polyisoprene rubber etc.; Butyl rubber; Styrene butadiene random copolymer, styrene-isoprene random copolymers, styrene butadiene-isoprene random copolymers etc., aromatic ethenyl-conjugated diolefine random copolymers; Styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene butadiene-isoprene block copolymer, SIS etc., aromatic ethenyl-conjugated diene block copolymer; The hydrogenation thing hydrogenation thing of styrene-butadiene copolymer etc., aromatic ethenyl-conjugated diene copolymer; Acrylonitrile-butadiene copolymer rubber, vinyl cyanide-isoprene copolymer rubber etc., vinyl cyanide based compound-conjugated diene copolymer; The hydrogenation thing hydrogenation thing of acrylonitrile butadiene copolymer etc., vinyl cyanide based compound-conjugated diene copolymer; Vinyl cyanide base-aromatic ethenyl-conjugated diene copolymer; The hydrogenation thing of vinyl cyanide based compound-aromatic ethenyl-conjugated diene copolymer; Vinyl cyanide based compound-conjugated diene copolymer with gather the mixture of (vinyl halides); ROHM; Polymethyl acrylic acid; Polymethyl acrylate; Polymethylmethacrylate; Polyethyl acrylate; Polyethyl methacrylate; Gather (n-butyl acrylate); Gather (n-BMA); Gather (2-EHA); Gather (methylacrylic acid 2-ethylhexyl); Gather (vinylformic acid-(n-butyl acrylate)); Gather (vinylformic acid-(2-EHA)); Gather (vinylformic acid-(n-butyl acrylate)-(2-EHA)); Gather (methylacrylic acid-(n-butyl acrylate)); Gather (methylacrylic acid-(2-EHA)); Gather (methylacrylic acid-(n-butyl acrylate)-(2-EHA)); Gather (vinylformic acid-methylacrylic acid-(n-butyl acrylate)); Gather (vinylformic acid-methylacrylic acid-(2-EHA)); Gather (vinylformic acid-methylacrylic acid-(n-butyl acrylate)-(2-EHA)); The ROHM stearyl; Polymethyl acrylic acid stearyl etc.; (methyl) XPA; Hydrin rubber, gather epoxy bromopropane rubber etc. and gather epoxyhalopropane rubber; Polyalkylene oxide such as polyethylene oxide, polypropyleneoxide; Ethylene-propylene-diene copolymer (EPDM); Organo-silicone rubber; Silicone resin; Viton; Fluoro-resin; Vilaterm; Ethylene-propylene copolymer, ethylene-butene copolymer etc., ethene-alpha-olefin copolymer; Vestolen PP 7052, poly-1-butylene, gather-alpha-olefinic polymer of 1-octene etc.; The poly-vinyl halide of PVC RESINS, polyvinyl bromide resin etc.; The poly(vinylidene chloride) resin, gather partially 1, it is inclined to one side 1 that 1-sym-dibromoethane resin etc. gathers, 1-acetylenedihalide resin; Epoxy resin; Resol; Polyphenylene oxide resin; Nylon-6, nylon-6,6, nylon-6,12 polymeric amide such as grade; Urethane; Polyester; Yodo Sol VC 400; Gather (ethylene-vinyl alcohol) etc.
In above-mentioned object lesson; Optimization aromatic vinyl-conjugated diene block copolymer and (methyl) XPA; Consider from the angle that tackiness, adhesivity are excellent, be more preferably polyethyl acrylate, the positive butyl ester of ROHM, ROHM-2-ethylhexyl, gather (vinylformic acid-(n-butyl acrylate)), gather (vinylformic acid-(ethyl acrylate)), gather (vinylformic acid-(n-butyl acrylate)-(2-EHA)), gather (methylacrylic acid-(n-butyl acrylate)), gather (methylacrylic acid-(2-EHA)), gather (methylacrylic acid-(n-butyl acrylate)-(2-EHA)), gather (vinylformic acid-methylacrylic acid-(n-butyl acrylate)), gather (vinylformic acid-methylacrylic acid-(2-EHA)), gather (vinylformic acid-methylacrylic acid-(n-butyl acrylate)-(2-EHA)) etc., contain and have acrylic acid alkyl ester units that carbonatoms is 2～8 alkyl and (methyl) XPA of monomeric unit as required with organic acid group.
Further preferably gather (n-butyl acrylate); Gather (2-EHA); Gather (vinylformic acid-(n-butyl acrylate)); Gather (vinylformic acid-(2-EHA)); Gather (vinylformic acid-(n-butyl acrylate)-(2-EHA)); Gather (methylacrylic acid-(n-butyl acrylate)); Gather (methylacrylic acid-(2-EHA)); Gather (methylacrylic acid-(n-butyl acrylate)-(2-EHA)); Gather (vinylformic acid-methylacrylic acid-(n-butyl acrylate)); Gather (vinylformic acid-methylacrylic acid-(2-EHA)); Gather (vinylformic acid-methylacrylic acid-(n-butyl acrylate)-(2-EHA)) etc.; Contain and have acrylic acid alkyl ester units that carbonatoms is 4～8 alkyl and (methyl) XPA of (methyl) acrylic acid units as required.
Especially preferably enumerate gather (vinylformic acid-(ethyl acrylate)), gather (methylacrylic acid-(ethyl acrylate)), gather (vinylformic acid-methylacrylic acid-(ethyl acrylate)) etc., contain and have acrylic acid alkyl ester units that carbonatoms is 8 alkyl and (methyl) XPA of (methyl) acrylic acid units as required.
The above-mentioned substance of enumerating as the object lesson of polymkeric substance (S) can use a kind of separately, also can be with two or more and use.
Adhesion-tackiness additives as being engaged in as required in the polymkeric substance (S) can use various known materials.Can enumerate for example petroleum resin, terpine resin, resol and Gum Rosin, wherein petroleum resin preferably.They can use a kind of separately, also can be with two or more and usefulness.
The object lesson of petroleum resin can be enumerated the C5 petroleum resin that obtained by amylene, pentadiene, isoprene etc.; The C9 petroleum resin that obtain by indenes, methyl indenes, Vinyl toluene, vinylbenzene, alpha-methyl styrene, Beta-methyl vinylbenzene etc.; The C5-C9 copolymerized petroleum resin that obtains by above-mentioned various monomers; The petroleum resin that obtain by cyclopentadiene, Dicyclopentadiene (DCPD); The hydrogenate of these petroleum resin; Modified petroleum resin that these petroleum resin are formed with modifications such as maleic anhydride, toxilic acid, fumaric acid, (methyl) vinylformic acid, phenol etc.
As the terpenic series resin, can enumerate α-Pai Xishuzhi, beta-pinene resin or the terpenic series resin of aromatic series modification that aromatic monomer copolymerization such as terpenes such as α-Pai Xi, beta-pinene and vinylbenzene are obtained etc.
Resol can use the condenses of phenols and formaldehyde.This phenols can be enumerated phenol, meta-cresol, 3; The 5-xylenol, to alkylphenol, Resorcinol etc., also can enumerate make these phenols and formaldehyde under alkaline catalysts, carry out addition reaction and resole or under acid catalyst, carry out condensation reaction and the novolak that obtains etc.In addition, can also enumerate through making the addition and carry out rosin phenolic resin that thermopolymerization obtains etc. under acid catalyst of phenol and rosin.
As Gum Rosin, can enumerate rubber rosin, wood rosin or starex use above-mentioned rosin to carry out disproportionation or hydrotreated stable rosin or polymerized rosin or with modifications such as maleic anhydride, toxilic acid, fumaric acid, (methyl) vinylformic acid, phenol modified rosin or their carboxylate etc.
As the alcohol that uses in the esterification that is used for obtaining above-mentioned carboxylate; Be preferably polyvalent alcohol; Its example can be enumerated the hexavalent alcohol etc. of tetravalent alcohol or Dipentaerythritol etc. of trivalent alcohol or tetramethylolmethane, two glycerine etc. of divalent alcohol, glycerine, trimethylolethane, TriMethylolPropane(TMP) of terepthaloyl moietie, Diethylene Glycol, Ucar 35, NSC 6366 etc. etc.; They can use a kind of separately, also can be with two or more and usefulness.
The softening temperature of these adhesion-tackiness additives is not special to be limited.As this adhesion-tackiness additives, can under material to room temperature, use for suitably selecting the aqueous material with the high softening-point about 200 ℃.
((methyl) acrylic ester polymer (A1) and mixture (M))
As the material that constitutes polymkeric substance (S), preferably (methyl) acrylic ester polymer (A1).In addition, (methyl) acrylic ester polymer (A1) special preferably through other (methyl) acrylic ester polymer (AP1) in the presence of polymkeric substance that (methyl) acrylate monomer (α 1) polymerization is obtained.
In addition, mixture of the present invention (M) be above-mentioned or following, (methyl) acrylic ester polymer (AP1) and (methyl) acrylate monomer (α 1) the two add up to 100 mass parts, expanded graphite powder (B) 1.8 mass parts～18 mass parts, SULPHOSUCCINIC ACID ESTER (C) 20 mass parts～130 mass parts, aluminum oxide (E) 100 mass parts～1000 mass parts and except that the mixture of expanded graphite powder (B) and flame retardant resistance heat conduction mineral compound (D) 160 mass parts～600 mass parts the aluminum oxide (E).
When making thermal conductivity pressure sensitive adhesive compositions (F) or thermal conductivity pressure sensitive glueyness sheet (G); After mixture (M) is configured as the flaky while or is being configured as sheet; (methyl) acrylate monomer (α 1) in the mixture (M) carries out polymerization and converts (methyl) acrylic ester polymer into; Mix and/or a part of bonding with the composition of (methyl) acrylic ester polymer (AP1), form (methyl) acrylic ester polymer (A1).(methyl) acrylic ester polymer (A1) is equivalent to whole (methyl) acrylic ester polymer composition in the thermal conductivity pressure sensitive glueyness sheet (G), is the notion of representing whole (methyl) acrylic ester polymer composition in the thermal conductivity pressure sensitive glueyness sheet (G) blanketly.
((methyl) acrylic ester polymer (AP1))
Below at length explain for (methyl) acrylic ester polymer (AP1).
(methyl) acrylic ester polymer (AP1) is not special to be limited; Preferably contain the unit (a1) of (methyl) acrylate monomer and have the monomeric unit (a2) of organic acid group, the unit (a1) of said (methyl) acrylate monomer is to form the monomeric unit of second-order transition temperature for the homopolymer below-20 ℃.
(methyl) acrylate monomer (a1m) for the unit of giving (methyl) acrylate monomer (a1); The unit (a1) of said (methyl) acrylate monomer is to form the monomeric unit of second-order transition temperature for the homopolymer below-20 ℃; Not special the qualification can be enumerated for example ethyl propenoate (second-order transition temperature of homopolymer is for-24 ℃), propyl acrylate (second-order transition temperature of homopolymer is for-37 ℃), Bing Xisuandingzhi (second-order transition temperature of homopolymer is for-54 ℃), sec-butyl acrylate (second-order transition temperature of homopolymer is for-22 ℃), vinylformic acid heptyl ester (second-order transition temperature of homopolymer is for-60 ℃), NSC 11786 (second-order transition temperature of homopolymer is for-61 ℃), Octyl acrylate (second-order transition temperature of homopolymer is for-65 ℃), 2-EHA (second-order transition temperature of homopolymer is for-50 ℃), vinylformic acid 2-methoxyl group ethyl ester (second-order transition temperature of homopolymer is for-50 ℃), vinylformic acid 3-methoxyl group propyl ester (second-order transition temperature of homopolymer is for-75 ℃), vinylformic acid 3-methoxyl group butyl ester (second-order transition temperature of homopolymer is for-56 ℃), vinylformic acid oxyethyl group methyl esters (second-order transition temperature of homopolymer is for-50 ℃), Octyl methacrylate (second-order transition temperature of homopolymer is for-25 ℃), decyl-octyl methacrylate (second-order transition temperature of homopolymer is for-49 ℃) etc.
These (methyl) acrylate monomers (a1m) can use a kind of separately, also can be with two or more and usefulness.
These (methyl) acrylate monomers (a1m) can be used for polymerization with following amount, and said amount is to make by this (methyl) acrylate monomer (a1m) deutero-monomeric unit (a1) in (methyl) acrylic ester polymer (AP1), to be preferably 80 quality %～99.9 quality %, the amount of 85 quality %～99.5 quality % more preferably.Usage quantity through making (methyl) acrylate monomer (a1m) is in above-mentioned scope, and near the pressure sensitive glueyness of thermal conductivity pressure sensitive glueyness sheet therefrom (G) room temperature is excellent.
Give not special qualification of monomer (a2m) of monomeric unit (a2) with organic acid group; As its representational monomer; Can enumerate the monomer of organic acid groups such as having carboxyl, anhydride group, sulfonic group; In addition, can also use monomer with sulfeno, sulfino, phosphate etc.
As monomeric object lesson with carboxyl; Can enumerate the for example α of vinylformic acid, methylacrylic acid, Ba Dousuan etc.; The α of β-ethene property unsaturated monocarboxylic or methylene-succinic acid, toxilic acid, fumaric acid etc.; The unsaturated polycarboxylic acid of β-ethene property also can be enumerated the α of monomethyl itaconate, butyl maleate, fumaric acid list propyl ester etc., β-unsaturated partial esters of polycarboxylic acids of ethene property etc. in addition.In addition, maleic anhydride, itaconic anhydride etc., have and can also can likewise use through the material that hydrolysis etc. derives the group of carboxyl.
As having sulfonic monomeric object lesson, can enumerate the α of allyl sulphonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylic amide-2-methyl propane sulfonic acid etc., β-unsaturated sulfonic acid and their salt.
Have in the monomer of organic acid group at these, be more preferably monomer with carboxyl, wherein, preferred especially vinylformic acid, methylacrylic acid.They are from can be in industry cheap and easily obtain, consider it also is preferred with the also good and productive angle of the copolymerization property of other monomer component.These monomers (a2m) with organic acid group can use a kind of separately, also can be with two or more and usefulness.
These monomers (a2m) with organic acid group preferably are used for polymerization with following amount, and said amount is that to make by this monomer (a2m) deutero-monomeric unit (a2) be the amount of 0.1 quality %～20 quality %, preferred 0.5 quality %～15 quality % in (methyl) acrylic ester polymer (AP1).Through monomeric unit (a2m) is used in above-mentioned scope, the viscosity of the polymerization system in the time of can be with polymerization remains on suitable scope.
And; Monomeric unit (a2) with organic acid group, as previously mentioned, the polymerization of the monomer (a2m) through having organic acid group; Be incorporated into easily in (methyl) acrylic ester polymer; Be preferred, but also can after generating (methyl) acrylic ester polymer, introduce organic acid group through known high molecular weight reactive.
(methyl) acrylic ester polymer (AP1) also can contain monomeric unit (a3), and this monomeric unit (a3) is by monomer (a3m) the deutero-monomeric unit that contains the functional group beyond the organic acid group.
As the functional group beyond the organic acid group, can enumerate hydroxy, amino, carboxamido-group, epoxy group(ing), sulfydryl etc.
As monomer with hydroxy, can enumerate (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester etc., (methyl) vinylformic acid hydroxyalkyl acrylate etc.
As containing amino monomer, can enumerate (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, amino-benzene ethene etc.
As monomer, can enumerate acrylic amide, USAF RH-1, N hydroxymethyl acrylamide, N-methylol methacrylamide, N, the α of N-DMAA etc., β-ethene property unsaturated carboxylic acid amide monomer etc. with carboxamido-group.
Monomer with epoxy group(ing) can be enumerated (methyl) vinylformic acid glycidyl esters, allyl glycidyl ether etc.
The monomer (a3m) that contains the functional group beyond the organic acid group can use a kind of separately, also can two or more and usefulness.
These have the monomer (a3m) of the functional group beyond the organic acid group, and are preferred so that be that such amount is used for polymerization below the 10 quality % in (methyl) acrylic ester polymer (AP1) by this monomer (a3m) deutero-monomeric unit (a3).Through using the monomer (a3m) below the 10 quality %, the viscosity in the time of can suitably keeping polymerization.
(methyl) acrylic ester polymer (AP1) except contain above-mentioned formation second-order transition temperature for (methyl) acrylate monomeric units (a1) of homopolymer below-20 ℃, the monomeric unit (a3) that has the monomeric unit (a2) of organic acid group and contain the functional group the organic acid group in addition, also can contain by the monomeric unit (a4) that can derive with the monomer (a4m) of these monomer copolymerizations.Monomer (a4m) can use a kind of separately, also can be with two or more and usefulness.
Amount by monomer (a4m) deutero-monomeric unit (a4) is preferably below the 10 quality % of acrylic ester polymer (AP1), more preferably below the 5 quality %.
Monomer (a4m) is not special to be limited; As its object lesson; Can enumerate (methyl) acrylate monomer, α except that forming (methyl) acrylate monomer (a1m) that second-order transition temperature is the homopolymer below-20 ℃, the full ester of the unsaturated polycarboxylic acid of β-ethene property, alkenyl aroma family monomer, conjugated diene monomer, non-conjugated diene are monomer, vinyl cyanide base monomer, the unsaturated alcohol ester of carboxylic acid, ethylene series monomer etc.
As the object lesson of (methyl) acrylate monomer except that forming (methyl) acrylate monomer (a1m) that second-order transition temperature is the homopolymer below-20 ℃, can enumerate methyl acrylate (second-order transition temperature of homopolymer is 10 ℃), TEB 3K (second-order transition temperature of homopolymer is 105 ℃), Jia Jibingxisuanyizhi (second-order transition temperature of homopolymer is 63 ℃), propyl methacrylate (second-order transition temperature of homopolymer is 25 ℃), NSC 20956 (second-order transition temperature of homopolymer is 20 ℃) etc.
As α, the object lesson of the full ester of the unsaturated polycarboxylic acid of β-ethene property can be enumerated dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate etc.
As the monomeric object lesson of alkenyl aroma family, can enumerate vinylbenzene, alpha-methyl styrene, methyl alpha-methyl styrene, Vinyl toluene and Vinylstyrene etc.
The monomeric object lesson of conjugated diene can be enumerated 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.
Non-conjugated diene is that monomeric object lesson can enumerate 1,4-hexadiene, Dicyclopentadiene (DCPD), ethylidene norbornene etc.
The monomeric object lesson of vinyl cyanide base can be enumerated vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, α-ethyl acrylonitrile etc.
The monomeric object lesson of the unsaturated alcohol ester of carboxylic acid can be enumerated vinyl-acetic ester etc.
The monomeric concrete example of ethylene series can be enumerated ethene, propylene, butylene, amylene etc.
The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (AP1) utilizes GPC (GPC method) to measure, and converting with polystyrene standard is preferably 100,000～400,000 scope, more preferably 150,000～300,000 scope.
(methyl) acrylic ester polymer (AP1) can through will form second-order transition temperature for (methyl) acrylate monomer (a1m) of homopolymer below-20 ℃, have the monomer (a2m) of organic acid group, the monomer (a3m) that contains the functional group beyond organic acidic group that uses as required and use as required can carry out copolymerization with the monomer (a4m) of these monomer copolymerizations, come to obtain especially suitably.
The polymeric method is not special to be limited, and can be any one of solution polymerization, emulsion polymerization, suspension polymerization, mass polymerization etc., also can be the method beyond this.Preferably solution polymerization wherein is more preferably the solution polymerization that polymer solvent has used the aromatic solvent of carboxylicesters such as ETHYLE ACETATE, ethyl lactate or benzene,toluene,xylene etc.
When polymerization, monomer can separately add in the polymerization container, but preferably whole amounts is added in the polymerization container together.
The method of initiated polymerization does not have special qualification, preferably uses thermal polymerization as polymerization starter.Thermal polymerization does not have special qualification, can be any one of superoxide and azo cpd.
As peroxidic polymerization initiators; Except the such superoxide of the such hydroperoxide of t-butyl hydroperoxide or Lucidol, cyclohexanone peroxide, can also enumerate the persulphate of Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc. etc.These superoxide can also with the reductive agent appropriate combination, use as the redox system catalyzer.
As the azo cpd polymerization starter, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
The usage quantity of polymerization starter is not special to be limited, and with respect to monomer 100 mass parts, is preferably the scope of 0.01 mass parts～50 mass parts.
These monomeric other not special qualifications of polymerizing condition (polymerization temperature, pressure, agitation condition etc.).
After polyreaction finishes, as required the polymkeric substance of gained is separated from polymerisation medium.Isolating method is not special to be limited, and for the situation of solution polymerization, can polymeric solution be placed under the reduced pressure, and polymer solvent is removed in distillation, can obtain (methyl) acrylic ester polymer (AP1) thus.
The weight-average molecular weight of (methyl) acrylic ester polymer (AP1) can be through suitably the amount of the polymerization starter that uses of adjustment, the amount of chain-transfer agent are controlled when the polymerization.
((methyl) acrylate monomer (α 1))
As stated; As the material that constitutes polymkeric substance (S); (methyl) acrylic ester polymer (A1) preferably, (methyl) acrylic ester polymer (A1) is the material through in the presence of (methyl) acrylic ester polymer (AP1), (methyl) acrylate monomer (α 1) polymerization being obtained especially preferably.
(methyl) acrylate monomer (α 1) is as long as contain (methyl) acrylate monomer, and just not special the qualification preferably contained formation second-order transition temperature (methyl) acrylate monomer (a5m) for the homopolymer below-20 ℃.
As forming second-order transition temperature be the example of (methyl) acrylate monomer (a5m) of the homopolymer below-20 ℃, and (methyl) acrylate monomer (a1m) that can enumerate with use in (methyl) acrylic ester polymer (AP1) synthetic is same (methyl) acrylate monomer.(methyl) acrylate monomer (a5m) can use a kind of separately, also can be with two or more and usefulness.
In addition, (methyl) acrylate monomer (α 1) also can be used as (methyl) acrylate monomer (a5m) and can use with the monomeric mixture of its copolymerization.
Preferred especially (methyl) acrylate monomer (α 1), comprise form second-order transition temperature for (methyl) acrylate monomer (a5m) of the homopolymer below-20 ℃ and can with the monomer (a7m) of these (methyl) acrylate monomer (a5m) copolymerization.
The ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) is preferably 50 quality %～99.9 quality %, more preferably 75 quality %～99.5 quality %.Through the ratio that makes (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) is 50 quality %～99.9 quality %, can form the thermal conductivity pressure sensitive glueyness sheet (G) of pressure sensitive glueyness, flexibility excellence.
As can be as required and the example of (methyl) acrylate monomer (a5m) monomer copolymerization, that have organic acid group (a6m), can enumerate with the monomer of being enumerated as the monomer (a2m) of use in (methyl) acrylic ester polymer (AP1) synthetic be same monomer with organic acid group.Monomer (a6m) with organic acid group can use a kind of separately, also can be with two or more and use.
The ratio of the monomer with organic acid group (a6m) in (methyl) acrylate monomer (α 1) is preferably below the 30 quality %, more preferably below the 10 quality %.The ratio of the monomer (a6m) in (methyl) acrylate monomer (α 1) is 30 quality % when following, and the hardness of thermal conductivity pressure sensitive glueyness sheet (F) is suitable, and the pressure sensitive glueyness under the high temperature (100 ℃) is good.
Expectation (methyl) acrylate monomer (α 1) except the monomer with organic acid group (a6m) of (methyl) acrylate monomer (a5m) and copolymerization as required, also with preferred 0.1 quality %～20 quality %, more preferably 0.5 quality %～15 quality % scope use can with the monomer (a7m) of their copolymerization.
As the example of above-mentioned monomer (a7m), can enumerate with the monomer (a3m) of use in (methyl) acrylic ester polymer (AP1) synthetic, monomer (a4m) and be same monomer as the monomer that the multi-functional monomer shown in following is enumerated.
But, as stated, also can use multi-functional monomer with two above polymerizability unsaturated link(age)s as the monomer (a7m) of copolymerization.Through making multi-functional monomer copolymerization, can in multipolymer, introduce intramolecularly and/or intermolecular cross-linking, improve cohesive force as pressure-sensitive adhesive.
As multi-functional monomer; Can use 1; 6-pinakon two (methyl) propenoate, 1; 2-ethylene glycol bisthioglycolate (methyl) propenoate, 1; Multi-functional (methyl) propenoate or 2 of 12-dodecanediol two (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, W 166 two (methyl) propenoate, NSC 6366 two (methyl) propenoate, tetramethylolmethane two (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, two (trishydroxymethyl) propane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate etc.; Two (the trichloromethyl)-6-of 4-are to the replacement triazine of methoxy styrene-5-triazine etc., and can also use the so single ethene of 4-acryloxy UVNUL MS-40 in addition is unsaturated aromatic ketone etc.Wherein, preferred tetramethylolmethane two (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate.
(methyl) acrylate monomer (α 1) preferably contains above-mentioned multi-functional monomer.Multi-functional monomer can be used as monomer (a7m) all or part of use; Expectation is as multi-functional monomer; With respect to (methyl) acrylate monomer (α 1) 100 quality %, with preferred 0.1 quality %～5 quality %, more preferably the amount of 0.5 quality %～3 quality % contains.
In the present invention; The amount of (methyl) acrylate monomer (α 1) in the mixture (M), with respect to (methyl) acrylic ester polymer (AP1) 100 mass parts, lower limit is preferably 100 mass parts; More preferably 200 mass parts, further preferred 250 mass parts.In addition, the upper limit is preferably 1000 mass parts, more preferably 800 mass parts, further preferred 600 mass parts.If the amount of (methyl) acrylate monomer (α 1) in the mixture (M) is less than 100 mass parts or surpass 1000 mass parts, the plasticity of thermal conductivity pressure sensitive glueyness sheet (G) variation sometimes then.
When thermal conductivity pressure sensitive glueyness sheet (G) is shaped, (methyl) acrylate monomer (α 1) polymerization in the mixture (M).In order to promote this polymerization, mixture (M) preferably except containing (methyl) acrylate monomer (α 1), also further contains polymerization starter.
Polymerization starter can be enumerated Photoepolymerizationinitiater initiater, azo is thermal polymerization, organo-peroxide thermal polymerization etc.; Consider from the angle of the adhesive power of the thermal conductivity pressure sensitive glueyness sheet (G) of gained etc., can preferably use the organo-peroxide thermal polymerization.
Photoepolymerizationinitiater initiater can use known various Photoepolymerizationinitiater initiater.Wherein preferred acylphosphine oxide based compound.Preferably can enumerate two (2,4, the 6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. as the acylphosphine oxide based compound of Photoepolymerizationinitiater initiater.
Azo is that thermal polymerization can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
The organo-peroxide thermal polymerization can be enumerated the such hydroperoxide of t-butyl hydroperoxide; Or Lucidol, cyclohexanone peroxide, 1; Two (the t-butylperoxy ketonic oxygen base) hexanes, 1 of 6-; 1-bis(t-butylperoxy)-3,3, the superoxide that the 5-trimethylcyclohexanone is such etc.Wherein, preferably when thermolysis, do not discharge the volatile matter that causes forming stink.In the organo-peroxide thermal polymerization, preferred 1 minute half life temperature is the organo-peroxide thermal polymerization more than 100 ℃ and below 170 ℃.
The usage quantity of the polymerization starter of organo-peroxide thermal polymerization etc.; With respect to (methyl) acrylate monomer (α 1) 100 mass parts; Its lower limit is preferably 0.1 mass parts; More preferably 0.5 mass parts, further preferred 1 mass parts, the upper limit are preferably 30 mass parts, more preferably 20 mass parts, further preferred 15 mass parts.
The polymerisation conversion of (methyl) acrylate monomer (α 1) is preferably more than the 95 quality %.If polymerisation conversion is low excessively, then the thermal conductivity pressure sensitive glueyness sheet (G) of gained is residual has the monomer stink, so not preferred.
＜BET specific surface area is 1m 2Aluminum oxide (E) more than/g＞
In order to give thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G) thermal conductivity, consider in thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M), to contain following expanded graphite powder (B).But if increase the content of expanded graphite powder (B), then the dielectric breakdown strength of thermal conductivity pressure sensitive glueyness sheet (G) significantly reduces.Discoveries such as the inventor are 1m through in thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M), containing the BET specific surface area 2Aluminum oxide (E) that/g is above and following flame retardant resistance heat conduction mineral compound (D); Even reduce the amount of the expanded graphite powder (B) that contains in order to give thermal conductivity pressure sensitive glueyness sheet (G) thermal conductivity, also can give thermal conductivity pressure sensitive glueyness sheet (G) thermal conductivity.In addition; If increase the content of the flame retardant resistance heat conduction mineral compound (D) of the flame retardant resistance be used to improve thermal conductivity pressure sensitive glueyness sheet (G); Then the viscosity of thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M) increases sometimes, the plasticity variation of thermal conductivity pressure sensitive glueyness sheet (G).Also find resolution policy as the problems referred to above; Through aluminum oxide (E) and flame retardant resistance heat conduction mineral compound (D) are also used; Even reduce the content of flame retardant resistance heat conduction mineral compound (D), also can make thermal conductivity pressure sensitive glueyness sheet (G) have flame retardant resistance.
When using aluminum oxide as the thermal conductivity filler, the preferred usually so little aluminum oxide of specific surface area of spherical alumina that uses.This is because can suppress to contain the viscosity of the compsn of aluminum oxide increases, and is easy to make this aluminum oxide to be blended in the said composition.But the inventor etc. find that thermal conductivity pressure sensitive glueyness sheet (G) has high thermal conductivity, insulativity, and has high flame retardant resistance through using the big aluminum oxide of BET specific surface area.The BET specific surface area of the aluminum oxide that therefore, can use in the present invention (E) is 1m 2More than/the g.In order to improve the flame retardant resistance of thermal conductivity pressure sensitive glueyness sheet (G), the BET specific surface area of aluminum oxide (E) is preferably big.On the other hand; Though also depend on the content of aluminum oxide (E); If but used the big aluminum oxide (E) of BET specific surface area, then the viscosity of thermal conductivity pressure sensitive adhesive compositions (F), mixture (M) would increase, and is difficult to thermal conductivity pressure sensitive glueyness sheet (G) is shaped.Therefore, if only only consider the productivity of thermal conductivity pressure sensitive glueyness sheet (G), then the upper limit of the BET specific surface area of aluminum oxide (E) is preferably 10m 2/ g, more preferably 5m 2/ g, further preferred 3m 2/ g.
And in the present invention, the BET specific surface area is meant the specific surface area of utilizing following method to measure.
At first, in the mixed gas importing BET specific area measuring device with nitrogen and helium, the sample box (セ Le) that will put into sample (the determination object thing of BET specific surface area) is immersed in liquid nitrogen, makes nitrogen adsorption on specimen surface.After reaching adsorption equilibrium, sample box is placed in the water-bath, is heated to normal temperature, make attached to the nitrogen desorb on the sample.Ratio of mixture through the gas before and after the sample box when the absorption of nitrogen, desorb changes, therefore with the ratio of mixture of nitrogen and helium be certain gas as contrast, detect with thermal conductivity detector (TCD) and to be somebody's turn to do variation, try to achieve the adsorptive capacity and the desorption quantity of nitrogen.In the nitrogen gatherer with unit vol before measuring, calibrate, try to achieve the value with the corresponding surface-area of value that detects with TCD, try to achieve the surface-area of this sample thus.In addition, through with the quality of surface-area divided by this sample, can be in the hope of the BET specific surface area.
In addition, the lower limit of the peak particle diameter of the aluminum oxide that can use in the present invention (E) is preferably 0.1 μ m, and more preferably 0.5 μ m further is preferably 1.0 μ m.The particle diameter of aluminum oxide (E) is big if this is, then is easy to improve the thermal conductivity of thermal conductivity pressure sensitive glueyness sheet (G), and dielectric breakdown strength also improves easily.On the other hand, the upper limit of the peak particle diameter of aluminum oxide (E) is preferably 500 μ m, and more preferably 200 μ m further are preferably 100 μ m.The peak particle diameter is excessive if this is, the surface irregularity of thermal conductivity pressure sensitive glueyness sheet (G) sometimes then reduces for the shape conformability of adherend.
And in the present invention, particle diameter short of special instruction in peak all is meant the particle diameter that the method below utilizing is measured.
When having disperseed the solution irradiates light of sample (the determination object thing of particle diameter), light scattering through sample.This scattered intensity and angle depend on the size of suspended particles largely, therefore distribute through detecting scattered intensity, can be in the hope of size-grade distribution.Particle diameter that will be corresponding with the peak in this size distribution curve is as the peak particle diameter of this sample.
The aluminum oxide that can use in the present invention further, (E) preferably has a plurality of peaks in size-grade distribution.The aluminum oxide (E) that has a plurality of peaks in the size-grade distribution for example can mix and obtains through making size-grade distribution defer to normal distribution, peak particle diameter different oxidation aluminium (E).And, after can mixing in advance, mixes with polymkeric substance (S) etc. again in peak particle diameter different oxidation aluminium (E), also can mix with polymkeric substance (S) etc. respectively.When in using size-grade distribution, having the aluminum oxide (E) at a plurality of peaks, the peak particle diameter of maximum particle diameter side is preferably more than 10 with the ratio of the peak particle diameter of minimum grain size side.Like this, contain the aluminum oxide (E) that particle diameter has the particle of big difference, be easy to improve the dielectric breakdown strength and the thermal conductivity of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G) through use.In addition, if consider the operability of aluminum oxide, then the peak particle diameter of maximum particle diameter side is preferably below 5000 with the ratio of the peak particle diameter of minimum grain size side.
When in using size-grade distribution, having the aluminum oxide (E) at a plurality of peaks; Belong to the aluminum oxide at 1 peak that accounts for maximum content amount, be preferably (1:10)～(10:1) with the mass ratio of total amount of the aluminum oxide that belongs to other whole peaks; More preferably (1:5)～(5:1); Further preferred (1:3)～(3:1), preferred (1:2)～(2:1) especially.If in above-mentioned preferred range, then thermal conductivity and dielectric breakdown strength all uprise, and both tendencies with high horizontal equalization are arranged.
In addition, when in using size-grade distribution, having the aluminum oxide (E) at a plurality of peaks, especially preferably use the aluminum oxide (E) that has 2 peaks in the size-grade distribution.
The total amount of the aluminum oxide (E) that contains in the thermal conductivity pressure sensitive adhesive compositions (F) when being 100 mass parts with polymkeric substance (S), is 100 mass parts～1000 mass parts.In addition; When in mixture (M), containing aluminum oxide (E); With respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), the amount of this aluminum oxide (E) is 100 mass parts～1000 mass parts.
Consider that from the angle of paying attention to flexibility, plasticity lower limit is preferably 150 mass parts, more preferably 200 mass parts.Likewise, consider that from the angle of paying attention to flexibility, plasticity the upper limit is preferably 600 mass parts, more preferably 500 mass parts.Content through making aluminum oxide (E) is in above-mentioned preferred range, and the viscosity that can suppress thermal conductivity pressure sensitive adhesive compositions (F), mixture (M) increases, and the plasticity of thermal conductivity pressure sensitive glueyness sheet (G) becomes good.
On the other hand, when the thin thickness (being below the 1.5mm specifically) of thermal conductivity pressure sensitive glueyness sheet (G), from paying attention to the isostatic angle consideration of plasticity and flame retardant resistance, lower limit is preferably 110 mass parts, more preferably 120 mass parts.The upper limit is preferably 500 mass parts, more preferably 300 mass parts.
In addition, consider that with the angle of high horizontal equalization lower limit is preferably 500 mass parts from paying attention to thermal conductivity, flame retardant resistance and insulativity, more preferably 600 mass parts, further preferred 800 mass parts.In addition, consider that with the angle of high horizontal equalization the upper limit is preferably 1000 mass parts from paying attention to thermal conductivity, flame retardant resistance and insulativity.When the content of aluminum oxide (E) was in above-mentioned scope, thermal conductivity, flame retardant resistance and the insulativity of thermal conductivity pressure sensitive glueyness sheet (G) all became good.When the content of aluminum oxide (E) than 100 mass parts after a little while, make the thermal conductivity of thermal conductivity pressure sensitive glueyness sheet (G) and effect that flame retardant resistance the improves inadequate tendency that becomes.On the other hand, when the content of aluminum oxide (E) during more than 1000 mass parts, the viscosity of thermal conductivity pressure sensitive adhesive compositions (F), mixture (M) too increases sometimes, the plasticity variation of thermal conductivity pressure sensitive glueyness sheet (G).
＜expanded graphite powder (B)＞
Example as the expanded graphite powder (B) that can use in the present invention; Can enumerate the expanded graphite powder that obtains through following operation; Said operation is to comprise the graphite of s.t. is heat-treated at 500 ℃～1200 ℃; Make it be expanded to 100ml/g～300ml/g, the operation of then pulverizing.More preferably, can enumerate the expanded graphite powder that obtains through following operation, said operation be comprise with graphite with strong acid treatment after; In alkali, carry out sintering; And then use strong acid treatment, the material that obtains is thus heat-treated at 500 ℃～1200 ℃, when removing disacidify; Make it be expanded to 100ml/g～300ml/g, the operation of then pulverizing.Above-mentioned heat treated temperature is preferably 800 ℃～1000 ℃ especially.
The median size of the expanded graphite powder (B) that uses among the present invention is preferably 1 μ m～500 μ m, and more preferably 10 μ m～400 μ m further are preferably 20 μ m～300 μ m.When the median size of expanded graphite powder (B) during less than 1 μ m, the thermal conductivity of the thermal conductivity pressure sensitive glueyness sheet (G) that is obtained by thermal conductivity pressure sensitive adhesive compositions (F) has the tendency of step-down.On the other hand; If the median size of expanded graphite powder (B) surpasses 500 μ m; Then through making expanded graphite powder (B) be present in the surface of the thermal conductivity pressure sensitive glueyness sheet (G) that obtains by thermal conductivity pressure sensitive adhesive compositions (F) with big zone; Be easy to produce the space at interface, sometimes the thermal conductivity of this thermal conductivity pressure sensitive glueyness sheet (G) and adhesivity step-down, plasticity variation with adherend.
The median size of expanded graphite powder (B) is used laser type particle size measurement machine (セ イ シ Application enterprise of Co., Ltd. system); Measure through differential class (マ イ Network ロ ソ ー テ ィ Application グ) mode (only in measuring the zone, the determination object particle is passed through, improve the mode of the safety of measuring).For this measuring method; Through in box, flowing into expanded graphite powder (B) 0.01g～0.02g as determination object; And in measuring the zone, be the semiconductor laser of 670nm to mobile expanded graphite powder (B) illumination wavelength; Utilize the mensuration machine to measure laser scattering of light and the diffraction of this moment, calculate median size and size distribution by the diffraction principle of Fraunhofer (Off ラ Application ホ ー Off ァ) thus, and show its result.
The amount of the expanded graphite powder (B) that contains in the thermal conductivity pressure sensitive adhesive compositions (F) when being 100 mass parts with polymkeric substance (S), is 1.8 mass parts～18 mass parts.Consider from the isostatic angle of paying attention to insulativity and high thermal conductivity, that is, consider that from making the angle that dielectric breakdown strength surpasses 5.0kV/mm and have a material of high thermal conductivity the upper limit is preferably 12 mass parts, more preferably 10 mass parts.Under this situation, lower limit is preferably 2 mass parts in addition, more preferably 3 mass parts.On the other hand; Consider from the angle of paying attention to further improving thermal conductivity, that is, be below the 5.0kV/mm, have but then and then the angle of the material of high thermal conductivity is considered from making dielectric breakdown strength; The upper limit is preferably 15 mass parts, more preferably 13 mass parts.Under this situation, lower limit is preferably 5 mass parts in addition, more preferably 8 mass parts.In addition; When containing expanded graphite powder (B) in the mixture (M); With respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), the amount of this expanded graphite powder (B) is 1.8 mass parts～18 mass parts.Consider from the isostatic angle of insulativity and high thermal conductivity, that is, consider that from making the angle that dielectric breakdown strength surpasses 5.0kV/mm and have a material of high thermal conductivity the upper limit is preferably 12 mass parts, more preferably 10 mass parts.Under this situation, lower limit is preferably 2 mass parts in addition, more preferably 3 mass parts.On the other hand; Consider from the angle of paying attention to further improving thermal conductivity, that is, be below the 5.0kV/mm, have but then and then the angle of the material of high thermal conductivity is considered from making dielectric breakdown strength; The upper limit is preferably 15 mass parts, more preferably 13 mass parts.Under this situation, lower limit is preferably 5 mass parts in addition, more preferably 8 mass parts.If the content of expanded graphite powder (B) is less than 1.8 mass parts, then the thermal conductivity of thermal conductivity pressure sensitive adhesive compositions (F) and conductivity pressure sensitive glueyness sheet (G) has the tendency of variation.On the other hand, if the content of expanded graphite powder (B) surpasses 18 mass parts, then the dielectric breakdown strength of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive adhesive compositions (G) has the tendency of variation.
＜SULPHOSUCCINIC ACID ESTER (C)＞
Through in thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M), containing the SULPHOSUCCINIC ACID ESTER (C) of specified amount, can improve the flame retardant resistance of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G).The SULPHOSUCCINIC ACID ESTER that can use in the present invention (C) is that the viscosity in the time of 25 ℃ is the SULPHOSUCCINIC ACID ESTER more than the 3000mPa s.When the viscosity of SULPHOSUCCINIC ACID ESTER (C) is crossed when low the plasticity variation of thermal conductivity pressure sensitive glueyness sheet (G).And among the present invention, " viscosity " of SULPHOSUCCINIC ACID ESTER is meant the viscosity of measuring through the method for following explanation.
(viscosity measurement of SULPHOSUCCINIC ACID ESTER)
Used Brookfield viscometer (Tokyo Keiki Inc.'s system) in the viscosimetric analysis of SULPHOSUCCINIC ACID ESTER, carried out through the step shown in following.
(1) under the environment of normal temperature, measures the 300ml SULPHOSUCCINIC ACID ESTER, put into the container of 500ml.
(2) select to stir with among the rotor No.1,2,3,4,5,6,7 any one, be installed on the viscometer.
(3) container that will put into SULPHOSUCCINIC ACID ESTER places on the viscometer, and rotor is sunk in the condensed phosphoric acid esters in this container.At this moment, so that the indenture that forms the rotor mark sink in the mode at the aqueous interface of SULPHOSUCCINIC ACID ESTER just.
(4) from 20,10,4,2, select rotating speed.
(5) open the stirring switch, read the numerical value after 1 minute.
(6) numerical value that reads multiply by coefficient A and value be viscosity ［ mPa s ］.
And coefficient A is as shown in table 1 below, is decided by rotor No. and the rotating speed selected.
(table 1)
In addition, the SULPHOSUCCINIC ACID ESTER that uses among the present invention (C) 15 ℃～100 ℃ temperature province under atmospheric pressure is generally liquid.This is that then operability is poor, is difficult to thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M) are configured as sheet because SULPHOSUCCINIC ACID ESTER (C) is not if be liquid when mixing.When thermal conductivity pressure sensitive adhesive compositions (F) that obtains containing SULPHOSUCCINIC ACID ESTER (C) or mixture (M), under 15 ℃～100 ℃ environment, will constitute each material mixing of thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M) usually.Temperature when mixing if this is is low excessively, and the second-order transition temperature of polymkeric substance (S) is descended, if too high, then causes the volatilization or the polyreaction of monomer etc. sometimes, thus environment property and operability variation.
Among the present invention, SULPHOSUCCINIC ACID ESTER (C) can use condensed phosphoric acid esters, also can use non-condensed phosphoric acid esters.Here so-called " condensed phosphoric acid esters " is meant that at the SULPHOSUCCINIC ACID ESTER of 1 molecular memory at a plurality of SULPHOSUCCINIC ACID ESTERs position, " non-condensed phosphoric acid esters " is meant the SULPHOSUCCINIC ACID ESTER that only has 1 SULPHOSUCCINIC ACID ESTER position at 1 intramolecularly.Below listed the object lesson of the SULPHOSUCCINIC ACID ESTER (C) that satisfies the above-mentioned condition of having explained.
The concrete example of condensed phosphoric acid esters can enumerate 1, the aromatic condensation SULPHOSUCCINIC ACID ESTER of 3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester), Resorcinol two (diphenyl phosphoester) etc.; The Halogen prime system condensed phosphoric acid esters of the two dichloro alkyl phosphates of polyoxyalkylene etc.; The non-halogen of non-aromatic is a condensed phosphoric acid esters; Deng.Wherein less from proportion, as not discharge objectionable impurities (halogen etc.) danger, the angle that is easy to obtain etc. are considered, are preferably the aromatic condensation SULPHOSUCCINIC ACID ESTER, more preferably 1, and 3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester).
The object lesson of non-condensed phosphoric acid esters can be enumerated triphenyl, trimethylphenyl SULPHOSUCCINIC ACID ESTER, three (xylyl) SULPHOSUCCINIC ACID ESTER, tolyl diphenyl phosphoester, tolyl-2, the aromatic phosphoric ester of 6-xylyl SULPHOSUCCINIC ACID ESTER, 2-ethylhexyl diphenyl phosphate etc.; The Halogen prime system SULPHOSUCCINIC ACID ESTER of three (β-chloropropyl) SULPHOSUCCINIC ACID ESTER, three (two chloropropyls) SULPHOSUCCINIC ACID ESTER, three (tribromo neo-pentyl) SULPHOSUCCINIC ACID ESTER etc. etc.The angle that wherein never produces objectionable impurities (halogen etc.) etc. is considered the optimization aromatic SULPHOSUCCINIC ACID ESTER.
Among the present invention, SULPHOSUCCINIC ACID ESTER (C) can be selected a kind ofly to use separately from above-mentioned object lesson etc., but preferably with more than two kinds and use.Through using different SULPHOSUCCINIC ACID ESTERs such as composition, molecular weight, be easy to improve the thermal conductivity of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G).
The amount of the SULPHOSUCCINIC ACID ESTER (C) that contains in the thermal conductivity pressure sensitive adhesive compositions (F) when being 100 mass parts with polymkeric substance (S), is 20 mass parts～130 mass parts.In addition; When containing SULPHOSUCCINIC ACID ESTER (C) in the mixture (M); With respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), the amount of this SULPHOSUCCINIC ACID ESTER (C) is 20 mass parts～130 mass parts.If the content of SULPHOSUCCINIC ACID ESTER (C) is too much, the plasticity variation of thermal conductivity pressure sensitive glueyness sheet (G) sometimes then, if very few, then the flame retardant resistance of thermal conductivity pressure sensitive glueyness sheet (G) has poor tendency.
＜remove expanded graphite powder (B) and the BET specific surface area is 1m 2In addition flame retardant resistance heat conduction mineral compound (D) of the above aluminum oxide (E) of/g＞
Can use in the present invention, remove expanded graphite powder (B) and the BET specific surface area is 1m 2Aluminum oxide (E) the flame retardant resistance heat conduction mineral compound (D) in addition that/g is above, in the present invention, so long as remove expanded graphite powder (B) and the BET specific surface area is 1m 2The above aluminum oxide (E) of/g in addition, have thermal conductivity and can improve thermal conductivity pressure sensitive adhesive compositions (F) and the mineral compound of the flame retardant resistance of thermal conductivity pressure sensitive glueyness sheet (G) gets final product, do not have special qualification.As the object lesson of the flame retardant resistance heat conduction mineral compound (D) that can use in the present invention, can enumerate white lake, Gallium trihydroxide, indium hydroxide, Marinco H, calcium hydroxide, strontium hydroxide, hydrated barta, two hydrated gypsum, zinc borate, kaolin, calcium aluminate, lime carbonate, aluminium carbonate, dawsonite etc.Flame retardant resistance heat conduction mineral compound (D) can use a kind of separately, also can be with two or more and usefulness.
The shape of flame retardant resistance heat conduction mineral compound (D) is not special yet to be limited, and can be the random shape of spherical, needle-like, fibrous, flakey, dendroid, tabular and amorphous.
In flame retardant resistance heat conduction mineral compound (D), the oxyhydroxide of the metal of preferred elements periodictable IIA family or group III A.The metal of IIA family can be enumerated magnesium, calcium, strontium, barium etc., and the metal of group III A can be enumerated aluminium, gallium, indium etc.
In the oxyhydroxide of the metal of above-mentioned periodic table of elements IIA family or group III A, preferred especially white lake.Through using white lake, can give thermal conductivity pressure sensitive glueyness sheet (G) excellent flame.
White lake uses the white lake of the particle diameter with 0.2 μ m～150 μ m, preferred 0.7 μ m～100 μ m usually.In addition, the median size that preferably has 1 μ m～80 μ m.Median size makes the viscosity of thermal conductivity pressure sensitive adhesive compositions (F) increase less than the white lake of 1 μ m sometimes, and hardness also increases simultaneously in addition, the shape conformability of thermal conductivity pressure sensitive glueyness sheet (G) is descended, and have the tendency of thermal conductivity step-down.On the other hand, the white lake that median size surpasses 80 μ m makes the surface irregularity of thermal conductivity pressure sensitive glueyness sheet (G) sometimes, reduces for the shape conformability of adherend.And the median size of so-called white lake here is meant and uses the size-grade distribution of measuring through following method, by the accumulative total volume (volume of almost spherical) of the little particle gained of the granularity particle diameter for 50 volume % of the object integral body of having measured size-grade distribution.At first, make the sample particle be dispersed in the solution and irradiates light.At this moment, the light of irradiation is scattered through the sample particle.This scattered intensity and angle largely depend on the size of suspended particles (being dispersed in the sample particle in the solution), therefore through detecting the intensity distribution of scattered light with respect to scattering angle, and can be in the hope of size-grade distribution.
The amount of the flame retardant resistance heat conduction mineral compound (D) that contains in the thermal conductivity pressure sensitive adhesive compositions (F) when being 100 mass parts with polymkeric substance (S), is 160 mass parts～600 mass parts.The upper limit is preferably 400 mass parts, more preferably 300 mass parts.Lower limit is preferably 180 mass parts, more preferably 200 mass parts.In addition; When in mixture (M), containing flame retardant resistance heat conduction mineral compound (D); With respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), the amount of this flame retardant resistance heat conduction mineral compound (D) is 160 mass parts～600 mass parts.The upper limit is preferably 400 mass parts, more preferably 300 mass parts.Lower limit is preferably 180 mass parts, more preferably 200 mass parts.If the content of flame retardant resistance heat conduction mineral compound (D) surpasses 600 mass parts, the tendency that hardness increases, the shape conformability reduces of thermal conductivity pressure sensitive glueyness sheet (G) is arranged then.On the other hand, if the content of flame retardant resistance heat conduction mineral compound (D) less than 160 mass parts, the flame retardant resistance variation of thermal conductivity pressure sensitive glueyness sheet (G) sometimes then.
On the other hand, when the thin thickness (being below the 1.5mm specifically) of thermal conductivity pressure sensitive glueyness sheet (G), from paying attention to the isostatic angle consideration of plasticity and flame retardant resistance, the upper limit is preferably 550 mass parts, more preferably 500 mass parts.Lower limit is preferably 200 mass parts, more preferably 300 mass parts.
＜whipping agent (H)＞
In thermal conductivity pressure sensitive adhesive compositions of the present invention (F) or mixture (M), can contain whipping agent (H) as any composition with specified amount.Through in thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M), containing whipping agent (H), can further improve the flame retardant resistance of the thermal conductivity pressure sensitive glueyness sheet (G) that obtains by this thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M).
As the whipping agent (H) that uses in the present invention, preferably pyrolytic whipping agent.Further,, preferably have the pyrolytic whipping agent of the decomposition starting temperature more than 80 ℃ and below 500 ℃, be more preferably the pyrolytic whipping agent of the decomposition starting temperature that has more than 120 ℃ and below 300 ℃ as the pyrolytic whipping agent.
As the object lesson of this pyrolytic whipping agent, can enumerate 4,4 '-OBSH, Cellmic C 121 etc.Being higher than in 500 ℃ the whipping agent with the following frothing aid of a certain amount of mixing in the thermolysis starting temperature, is that foaming system below 500 ℃ also can likewise form the pyrolytic whipping agent and make the thermolysis starting temperature.
Above-mentioned frothing aid can be enumerated the mixture, StNa, sodium laurate, Sodium pentadecanecarboxylate, potassium stearate, potassium laurate, potassium palmitate etc. of mixture, zinc palmitate, palmitinic acid and zinc white of mixture, zinc laurate, LAURIC ACID 99 MIN and the zinc white of Zinic stearas, Triple Pressed Stearic Acid and zinc white (zinc oxide).
The amount of the whipping agent (H) that contains in the thermal conductivity pressure sensitive adhesive compositions (F) when being 100 mass parts with polymkeric substance (S), is 0.02 mass parts～15 mass parts.The upper limit is preferably 5 mass parts, more preferably 1 mass parts, further preferred 0.5 mass parts.Lower limit is preferably 0.03 mass parts, more preferably 0.05 mass parts, further preferred 0.1 mass parts.In addition; When containing whipping agent (H) in the mixture (M); With respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), the amount of this whipping agent (H) is 0.02 mass parts～15 mass parts.The upper limit is preferably 5 mass parts, more preferably 1 mass parts, further preferred 0.5 mass parts.Lower limit is preferably 0.03 mass parts, more preferably 0.05 mass parts, further preferred 0.1 mass parts.If the content of whipping agent (H) surpasses 15 mass parts, then hindered the thermal conduction of thermal conductivity pressure sensitive glueyness sheet (G) sometimes.On the other hand,, then be difficult to bring into play effect, be difficult to make the sheet material foaming as whipping agent if less than 0.02 mass parts.
＜spun glass (I)＞
In thermal conductivity pressure sensitive adhesive compositions of the present invention (F) or mixture (M), the spun glass (I) that can contain specified amount is as any composition.Through in thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M), containing spun glass (I), can improve the insulativity of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G).
The spun glass that uses among the present invention (I) optimum fiber length is 0.1mm～4mm.If less than 0.1mm, then there is following tendency in the length of spun glass, the effect of the insulativity of the thermal conductivity pressure sensitive glueyness sheet (G) that obtains by thermal conductivity pressure sensitive adhesive compositions (F) of promptly being difficult to be improved.On the other hand,, then there is following tendency, that is, the thermal conductivity of the thermal conductivity pressure sensitive glueyness sheet (G) that is obtained by thermal conductivity pressure sensitive adhesive compositions (F) reduced, and be difficult to be shaped if the length of spun glass surpasses 4mm.
The amount of the spun glass (I) that contains in the thermal conductivity pressure sensitive adhesive compositions (F) when being 100 mass parts with polymkeric substance (S), is preferably below 100 mass parts.The upper limit is 50 mass parts more preferably, further are preferably 10 mass parts.Lower limit is 1 mass parts more preferably, further is preferably 1.5 mass parts.In addition; When containing spun glass (I) in the mixture (M); With respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), the amount of this spun glass (I) is preferably below 100 mass parts.The upper limit is 50 mass parts more preferably, further are preferably 10 mass parts.Lower limit is 1 mass parts more preferably, further is preferably 1.5 mass parts.If the amount of the spun glass (I) that contains in thermal conductivity pressure sensitive adhesive compositions (F) or the mixture (M) surpasses 100 mass parts, then have to be difficult to by the tendency of thermal conductivity pressure sensitive adhesive compositions (F) with thermal conductivity pressure sensitive glueyness sheet (G) shaping.
＜other the thermal conductivity mineral compound＞
In the thermal conductivity pressure sensitive adhesive compositions of the present invention (F), except contain expanded graphite powder (B), the BET specific surface area is 1m 2Aluminum oxide (E) that/g is above and flame retardant resistance heat conduction mineral compound (D) can also contain other any composition of thermal conductivity mineral compound conduct in addition.Below enumerate for this thermal conductivity mineral compound.
(PITCH based carbon fiber (J))
PITCH based carbon fiber (J) is meant that with pitch (by product of oil, coal, coal tar wet goods) be the thomel of raw material, has the high such speciality of thermal conductivity.When in thermal conductivity pressure sensitive adhesive compositions (F), containing PITCH based carbon fiber (J), expect its content, be preferably below 20 mass parts when being 100 mass parts with polymkeric substance (S), more preferably below 15 mass parts, further below preferred 10 mass parts.In addition; When in mixture (M), containing PITCH based carbon fiber (J); Expect total 100 mass parts of the content of this PITCH based carbon fiber (J) with respect to above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), be preferably below 20 mass parts, more preferably below 15 mass parts, further below preferred 10 mass parts.If the content of PITCH based carbon fiber (J) surpasses 20 mass parts, the dielectric breakdown strength of the thermal conductivity pressure sensitive glueyness sheet (G) that is then obtained by thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M) has the tendency of variation.
(the BET specific surface area is less than 1m 2The aluminum oxide of/g (K))
The BET specific surface area is less than 1m 2The aluminum oxide of/g (K) can improve the thermal conductivity of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G).When in thermal conductivity pressure sensitive adhesive compositions (F), containing the BET specific surface area less than 1m 2During the aluminum oxide of/g (K), expect its content, when being 100 mass parts, be preferably below 500 mass parts with polymkeric substance (S), more preferably below 400 mass parts, further below preferred 350 mass parts.In addition; When in mixture (M), containing aluminum oxide (K); This aluminum oxide (K) is with respect to total 100 mass parts of above-mentioned (methyl) acrylic ester polymer (AP1) and above-mentioned (methyl) acrylate monomer (α 1), be preferably below 500 mass parts, more preferably below 400 mass parts, further below preferred 350 mass parts.If the BET specific surface area is less than 1m 2The content of the aluminum oxide of/g (K) surpasses 500 mass parts, and then the flame retardant resistance of thermal conductivity pressure sensitive adhesive compositions (F) and thermal conductivity pressure sensitive glueyness sheet (G) has the tendency of variation.
＜other composition＞
In thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M); As required, can further contain outside linking agent, pigment, other known various additives such as packing material, inhibitor, thickening material with the scope of not damaging effect of the present invention.
(outside linking agent)
In order to improve cohesive force, to increase thermotolerance etc. as pressure-sensitive adhesive; In thermal conductivity pressure sensitive adhesive compositions (F), add outside linking agent, can in the polymkeric substance that in the presence of (methyl) acrylic ester polymer (AP1), (methyl) acrylate monomer (α 1) is polymerized, introduce crosslinking structure.
As the example of outside linking agent, can enumerate multi-functional isocyanate-based linking agents such as tolylene diisocyanate, TriMethylolPropane(TMP) vulcabond, ditan triisocyanate; Diglycidylether, polyethyleneglycol diglycidylether, epoxy crosslinking agents such as trihydroxymethylpropanyltri diglycidyl ether; The melmac linking agent; Amino resin crosslinking agent; The metal-salt linking agent; The metallo-chelate linking agent; Peroxide cross-linking agent etc.
Outside linking agent is after obtaining following polymkeric substance; In this polymkeric substance, add; At the intramolecularly and/or the crosslinked material of intermolecular formation of multipolymer, said polymkeric substance is the polymkeric substance that in the presence of (methyl) acrylic ester polymer (AP1), (methyl) acrylate monomer (α 1) is polymerized through carrying out heat treated, radiation exposure to handle.
(other)
As pigment, no matter organic system, inorganic systems such as carbon black or titanium oxide can use.As other packing material, can enumerate mineral compound of clay etc. etc.Also can add nanoparticles such as soccerballene, carbon nanotube.As inhibitor, therefore the possibility height owing to hindering radical polymerization does not use usually, but can use the inhibitor of polyphenol system, quinhydrones system, hindered amine system etc. as required.As thickening material, can use such reactive inorganic compound such as mineral compound micropartical, Natural manganese dioxide of acrylic acid polymer particle, silicas etc.
2. thermal conductivity pressure sensitive glueyness sheet (G)
Thermal conductivity pressure sensitive glueyness sheet of the present invention (G) is the object of the sheet form of thermal conductivity pressure sensitive adhesive compositions (F).(F) is configured as sheet with the thermal conductivity pressure sensitive adhesive compositions, can form thermal conductivity pressure sensitive glueyness sheet (G).The sexy adhesive compound of heat conduction (F) when being configured as sheet, is preferably being heated.
Thermal conductivity pressure sensitive glueyness sheet of the present invention (G) preferably obtains as following: the two adds up to 100 mass parts, expanded graphite powder (B) 1.8 mass parts～18 mass parts, above-mentioned SULPHOSUCCINIC ACID ESTER (C) 20 mass parts～130 mass parts, above-mentioned aluminum oxide (E) 100 mass parts～1000 mass parts and is configured as sheet except that the mixture (M) of expanded graphite powder (B) and flame retardant resistance heat conduction mineral compound (D) 160 mass parts～600 mass parts the above-mentioned aluminum oxide (E) with (methyl) acrylic ester polymer (AP1) and (methyl) acrylate monomer (α 1); Meanwhile or after being configured as sheet, in the presence of above-mentioned (methyl) acrylic ester polymer (AP1) in said mixture (M) with above-mentioned (methyl) acrylate monomer (α 1) polymerization in the said mixture.
Thermal conductivity pressure sensitive glueyness sheet of the present invention (G) can be the sheet material that only comprises thermal conductivity pressure sensitive adhesive compositions (F), also can be to comprise base material and the mixture of the thermal conductivity pressure sensitive adhesive compositions (F) that is shaped on its single face or two sides.
The thickness of the layer of the thermal conductivity pressure sensitive adhesive compositions (F) in the thermal conductivity pressure sensitive glueyness sheet of the present invention (G) is not special to be limited, but is preferably 100 μ m～3000 μ m.If thinner than 100 μ m, be easy to bring into air when then being attached on heating element and the radiator sometimes, the result can not obtain sufficient thermal conductivity, or to the operability variation of the attaching operation of adherend.On the other hand, if thicker than 3000 μ m, then the thermal resistance of the thickness direction of thermal conductivity pressure sensitive glueyness sheet (G) becomes big sometimes, and thermal diffusivity suffers damage.
When on the single face of base material or two sides the layer of thermal conductivity pressure sensitive adhesive compositions (F) being shaped, base material is not special to be limited.
As the object lesson of above-mentioned base material, can use metal and the alloy of excellent thermal conductivity such as aluminium, copper, stainless steel, beryllium copper paper tinsel shape thing, comprise flap, the thermal conductivity plastic film that contains the thermal conductivity filler, various non-woven fabrics, woven fiber glass or the honeycomb molded body etc. of the polymkeric substance of heat-conductive silicone etc. self excellent thermal conductivity.
Plastic film can use the film of thermally stable polymers such as comprising polyimide, polyethylene terephthalate, PEN, tetrafluoroethylene, polyetherketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfones, polyphenylene sulfide, polyamidoimide, polyester-imide, aromatic polyamide.
Thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M) are configured as the not special qualification of flaky method.As suitable method, for example can enumerate thermal conductivity pressure sensitive adhesive compositions (F) is coated on the teeming practice on the engineering paper such as polyester film that carried out lift-off processing; With thermal conductivity pressure sensitive adhesive compositions (F) or mixture (M) be clipped in as required between two engineering paper that carried out lift-off processing, and through the method between the roller; The through port mould comes the method for control thickness etc. when extruding with the use forcing machine.
When forming sheet material or after forming sheet material,, can obtain thermal conductivity pressure sensitive glueyness sheet (G) suitably through for example utilizing hot blast, electric heater, infrared rays etc. to heat in mixture (M).The Heating temperature of this moment preferably makes the organo-peroxide thermal polymerization decompose, carry out the polymeric condition of (methyl) acrylate monomer (α 1) efficiently.TR is preferably 100 ℃～200 ℃, more preferably 130 ℃～180 ℃ according to the kind of the organo-peroxide thermal polymerization that uses and different.
Thermal conductivity pressure sensitive glueyness sheet (G) is preferably sheet-like formed body; Said sheet-like formed body is through being configured as sheet with mixture (M); And be heated to more than 100 ℃ and the temperature below 200 ℃; And make mixture (M) formation sheet material and carry out the polymerization of (methyl) acrylate monomer (α 1) in the mixture (M), obtain thus.
3. electron device
The thermal conductivity pressure sensitive glueyness sheet (G) of the invention described above can be used as the part of electron device and uses.At this moment, also can be on the such base material of radiator direct forming, as the part of electron device and provide.As the object lesson of this electron device, can enumerate have electroluminescent cell (EL), instrument or parts that parts, fuel cell, solar cell, store battery, portable phone, PDA(Personal Digital Assistant), notebook computer, liquid crystal, surface conductance type electron emission display device (SED), plasma display panel (PDP) or the unicircuit (IC) etc. of the power-equipment periphery of the parts of the heat generating part of the instrument of photodiode (LED) light source periphery, automobile etc. have heat generating part.
And, be used for an example of the method for use of electronic machine as thermal conductivity pressure sensitive glueyness sheet of the present invention (G), can enumerate led light source is used for concrete example with the method that is described below.That is, directly be attached at led light source; Be clipped between led light source and the heat sink material (scatterer, fan, Peltier's element, heat pipe, graphite flake etc.); Be attached at the heat sink material (scatterer, fan, Peltier's element, heat pipe, graphite flake etc.) that is connected in led light source; Use as the housing that surrounds led light source; Paste the housing of paying in surrounding led light source; Imbed the methods such as gap between led light source and the housing.As the example of the purposes of led light source, can enumerate, have the back lighting device (TV, mobile phone, PC, notebook computer, PDA etc.) of display unit of the liquid crystal board of infiltration type; Lamps apparatus for vehicle; Industrial illumination; Commercial with illumination; General dwelling house is used illumination etc.
In addition, as the concrete example outside the led light source, can be listed below.That is PDP plate; The IC heat generating part; 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 etc.
Further, as the method for use of thermal conductivity pressure sensitive glueyness sheet of the present invention (G), can enumerate housing that is attached at device etc.For example, at the device that is used for automobile etc., be attached at the inside of the housing that automobile has; Be attached at the outside of the housing that automobile has; Heat generating part in the inside of the housing that automobile had (auto-navigation system/fuel cell/heat exchanger) is connected with this housing; Be attached at heating panel that the heat generating part (auto-navigation system/fuel cell/heat exchanger) in the inside of the housing that is had with automobile is connected etc.
And, except automobile, also can use thermal conductivity pressure sensitive glueyness sheet of the present invention (G) with same method.For example, can enumerate PC; Dwelling house; TV; Portable telephone; Vending machine; Refrigerator; Solar cell; Surface conductance type electron emission display device (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; Drying and washing machine; The optical semiconductor device of optical semiconductor and fluor combination; Various power-equipments; Game machine; Electrical condenser etc.
Further, thermal conductivity pressure sensitive glueyness sheet of the present invention (G) is not limited to above-mentioned method of use, can use according to purposes.For example, use for the heat uniforming that makes carpet or heating pad etc.; Sealing agent as led light source/thermal source; Sealing agent as solar battery group; Backboard as solar cell; Be used between the backboard and roof of solar cell; The inboard that is used for the inner thermal insulation layer of vending machine; Use jointly at the enclosure interior of organic EL illumination and siccative or moisture adsorbent; At the heat-conducting layer of the enclosure interior of organic EL illumination and use jointly with siccative or moisture adsorbent above that; The heat-conducting layer of the enclosure interior of organic EL illumination, heat dissipating layer and on use jointly with siccative or moisture adsorbent; The heat dissipating layer of the heat-conducting layer of the enclosure interior of organic EL illumination, epoxy system and on use jointly with siccative or moisture adsorbent; For cooling components such as the device that is used to cool off the human or animal, clothing, towel, bed sheets, be used for the face opposite with health; The pressing element that is used for the fixing device that image processing systems such as electronic photo duplicating machine, electrophotographic printer carry; As the pressing element of the fixing device that carries in the image processing systems such as electronic photo duplicating machine, electrophotographic printer itself; Heat transfer part is used in hot-fluid control as the process object thing that carries film forming apparatus; Heat transfer part is used in the hot-fluid control that is used to carry the process object thing of film forming apparatus; Be used to hold between the skin and internal packing of bomb; Be used for being provided with the casing of the solar panels that absorb solar ray; Be used between CCFL reflector backlight and the aluminum base etc.
Embodiment
Below, utilize embodiment that the present invention is described in further detail, but the invention is not restricted to embodiment.And " part " used herein, " % " short of special explanation all are quality criterias.
＜condition of surface＞
As illustrated later, making thickness is the thermal conductivity pressure sensitive glueyness sheet of 2mm, carries out the affirmation of its condition of surface through range estimation, and the result is shown in table 2～table 4.In the evaluation result of the condition of surface shown in table 2～table 4, " well " is meant does not have significantly concavo-convex (difference of height more than the 0.5mm) on the surface of sheet material." coarse " is meant and forms significantly concavo-convex on the surface of sheet material." * " is meant and can not be configured as sheet.
＜thermal conductivity＞
Prepare to use scissors thickness to be cut into the test film of the size of width 50mm * length 110mm as the thermal conductivity pressure sensitive glueyness sheet of 2mm.Peel off the polyethylene terephthalate film that covers this test film (below be referred to as " demoulding PET film "), on the face that has peeled demoulding PET film, stick preservative film with the mode that does not get into air.The size of this preservative film so long as the size bigger than the surface of adherence of test film get final product.Then, use the test film that has sticked this preservative film to measure thermal conductivity.(unit: mensuration W/m K) is used quick conductive coefficient measuring instrument (trade(brand)name " QTM-500 ", capital of a country electronic industry Co., Ltd. system) to thermal conductivity, carries out through unstable state hot line relative method.And, on datum plate, use silicon sponge (current value: 1A), organo-silicone rubber (current value: 2A) and quartzy (current value: 4A) successively.In addition, surpass the sheet material of 1.5W/m K, on datum plate, use organo-silicone rubber (current value: 2A), quartzy (current value: 4A) and zirconium white (current value: 6A) successively for thermal conductivity.Its result is shown in table 2～table 4.If the result who is obtained by this evaluation then we can say excellent thermal conductivity greater than 1.0W/m K.
＜flame retardant resistance (2.0mm)＞
Preparing 5 is the test film that the thermal conductivity pressure sensitive glueyness sheet of 2mm is cut into the size of width 10mm * length 150mm with thickness.The flow of air of adjustment Bunsen burner, forming highly is the blue flame about 20mm, the flame interaction that makes blowtorch in vertical support test film lower end (intersecting about 10mm) with flame and kept for 10 seconds after, test film is separated with torch flame.Then, if the fray-out of flame of test film then directly makes torch flame act on test film, further kept for 10 seconds after, test film is separated with torch flame.Have flame and flame-less combusting continuous time, the having or not of dropping (drop) of burning to contacting after finishing with the 2nd time flame for the 1st time are estimated, and carry out the judgement of UL-94 (flame-retardancy standards).Promptly; That utilizes flaming combustion time length and the total of flame-less combusting continuous time after flaming combustion time length of contacting with the 2nd time flame for the 1st time after finishing, the 2nd time flame contact finish, 5 test films has having or not of flame and the total of flameless combustion time and burning dropping (drop), judges which person who is equivalent to V-0 and V-2.Following situation note is made V-0; That is, the 1st time, the 2nd time all 10 seconds with interior end flaming combustion, being aggregated in 30 seconds of the 2nd time flaming combustion time length and flameless combustion time; And then 5 test films have being aggregated in 50 seconds of flame and flameless combustion time, and drop does not burn.In addition; Following situation note is made V-2; That is, the 1st time, the 2nd time all 30 seconds with interior end flaming combustion, being aggregated in 60 seconds of the 2nd time flaming combustion time length and flameless combustion time; And then 5 test films have being aggregated in 250 seconds of flame and flameless combustion time, and the burning drop is arranged.Further, all the incendiary situation is designated as outside the standard.Its result is shown in table 2～table 4.If estimate according to this, satisfy the condition of V-0, then we can say excellent in flame retardance.
＜flame retardant resistance (1.0mm)＞
Preparing 5 is the test film that the thermal conductivity pressure sensitive glueyness sheet of 1mm is cut into the size of width 10mm * length 150mm with thickness.The flow of air of adjustment Bunsen burner, forming highly is the blue flame about 20mm, the flame interaction that makes blowtorch in vertical support test film lower end (intersecting about 10mm) with flame and kept for 10 seconds after, test film is separated with torch flame.Then, if the fray-out of flame of test film then directly makes torch flame act on test film, further kept for 10 seconds after, test film is separated with torch flame.Have flame and flame-less combusting continuous time, the having or not of dropping (drop) of burning to contacting after finishing with the 2nd time flame for the 1st time are estimated, and carry out the judgement of UL-94 (flame-retardancy standards).Promptly; That utilizes flaming combustion time length and the total of flame-less combusting continuous time after flaming combustion time length of contacting with the 2nd time flame for the 1st time after finishing, the 2nd time flame contact finish, 5 test films has having or not of flame and the total of flameless combustion time and burning dropping (drop), judges which person who is equivalent to V-0 and V-2.Following situation note is made V-0; That is, the 1st time, the 2nd time all 10 seconds with interior end flaming combustion, being aggregated in 30 seconds of the 2nd time flaming combustion time length and flameless combustion time; And then 5 test films have being aggregated in 50 seconds of flame and flameless combustion time, and drop does not burn.In addition; Following situation note is made V-2; That is, the 1st time, the 2nd time all 30 seconds with interior end flaming combustion, being aggregated in 60 seconds of the 2nd time flaming combustion time length and flameless combustion time; And then 5 test films have being aggregated in 250 seconds of flame and flameless combustion time, and the burning drop is arranged.Further, all the incendiary situation is designated as outside the standard.Its result is shown in table 2～table 4.The thickness of thermal conductivity pressure sensitive glueyness sheet is thin more, is difficult to keep flame retardant resistance more, therefore for the sheet material of 1mm, if satisfy the V-2 standard, then we can say excellent in flame retardance.For the sheet material that satisfies V-0, be evaluated as and have special excellent flame.
＜dielectric breakdown strength＞
Through estimate the dielectric breakdown strength of thermal conductivity pressure sensitive glueyness sheet according to the method for JIS K6249.That is, adopt the short period of time method, in 23 ℃ of silicone oil, will detect electric current and be made as 10mA, dipping was measured with interior at 15 minutes after 2 minutes in oil.Its result is shown in table 2～4.And for the mensuration of dielectric breakdown strength, preparation thickness is that the thermal conductivity pressure sensitive glueyness sheet of 0.5mm carries out.Wherein, measured value is scaled kV/mm and explains.
＜plasticity＞
With the diameter of thermal conductivity pressure sensitive adhesive compositions 50g on the aluminium sheet of 30cm * 15cm * 1.5mm is in the circle of 7cm; Mode to form chevron leaves standstill; Kept 30 seconds with aluminium sheet inclination 45 degree and with this state immediately then, confirm the flowability of thermal conductivity pressure sensitive adhesive compositions.Flowability is good more, and it is more excellent to be evaluated as plasticity.Evaluation is through carrying out to get off.
◎: the above situation of 10cm flows.
Zero: the 5cm that flows is above and less than the situation of 10cm.
△: the 1cm that flows is above and less than the situation of 5cm.
*: flow less than the situation of 1cm.
(embodiment 1)
In reactor drum; 100 parts of monomer mixtures that adding is formed by 2-EHA 94% and vinylformic acid 6%, 2,0.03 part of 2 '-Diisopropyl azodicarboxylate and 700 parts in ETHYLE ACETATE dissolve equably; After carrying out the nitrogen displacement, 80 ℃ of polyreactions of carrying out 6 hours.Polymerisation conversion is 97%.The polymkeric substance of gained is carried out drying under reduced pressure, make ETHYLE ACETATE evaporation, obtain having (methyl) acrylic ester polymer of the solid-like of viscosity.The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer is 270,000, and 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 utilized polystyrene standard to convert and are tried to achieve through being the GPC of elutriant with the THF.
Then; Use electronic balance successively weighing with the mixed of 60:35:5 84.1 parts of 0.9 part of the multi-functional monomers of pentaerythritol triacrylate, tetramethylol methane tetraacrylate and pentaerythritol diacrylate, 2-EHA (below be abbreviated as " 2EHA "), as 1 of organo-peroxide thermal polymerization; Two (t-butylperoxy ketonic oxygen base) hexanes of 6-(below be abbreviated as " tBCH ") (half life temperature was 150 ℃ in 1 minute) 0.5 part; And mix, obtain liquid starting material.
Then, with 53 parts of 15 parts of above-mentioned (methyl) acrylic ester polymers, aforesaid liquid raw material, SULPHOSUCCINIC ACID ESTER 1 (trade(brand)name " CR-741 ", Daihachi Chemical Industry Co., Ltd.'s system, viscosity 25 ℃ time the: 32000mPa s (rotating speed 10, rotor No.5 (reference table 1), numerical value 80), under atmospheric pressure 15 ℃～100 ℃ temperature province are generally liquid, compound name " dihydroxyphenyl propane two (diphenyl phosphoester) "), white lake (trade(brand)name " BF083 ", Nippon Light Metal Co., Ltd's system, median size: 8 μ m) 266 parts, aluminum oxide 1 (trade(brand)name " AL-47-H ", Showa Denko K. K's system, BET specific surface area: 1.8m 2/ g, peak particle diameter: 2 μ m) 281 parts and expanded graphite powder (trade(brand)name " EC-50 ", itoite China ink Industrial Co., Ltd system, median size: 250 μ m) 3.8 parts; Use thermostatic bath (trade(brand)name " PVC ス コ メ イ ト 150III ", Toki Sangyo Co., Ltd.'s system) and Kazakhstan bit formula amalgamator (trade(brand)name " ACM-5LVT type ", capacity: 5L, the little flat making of Co., Ltd. are made) under reduced pressure to mix; Carry out deaeration simultaneously, obtain the thermal conductivity pressure sensitive adhesive compositions.The temperature adjusting of breathing out bit formula container is set in 60 ℃.Concrete blending means is described below.
At first, the composition beyond the filler composition is joined in the bit formula container of Kazakhstan, mix with 3 * 10 minutes condition of rotating speed scale.Then, the filler composition beyond the expanded graphite powder is joined in the bit formula container of above-mentioned Kazakhstan, mix with 5 * 10 minutes condition of rotating speed scale.Then, in the above-mentioned Kazakhstan bit formula container that the expanded graphite powder is added, with rotating speed scale 3 * 10 minutes ,-condition of 0.1MPa carries out vacuum defoamation, mixes simultaneously.
Then; The mixture (M1) of gained is clamped with demoulding PET film; Above demoulding PET film, be configured as sheet, utilize 150 ℃ hotblast stove to carry out 15 minutes polymerization, obtain the thermal conductivity pressure sensitive glueyness sheet (G1) that the two sides is covered with demoulding PET film with roller.By the polymerisation conversion of the calculating of the levels of residual monomers in the thermal conductivity pressure sensitive glueyness sheet (G1) (methyl) acrylate monomer blend, the result is 99.9%.
(embodiment 2～18, comparative example 1～15)
Shown in table 2～table 4; Except change each title complex with its amount; Other and embodiment 1 attempt the making of thermal conductivity pressure sensitive glueyness sheet (G2)～(G19), (GC1)～(GC15) equally, obtain thermal conductivity pressure sensitive glueyness sheet (G2)～(G19), (GC1)～(GC10), (GC13), (GC14).For comparative example 11, comparative example 12 and comparative example 15, can not make thermal conductivity pressure sensitive glueyness sheet.
For thermal conductivity pressure sensitive glueyness sheet (G1～G19, GC1), make the sheet material that thickness is 2mm, 1mm and 0.5mm respectively, estimate.For thermal conductivity pressure sensitive glueyness sheet (GC2～GC10, GC13, GC14), make the sheet material that thickness is 2mm and 1mm respectively, estimate.
And the title complex that in embodiment 1, does not have to use is described below.
The expanded graphite powder:
Trade(brand)name " EC-500 ", the itoite China ink median size 30 μ m of Co., Ltd.
SULPHOSUCCINIC ACID ESTER 2:
Trade(brand)name " レ オ Off ォ ス 65 "; Monosodium glutamate Off ァ イ Application テ Network ノ Co., Ltd. system; Viscosity in the time of 25 ℃: 5800mPa s (rotating speed 10, rotor N0.3 (reference table 1), numerical value 58); 15 ℃～100 ℃ temperature province under atmospheric pressure is generally liquid, compound name " tricresyl phosphate allyl group isopropyl ester thing "
SULPHOSUCCINIC ACID ESTER 3:
Trade(brand)name " レ オ Off ォ ス 35 "; Monosodium glutamate Off ァ イ Application テ Network ノ Co., Ltd. system; Viscosity in the time of 25 ℃: 1200mPa s (rotating speed 10, rotor No.3 (reference table 1), numerical value 12); 15 ℃～100 ℃ temperature province under atmospheric pressure is generally liquid, compound name " tricresyl phosphate allyl group isopropyl ester thing "
Spun glass:
Trade(brand)name " チ ョ プ De ス ト ラ Application De " ， オ ー ウ ェ Application ス コ ー ニ Application グ ジ ャ パ Application Co., Ltd. system, staple length: 3mm
Aluminum oxide 2:
Trade(brand)name " AL-13-H ", Showa Denko K. K's system, BET specific surface area: 1.2m 2/ g, peak particle diameter: 60 μ m
Aluminum oxide 3:
Trade(brand)name " A-42-2 ", Showa Denko K. K's system, BET specific surface area: 1.1m 2/ g, peak particle diameter: 5 μ m
Aluminum oxide 4:
Trade(brand)name " A-43-L ", Showa Denko K. K's system, BET specific surface area: 8.3m 2/ g, peak particle diameter: 1.4 μ m
Aluminum oxide 5:
Trade(brand)name " A-13-H ", Showa Denko K. K's system, BET specific surface area: 0.8m 2/ g, peak particle diameter: 57 μ m
Aluminum oxide 6:
Trade(brand)name " AS-10 ", Showa Denko K. K's system, BET specific surface area: 0.5m 2/ g, peak particle diameter: 39 μ m
SP 1:
Trade(brand)name " PT-120 ", モ メ Application テ ィ Block パ フ ォ ー マ Application ス マ テ リ ア Le ズ ジ ャ パ Application contract commercial firm system, BET specific surface area: 2m 2/ g, median size: 8 μ m～14 μ m
Talcum:
Trade(brand)name " MS-P ", Japanese talcum Co., Ltd. system, BET specific surface area: 4.5m 2/ g, median size: 13 μ m
Lime carbonate:
Trade(brand)name " SL-100 ", the former chemical industry of bamboo Co., Ltd. system, BET specific surface area: 0.8m 2/ g, median size: 6 μ m
Whipping agent:
Trade(brand)name " ネ オ セ Le ボ Application N#1000S ", Yonghe County changes into Industrial Co., Ltd's system, the 4.4-OBSH.
＜performance evaluation＞
The evaluation result of the sheet material of making in sheet material of making among the embodiment (G1)～(G19) and the comparative example (GC1)～(GC10), (GC13), (GC14) is shown in table 2～table 4.And, in the sheet material of comparative example, except the sheet material (GC1) of comparative example 1, in the evaluation arbitrarily of condition of surface, thermal conductivity and flame retardant resistance,, therefore do not carry out the evaluation of dielectric breakdown strength all for not preferred result.In addition; The content of comparative example 11 and white lake that surpasses the scope of the present invention's regulation for the content of expanded graphite powder surpasses the comparative example 12 of the scope of the present invention's regulation; The viscosity of its thermal conductivity pressure sensitive adhesive compositions is too high, can not form sheet material, does not therefore carry out performance evaluation.For the comparative example 15 of the content of the SULPHOSUCCINIC ACID ESTER that has used the viscosity lower than the scope of the present invention regulation, the thermal conductivity pressure sensitive adhesive compositions does not solidify, and can not form sheet material, does not therefore carry out performance evaluation.
[table 2]
Figure 987449DEST_PATH_IMAGE002
[table 3]
Figure 360662DEST_PATH_IMAGE003
[table 4]
Figure 755871DEST_PATH_IMAGE004
Shown in table 2 and table 3, for the sheet material among the embodiment (G1)～(G19), condition of surface is all good, thermal conductivity (thermal conductivity), flame retardant resistance, plasticity, dielectric breakdown strength excellence.Especially, with the sheet material (G5) of the embodiment 5 of median size different oxidation aluminium and usefulness, compare with the situation of the aluminum oxide that uses a kind and equivalent, dielectric breakdown strength is excellent.In addition, will form the sheet material (G17) with molecular weight (on the viscosity when being reflected in 25 ℃) different SULPHOSUCCINIC ACID ESTER and the embodiment of usefulness 17, and compare with the situation of the SULPHOSUCCINIC ACID ESTER that uses a kind and equivalent, dielectric breakdown strength is also excellent.
On the other hand, shown in table 3 and table 4, for the sheet material in the comparative example (GC1)～(GC10), (GC13), (GC14), any one of above-mentioned performance is all poor.Specifically, like the following stated.
Comparative example 1: surpass the sheet material (GC1) of comparative example 1 of the scope of the present invention's regulation for the content of expanded graphite powder, its dielectric breakdown strength is poor.
Comparative example 2: for the sheet material (GC2) of the comparative example that does not contain aluminum oxide 2, its thermal conductivity and plasticity are poor.
Comparative example 3,4: for containing and the sheet material (GC3) of the comparative example 3 of regulation different oxidation aluminium of the present invention and the sheet material (GC4) of comparative example 4, flame retardant resistance is all poor.
Comparative example 5: for containing the sheet material (GC5) that talcum replaces the comparative example 5 of aluminum oxide, its condition of surface is poor, thermal conductivity and poor fire.
Comparative example 6: for containing the sheet material (GC6) that lime carbonate replaces the comparative example 6 of aluminum oxide, thermal conductivity and poor fire.
Comparative example 7: the sheet material (GC7) of the comparative example 7 of the scope that discontented unabridged version invention is stipulated for the content of expanded graphite powder, its poor thermal conductivity.
Comparative example 8: for containing the sheet material (GC8) that SP 1 replaces the comparative example 8 of aluminum oxide, its condition of surface is poor, poor fire.
Comparative example 9: the sheet material (GC9) of the comparative example 9 of the scope that discontented unabridged version invention is stipulated for the content of white lake, its poor fire.
Comparative example 10: the sheet material (GC10) of the comparative example 10 of the scope that discontented unabridged version invention is stipulated for the content of aluminum oxide, its thermal conductivity and poor fire.
Comparative example 13: the sheet material (GC13) of the comparative example 13 of the scope that discontented unabridged version invention is stipulated for the content of SULPHOSUCCINIC ACID ESTER, its poor fire.
Comparative example 14: surpass the sheet material (GC14) of comparative example 14 of the scope of the present invention's regulation for the content of SULPHOSUCCINIC ACID ESTER, its condition of surface is poor, poor thermal conductivity.
＜between thermal source and scatterer the time temperature decreasing effect＞
With ceramic heater (trade(brand)name " MS-5 "; 25mm * 25mm; Sakaguchi Dennetsu Kabushiki Kaisha's system), thermal conductivity pressure sensitive glueyness sheet (25mm * 25mm * thickness 1.5mm) and aluminium sheet (150mm * 150mm * thickness 1.5mm) lamination successively; Ceramic heater is heated with the 45W running, measure the top temperature on the surface of the ceramic heater after 60 minutes.Its result is shown in table 5.
(embodiment A)
Use with the sheet material (G1) of the foregoing description 1 and carry out said determination for the same sheet material of forming (G1 ').
(Embodiment B)
Use with the sheet material (G5) of the foregoing description 5 and carry out said determination for the same sheet material of forming (G5 ').
(Comparative examples A)
Use with the sheet material (GC7) of above-mentioned comparative example 7 and carry out said determination for the same sheet material of forming (GC7 ').
(table 5)
Figure 570243DEST_PATH_IMAGE005
Shown in above test-results, the insulativity of the sheet material among the embodiment and excellent in flame retardance.Further, can know that the sheet material among the embodiment can be realized effective heat radiation by the result shown in the table 5.
More than; Relate to and think now tool practicality and preferred embodiment; Describe the present invention; But the present invention is not limited to disclosed embodiment in the present specification; In the scope of the purport of not violating the invention that to learn by the scope and the description in its entirety of claim or thought, can suitably change, follow thermal conductivity pressure sensitive adhesive compositions, thermal conductivity pressure sensitive glueyness sheet and the electron device of this change also must understand as being included in the technical scope of the present invention.

Claims (9)

1. thermal conductivity pressure sensitive adhesive compositions (F), it contains
At least a polymkeric substance (S) 100 mass parts,
Expanded graphite powder (B) 1.8 mass parts～18 mass parts,
In the time of 25 ℃ viscosity be above and 15 ℃～100 ℃ the temperature province under atmospheric pressure of 3000mPa s be liquid SULPHOSUCCINIC ACID ESTER (C) 20 mass parts～130 mass parts,
The BET specific surface area is 1m 2Aluminum oxide (E) 100 mass parts～1000 mass parts that/g is above and
Except that expanded graphite powder (B) and flame retardant resistance heat conduction mineral compound (D) 160 mass parts～600 mass parts the above-mentioned aluminum oxide (E).
2. thermal conductivity pressure sensitive adhesive compositions as claimed in claim 1 (F), wherein, above-mentioned aluminum oxide (E) has a plurality of peaks in size-grade distribution, and the peak particle diameter of maximum particle diameter side is more than 10 with the ratio of the peak particle diameter of minimum grain size side.
3. according to claim 1 or claim 2 thermal conductivity pressure sensitive adhesive compositions (F), wherein, SULPHOSUCCINIC ACID ESTER (C) mixes through forming the SULPHOSUCCINIC ACID ESTER more than 2 kinds different with molecular weight.
4. like each described thermal conductivity pressure sensitive adhesive compositions (F) in the claim 1～3, wherein, above-mentioned polymkeric substance (S) is (methyl) acrylic ester polymer (A1).
5. thermal conductivity pressure sensitive adhesive compositions as claimed in claim 4 (F); Wherein, above-mentioned (methyl) acrylic ester polymer (A1) is the polymkeric substance that (methyl) acrylate monomer (α 1) polymerization is obtained through in the presence of other (methyl) acrylic ester polymer (AP1).
6. thermal conductivity pressure sensitive glueyness sheet (G), it forms through each described thermal conductivity pressure sensitive adhesive compositions (F) in the claim 1～5 is configured as sheet.
7. thermal conductivity pressure sensitive glueyness sheet (G), it obtains through following step:
With (methyl) acrylic ester polymer (AP1) and (methyl) acrylate monomer (α 1) the two to add up to 100 mass parts, expanded graphite powder (B) 1.8 mass parts～18 mass parts, SULPHOSUCCINIC ACID ESTER (C) 20 mass parts～130 mass parts, BET specific surface area be 1m 2Aluminum oxide (E) 100 mass parts～1000 mass parts that/g is above and be configured as sheet except that the mixture (M) of above-mentioned expanded graphite powder (B) and flame retardant resistance heat conduction mineral compound (D) 160 mass parts～600 mass parts the above-mentioned aluminum oxide (E); After being configured as the flaky while or being configured as sheet, in the presence of above-mentioned (methyl) acrylic ester polymer (AP1) in said mixture (M) above-mentioned (methyl) acrylate monomer (α 1) in the said mixture (M) is carried out polymerization.
8. electron device, it has claim 6 or 7 described thermal conductivity pressure sensitive glueyness sheets (G).
9. electron device as claimed in claim 8, it is power-equipment, fuel cell, solar cell, store battery, portable phone, PDA(Personal Digital Assistant), notebook computer, liquid crystal, surface-conduction-electron emission display (SED), plasma display panel (PDP) or the unicircuit (IC) of instrument with electroluminescent cell (EL), photodiode (LED) light source, automobile etc.
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