CN103874739A - Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-form molded body, manufacturing method of these, and electronic component - Google Patents

Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-form molded body, manufacturing method of these, and electronic component Download PDF

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Publication number
CN103874739A
CN103874739A CN201280050873.2A CN201280050873A CN103874739A CN 103874739 A CN103874739 A CN 103874739A CN 201280050873 A CN201280050873 A CN 201280050873A CN 103874739 A CN103874739 A CN 103874739A
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China
Prior art keywords
methyl
mass parts
thermal conductivity
sensitive adhesive
sheet
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Chinese (zh)
Inventor
熊本拓朗
北川明子
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Zeon Corp
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Nippon Zeon Co Ltd
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Publication of CN103874739A publication Critical patent/CN103874739A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H01L23/3737—Organic materials with or without a thermoconductive filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

This mixed composition contains 100 parts by mass of a (methyl)acrylate resin composition (A) containing (methyl)acrylate acid ester polymers (A1) and (methyl)acrylate acid ester monomers (alpha1), 90-1200 parts by mass of a thermally conductive filler (B), 0.2-8 parts by mass of polyfunctional monomers (D) having multiple polymerizable unsaturated bonds, and 0.3-5.0 parts by mass of a polyfunctional epoxy compound (E) having 2 to 10000 functional groups and a viscosity at 25 DEG C of 600mPa*s or less. This composition is characterized by performing a polymerization reaction between the (methyl)acrylate acid ester monomers (alpha1) and the polyfunctional monomers (D), and a crosslinking reaction of the (methyl)acrylate acid ester polymers (A1) and/or polymers containing structural units derived from the (methyl)acrylate acid ester monomers (alpha1).

Description

Thermal conductivity pressure-sensitive adhesive composite, the sheet-like formed body of thermal conductivity pressure-sensitive adhesive, their manufacture method and electronic unit
Technical field
The present invention relates to thermal conductivity pressure-sensitive adhesive composite, the sheet-like formed body of thermal conductivity pressure-sensitive adhesive, they manufacture method and possess this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of the sheet-like formed body of this thermal conductivity pressure-sensitive adhesive.
Background technology
In recent years, for such electronic units such as plasma display (PDP), unicircuit (IC) chips, follow its high performance thermal value to increase.Its result, need to take the handicapped countermeasure causing due to temperature rise.Typically, adopt the radiators such as metal scatterer, heating panel, radiator element are installed on the heating element possessing in electronic unit etc., thereby make the method for its heat radiation.In order effectively to carry out the heat conduction from heating element to radiator, use the member (conducting strip) of the sheet that thermal conductivity is high.Typically, in the purposes that heating element and radiator are fixed, need to except thermal conductivity, also there is the composition (hereinafter referred to as " thermal conductivity pressure-sensitive adhesive composite ") of pressure-sensitive adhesive or the member (hereinafter referred to as " the sheet-like formed body of thermal conductivity pressure-sensitive adhesive ") of sheet.
Above-mentioned thermal conductivity pressure-sensitive adhesive composite and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive are to use to radiator heat by conduction as one of object from heating element, thereby requirement can be sealed at the flexibility of heating element and radiator.As the technology of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive that relates to flexibility excellence, for example, there is in patent documentation 1 disclosed conducting strip in disclosed flame retardant resistance radiator element, patent documentation 2.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-176640 communique
Patent documentation 2: TOHKEMY 2010-132856 communique.
Summary of the invention
The problem that invention will solve
In order to use thermal conductivity pressure-sensitive adhesive composite or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive effectively heat to be conducted to radiator from heating element, as mentioned above, thereby can consider to improve flexibility and improve the adaptation of heating element and radiator.In addition, in order to use thermal conductivity pressure-sensitive adhesive composite or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive effectively from heating element to radiator heat by conduction, for example, thereby can consider them to be shaped thinly and to reduce the thermal resistance of thickness direction.
But there is following problem in thermal conductivity pressure-sensitive adhesive composite in the past or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive: if be shaped thinly, be difficult to obtain the tensile strength requiring as goods.In addition, when wish adjustment composition makes it have tensile strength, hardness also increases, and flexibility is impaired.If hardening, thus likely and clung body between there is the heat transfer efficiency variation from heating element to radiator such as inclusion of air.Thus, for technology in the past, when thermal conductivity pressure-sensitive adhesive composite or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive are shaped thinly, be difficult to have concurrently flexibility and tensile strength.
Therefore, problem of the present invention is, is shaped and also can possesses thermal conductivity pressure-sensitive adhesive composite and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive and their manufacture method of flexibility and tensile strength and possess this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of the sheet-like formed body of this thermal conductivity pressure-sensitive adhesive even if provide thinly.
The technique means of dealing with problems
The 1st mode of the present invention is thermal conductivity pressure-sensitive adhesive composite (F), it is (methyl) acrylic resin composition (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that contains 100 mass parts, thermal conductivity filler (B) more than 90 mass parts and below 1200 mass parts, the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s more than 0.2 mass parts and below 8 mass parts, the viscosity having at functional group more than 2 and below 10000 and 25 DEG C above with 0.3 mass parts and below 5.0 mass parts is the blend compositions of the multi-functional epoxy compound (E) below 600mPa s, it carries out the polyreaction of (methyl) acrylate monomer (α 1) and multi-functional monomer (D), and the crosslinking reaction of (methyl) acrylic ester polymer (A1) and/or the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) forms.
" (methyl) vinylformic acid " expression " vinylformic acid and/or methacrylic acid " in this specification sheets." thermal conductivity filler (B) " refer to, by add can improve thermal conductivity pressure-sensitive adhesive composite (F) or afterwards the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) of explanation thermal conductivity, the filler of thermal conductivity more than 1W/m K." polyreaction of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) " refers to, one or more polyreactions in copolyreaction, the polyreaction of (methyl) acrylate monomer (α 1) and the polyreaction of multi-functional monomer (D) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D)." crosslinking reaction of (methyl) acrylic ester polymer (A1) and/or the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) " refers to, one or more crosslinking reactions in the crosslinking reaction of crosslinking reaction each other of (methyl) acrylic ester polymer (A1), the crosslinking reaction each other of polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1).
The 2nd mode of the present invention is the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), it will comprise (methyl) acrylic resin composition (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts, thermal conductivity filler (B) more than 90 mass parts and below 1200 mass parts, the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s more than 0.2 mass parts and below 8 mass parts, the viscosity at functional group more than 2 and below 10000 and 25 DEG C of having above with 0.3 mass parts and below 5.0 mass parts is that the blend compositions of the multi-functional epoxy compound (E) below 600mPa s is configured as after sheet, or when this blend compositions is configured as to sheet, carry out the polyreaction of (methyl) acrylate monomer (α 1) and multi-functional monomer (D), and the crosslinking reaction of (methyl) acrylic ester polymer (A1) and/or the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) forms.
The 3rd mode of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), it comprises following operation: make and comprise (A), (B), (D), (E) operation of blend compositions, described (A), (B), (D), (E) be: (methyl) acrylic resin composition (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts, thermal conductivity filler (B) more than 90 mass parts and below 1200 mass parts, the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s more than 0.2 mass parts and below 8 mass parts, the viscosity having at functional group more than 2 and below 10000 and 25 DEG C above with 0.3 mass parts and below 5.0 mass parts is the multi-functional epoxy compound (E) below 600mPa s, and, in this blend compositions, the operation of the crosslinking reaction of the polymkeric substance that carries out polyreaction, (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1).
The 4th mode of the present invention is the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), it comprises following operation: make and comprise (A), (B), (D), (E) operation of blend compositions, described (A), (B), (D), (E) be: (methyl) acrylic resin composition (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts, thermal conductivity filler (B) more than 90 mass parts and below 1200 mass parts, the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s more than 0.2 mass parts and below 8 mass parts, the viscosity having at functional group more than 2 and below 10000 and 25 DEG C above with 0.3 mass parts and below 5.0 mass parts is the multi-functional epoxy compound (E) below 600mPa s, and, this blend compositions is being configured as after sheet, or when this blend compositions is configured as to sheet, the operation of the crosslinking reaction of the polymkeric substance that carries out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1).
The 5th mode of the present invention is electronic unit, and it possesses radiator and fits in the thermal conductivity pressure-sensitive adhesive composite (F) of the 1st mode of the present invention of this radiator or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) that possesses radiator and fit in the 2nd mode of the present invention of this radiator.
Invention effect
Be shaped and also can there is thermal conductivity pressure-sensitive adhesive composite and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive and their manufacture method of flexibility and tensile strength and possess this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of the sheet-like formed body of this thermal conductivity pressure-sensitive adhesive even if can provide according to the present invention thinly.
Embodiment
1. thermal conductivity pressure-sensitive adhesive composite (F), the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G)
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F), it is comprising following (A), (B), (D), (E) in blend compositions: (methyl) acrylic resin composition (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), thermal conductivity filler (B), there is the multi-functional monomer (D) (sometimes referred to as " multi-functional monomer (D) ") of multiple polymerizability unsaturated link(age)s, with the viscosity having at functional group more than 2 and below 10000 and 25 DEG C be the multi-functional epoxy compound (E) (sometimes referred to as " multi-functional epoxy compound (E) ") below 600mPa s, at least carry out the copolyreaction of (methyl) acrylate monomer (α 1) and multi-functional monomer (D), the polyreaction of (methyl) acrylate monomer (α 1), and at least any polyreaction in the polyreaction of multi-functional monomer (D), and (methyl) acrylic ester polymer (A1) crosslinking reaction each other, the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) crosslinking reaction each other, and at least any crosslinking reaction in the crosslinking reaction of (methyl) acrylic ester polymer (A1) and the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) forms.
In addition, the sheet-like formed body of thermal conductivity pressure-sensitive adhesive of the present invention (G), it is configured as above-mentioned blend compositions after sheet, or when above-mentioned blend compositions is configured as to sheet, at least carry out the copolyreaction of (methyl) acrylate monomer (α 1) and multi-functional monomer (D), the polyreaction of (methyl) acrylate monomer (α 1), and at least any polyreaction in the polyreaction of multi-functional monomer (D), and (methyl) acrylic ester polymer (A1) crosslinking reaction each other, the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) crosslinking reaction each other, and at least any crosslinking reaction in the crosslinking reaction of (methyl) acrylic ester polymer (A1) and the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1) forms.
Describe for forming such thermal conductivity pressure-sensitive adhesive composite (F) and the material of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) below.
< (methyl) acrylic resin composition (A) >
Contain (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) for (methyl) of the present invention acrylic resin composition (A).It should be noted that, as mentioned above, while obtaining thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), the crosslinking reaction of the polymkeric substance that obtains polyreaction and (methyl) acrylic ester polymer (A1) of the polymkeric substance that produces the structural unit that derives from (methyl) acrylate monomer (α 1) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1).Mix and/or a part of bonding with the composition of (methyl) acrylic ester polymer (A1) by the polymkeric substance that carries out this polyreaction and crosslinking reaction, contain the structural unit that derives from (methyl) acrylate monomer (α 1).
In the present invention, about the consumption of acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), with respect to (methyl) acrylic resin composition (A) 100 quality %, preferably (methyl) acrylic ester polymer (A1) is that 5 quality % are above and 50 quality % are following, (methyl) acrylate monomer (α 1) is more than 50 quality % and below 95 quality %.Be above-mentioned scope by the ratio that contains that makes (methyl) acrylate monomer (α 1), the thermal conductivity that is easily shaped pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).
((methyl) acrylic ester polymer (A1))
Can be used in (methyl) of the present invention acrylic ester polymer (A1) and be not particularly limited, preferably contain form second-order transition temperature be-20 DEG C of following homopolymer (methyl) acrylate monomer unit (a1) and there is the monomeric unit (a2) of organic acidic group.
(methyl) acrylate monomer (a1m) of giving the unit (a1) of above-mentioned (methyl) acrylate monomer is not particularly limited, for example, can list ethyl propenoate (second-order transition temperature of homopolymer is-24 DEG C), vinylformic acid n-propyl (second-order transition temperature of homopolymer is-37 DEG C), n-butyl acrylate (second-order transition temperature of homopolymer is-54 DEG C), sec-butyl acrylate (second-order transition temperature of homopolymer is-22 DEG C), the positive heptyl ester of vinylformic acid (second-order transition temperature of homopolymer is-60 DEG C), the just own ester of vinylformic acid (second-order transition temperature of homopolymer is-61 DEG C), vinylformic acid n-octyl (second-order transition temperature of homopolymer is-65 DEG C), 2-EHA (second-order transition temperature of homopolymer is-50 DEG C), vinylformic acid 2-methoxyl group ethyl ester (second-order transition temperature of homopolymer is-50 DEG C), vinylformic acid 3-methoxyl group propyl ester (second-order transition temperature of homopolymer is-75 DEG C), vinylformic acid 3-methoxyl group butyl ester (second-order transition temperature of homopolymer is-56 DEG C), vinylformic acid oxyethyl group methyl esters (second-order transition temperature of homopolymer is-50 DEG C), n octyl methacrylate (second-order transition temperature of homopolymer is-25 DEG C), methacrylic acid ester in the positive last of the ten Heavenly stems (second-order transition temperature of homopolymer is-49 DEG C) etc.Wherein, be preferably n-butyl acrylate, 2-EHA, vinylformic acid 2-methoxyl group ethyl ester, more preferably n-butyl acrylate, 2-EHA, more preferably 2-EHA.
These (methyl) acrylate monomers (a1m) can use separately one, also can be used in combination two or more.
More than (methyl) acrylate monomer (a1m) reaches in (methyl) acrylic ester polymer (A1) with monomeric unit therefrom (a1) and is preferably 80 quality % and below 99.9 quality %, more preferably the mode of the amount more than 85 quality % and below 99.5 quality % is for polymerization.The consumption of (methyl) acrylate monomer (a1m) is in above-mentioned scope time, and the viscosity of the polymerization system during easily by polymerization remains on suitable scope.
Then, the monomeric unit (a2) with organic acidic group is described.The monomer (a2m) of giving the monomeric unit (a2) with organic acidic group is not particularly limited, and as its representational example, can list the monomer of organic acidic groups such as having carboxyl, anhydride group, sulfonic group.In addition, in addition to these, can also use the monomer that contains sulfeno, sulfino, phosphate etc.
As the concrete example of monomer with carboxyl, can list the α such as such as vinylformic acid, methacrylic acid, β-crotonic acid, β-olefinic unsaturated monocarboxylic; The α such as methylene-succinic acid, toxilic acid, fumaric acid, the unsaturated polycarboxylic acid of β-olefinic, and the α such as monomethyl itaconate, butyl maleate, fumaric acid list propyl ester, the unsaturated partial esters of polycarboxylic acids of β-olefinic etc.In addition, can similarly use maleic anhydride, itaconic anhydride etc. to there is the material that can obtain by hydrolysis etc. the group of carboxyl.
As the concrete example with sulfonic monomer, can list the α such as allyl sulphonic acid, methallylsulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide-2-methyl propane sulfonic, β-unsaturated sulfonic acid and their salt.
As monomer (a2m), above among the illustrative monomer with organic acidic group, more preferably there is the monomer of carboxyl, wherein, be particularly preferably the monomer with vinylformic acid or methacrylic acid.These monomers are from can easily obtaining with cheapness industrial, and it is preferred setting out with the copolymerizable of other monomer component also good, productive viewpoint.It should be noted that, monomer (a2m) can use separately one, also can be used in combination two or more.
More than the monomer (a2m) with organic acidic group reaches in (methyl) acrylic ester polymer (A1) with monomeric unit therefrom (a2) and is preferably 0.1 quality % and below 20 quality %, more preferably the mode of the amount more than 0.5 quality % and below 15 quality % is for polymerization.The consumption of monomer (a2m) with organic acidic group is in above-mentioned scope time, and the viscosity of the polymerization system during easily by polymerization remains on suitable scope.
It should be noted that, by having the polymerization of monomer (a2m) of organic acidic group, to import in (methyl) acrylic ester polymer (A1) be easy to the monomeric unit (a2) with organic acidic group as previously mentioned, thereby preferably, also can, after (methyl) acrylic ester polymer (A1) generates, import organic acidic group by known high molecular weight reactive.
In addition, (methyl) acrylic ester polymer (A1) also can contain the monomeric unit (a3) being obtained by the monomer (a3m) with the functional group beyond organic acidic group.As the functional group beyond above-mentioned organic acidic group, can list hydroxyl, amino, amide group, epoxy group(ing), sulfydryl etc.
As the monomer with hydroxyl, can list (methyl) vinylformic acid hydroxyalkyl acrylate such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester etc.
As thering is amino monomer, can list (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, amino-benzene ethene etc.
As the monomer with amide group, can list the α such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA, β-ethylenically unsaturated carboxylic acids amide monomer etc.
As the monomer with epoxy group(ing), can list (methyl) glycidyl acrylate, glycidyl allyl ether etc.
The monomer (a3m) with organic acidic group functional group in addition can use separately one, also can be used in combination two or more.
There is mode that the monomer (a3m) of the functional group beyond these organic acidic groups preferably reaches the amount below 10 quality % with monomeric unit therefrom (a3) in (methyl) acrylic ester polymer (A1) for polymerization.By using the monomer (a3m) below 10 quality %, the viscosity of the polymerization system during easily by polymerization remains on suitable scope.
The monomeric unit (a3) that (methyl) acrylic ester polymer (A1) forms except containing (methyl) acrylate monomeric units (a1) that above-mentioned second-order transition temperature is-20 DEG C of following homopolymer, have the monomeric unit (a2) of organic acidic group and have a functional group organic acidic group in addition, can also contain by the monomeric unit (a4) that can obtain with the monomer of above-mentioned monomer copolymerization (a4m).
Monomer (a4m) is not particularly limited, as its concrete example, can list above-mentioned (methyl) acrylate monomer (a1m) (methyl) acrylate monomer, α in addition, the full ester of the unsaturated polycarboxylic acid of β-olefinic, 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 concrete example of above-mentioned (methyl) acrylate monomer (a1m) (methyl) acrylate monomer in addition, can list methyl acrylate (second-order transition temperature of homopolymer is 10 DEG C), methyl methacrylate (second-order transition temperature of homopolymer is 105 DEG C), β-dimethyl-aminoethylmethacrylate (second-order transition temperature of homopolymer is 63 DEG C), n propyl methacrylate (second-order transition temperature of homopolymer is 25 DEG C), n-BMA (second-order transition temperature of homopolymer is 20 DEG C) etc.
As α, the concrete example of the full ester of the unsaturated polycarboxylic acid of β-olefinic, can list dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate etc.
As the concrete example of alkenyl aroma family monomer, can list vinylbenzene, alpha-methyl styrene, methyl alpha-methyl styrene, Vinyl toluene and Vinylstyrene etc.
As the concrete example of conjugated diene monomer, can list 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (with isoprene synonym), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, chlorbutadiene, cyclopentadiene etc.
Be the concrete example of monomer as non-conjugated diene, can list Isosorbide-5-Nitrae-hexadiene, Dicyclopentadiene (DCPD), ethylidene norbornene etc.
As the concrete example of vinyl cyanide base monomer, can list vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, α-ethyl acrylonitrile etc.
As the concrete example of the unsaturated alcohol ester monomer of carboxylic acid, can list vinyl acetate etc.
As the concrete example of ethylene series monomer, can list ethene, propylene, butylene, amylene etc.
Monomer (a4m) can use separately one, also can be used in combination two or more.
Monomer (a4m) reach in (methyl) acrylic ester polymer (A1) with the amount of monomeric unit therefrom (a4) be preferably below 10 quality %, more preferably the mode of the amount below 5 quality % is for polymerization.
(methyl) acrylic ester polymer (A1) particularly preferably by by above-mentioned formation second-order transition temperature be-20 DEG C of following homopolymer (methyl) acrylate monomer (a1m), have the monomer (a2m) of organic acidic group, as required the monomer (a3m) that contains the functional group beyond organic acidic group that uses and use as required can be with the monomer of these monomer copolymerizations (a4m) thus carrying out copolymerization obtains.
Polymerization process while obtaining (methyl) acrylic ester polymer (A1) is not particularly limited, and can be any of solution polymerization, letex polymerization, suspension polymerization, mass polymerization etc., also can these methods in addition.But, among these polymerization processs, be preferably solution polymerization, wherein more preferably use the solution polymerization of the aromatic solvents such as the carboxylicesters such as vinyl acetic monomer, ethyl lactate or benzene,toluene,xylene as polymer solvent.When polymerization, monomer can portion-wise addition in polymerization container, preferably total amount is added quickly.The method that polymerization causes is not particularly limited, and as polymerization starter, is preferably thermal polymerization.This thermal polymerization is not particularly limited, for example, can use peroxidic polymerization initiators, azo-compound polymerization starter.
As peroxidic polymerization initiators, except the such superoxide of the such hydrogen peroxide of tertbutyl peroxide, benzoyl peroxide, cyclohexanone peroxide, can also list the persulphates such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.These superoxide can use with the appropriately combined form with redox series catalysts of reductive agent.
As azo-compound polymerization starter, can list 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
The consumption of polymerization starter is not particularly limited, and is preferably the scope more than 0.01 mass parts and below 50 mass parts with respect to monomer 100 mass parts.
The not special system limit of other polymerizing condition (polymerization temperature, pressure, agitation condition etc.) of these monomers.
After finishing, polyreaction as required obtained polymkeric substance is separated from polymerisation medium.The method separating is not particularly limited.For example, in the situation of solution polymerization, polymeric solution can be placed under decompression, heat up in a steamer polymer solvent, thereby obtain (methyl) acrylic ester polymer (A1).
The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (A1) is measured by gel permeation chromatography (GPC method), the scope preferably converting more than 100,000 and below 1,000,000 in polystyrene standard, the more preferably scope more than 200,000 and below 500,000.The weight-average molecular weight of (methyl) acrylic ester polymer (A1) can be by adjusting the amount of the polymerization starter of using when polymerization, the amount of chain-transfer agent is controlled.
((methyl) acrylate monomer blend (α 1))
(methyl) acrylate monomer (α 1), as long as the monomer that contains (methyl) acrylate monomer is just not particularly limited, preferably contains and forms (methyl) acrylate monomer (a5m) that second-order transition temperature is-20 DEG C of following homopolymer.
As forming the example that second-order transition temperature is (methyl) acrylate monomer (a5m) of-20 DEG C of following homopolymer, can list with for identical (methyl) acrylate monomer of synthetic (methyl) acrylate monomer (a1m) of (methyl) acrylic ester polymer (A1).(methyl) acrylate monomer (a5m) can use separately one, also can be used in combination two or more.
More than the ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) is preferably 50 quality % and below 100 quality %, more preferably more than 75 quality % and below 100 quality %.Be above-mentioned scope by the ratio that makes (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1), easily obtain thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) of pressure-sensitive adhesive, flexibility excellence.
In addition, (methyl) acrylate monomer (α 1) can be (methyl) acrylate monomer (a5m) and can with the mixture of the monomer of its copolymerization.
(methyl) acrylate monomer (α 1) can be form (methyl) acrylate monomer (a5m) that second-order transition temperature is-20 DEG C of following homopolymer and can with the mixture of the monomer with organic acidic group (a6m) of these copolymerization.
As the example of above-mentioned monomer (a6m), can list with synthetic monomer (a2m) as for (methyl) acrylic ester polymer (A1) and the identical monomer with organic acidic group of the monomer exemplifying.Monomer (a6m) can use separately one, also can be used in combination two or more.
The ratio of the monomer (a6m) in (methyl) acrylate monomer (α 1) is preferably below 30 quality %, more preferably below 10 quality %.Be above-mentioned scope by the ratio that makes the monomer (a6m) in (methyl) acrylate monomer (α 1), easily obtain thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) of pressure-sensitive adhesive, flexibility excellence.
(methyl) acrylate monomer (α 1), except being (methyl) acrylate monomer (a5m) and can carrying out the mixture of the monomer with organic acidic group (a6m) of copolymerization according to hope, can be also they and the mixture that can carry out with them monomer (a7m) of copolymerization.
As the example of above-mentioned monomer (a7m), can list with synthetic monomer (a3m) as for (methyl) acrylic ester polymer (A1) and monomer (a4m) and the identical monomer of the monomer exemplifying.Monomer (a7m) can use separately one, also can be used in combination two or more.
The ratio of the monomer (a7m) in (methyl) acrylate monomer (α 1) is preferably below 20 quality %, more preferably below 15 quality %.
< polymerization starter >
While obtaining thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), polymerization (methyl) acrylate monomer (α 1) and multi-functional monomer described later (D).In order to promote this polymerization, preferably use polymerization starter.As this polymerization starter, can list Photoepolymerizationinitiater initiater, azo is thermal polymerization, organo-peroxide thermal polymerization etc.From giving the viewpoints such as the excellent cementability of obtained thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), preferably use organo-peroxide thermal polymerization.
As Photoepolymerizationinitiater initiater, can use known various Photoepolymerizationinitiater initiater.Wherein, be preferably acylphosphine oxide based compound.Can list two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxides, 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide etc. as the acylphosphine oxide based compound of preferred Photoepolymerizationinitiater initiater.
Be thermal polymerization as azo, can list 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile) etc.
As organo-peroxide thermal polymerization, can list the such hydrogen peroxide of tertbutyl peroxide, benzoyl peroxide, cyclohexanone peroxide, 1, two (the tert-butyl hydroperoxide ketonic oxygen base) hexanes, 1 of 6-, two (tert-butyl hydroperoxide)-3 of 1-, the superoxide that 3,5-trimethylcyclohexanone is such etc.Wherein, preferably in the time of thermolysis, can not emit the initiator of the volatile matter that becomes foul smell reason.In addition, among organo-peroxide thermal polymerization, preferably 1 minute half life temperature is 100 DEG C of above and 170 DEG C of following initiators.
With respect to (methyl) acrylic resin composition (A) 100 mass parts, more than the consumption of above-mentioned polymerization starter is preferably 0.01 mass parts and below 10 mass parts, more preferably more than 0.1 mass parts and below 5 mass parts, more preferably more than 0.3 mass parts and below 2 mass parts.Be above-mentioned scope by making the consumption of polymerization starter, easily making the polymerisation conversion of (methyl) acrylate monomer blend (α 1) is suitable scope, easily prevents that in thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), residual monomer is smelly.It should be noted that, more than the polymerisation conversion of (methyl) acrylate monomer (α 1) is preferably 95 quality %.The polymerisation conversion of (methyl) acrylate monomer (α 1) is 95 quality % when above, easily prevents that in thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), residual monomer is smelly.In addition, be above-mentioned scope by making the consumption of polymerization starter, easily prevent the carrying out of initiated polymerization exceedingly owing to adding polymerization starter, its sheet-like formed body of result thermal conductivity pressure-sensitive adhesive (G) can not become level and smooth sheet, causes the situation of material damage.
The multi-functional monomer of < (D) >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), use multi-functional monomer (D).As multi-functional monomer (D), the monomer that use can be carried out copolymerization with the monomer that contains in (methyl) acrylate monomer (α 1).In addition, multi-functional monomer (D) preferably has multiple polymerizability unsaturated link(age)s, has endways this unsaturated link(age).By using so multi-functional monomer (D), in multipolymer, import in molecule and/or intermolecular cross-linking, can improve the cohesive force as pressure adhesive of thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).
Conventionally in the time of the polymerizations such as free radical thermopolymerization, even if do not use multi-functional monomer, crosslinking reaction to a certain degree is also carried out.Wherein, can think according to the present invention, by the multi-functional epoxy compound (E) who is used in combination multi-functional monomer (D) and describe in detail below, in thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), be formed uniformly crosslinking structure, maintain flexibility, improve tensile strength simultaneously.
As multi-functional monomer (D), for example can use 1, 6-hexylene glycol two (methyl) acrylate, 1, 2-ethylene glycol bisthioglycolate (methyl) acrylate, 1, 12-decanediol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, two trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, multi-functional (methyl) acrylate such as Dipentaerythritol six (methyl) acrylate, 2, two (the trichloromethyl)-6-of 4-replace triazine to methoxy styrene-5-triazine etc., and the such monoene of 4-acryloxy benzophenone belongs to unsaturated aromatic ketone etc.Wherein, be preferably tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate.Multi-functional monomer (D) can use separately one, also can be used in combination two or more.
With respect to 100 mass parts (methyl) acrylic resin compositions (A), the amount of the multi-functional monomer (D) using in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) is more than 0.2 mass parts and below 8 mass parts, more than being preferably 0.5 mass parts and below 2 mass parts.Be above-mentioned scope by making the consumption of multi-functional monomer (D), easily make thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) have flexibility and the tensile strength as pressure adhesive concurrently.
< thermal conductivity filler (B) >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), use thermal conductivity filler (B).Thermal conductivity filler (B) is that can to improve thermal conductivity pressure-sensitive adhesive composite (F), the thermal conductivity of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), thermal conductivity be filler more than 1W/m K by adding.
Thermal conductivity filler (B) can use known thermal conductivity filler.As the concrete example of thermal conductivity filler (B), can list aluminium hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, zinc borate hydrate, kaolin, calcium aluminate hydrate, calcium carbonate, aluminium carbonate, dawsonite, aluminum oxide (aluminum oxide), magnesium oxide, zinc oxide, boron nitride, aluminium nitride, silicon-dioxide etc.Among these, calcium carbonate, aluminium hydroxide and aluminum oxide, owing to easily obtaining, chemical is also stable and can coordinate in a large number and preferably more preferably aluminium hydroxide and aluminum oxide.Thermal conductivity filler (B) can use separately one, also can be used in combination two or more.
The amount of the thermal conductivity filler (B) using in thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) is more than 90 mass parts and below 1200 mass parts with respect to (methyl) acrylic resin composition (A) 100 mass parts, more than being preferably 100 mass parts and below 1000 mass parts, more preferably more than 200 mass parts and below 900 mass parts.When the content of thermal conductivity filler (B) exceedes above-mentioned scope, the excess stickiness ground that becomes the raw-material blend compositions of thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) increases, thermal conductivity pressure-sensitive adhesive composite (E) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (F) are likely difficult to be shaped, or allow to be shaped, the hardness of thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) increases, and product having shape-following-up properties (to the adaptation of clung body) reduces.On the other hand, thermal conductivity filler (B) when the above-mentioned scope of quantity not sufficient, likely, by using thermal conductivity filler (B), the effect of the thermal conductivity of raising thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) is insufficient.
In addition, the BET specific surface area of thermal conductivity filler (B) is preferably 1.0m 2above and the 10m of/g 2below/g, more preferably 1.0m 2above and the 5.0m of/g 2below/g, more preferably 1.0m 2above and the 3.0m of/g 2below/g.By making the BET specific surface area of thermal conductivity filler (B) in above-mentioned scope, the excess stickiness ground that suppresses the raw-material blend compositions that becomes thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) increases, and easily makes thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) have tensile strength and flexibility concurrently simultaneously.Wherein, as thermal conductivity filler (B), can be used in combination BET specific surface area in the thermal conductivity filler (B1) of above-mentioned scope and BET specific surface area lower than 1.0m 2the thermal conductivity filler (B2) of/g.For BET specific surface area now at the thermal conductivity filler (B1) of above-mentioned scope with the BET specific surface area using according to hope lower than 1.0m 2the amount ratio of the thermal conductivity filler (B2) of/g, mass ratio (thermal conductivity filler (B1): thermal conductivity filler (B2)) is preferably (100:0)～(20:80), more preferably (80:20)～(30:70).Thus, by being used in combination like this thermal conductivity filler (B) that BET specific surface area is different, the excess stickiness that can suppress above-mentioned blend compositions increases, and can in this blend compositions, coordinate in large quantities thermal conductivity filler (B) simultaneously.It should be noted that, in the present invention, " BET specific surface area " refers to the value measuring by the following method.First, the mixed gas of nitrogen and helium is imported in BET specific area measuring device, the sample cell that is placed with sample (the determination object thing of BET specific surface area) is immersed in liquid nitrogen, make nitrogen adsorption in specimen surface.Reach after adsorption equilibrium, sample cell is put into water-bath and be heated to normal temperature, make the nitrogen desorption adhering on sample.Ratio of mixture by the gas before and after sample cell when nitrogen adsorption, desorption changes, thereby taking the constant gas of the ratio of mixture of nitrogen and helium as contrast, detects this variation by Heat conductivity detector (TCD), obtains adsorptive capacity and the desorption rate of nitrogen.Before measuring, by demarcating in the nitrogen gatherer of unit vol, obtain in advance the value of the surface-area corresponding with the value detecting by TCD, thereby obtain the surface-area of this sample.In addition, by the quality divided by this sample by surface-area, can obtain BET specific surface area.
< multi-functional epoxy compound (E) >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), use multi-functional epoxy compound (E).Multi-functional epoxy compound (E) can with (methyl) acrylic ester polymer (A1) in organic acid radical reaction form crosslinking structure.In addition, in the situation that similarly (methyl) acrylate monomer (α 1) contains the monomer with organic acidic group, due to can with this organic acid radical reaction, can in the polymkeric substance that contains the structural unit that derives from (methyl) acrylate monomer (α 1), form crosslinking structure.
Viscosity at 25 DEG C of multi-functional epoxy compound (E) is below 600mPa s, is preferably below 500mPa s, more preferably below 400mPa s.Can think when multi-functional epoxy compound's viscosity is too high, in the raw-material blend compositions that becomes thermal conductivity pressure-sensitive adhesive composite and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive, be difficult to disperse equably multi-functional epoxy compound, the above-mentioned crosslinking structure based on multi-functional epoxy compound is difficult to be formed uniformly.Its result, can think that tensile strength reduces by form locally weak part in thermal conductivity pressure-sensitive adhesive composite and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive.It should be noted that, multi-functional epoxy compound's (E) viscosity can similarly operate and measure with following phosphoric acid ester (C).
According to the present invention, can think by the to a certain degree low multi-functional epoxy compound (E) of use viscosity described above, above-mentioned multi-functional monomer (D) and multi-functional epoxy compound (E) disperse equably in the raw-material blend compositions that becomes thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), in thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), are easily formed uniformly crosslinking structure.Its result, can obtain the thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) that when maintaining flexibility, improve tensile strength.
The multi-functional epoxy compound (E) who uses in the present invention has the functional group's (epoxy group(ing)) more than 2 and below 10000, and the number of functional group is preferably more than 2 and below 1000, more preferably more than 2 below 10.By making multi-functional epoxy compound's (E) the number of functional group in above-mentioned scope, easily make thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) have tensile strength and flexibility concurrently.
As the concrete example for multi-functional epoxy compound of the present invention (E), can list Resorcinol diglycidyl ether, ethylene glycol bisthioglycolate glycidyl ether, 1, 6-hexylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Hydrogenated Bisphenol A diglycidyl ether, glycerine poly epihydric alcohol base ether, trimethylolpropane tris glycidyl ether, tetramethylolmethane diglycidyl ether, tetramethylolmethane triglycidyl group ether, tetramethylolmethane four glycidyl group ether, two glycerine four glycidyl group ethers, Polyglycerine poly epihydric alcohol base ether, Sorbitol Powder poly epihydric alcohol base ether etc.Wherein, even if tetramethylolmethane four glycidyl group ether also can form crosslinking structure on a small quantity effectively, thereby preferably.Multi-functional epoxy compound (E) can be used singly or in combination of two or more.
With respect to (methyl) acrylic resin composition (A) 100 mass parts, the multi-functional epoxy compound's (E) who uses in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) amount is more than 0.3 mass parts and below 5.0 mass parts, more than being preferably 0.4 mass parts and below 4.0 mass parts, more preferably more than 0.5 mass parts and below 3.0 mass parts.Be above-mentioned scope by making multi-functional epoxy compound's (E) consumption, easily make thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) have tensile strength and flexibility concurrently.
< phosphoric acid ester (C) >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), preferably use phosphoric acid ester (C).By using phosphoric acid ester (C), easily give thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) excellent flame retardant resistance.In addition, while using in large quantities phosphoric acid ester (C), the operability that forms the front blend compositions of thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) worsens, by being used in combination phosphoric acid ester (C) and above-mentioned thermal conductivity filler (B1), can suppress the consumption of phosphoric acid ester (C), drippage while suppressing thermal conductivity pressure-sensitive adhesive composite (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) burning improves flame retardant resistance, and the operability of blend compositions also improves.
Phosphoric acid ester (C) the preferably viscosity at 25 DEG C is more than 3000mPa s.By making the viscosity of phosphoric acid ester (C) in above-mentioned scope, easily prevent the plasticity variation of thermal conductivity pressure-sensitive adhesive composite (F) or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).It should be noted that, in the present invention, " viscosity " of phosphoric acid ester refers to the viscosity of measuring by the method for following explanation.
(viscosity measurement of phosphoric acid ester)
The viscosimetric analysis of phosphoric acid ester is used Brookfield viscometer (Tokyo Keiki Inc.'s system) to carry out according to step shown below.　
(1) under the environment of normal temperature, measure 300ml phosphoric acid ester, put into the container of 500ml.　
(2) from stirring with selecting any to be installed on viscometer rotor No.1,2,3,4,5,6,7.　
(3) container that is placed with phosphoric acid ester is placed on viscometer, rotor is submerged in the condensed phosphoric acid esters in this container.Now, using the whole mode that arrives well the liquid interface of phosphoric acid ester of the recess as the rotor mark rotor that avales.　
(4) rotating speed is selected from 20,10,4,2.　
(5) press stirring switch, read the numerical value after 1 minute.　
(6) numerical value reading is multiplied by coefficient A and the value that obtains is viscosity ［ mPa s ］.
It should be noted that, coefficient A, as shown in following table 1, is determined by rotor No. and the rotating speed selected.
[table 1]
Figure 312527DEST_PATH_IMAGE001
In addition, in the preferred temperature provinces more than 15 DEG C and below 100 DEG C under atmospheric pressure of phosphoric acid ester (C), be liquid always.Phosphoric acid ester (C) if mix time liquid, operability is good, the thermal conductivity that is easily shaped pressure-sensitive adhesive composite (F) or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).When the thermal conductivity pressure-sensitive adhesive composite (F) that shaping contains phosphoric acid ester (C) or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), preferably, in the environment more than 15 DEG C and below 100 DEG C, the each material that forms thermal conductivity pressure-sensitive adhesive composite (F) or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) is mixed.Temperature when making to mix is in above-mentioned scope, more than the second-order transition temperature for (methyl) acrylic resin composition (A), the volatilization or the polyreaction that easily prevent monomer containing in (methyl) acrylic resin composition (A) etc. start, thus can make environment and operability good.
Phosphoric acid ester (C) in the present invention can also be used condensed phosphoric acid esters or non-condensed phosphoric acid esters." condensed phosphoric acid esters " described here refers to, 1 molecular memory is at the condensed phosphoric acid esters at multiple phosphoric acid ester position, and " non-condensed phosphoric acid esters " refers to, only has the ester at 1 phosphoric acid ester position in 1 molecule.Below list the concrete example of the phosphoric acid ester (C) of the condition that meets explanation so far.
As the concrete example of condensed phosphoric acid esters, can list the aromatic condensation phosphoric acid ester such as 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester), Resorcinol two (diphenyl phosphoester); The Halogen prime system condensed phosphoric acid esters such as the two dichloro alkyl phosphates of polyoxy alkylidene group; The non-halogen of non-aromatic is condensed phosphoric acid esters; Deng.Among these, aromatic condensation phosphoric acid ester because proportion is smaller, there is no objectionable impurities the emitting danger, also easily obtain etc. of (halogen etc.), and preferably, more preferably 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester).
As the concrete example of non-condensed phosphoric acid esters, can list Triphenyl phosphate, lindol, tricresyl phosphate (xylyl) ester, tricresyl phosphate base diphenyl, tricresyl phosphate base-2, the aromatic phosphoric esters such as 6-xylyl ester, phosphoric acid 2-ethylhexyl diphenyl; The Halogen prime system phosphoric acid ester such as three (β-chloropropyl) phosphoric acid ester, tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (tribromo neo-pentyl) ester; Deng.Among these, aromatic phosphoric ester owing to not producing objectionable impurities (halogen etc.) etc. preferably.
Phosphoric acid ester (C) can be used separately one, also can be used in combination two or more.
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), use in the situation of phosphoric acid ester (C), with respect to (methyl) acrylic resin composition (A) 100 mass parts, more than its amount is preferably 45 mass parts and below 190 mass parts, more preferably more than 55 mass parts and below 150 mass parts, more preferably more than 70 mass parts and below 120 mass parts.By making the content of phosphoric acid ester (C) in above-mentioned scope, easily improve the flame retardant resistance of thermal conductivity pressure-sensitive adhesive composite (F) or the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).
Other additive of < >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), except above-mentioned substance, can also in the scope that does not hinder the above-mentioned effect producing by cooperation above-mentioned substance, add known various additive.As known additive, can list whipping agent (comprising frothing aid); The flame retardant resistance such as oxyhydroxide, the metal salt hydrates heat conduction mineral compound of above-mentioned thermal conductivity filler (B) metal in addition; Glass fibre; Above-mentioned thermal conductivity filler (B) the thermal conductivity mineral compound in addition such as expansion fossil ink powder, PITCH based carbon fiber; Outside linking agent; The pigment such as carbon black, titanium dioxide; Other compaction material such as clay; The nanoparticle such as soccerballene, carbon nanotube; The antioxidants such as polyphenol system, quinhydrones system, hindered amine system; The thickening materials such as acrylic acid polymer particle, silica particle, magnesium oxide; Deng.
2. manufacture method
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) can obtain as follows: the each material having illustrated is so far carried out after mixing manufacture blend compositions, the crosslinking reaction of the polymkeric substance that at least carries out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1), thus obtain.
, the manufacture method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F) comprises following operation: the operation of making the blend compositions that comprises (methyl) acrylic resin composition (A), thermal conductivity filler (B), multi-functional monomer (D) and the multi-functional epoxy compound (E) of containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); And the crosslinking reaction of the polymkeric substance that at least carries out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1) in this blend compositions.It should be noted that, other material that can use, each material preferably contain ratio etc. as mentioned above, omit detailed explanation here.
In the manufacture method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F), in the time carrying out above-mentioned polymerization and crosslinking reaction, preferably heat.This heating can be used such as hot blast, electric heater, infrared rays etc.The temperature that Heating temperature is now preferably that polymerization starter efficiency is decomposed well, the polymerization of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) advances.Temperature range is according to the kind of used polymerization starter and difference, be preferably 100 DEG C above and below 200 DEG C, more preferably 130 DEG C above and below 180 DEG C.
The sheet-like formed body of thermal conductivity pressure-sensitive adhesive of the present invention (G) can obtain as follows: each material of explanation is so far mixed, make blend compositions, this blend compositions is configured as after sheet, or when this blend compositions is configured as to sheet, the crosslinking reaction of the polymkeric substance that at least carries out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1), thus obtain.
, the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive of the present invention (G) comprises following operation: the operation of making the blend compositions that comprises (methyl) acrylic resin composition (A), thermal conductivity filler (B), multi-functional monomer (D) and the multi-functional epoxy compound (E) of containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1); And this blend compositions is configured as after sheet, or when this blend compositions is configured as to sheet, the operation of the crosslinking reaction of the polymkeric substance that at least carries out polyreaction and (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) and/or contain the structural unit that derives from (methyl) acrylate monomer (α 1).It should be noted that, other material that can use, each material preferably contain ratio etc. as mentioned above, detailed here.
In the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive of the present invention (G), while carrying out above-mentioned polymerization and crosslinking reaction, preferably heat.This heating can be used such as hot blast, electric heater, infrared rays etc.The temperature that Heating temperature is now preferably that polymerization starter decomposes effectively, the polymerization of (methyl) acrylate monomer (α 1) and multi-functional monomer (D) advances.Temperature range is according to the kind of used polymerization starter and difference, be preferably 100 DEG C above below 200 DEG C, more preferably 130 DEG C above below 180 DEG C.
The method that above-mentioned blend compositions is configured as to sheet is not particularly limited.As suitable method, can list the casting method (キ ャ ス ト method) of for example blend compositions being coated in the mold release film such as the polyester film through demoulding processing, blend compositions is held between two mold release film of passing through as required demoulding processing and makes it pass through the method between roller, and use forcing machine to make its method by mould control thickness etc. while extruding blend compositions.
The sheet-like formed body of thermal conductivity pressure-sensitive adhesive of the present invention (G) though than the sheet-like formed body of thermal conductivity pressure-sensitive adhesive in the past more unfertile land be shaped and also can possess excellent flexibility and tensile strength.In addition, by making the thin thickness of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), can reduce the thermal resistance of the thickness direction of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).The thickness of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) can be for example more than 0.05mm and below 3.0mm, more than being preferably 0.1mm, is preferably below 1.0mm, more preferably below 0.5mm.By making the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) more than above-mentioned lower limit, easily prevent from being involved in air in the time that the sheet-like formed body of this thermal conductivity pressure-sensitive adhesive (G) is attached to heating element and radiator, result can prevent the increase of thermal resistance, makes the operability in the attaching operation of clung body good.
In addition, the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) can be shaped at the one side of base material or two sides.The material that forms this base material is not particularly limited.As the concrete example of this base material, can list the metal of the excellent thermal conductivity such as aluminium, copper, stainless steel, beryllium copper and paper tinsel shape thing, the heat-conductive silicone etc. of alloy by the flap of the polymer formation of himself excellent thermal conductivity, contain the thermal conductivity plastic film that thermal conductivity additive forms, various non-woven fabrics, woven fiber glass, honeycomb structured body etc.As plastic film, can use the film of the thermally stable polymers such as polyimide, polyethylene terephthalate, PEN, tetrafluoroethylene, polyetherketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfones, polyphenylene sulfide, polyamidoimide, polyester-imide, aromatic polyamide.
3. example
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) can be as parts for electronic unit.Now, can provide as a part for electronic unit in the such direct forming on base material of radiator.As the concrete example of this electronic unit, can list there is electroluminescent cell (EL), equipment or parts that the power device of heating part in the equipment of photodiode (LED) light source parts, automobile etc. around parts, fuel cell, solar cell, battery, mobile phone, palm PC (PDA), notebook computer, liquid crystal, Surface conducting electronic emitting component indicating meter (SED), plasma display (PDP) or unicircuit (IC) etc. around have heating part.
It should be noted that, method as thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) for electronics, as an example time, can illustrate following such using method for the situation of LED light source.Have and be directly attached at LED light source; Be held between LED light source and heat sink material (scatterer, fan, Peltier element, heat pipe, graphite sheet etc.); Be attached at the heat sink material (scatterer, fan, Peltier element, heat pipe, graphite sheet etc.) being connected with LED light source; Use as the basket that surrounds LED light source; Be attached at the basket that surrounds LED light source; Be embedded in the gap of LED light source and basket; Etc. method.In addition, as the purposes example of LED light source that possesses thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), can list the backlight arrangement (TV, mobile phone, PC, notebook PC, PDA etc.) of the display unit with liquid crystal panel of transmission-type; Lamps apparatus for vehicle; Industrial illumination; Illumination for business; General illumination for house; Deng.
In addition, as the example except LED light source of thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), can list following such purposes.It is PDP panel; IC heating part; Cold-cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High brightness luminescent LED light source; The organic EL light source of high brightness luminescent; The inorganic EL light source of high brightness luminescent; CPU; MPU; Semiconductor element; Deng in also can use thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G).
Further, the using method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) is not limited to above-mentioned form, also can be attached at exemplify so far beyond the use such as basket of device.For example, in the device that, also can possess at automobile etc., use., can list the inside of the basket that is attached at the device that automobile possesses; Be attached at the outside of the basket that automobile possesses; The heating part (auto-navigation system/fuel cell/heat exchanger) of the inside that is positioned at the basket that automobile possesses is connected with this basket; Be attached at the heating panel being connected with the heating part (auto-navigation system/fuel cell/heat exchanger) of inside that is positioned at the basket that automobile possesses; Deng.
It should be noted that, except automobile, also can use thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) by same method.As its object, can list for example computer; House; Televisor; Mobile phone; Vending machine; Refrigerator; Solar cell; Surface conducting electronic emitting component indicating meter (SED); OLED display; Inorganic EL indicating meter; Organic EL illuminating; Inorganic EL illumination; OLED display; Notebook computer; PDA; Fuel cell; Semiconductor device; Electric cooker; Washing machine; Scrubbing-and-drying unit; The optical semiconductor device that optical semiconductor and fluor combine; Various power devices; Game machine; Electrical condenser; Deng.
Further, thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) can not only be used for above-mentioned using method, can also use by other method according to purposes.Can list for example for making the heat uniforming such as carpet, warm pad; As the sealing agent of LED light source/thermal source; As the sealing agent of solar battery cell; As the backboard of solar cell; For between the backboard and roof of solar cell; Be used for the inner side of the thermofin of vending machine inside; Basket inside at organic EL illuminating is used together with siccative, moisture adsorbent; The heat-conducting layer of the basket inside of organic EL illuminating with and on use together with siccative, moisture adsorbent; On the heat-conducting layer of the basket inside of organic EL illuminating, heat dissipating layer and them, use together with siccative, moisture adsorbent; The heat dissipating layer of the heat-conducting layer of the basket inside of organic EL illuminating, epoxy system, with and on use together with siccative, moisture adsorbent; For cooling components such as the device for making people, animal cooling, clothing, towel, sheet materials, using with the opposition side of health; Be used for the pressing element of the stationary installation of carrying at image processing systems such as electronic photo duplicating machine, electrophotographic printers; As the pressing element of the stationary installation of carrying in the image processing systems such as electronic photo duplicating machine, electrophotographic printer itself; Be used as the hot-fluid control heat transfer part of the handling object body of mounting film forming apparatus; Be used for the hot-fluid control heat transfer part of the handling object body that loads film forming apparatus; Hold between the skin and interior trim of container for radioactive substance; In the casing that is provided with the solar panel that absorbs solar ray, use; Between the reflective sheet of CCFL backlight and aluminum cabinet, use; Deng.
Finally, in the manufacture method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F), the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), thermal conductivity pressure-sensitive adhesive composite (F) and the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), preferred thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
In addition, at thermal conductivity pressure-sensitive adhesive composite of the present invention (F), the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), in the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), (methyl) acrylic resin composition (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that comprises 100 mass parts, thermal conductivity filler (B) more than 90 mass parts and below 1200 mass parts, the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s more than 0.2 mass parts and below 8 mass parts, the viscosity having at functional group more than 2 and below 10000 and 25 DEG C above with 0.3 mass parts and below 5.0 mass parts is the blend compositions of the multi-functional epoxy compound (E) below 600mPa s, preferably further containing with respect to aforementioned (methyl) acrylic resin composition (A) 100 mass parts is the phosphoric acid ester (C) more than 45 mass parts and below 190 mass parts.
In addition, in the manufacture method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F), the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), thermal conductivity pressure-sensitive adhesive composite (F) and the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), it is the polymerization starter more than 0.01 mass parts and below 10 mass parts that aforementioned blend compositions preferably further contains with respect to aforementioned (methyl) acrylic resin composition (A) 100 mass parts.
Embodiment
Further describe by the following examples the present invention, but the present invention is not subject to the restriction of embodiment.It should be noted that, " part " used herein, " % ", when without special instruction, are quality criteria.
< hardness (flexibility) >
Make like that as described later the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), be cut into the size of 30mm × 50mm, the mold release film using while preparing multiple by making (has been implemented the polyethylene terephthalate film of demoulding processing.Hereinafter referred to as " demoulding PET film ") peel off and the sheet material that obtains.Sheet material that this is cut out uses talcum to dust (powder is beaten Chi), to reach the stacked identical sheet material of mode of 6mm left and right thickness, loads on the sample bench of sclerometer (polymer gauge Co., Ltd. system " CL-150 ", according to JIS K7312).Then, putting down deoscillator (ダ ン パ ー) starts to measure.Deoscillator is arrived to the value that moment of sample rises after 20 seconds to be read as the measured value of hardness.The results are shown in table 2.It should be noted that, while peeling off from demoulding PET film, the sheet material that cannot peel off for pulverizing, as evaluating.
< tensile strength >
Make like that as described later the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), the demoulding PET film using during by making is peeled off by following method and is measured breaking tenacity.The results are shown in table 2.It should be noted that, while peeling off from demoulding PET film, the sheet material that cannot peel off for pulverizing, as evaluating.
Stamping-out sword No. 1, dumbbell ((No. 1, ダ Application ベ Le)) is loaded into stamping-out device (Dumb Bell Ltd. SDL-100 processed), tighten the screws.Assembling plastic plate and stamping-out plate, the sheet-like formed body of mode stamping-out thermal conductivity pressure-sensitive adhesive (G) taking the length direction of stamping-out device as the MD direction of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G), makes test film.Assembling universal trier (Shimadzu Seisakusho Ltd.'s system, AGIS-20kN), presses power supply and waits for 15 minutes (load cell: 1kN).Select test conditions (trial speed: 300mm/min), the thickness of the test film that input is measured by thickness gauge (TOYOSEIKI system numeral thickness measuring machine).Test film is held on to chuck and starts test, the stress while reading test film fracture.
The making > of the sheet-like formed body of < thermal conductivity pressure-sensitive adhesive
(embodiment 1)
To adding 100 parts of the monomer mixtures that are made up of 2-EHA 94% and vinylformic acid 6%, 2 in reactor, 700 parts of 0.03 part of 2 '-azobis isobutyronitrile and vinyl acetic monomers, dissolve equably, after nitrogen displacement, carries out 6 hours polyreactions at 80 DEG C.Polymerisation conversion is 97%.Obtained polymkeric substance is carried out to drying under reduced pressure and make vinyl acetic monomer evaporation, obtain (methyl) acrylic ester polymer (A1-1) of sticking solid state.The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (A1-1) is 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 converted and obtain with polystyrene standard by the gel permeation chromatography using tetrahydrofuran (THF) as elutriant.
Then, measure pentaerythritol triacrylate with electronics Libra, 1.0 parts of the multi-functional monomers that tetramethylol methane tetraacrylate and pentaerythritol diacrylate mix with the ratio of 60:35:5, 70 parts of 2-EHAs (2EHA), organo-peroxide thermal polymerization (1, two (the tert-butyl hydroperoxide ketonic oxygen base) hexanes (half life temperature was 150 DEG C in 1 minute) of 6-) 1.0 parts, multi-functional epoxy compound's (Nagase ChemteX Corporation system, EX-1410, functional group's number: 4, viscosity: 320mPa s, total chlorine: 0.5% >, epoxy equivalent (weight): 160) 1.0 parts, they are mixed with 30 parts of above-mentioned (methyl) acrylic ester polymers (A1-1).Mix and use thermostatic bath (Toki Sangyo Co., Ltd.'s system, trade(brand)name " VISCOMATE 150III ") and Hobart mixing tank (the little flat making of Co., Ltd. is made, trade(brand)name " ACM-5LVT type ", capacity: 5L).The Temperature Setting of Hobart container is 60 DEG C, and making rotating speed scale is 3 stirring 10 minutes.This operation is called to the 1st mixed processes.
Then, 70 parts of metering phosphoric acid ester (Ajinomoto Fine-Techno Co., Inc. system, trade(brand)name " レ オ Off ォ ス 65 ", compound name " tricresyl phosphate aryl sec.-propyl compound "), aluminium hydroxide (Nippon Light Metal Co., Ltd's system, trade(brand)name " BF-083 ", median size: 8 μ m, BET specific surface area: 0.8m 2/ g) 400 parts, aluminum oxide (Showa Denko K. K's system, trade(brand)name " AL-47-H ", median size: 2 μ m, BET specific surface area: 1.1m 2/ g) 1 part, 400 parts and zinc oxide (ア of Co., Ltd. system テ ッ Network system, パ Na テ ト ラ WZ-0511), drops in above-mentioned Hobart container, is 60 DEG C by the Temperature Setting of Hobart container, and making rotating speed scale is 5 stirring 10 minutes.This operation is called to the 2nd mixed processes.
Then, the blend compositions obtaining through the above-mentioned the 1st and the 2nd mixed processes is hung to the demoulding PET film of thickness 75 μ m, other demoulding PET film of further coating thickness 75 μ m on this blend compositions.Make blend compositions by demoulding PET film clamp this duplexer forming by between the two every being made as between the roller of 0.45mm, be configured as sheet., this duplexer dropped in stove, with 150 DEG C of heating 15 minutes thereafter.By this heating process, make (methyl) acrylate monomer and multi-functional monomer carry out polyreaction, almost make in addition the polymkeric substance of (methyl) acrylic ester polymer (A1-1) and (methyl) acrylate monomer carry out crosslinking reaction simultaneously, obtain the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (following simple marking is " sheet material ") (G1).It should be noted that, calculated the polymerisation conversion of (methyl) acrylate monomer by the remaining amount of monomer in sheet material (G1), result is 99.9%.
(embodiment 2 and even 6 and comparative example 1 and even 3)
Change like that as shown in table 2 the cooperation of each material, operation similarly to Example 1, makes the sheet material (G2～G6) of embodiment 1～6 and the sheet material (GC1～GC4) of comparative example 1～4 in addition.Evaluation result is shown in to table 2.It should be noted that the EX-1310(functional group number that the multi-functional epoxy compound who uses in embodiment 6 is Nagase ChemteX Corporation system: 3, viscosity: 110mPa s, total chlorine: 0.5% >, epoxy equivalent (weight): 180).
[table 2]
Figure 229667DEST_PATH_IMAGE002
As shown in table 2, sheet material described in embodiment (G1～G6) is that hardness is low, tensile strength is strong.That is, known according to the present invention, even if be shaped and also can obtain the sheet-like formed body of thermal conductivity pressure-sensitive adhesive that possesses flexibility and tensile strength thinly.On the other hand, sheet material described in comparative example (GC1～GC4) cannot have flexibility and tensile strength concurrently.

Claims (17)

1. thermal conductivity pressure-sensitive adhesive composite (F), it is in the blend compositions that contains following (A), (B), (D), (E):
(methyl) acrylic resin compositions (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts,
Above and the thermal conductivity filler (B) below 1200 mass parts of 90 mass parts,
Above and the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s below 8 mass parts of 0.2 mass parts,
The 0.3 mass parts viscosity having at functional group more than 2 and below 10000 and 25 DEG C above and below 5.0 mass parts is the multi-functional epoxy compound (E) below 600mPa s,
The crosslinking reaction of the polymkeric substance that carries out polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and described multi-functional monomer (D) and/or contain the structural unit that derives from described (methyl) acrylate monomer (α 1) forms.
2. thermal conductivity pressure-sensitive adhesive composite according to claim 1 (F), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
3. thermal conductivity pressure-sensitive adhesive composite according to claim 1 and 2 (F), wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and phosphoric acid ester (C) below 190 mass parts of 45 mass parts to described blend compositions.
4. according to the thermal conductivity pressure-sensitive adhesive composite (F) described in any one in claim 1～3, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and polymerization starter below 10 mass parts of 0.01 mass parts to described blend compositions.
5. the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G),
The blend compositions of its following by containing (A), (B), (D), (E) is configured as after sheet, or when described blend compositions is configured as to sheet, the crosslinking reaction of the polymkeric substance that carries out polyreaction and following (methyl) acrylic ester polymer (A1) of following (methyl) acrylate monomer (α 1) and following multi-functional monomer (D) and/or contain the structural unit that derives from following (methyl) acrylate monomer (α 1) forms;
Described (A), (B), (D), (E) are: (methyl) acrylic resin compositions (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts,
Above and the thermal conductivity filler (B) below 1200 mass parts of 90 mass parts,
Above and the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s below 8 mass parts of 0.2 mass parts,
The 0.3 mass parts viscosity having at functional group more than 2 and below 10000 and 25 DEG C above and below 5.0 mass parts is the multi-functional epoxy compound (E) below 600mPa s.
6. the sheet-like formed body of thermal conductivity pressure-sensitive adhesive according to claim 5 (G), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
7. according to the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) described in claim 5 or 6, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and phosphoric acid ester (C) below 190 mass parts of 45 mass parts to described blend compositions.
8. according to the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) described in any one in claim 5～7, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and polymerization starter below 10 mass parts of 0.01 mass parts to described blend compositions.
9. the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), it comprises following operation: make the operation of blend compositions that contains following (A), (B), (D), (E), described (A), (B), (D), (E) are: (methyl) acrylic resin compositions (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts,
Above and the thermal conductivity filler (B) below 1200 mass parts of 90 mass parts,
Above and the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s below 8 mass parts of 0.2 mass parts,
The 0.3 mass parts viscosity having at functional group more than 2 and below 10000 and 25 DEG C above and below 5.0 mass parts is the multi-functional epoxy compound (E) below 600mPa s; And
In described blend compositions, the operation of the crosslinking reaction of the polymkeric substance that carries out polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and described multi-functional monomer (D) and/or contain the structural unit that derives from described (methyl) acrylate monomer (α 1).
10. the manufacture method of thermal conductivity pressure-sensitive adhesive composite according to claim 9 (F), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
11. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 9 or 10, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and phosphoric acid ester (C) below 190 mass parts of 45 mass parts to described blend compositions.
12. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) described in any one in claim 9～11, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and polymerization starter below 10 mass parts of 0.01 mass parts to described blend compositions.
The manufacture method of the sheet-like formed body of 13. thermal conductivity pressure-sensitive adhesive (G), it comprises following operation: make the operation of blend compositions that contains following (A), (B), (D), (E), described (A), (B), (D), (E) are: (methyl) acrylic resin compositions (A) that contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) of 100 mass parts,
Above and the thermal conductivity filler (B) below 1200 mass parts of 90 mass parts,
Above and the multi-functional monomer (D) with multiple polymerizability unsaturated link(age)s below 8 mass parts of 0.2 mass parts,
The 0.3 mass parts viscosity having at functional group more than 2 and below 10000 and 25 DEG C above and below 5.0 mass parts is the multi-functional epoxy compound (E) below 600mPa s; And,
Described blend compositions is configured as after sheet, or when described blend compositions is configured as to sheet, the operation of the crosslinking reaction of the polymkeric substance that carries out polyreaction and described (methyl) acrylic ester polymer (A1) of described (methyl) acrylate monomer (α 1) and described multi-functional monomer (D) and/or contain the structural unit that derives from described (methyl) acrylate monomer (α 1).
The manufacture method of the 14. sheet-like formed bodies of thermal conductivity pressure-sensitive adhesive according to claim 13 (G), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
15. according to the manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) described in claim 13 or 14, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and phosphoric acid ester (C) below 190 mass parts of 45 mass parts to described blend compositions.
The manufacture method of the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) in 16. claims 13～15 described in any one, wherein, further to contain with respect to described (methyl) acrylic resin composition (A) 100 mass parts be the above and polymerization starter below 10 mass parts of 0.01 mass parts to described blend compositions.
17. electronic units, it possesses radiator and fits in the thermal conductivity pressure-sensitive adhesive composite (F) described in any one in the claim 1～4 of this radiator, or possesses radiator and fit in the sheet-like formed body of thermal conductivity pressure-sensitive adhesive (G) described in any one in the claim 5～8 of this radiator.
CN201280050873.2A 2011-10-28 2012-10-16 Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-form molded body, manufacturing method of these, and electronic component Pending CN103874739A (en)

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