CN103562334A - Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded body, method for producing thermally conductive pressure-sensitive adhesive composition, method for producing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic component - Google Patents

Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded body, method for producing thermally conductive pressure-sensitive adhesive composition, method for producing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic component Download PDF

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Publication number
CN103562334A
CN103562334A CN201280023461.XA CN201280023461A CN103562334A CN 103562334 A CN103562334 A CN 103562334A CN 201280023461 A CN201280023461 A CN 201280023461A CN 103562334 A CN103562334 A CN 103562334A
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mass parts
thermal conductivity
methyl
sensitive adhesive
conductivity pressure
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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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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Provided is a thermally conductive pressure-sensitive adhesive composition which has insulating properties and thermal conductivity in a balanced manner and is obtained by carrying out a polymerization reaction of a (meth)acrylic acid ester monomer mixture and a crosslinking reaction of a polymer that comprises a structural unit derived from a (meth)acrylic acid ester polymer (A1) and/or a (meth)acrylic acid ester monomer (alpha1) in a mixed composition that contains: 100 parts by mass of a (meth)acrylic resin composition (A) that contains the (meth)acrylic acid ester polymer (A1) and the (meth)acrylic acid ester monomer (alpha1); from 0.5 parts by mass to 40 parts by mass (inclusive) of a zinc oxide (C) having a needle-like portion; from 0.5 parts by mass to 20 parts by mass (inclusive) of an expanded graphite powder (D); and from 600 parts by mass to 1,400 parts by mass (inclusive) of an insulating thermally conductive filler (B) that is other than the zinc oxide (C) having a needle-like portion and the expanded graphite powder (D). Also provided are: a thermally conductive pressure-sensitive adhesive sheet-like molded body; a method for producing the thermally conductive pressure-sensitive adhesive composition; a method for producing the thermally conductive pressure-sensitive adhesive sheet-like molded body; and an electronic component which is provided with the thermally conductive pressure-sensitive adhesive composition or the thermally conductive pressure-sensitive adhesive sheet-like molded body.

Description

Thermal conductivity pressure-sensitive adhesive composite, thermal conductivity pressure-sensitive adhesive sheet-like formed body, their manufacture method and electronic unit
Technical field
The present invention relates to thermal conductivity pressure-sensitive adhesive composite, thermal conductivity pressure-sensitive adhesive sheet-like formed body, they manufacture method and possess this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
Background technology
In recent years, the electronic units such as plasma display panel (PDP) (PDP), unicircuit (IC) chip are along with its high performance, and thermal value increases to some extent.This result is necessary the handicapped countermeasure of taking Yin Wendu to rise and cause.In general, adopt the method that makes its heat radiation in the heating element that electronic unit etc. possesses by the radiators such as metal scatterer, heating panel, radiator element are arranged on.In order to carry out efficiently the thermal conduction to radiator by heating element, use various conducting strips.In general, in the purposes of fixedly heating element and radiator, need to be except thermal conductivity, also possess composition (hereinafter referred to as " thermal conductivity pressure-sensitive adhesive composite "), the sheet material (hereinafter referred to as " thermal conductivity pressure-sensitive adhesive sheet-like formed body ") of pressure-sensitive adhesive.
Above-mentioned thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body are as main purpose for conducting heat by heating element to radiator, and therefore preferably thermal conductivity is high.In order to reduce the thermal resistance of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, such as considering, add wherein expansion fossil ink powder etc.But expansion fossil ink powder, when having high thermal conductivity, also has high conductivity.Therefore, by volume contain thermal conductivity pressure-sensitive adhesive composite and the thermal conductivity pressure-sensitive adhesive sheet-like formed body that expansion fossil ink powder improves thermal conductivity have situation about cannot use in the purposes that also requires insulativity.On the other hand, as the filler that can improve thermal conductivity, there is the situation (patent documentation 1 ~ 3) of using zinc oxide.
Prior art document
Patent documentation 1: TOHKEMY 2008-163145 communique
Patent documentation 2: TOHKEMY 2008-127482 communique
Patent documentation 3: TOHKEMY 2008-127481 communique.
Summary of the invention
The technical problem that invention will solve
Zinc oxide, because electroconductibility is lower than expansion fossil ink powder, therefore, when adding zinc oxide in thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body, is compared to and adds expansion fossil ink powder, can more suppress the rising of electroconductibility.
But, though the electroconductibility of zinc oxide is lower than expansion fossil ink powder, but when when improving the thermal conductivity of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body by zinc oxide add the zinc oxide of volume as the technology that patent documentation 1 ~ 3 is recorded, the situation that has the electroconductibility of thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body to increase, cannot use in requiring the purposes of insulativity.So, in the prior art, thermal conductivity pressure-sensitive adhesive composite and thermal conductivity pressure-sensitive adhesive sheet-like formed body are difficult to balance and possess well insulativity and thermal conductivity.
Therefore, problem of the present invention be to provide thermal conductivity pressure-sensitive adhesive composite that balance possesses insulativity and thermal conductivity well and thermal conductivity pressure-sensitive adhesive sheet-like formed body, they manufacture method and possess this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
For solving the method for problem
The discoveries such as the inventor, by being used in combination in the proper ratio a plurality of fillers with thermal conductivity, can solve above-mentioned problem, and then complete the present invention.
The 1st mode of the present invention is thermal conductivity pressure-sensitive adhesive composite (F), its crosslinking reaction that is the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1) in blend compositions forms, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except thering is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) expansion fossil ink powder (D).
The definition of the words and phrases that use in following notebook specification sheets." (methyl) vinylformic acid " refers to " vinylformic acid and/or methacrylic acid "." zinc oxide (C) with needle-like portion " refers to the zinc oxide like that as described later with needle-like portion." expansion fossil ink powder (D) " refers to the coccoid that makes like that as described later graphite expansion, pulverizing." except having the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) expansion fossil ink powder (D) " refer to except the zinc oxide with needle-like portion (C) and expansion fossil ink powder (D), by add the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) that can improve thermal conductivity pressure-sensitive adhesive composite (F) or illustrate below thermal conductivity, resistivity is 10 12Ω m is above, thermal conductivity is filler more than 1W/m k." polyreaction of (methyl) acrylate monomer (α 1) " refers to the polyreaction that obtains the polymkeric substance that produces the structural unit that comes from (methyl) acrylate monomer (α 1).One or more crosslinking reactions in the crosslinking reaction of the crosslinking reaction between the polymkeric substance that " crosslinking reaction of (methyl) acrylic ester polymer (A1) and/or the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1) " refer to crosslinking reaction between (methyl) acrylic ester polymer (A1), contain the structural unit that comes from (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1).
The 2nd mode of the present invention is a kind of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), it is for after being shaped to sheet by blend compositions or when blend compositions is shaped to sheet, the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1) forms, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except thering is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) expansion fossil ink powder (D).
The 3rd mode of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F), it comprises following operation: the operation of making blend compositions, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except thering is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) expansion fossil ink powder (D), and the operation of the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1) in this blend compositions.
The 4th mode of the present invention is the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), it comprises following operation: the operation of making blend compositions, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except thering is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) expansion fossil ink powder (D), and after blend compositions is shaped to sheet or when blend compositions is shaped to sheet, the operation of the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1).
The 5th mode of the present invention is electronic unit, it possesses radiator and fits in the thermal conductivity pressure-sensitive adhesive composite (F) of the present invention's the 1st mode of this radiator, or possesses radiator and fit in the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of the present invention's the 2nd mode of this radiator.
Invention effect
By the present invention, can provide thermal conductivity pressure-sensitive adhesive composite that balance possesses insulativity and thermal conductivity well and thermal conductivity pressure-sensitive adhesive sheet-like formed body, they manufacture method and possess this thermal conductivity pressure-sensitive adhesive composite or the electronic unit of this thermal conductivity pressure-sensitive adhesive sheet-like formed body.
Embodiment
1. thermal conductivity pressure-sensitive adhesive composite (F), thermal conductivity pressure-sensitive adhesive sheet-like formed body (G)
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) for obtaining the polyreaction of the polymkeric substance that produces the structural unit that comes from (methyl) acrylate monomer (α 1) and the crosslinking reaction between (methyl) acrylic ester polymer (A1) in blend compositions, at least any crosslinking reaction in the crosslinking reaction of the crosslinking reaction between the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1) forms, (methyl) acrylic acid resin composition (A) that described blend compositions contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), the zinc oxide (C) (also only having below the situation that is called " zinc oxide (C) ") with needle-like portion, expansion fossil ink powder (D), except thering is zinc oxide (C) and the insulativity thermal conductivity filler (B) expansion fossil ink powder (D) (also only having below the situation that is called " thermal conductivity filler (B) ") of needle-like portion.
In addition, thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G) for when being shaped to sheet after above-mentioned blend compositions is shaped to sheet or by above-mentioned blend compositions, obtain the polyreaction of the polymkeric substance that produces the structural unit that comes from (methyl) acrylate monomer (α 1) and the crosslinking reaction between (methyl) acrylic ester polymer (A1), at least any crosslinking reaction in the crosslinking reaction of the crosslinking reaction between the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1) forms.
Below explanation forms the material of this thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
<(methyl) acrylic acid resin composition (A) >
(methyl) acrylic acid resin composition (A) using in the present invention contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1).Be explained, as mentioned above when obtaining thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), the crosslinking reaction of the polyreaction that obtains the polymkeric substance that produces the structural unit that comes from (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or the polymkeric substance that contains the structural unit that comes from (methyl) acrylate monomer (α 1).By carrying out this polyreaction and crosslinking reaction, contain coming from the polymkeric substance of structural unit and the composition of (methyl) acrylic ester polymer (A1) of (methyl) acrylate monomer (α 1), mix and/or part bonding.
In the present invention, the consumption of acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) is with respect to (methyl) acrylic acid resin composition (A) 100 quality %, and preferably (methyl) acrylic ester polymer (A1) is that the above 40 quality % of 5 quality % are following, (methyl) acrylate monomer (α 1) is below the above 95 quality % of 60 quality %.By making the ratio that contains of (methyl) acrylate monomer (α 1), be above-mentioned scope, thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) carried out to moulding and become easy.
((methyl) acrylic ester polymer (A1))
(methyl) acrylic ester polymer (A1) that can use in the present invention is not particularly limited, preferably contain form second-order transition temperature reach-20 ℃ of following homopolymer (methyl) acrylate monomer unit (a1) and there is the monomeric unit (a2) of organic acid group.
Provide (methyl) acrylate monomer (a1m) of the unit (a1) of above-mentioned (methyl) acrylate monomer to be not particularly limited, for example can enumerate ethyl propenoate (second-order transition temperature of homopolymer is-24 ℃), vinylformic acid n-propyl (with-37 ℃), n-butyl acrylate (with-54 ℃), sec-butyl acrylate (with-22 ℃), vinylformic acid n-pentyl ester (with-60 ℃), the just own ester of vinylformic acid (with-61 ℃), vinylformic acid n-octyl (with-65 ℃), 2-EHA (with-50 ℃), vinylformic acid 2-methoxyl group ethyl ester (with-50 ℃), vinylformic acid 3-methoxyl group propyl ester (with-75 ℃), vinylformic acid 3-methoxyl group butyl ester (with-56 ℃), vinylformic acid oxyethyl group methyl esters (with-50 ℃), n octyl methacrylate (with-25 ℃), methacrylic acid ester in the positive last of the ten Heavenly stems (with-49 ℃) etc.Wherein, preferred 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 be used alone a kind, also can and use two or more.
(methyl) acrylate monomer (a1m) preferably reaches more than 80 quality % below 99.9 quality %, more preferably reaches more than 85 quality % the amount below 99.5 quality % for to polymerization in (methyl) acrylic ester polymer (A1) with the monomeric unit by its importing (a1).The consumption of (methyl) acrylate monomer (a1m) is in above-mentioned scope time, and the viscosity of the polymerization system while being easy to polymerization remains in suitable scope.
Then, to thering is the monomeric unit (a2) of organic acid group, describe.Provide the monomer (a2m) of the monomeric unit (a2) with organic acid group to be not particularly limited, as its representative, can enumerate the monomer of organic acid groups such as thering is carboxyl, anhydride group, sulfonic group.In addition, except these, also can use the monomer that contains sulfeno, sulfino, phosphate etc.
As the object lesson with the monomer of carboxyl, such as removing the α such as vinylformic acid, methacrylic acid, β-crotonic acid, β-ethylenic unsaturated monocarboxylic, the α such as methylene-succinic acid, toxilic acid, fumaric acid, outside the unsaturated polycarboxylic acid of β-ethylenic, also can enumerate the α such as monomethyl itaconate, butyl maleate, fumaric acid list propyl ester, the unsaturated polycarboxylic acid part of β-ethylenic ester etc.In addition, maleic anhydride, itaconic anhydride etc. have the material that can be derivatized to the group of carboxyl by hydrolysis etc. and also can similarly use.
As the object lesson with sulfonic monomer, can enumerate the α such as allyl sulphonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide-2-methyl propane sulfonic, β-unsaturated sulfonic acid and their salt.
As monomer (a2m), in the monomer with organic acid group of crossing in above example, more preferably there is the monomer of carboxyl, wherein particularly preferably there is the monomer of acrylic or methacrylic acid.These monomers in industrial cheapness, can easily obtain, also good with the copolymerizable of other monomer components, also preferred aspect productivity.Be explained, monomer (a2m) can be used alone a kind, also can and use two or more.
The monomer (a2m) with organic acid group preferably reaches more than 0.1 quality % below 20 quality %, more preferably reaches more than 0.5 quality % the amount below 15 quality % for to polymerization in (methyl) acrylic ester polymer (A1) with the monomeric unit by its importing (a2).The consumption with the monomer (a2m) of organic acid group is in above-mentioned scope time, and the viscosity of the polymerization system while being easy to polymerization remains in suitable scope.
Be explained, there is the monomeric unit (a2) of organic acid group as mentioned above, by thering is the polymerization of the monomer (a2m) of organic acid group, import in (methyl) acrylic ester polymer (A1) simple, therefore preferred, but also can generate (methyl) acrylic ester polymer (A1) afterwards by known high molecular weight reactive importing organic acid group.
In addition, (methyl) acrylic ester polymer (A1) can contain the monomeric unit (a3) being derived by the monomer (a3m) with organic acid group functional group in addition.Functional group as beyond above-mentioned organic acid group, can enumerate hydroxyl, amino, amide group, epoxy group(ing), sulfydryl etc.
As the monomer with hydroxyl, can enumerate (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester etc.
As thering is amino monomer, can enumerate (methyl) vinylformic acid N, N-dimethylamino methyl esters, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, amino-benzene ethene etc.
As the monomer with amide group, can enumerate the α such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N,N-DMAA, β-ethylenic unsaturated carboxylic acid amide monomer etc.
As the monomer with epoxy group(ing), can enumerate (methyl) glycidyl acrylate, allyl glycidyl ether etc.
The monomer (a3m) with organic acid group functional group in addition can be used separately a kind, also can and use two or more.
These monomers (a3m) with the functional group beyond organic acid group preferably reach amount below 10 quality % for polymerization in (methyl) acrylic ester polymer (A1) with the monomeric unit by its importing (a3).By using the monomer (a3m) below 10 quality %, the viscosity of the polymerization system while being easy to polymerization remains in suitable scope.
(methyl) acrylic ester polymer (A1) is except above-mentioned formation second-order transition temperature reaches (methyl) acrylate monomeric units (a1) of-20 ℃ of following homopolymer, the monomeric unit (a3) that has the monomeric unit (a2) of organic acid group and have a functional group organic acid group in addition, also can contain by monomeric unit (a4) that can be derivative with the monomer (a4m) of above-mentioned monomer copolymerization.
Monomer (a4m) is not particularly limited, as its object lesson, can enumerate above-mentioned (methyl) acrylate monomer (a1m) (methyl) acrylate monomer, α in addition, the complete Zhi, alkenyl aroma of the unsaturated polycarboxylic acid of β-ethylenic family monomer, conjugated diene monomer, non-conjugated diene are monomer, vinyl cyanide base monomer, the unsaturated alcohol ester of carboxylic acid, ethylene series monomer etc.
As the object lesson of above-mentioned (methyl) acrylate monomer (a1m) (methyl) acrylate monomer in addition, can enumerate methyl acrylate (second-order transition temperature of homopolymer is 10 ℃), methyl methacrylate (with 105 ℃), β-dimethyl-aminoethylmethacrylate (with 63 ℃), n propyl methacrylate (with 25 ℃), n-BMA (with 20 ℃) etc.
As α, the object lesson of the complete ester of the unsaturated polycarboxylic acid of β-ethylenic, can enumerate dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate, dimethyl itaconate etc.
As the object lesson of alkenyl aroma family monomer, can enumerate vinylbenzene, alpha-methyl styrene, methyl alpha-methyl styrene, Vinyl toluene and Vinylstyrene etc.
As the object lesson of conjugated diene monomer, can enumerate 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (with isoprene synonym), 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, chlorbutadiene, cyclopentadiene etc.
As non-conjugated diene, be the object lesson of monomer, can enumerate Isosorbide-5-Nitrae-hexadiene, Dicyclopentadiene (DCPD), ethylidene norbornene etc.
As the object lesson of vinyl cyanide base monomer, can enumerate vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, α-ethyl acrylonitrile etc.
As the object lesson of the unsaturated alcohol ester monomer of carboxylic acid, can enumerate vinyl-acetic ester etc.
As the object lesson of ethylene series monomer, can enumerate ethene, propylene, butylene, amylene etc.
Monomer (a4m) can be used alone a kind, also can and use two or more.
Monomer (a4m) preferably reaches below 10 quality %, more preferably reaches amount below 5 quality % for to polymerization with the amount of the monomeric unit by its importing (a4) in (methyl) acrylic ester polymer (A1).
(methyl) acrylic ester polymer (A1) by by second-order transition temperature is reached to-20 ℃ of following homopolymer and carries out moulding (methyl) acrylate monomer (a1m), have the monomer (a2m) of organic acid group, the monomer (a3m) that contains the functional group beyond organic acid group using as required and use as required can carry out copolymerization with the monomer (a4m) of these monomer copolymerizations, can especially suitably obtain.
Polymerization process while obtaining (methyl) acrylic ester polymer (A1) is not particularly limited, and can be solution polymerization, letex polymerization, suspension polymerization, mass polymerization etc. wantonly a kind, can also be except the method these.Wherein, in these polymerization processs, preferred solution polymerization, has wherein more preferably been used the solution polymerization of the aromatic solvents such as the carboxylicesterss such as ethyl acetate, ethyl lactate or benzene,toluene,xylene as polymer solvent.When polymerization, monomer can portion-wise addition to polymerization container, but preferably add together all amounts.The method that polymerization causes is not particularly limited, and as polymerization starter, preferably uses 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 superoxide such as hydrogen peroxide compound, benzoyl peroxide, cyclohexanone peroxide such as tertbutyl peroxide, also can enumerate the persulphates such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate etc.These superoxide also can be suitably and reductive agent combination, as redox series catalysts, uses.
As azo-compound polymerization starter, can enumerate 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 with respect to monomer 100 mass parts, is preferably the scope below above 50 mass parts of 0.01 mass parts.
Other polymerizing conditions of these monomers (polymerization temperature, pressure, agitation condition etc.) are not particularly limited.
After polyreaction finishes, as required that resulting polymers is separated from polymerisation medium.Separated method is not particularly limited.For example, during for solution polymerization, polymeric solution is positioned under decompression, polymer solvent distillation is removed, thereby can obtain (methyl) acrylic ester polymer (A1).
The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (A1) utilizes gel permeation chromatography (GPC method) to measure, in polystyrene standard, convert be preferably more than 100,000 in the scope below 1,000,000, more preferably more than 200,000 in the scope below 500,000.The amount of polymerization starter or the amount of chain-transfer agent when the weight-average molecular weight of (methyl) acrylic ester polymer (A1) can be by suitable adjustment polymerization, used are controlled.
((methyl) acrylate monomer blend (α 1))
(methyl) acrylate monomer (α 1) so long as contain (methyl) acrylate monomer and be not particularly limited, preferably contains second-order transition temperature is reached to (methyl) acrylate monomer (a5m) that-20 ℃ of following homopolymer carry out moulding.
As the homopolymer below second-order transition temperature being reached to-20 ℃, carry out the example of (methyl) acrylate monomer (a5m) of moulding, can enumerate (methyl) acrylate monomer same with synthetic middle (methyl) acrylate monomer (a1m) using of (methyl) acrylic ester polymer (A1).(methyl) acrylate monomer (a5m) can be used alone a kind, also can and use two or more.
The ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1) is preferably below the above 100 quality % of 50 quality %, more preferably below the above 100 quality % of 75 quality %.By making the ratio of (methyl) acrylate monomer (a5m) in (methyl) acrylate monomer (α 1), be above-mentioned scope, be easy to obtain thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of pressure-sensitive adhesive, flexibility excellence.
In addition, (methyl) acrylate monomer (α 1) can also for (methyl) acrylate monomer (a5m) and can with the mixture of the monomer of its copolymerization.
(methyl) acrylate monomer (α 1) can also carry out (methyl) acrylate monomer (a5m) of moulding and can carry out with them the mixture of the monomer with organic acid group (a6m) of copolymerization for second-order transition temperature being reached to-20 ℃ of following homopolymer.
As the example of above-mentioned monomer (a6m), can enumerate and the monomer equally with organic acid group of crossing as synthetic middle monomer (a2m) example of using of (methyl) acrylic ester polymer (A1).Monomer (a6m) can be used alone a kind, also can and use 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 %.By making the ratio of the monomer (a6m) in (methyl) acrylate monomer (α 1), be in above-mentioned scope, be easy to obtain thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) of pressure-sensitive adhesive, flexibility excellence.
(methyl) acrylate monomer (α 1) is except (methyl) acrylate monomer (a5m) and can make as required the monomer with organic acid group (a6m) of its copolymerization, can also for can carry out with them the mixture of the monomer (a7m) of copolymerization.
As the example of above-mentioned monomer (a7m), can enumerate and the same monomer of crossing as synthetic middle use monomer (a3m) and monomer (a4m) example of (methyl) acrylic ester polymer (A1).Monomer (a7m) can be used alone a kind, also can and use 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 >
When obtaining thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), (methyl) acrylate monomer (α 1) and multi-functional monomer described later carry out polymerization.In order to promote this polymerization, preferably use polymerization starter.As this polymerization starter, can enumerate Photoepolymerizationinitiater initiater, azo is thermal polymerization, organo-peroxide thermal polymerization etc.From the viewpoint of giving excellent cementability etc. to gained thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), preferably use organo-peroxide thermal polymerization.
As Photoepolymerizationinitiater initiater, can use known various Photoepolymerizationinitiater initiater.Wherein, preferred acylphosphine oxide based compound.As the acylphosphine oxide based compound of preferred light polymerization starter, can enumerate two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides, TMDPO etc.
As azo, be thermal polymerization, can enumerate 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 enumerate the hydrogen peroxide such as tertbutyl peroxide, benzoyl peroxide, cyclohexanone peroxide, 1, two (the tert-butyl hydroperoxide ketonic oxygen base) hexanes, 1 of 6-, two (tert-butyl peroxide)-3 of 1-, the superoxide such as 3,5-trimethylcyclohexanone etc.Wherein, be preferably not discharge when thermolysis and become the volatile matter of stink reason person.In addition, in organo-peroxide thermal polymerization, preferably 1 minute half life temperature is 100 ℃ of above and 170 ℃ of following persons.
The consumption of above-mentioned polymerization starter with respect to (methyl) acrylic acid resin composition (A) 100 mass parts be preferably above 10 mass parts of 0.01 mass parts following, more preferably above 5 mass parts of 0.1 mass parts following, be more preferably below above 1 mass parts of 0.3 mass parts.By making the consumption of polymerization starter, be in above-mentioned scope, the polymerisation conversion that is easy to make (methyl) acrylate monomer blend (α 1) is, in suitable scope, to be easy to prevent that monomer smell from residuing in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Be explained, 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, is easy to prevent that monomer smell from residuing in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).In addition, by making the consumption of polymerization starter, be in above-mentioned scope, owing to adding polymerization starter, can exceedingly bring out the carrying out of polyreaction, its result thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can not become level and smooth sheet, is easy to prevent from causing the situation of material damage.
The multi-functional monomer > of <
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), also preferably use multi-functional monomer.As multi-functional monomer, use can be carried out the monomer of copolymerization with the contained monomer of (methyl) acrylate monomer (α 1).In addition, multi-functional monomer has a plurality of polymerizability unsaturated link(age)s, preferably has endways this unsaturated link(age).By using this multi-functional monomer, can in multipolymer, import in molecule and/or intermolecular cross-linking, improve the cohesive force as the pressure adhesive of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
Conventionally, when the polymerizations such as free radical thermopolymerization, even if do not use multi-functional monomer, crosslinking reaction to a certain degree also can be carried out.But, in order more positively to form the crosslinking structure of aequum, preferably use multi-functional monomer.
As multi-functional monomer, for example, except 1, 6-hexylene glycol two (methyl) acrylate, 1, 2-ethylene glycol bisthioglycolate (methyl) acrylate, 1, 12-dodecanediol 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 (trishydroxymethyl) propane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, multi-functional (methyl) acrylate such as Dipentaerythritol six (methyl) acrylate, 2, two (the trichloromethyl)-6-of 4-are to outside the replacement triazines such as methoxy styrene-5-triazine, also can use the monoene keys such as 4-propenyloxy group benzophenone is unsaturated aromatic ketone etc.Wherein, preferred tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate.Multi-functional monomer can be used alone a kind, also can and use two or more.
The amount of the multi-functional monomer using in thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) be take (methyl) acrylic acid resin composition (A) as 100 mass parts, be preferably above 15 mass parts of 0.1 mass parts following, more preferably above 8 mass parts of 0.2 mass parts following, more preferably below above 2 mass parts of 0.5 mass parts.By making the consumption of multi-functional monomer, be in above-mentioned scope, be easy to thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) to give as the suitable cohesive force of pressure adhesive.
< zinc oxide (C) >
The zinc oxide using in the present invention (C) has needle-like portion.The length of this needle-like portion is preferably below the above 50 μ m of 2 μ m.Be explained, the length of the needle-like portion of zinc oxide (C) for example can utilize scanning electronic microscope to observe to measure.As rear explanation, think that by making the length of the needle-like portion of zinc oxide (C) be in above-mentioned scope, utilize and other combinations with the filler of thermal conductivity, be easy to make thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) to possess high thermal conductivity.
The zinc oxide using in the present invention (C) if shape there is needle-like portion.That is, zinc oxide (C) can possess one or more needle-like portions in the surrounding that becomes the part of core, also can only needle-like portion, consist of.But as described later, from being easy to there is the viewpoint connecting between the filler of thermal conductivity, the shape that preferably possesses a plurality of needle-like portions and stretch in different directions respectively in the surrounding that becomes the part of core with zinc oxide by being filled in other in (C) thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Preferred shape be the surrounding that becomes the part of core have in 3 above needle-like portions, this needle-like portion at least 1 with other needle-like portions shape at grade not.Be explained, the quantity that is present in 1 circumnuclear needle-like portion is preferably 3～6.During for this number of ranges, it is three-dimensional that the orientation of needle-like portion becomes, and become good with the connection of other fillers.The commercially available product that possesses the zinc oxide of a plurality of needle-like portion as the surrounding becoming the part of core, for example, can enumerate " the パ Na テ ト ラ (registered trademark) " of the ア of Co., Ltd. system テ ッ Network system.
The amount of the zinc oxide (C) using in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is below above 40 mass parts of 0.5 mass parts, is preferably below above 35 mass parts of 0.8 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.By making the content of zinc oxide (C), be in above-mentioned scope, utilize and other combinations with the filler of thermal conductivity, be easy to make thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) to possess high thermal conductivity.In addition, by making the content of zinc oxide (C), be in above-mentioned scope, the insulativity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can not reduce, except can using, also can obtain fully the effect of the thermal conductivity that improves thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) in requiring the purposes of insulativity.
< expansion fossil ink powder (D) >
Expansion fossil ink powder (D) makes pulverize and obtain after graphite expansion.Example as the expansion fossil ink powder (D) using in the present invention, can enumerate the material by comprising that the method for following operation obtains, described operation is for more than 500 ℃ to heat-treat having carried out acid-treated graphite below 1200 ℃, it is expanded to below the above 300ml/g of 100ml/g, then it is pulverized.More preferably, can enumerate the material by comprising that the method for following operation obtains, described operation is with carry out sintering after strong acid treatment graphite in alkali, again with strong acid, process afterwards, by gains more than 500 ℃ 1200 ℃ heat-treat below, acid is removed, make it be expanded to below the above 300ml/g of 100ml/g simultaneously, then pulverize.Above-mentioned heat treated temperature is particularly preferably 800 ℃ above below 1000 ℃.
The median size of the expansion fossil ink powder (D) using in the present invention be preferably the above 1000 μ m of 10 μ m following, more preferably the above 700 μ m of 20 μ m following, more preferably below the above 500 μ m of 30 μ m.Median size by the fossil ink powder (D) that makes to expand is in above-mentioned scope, in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), be easy to form the conducting path of heat, and be easy to prevent from expanding the destroyed situation of fossil ink powder (D).
Be explained, in the present invention, " median size " refers to the value of measuring by the method for following explanation.That is, use laser type particle size measurement machine (セイシン enterprise of Co., Ltd. system), utilize micro-selection control mode (making determination object particle only by the mode of measuring in region, reliability is measured in raising) to measure.Utilize this measuring method, by determination object particle 0.01g～0.02g is flowed in pond, to flowing into the semiconductor laser of measuring the determination object particle-irradiation wavelength 670nm in region, use measuring machine to measure sharp scattering of light and diffraction now, thereby calculate median size and size distribution by the diffraction principle of fraunhofer.
The amount of the expansion fossil ink powder (D) using in the present invention is below above 20 mass parts of 0.5 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.Amount by the fossil ink powder (D) that makes to expand is in above-mentioned scope, utilize and there is the combination of the filler of thermal conductivity with other, can be when suppressing to take the mobility reduction that thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) they be basic blend compositions, and balance makes thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) possess insulativity and thermal conductivity well.Amount by expansion fossil ink powder (D) is below the above-mentioned upper limit, can keep the insulativity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
< thermal conductivity filler (B) >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), except having the zinc oxide (C) and expansion fossil ink powder (D) of needle-like portion, also use the thermal conductivity filler (B) of insulativity.Thermal conductivity filler (B) be there is insulativity, by adding the filler of the thermal conductivity that can improve thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
As the object lesson of thermal conductivity filler (B), can enumerate calcium carbonate, aluminium hydroxide, magnesium hydroxide, aluminum oxide (alumina), magnesium oxide, silicon-dioxide, glass fibre, boron nitride and aluminium nitride etc.Wherein, calcium carbonate, aluminium hydroxide and aluminum oxide owing to obtaining easily, chemically stable and cooperation that can volume, therefore preferably, more preferably aluminium hydroxide and aluminum oxide.Thermal conductivity filler (B) can be used alone a kind, also can and use two or more.
The median size of the thermal conductivity filler (B) using in the present invention in addition, is preferably below the above 50 μ m of 0.1 μ m.
The amount of the middle thermal conductivity filler (B) using of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is below above 1400 mass parts of 600 mass parts, is preferably below above 1200 mass parts of 700 mass parts, more preferably below above 1000 mass parts of 800 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.By making the content of thermal conductivity filler (B), be in above-mentioned scope, the combination of utilization and other fillers, is easy to balance and makes well thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) possess insulativity and thermal conductivity.On the other hand, by making the content of thermal conductivity filler (B), be below the above-mentioned upper limit, suppress to become the raw-material blend compositions of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) tackify, prevent that the productivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) from reducing, suppress hardness simultaneously and increase, prevent that product having shape-following-up properties from reducing.By preventing that product having shape-following-up properties from reducing, in the time of on being attached at heating element and radiator, be easy to heat to be passed to radiator from heating element.In addition, by making the content of thermal conductivity filler (B), be more than above-mentioned lower limit, can obtain fully the effect of the thermal conductivity that improves thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
< is by the effect > of combination results with the filler of thermal conductivity
As mentioned above, when adding zinc oxide (C), expansion fossil ink powder (D) etc. and have the filler of electroconductibility and improve the thermal conductivity of resin combination, if volume ground adds these fillers, there is the problem of the insulativity that reduces this resin combination.On the other hand, while only depending on the insulativity filler as above-mentioned thermal conductivity filler (B), even if can prevent that the insulativity of resin combination from reducing, and is also difficult to improve fully thermal conductivity.According to the present invention, by being used in combination thermal conductivity filler (B), zinc oxide (C) and expansion fossil ink powder (D) with suitable amount respectively, even if the addition of the filler with electroconductibility as zinc oxide (C), expansion fossil ink powder (D) was less than respectively in the past, also can make thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) possess high thermal conductivity, the insulativity that can suppress thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) reduces.That is thermal conductivity pressure-sensitive adhesive composite (F) and the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) that, according to the present invention, can provide balance to possess well insulativity and thermal conductivity.Described in thinking that it the reasons are as follows.
By thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), in the inside of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), it is mainly the bang path of thermal conductivity filler (B) the formation heat of insulativity.But, owing to only depending on thermal conductivity filler (B), improve the effect of thermal conductivity of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) insufficient, so zinc oxide (C) and expansion fossil ink powder (D) supplement it.Infer that zinc oxide (C) is owing to having as mentioned above needle-like portion, therefore by utilizing this needle-like portion other to be had between the filler of thermal conductivity in thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), connect, can form the bang path of heat.As a rule, in order to attempt to improve thermal conductivity, add while thering is the filler of thermal conductivity, from being easy to improve the viewpoint of thermal conductivity, think that the particle diameter of this filler is the bigger the better.But, as mentioned above from utilizing the needle-like portion of zinc oxide (C) to be easy to that other are had to the viewpoint connecting between the filler of thermal conductivity, think the length that needle-like portion that preferred thermal conductivity filler (B) and expansion fossil ink powder (D) are the size of afore mentioned rules, zinc oxide (C) is afore mentioned rules.In addition, expansion fossil ink powder (D) is because thermal conductivity is high, electroconductibility is also high, therefore the scope that preferably usage quantity is afore mentioned rules, the scope that consumption by the fossil ink powder (D) that makes to expand is afore mentioned rules, can, when the insulativity that suppresses thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) reduces, improve thermal conductivity.
< phosphoric acid ester >
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), also can use phosphoric acid ester.By using phosphoric acid ester, be easy to improve the flame retardant resistance of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
The phosphoric acid ester of using in the present invention preferably the viscosity at 25 ℃ for more than 3000mPa s.By making the viscosity of phosphoric acid ester, be in above-mentioned scope, be easy to prevent the formability variation of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).Be explained, 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), according to order shown below, is carried out.
(1), at the environment lower-weighing phosphoric acid ester 300ml of normal temperature, put into the container of 500ml.
(2) from stirring with selecting any rotor No.1,2,3,4,5,6,7, be installed on viscometer.
(3) container that phosphoric acid ester is housed is placed on viscometer, rotor is sunk in the condensed phosphoric acid esters in this container.The mode that the depression of now, usining as rotor mark enters the aqueous interface of phosphoric acid ester just sinks to.
(4) from 20,10,4,2, select rotating speed.
(5) open stirring switch, read the numerical value after 1 minute.
(6) numerical value reading becomes viscosity ［ mPa s ］ divided by the value of coefficient A.Be explained, coefficient A as described in Table 1, is determined by selected rotor No. and rotating speed.
[table 1]
Figure 726971DEST_PATH_IMAGE001
In addition, in the preferred 15 ℃ of above 100 ℃ of following temperature provinces under atmospheric pressure of phosphoric acid ester of using in the present invention, be liquid always.Phosphoric acid ester is so long as be liquid when mixing, operability good, thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) carried out to moulding become easy.When the thermal conductivity pressure-sensitive adhesive composite (F) that contains phosphoric acid ester or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) are carried out to moulding, preferably, under the more than 15 ℃ environment below 100 ℃, to forming each material of thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), mix.Temperature when making to mix is in above-mentioned scope, more than being the second-order transition temperature of (methyl) acrylic acid resin composition (A), the volatilization or the polyreaction that are easy to prevent the contained monomer of (methyl) acrylic acid resin composition (A) etc. start, and therefore can make environment and operability become good.
In the present invention, as phosphoric acid ester, can use condensed phosphoric acid esters, also can use non-condensed phosphoric acid esters.Here said " condensed phosphoric acid esters " refers to that 1 molecular memory is at a plurality of phosphoric acid ester position, and " non-condensed phosphoric acid esters " refers to and in 1 molecule, only have 1 phosphoric acid ester position.Below list the object lesson of the phosphoric acid ester of the condition of explanation before meeting.
As the object lesson of condensed phosphoric acid esters, can enumerate 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 polyoxyalkylene; The non-halogen of non-aromatic is condensed phosphoric acid esters etc.Wherein, because proportion is less, (halogen etc.) danger that discharges that there is no objectionable impurities, obtain also easy etc., so optimization aromatic condensed phosphoric acid esters, more preferably 1,3-phenylene two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester).
Object lesson as non-condensed phosphoric acid esters, can enumerate triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, phosphate toluene diphenyl ester, tolyl-2, the aromatic phosphoric esters such as 6-xylyl phosphoric acid ester, 2-ethylhexyl diphenyl phosphate; The Halogen prime system phosphoric acid ester such as three (β-chloropropyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, three (tribromo neo-pentyl) phosphoric acid ester etc.Wherein, owing to can not producing objectionable impurities (halogen etc.) etc., so optimization aromatic phosphoric acid ester.
Phosphoric acid ester can be used alone a kind, also can and use two or more.
The amount of the phosphoric acid ester of using in thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) be take (methyl) acrylic acid resin composition (A) as 100 mass parts, is preferably below above 100 mass parts of 20 mass parts.By making the content of phosphoric acid ester, be in above-mentioned scope, become and be easy to improve the flame retardant resistance of thermal conductivity pressure-sensitive adhesive composite (F) or thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
Other additive > of <
In thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), except mentioned component, also can, in not hindering the scope of the above-mentioned effect being produced by interpolation mentioned component, add known various additive.As known additive, can enumerate whipping agent (containing foaming auxiliary); The flame retardant resistance heat conduction mineral compound such as the oxyhydroxide of metal, metal salt hydrates; Glass fibre; PITCH based carbon fiber or, variform thermal conductivity mineral compound big or small with above-mentioned thermal conductivity filler (B), zinc oxide (C) and expansion fossil ink powder (D); Outside linking agent; The pigment such as carbon black, titanium dioxide; Other the packing material such as clay; The nanoparticle such as soccerballene, carbon nanotube; The antioxidants such as polyphenol system, quinhydrones system, hindered amine system; The tackifier such as acrylic acid polymer particle, silica particle, magnesium oxide etc.
2. manufacture method
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) can obtain as follows: after the material of explanation is before mixed, the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes 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: make the operation of blend compositions, (methyl) acrylic acid resin composition (A) that described blend compositions contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), the zinc oxide (C) with needle-like portion, expansion fossil ink powder (D), remove and have the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) of expansion fossil ink powder (D); And the operation of the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1) in this blend compositions.Be explained, as mentioned above, description thereof is omitted here for the preferred median size that preferably contains ratio, each material of other spendable materials, each material etc.
In the manufacture method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F), preferably, when the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1), heat.This heating is such as using hot blast, electric heater, infrared rays etc.Heating temperature is now preferably the temperature that the polymerization of (methyl) acrylate monomer (α 1) and multi-functional monomer is decomposed, carried out to polymerization starter efficiency well.Temperature range is according to the kind of the polymerization starter using and difference, but be preferably 100 ℃ above 200 ℃ following, more preferably more than 130 ℃ below 180 ℃.
Thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G) can obtain as follows: the material of explanation is before mixed, after being shaped to sheet or when being shaped to sheet, the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1), thus obtain.
; the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G) comprises following operation: make the operation of blend compositions, (methyl) acrylic acid resin composition (A) that described blend compositions contains (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1), the zinc oxide (C) with needle-like portion, expansion fossil ink powder (D), remove and have the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) of expansion fossil ink powder (D); And after this blend compositions is shaped to sheet or when this blend compositions is shaped to sheet, the operation of the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1).Be explained, as mentioned above, description thereof is omitted here for the preferred median size that preferably contains ratio, each material of other spendable materials, each material etc.
In the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body of the present invention (G), preferably, when the crosslinking reaction of the polymkeric substance that carries out the polyreaction of (methyl) acrylate monomer (α 1) and (methyl) acrylic ester polymer (A1) and/or contain the structural unit that comes from (methyl) acrylate monomer (α 1), heat.This heating is such as using hot blast, electric heater, infrared rays etc.Heating temperature is now preferably the temperature that the polymerization of (methyl) acrylate monomer (α 1) and multi-functional monomer is decomposed, carried out to polymerization starter efficiency well.Temperature range is according to the kind of the polymerization starter using and difference, but be preferably 100 ℃ above 200 ℃ following, more preferably more than 130 ℃ below 180 ℃.
The method that above-mentioned blend compositions is shaped to sheet is not particularly limited.As preferred method, such as enumerating following methods: the method for above-mentioned blend compositions is coated on the engineering paper such as polyester film that carried out demoulding processing, sheet material being carried out to moulding; If be necessary, above-mentioned blend compositions is sandwiched between two engineering paper of processing through the demoulding, by pushing between roller, thus the method for sheet material being carried out to moulding; And use forcing machine that above-mentioned blend compositions is extruded, now by punch die, control thickness, thereby sheet material is carried out to the method etc. of moulding.
The thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be for below the above 5mm of 0.05mm.By making the thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), be below the above-mentioned upper limit, can reduce the thermal resistance of the thickness direction of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).By making the thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), be more than above-mentioned lower limit, when this thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is attached to heating element and radiator, be easy to prevent from being involved in air, result prevent thermal resistance increase, be easy to make to be become good by the operability of the attaching operation on convered structure.The thickness of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is preferably below the above 2mm of 0.1mm.
In addition, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is also plastic in the one or two sides of base material.The material that forms this base material is not particularly limited.As the object lesson of this base material, can use the metal of excellent thermal conductivity and the paper tinsel shape things of alloy such as aluminium, copper, stainless steel, beryllium copper; The formed flap of polymkeric substance by himself excellent thermal conductivity such as heat-conductive silicone; The thermal conductivity plastic film that contains thermal conductivity additive; Various non-woven fabrics; Glasscloth; Honeycomb structured body etc.As plastic film, can use the film of the thermally stable polymers such as polyimide, polyethylene terephthalate (PET), PEN, tetrafluoroethylene, polyetherketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfones, polyphenylene sulfide, polyamidoimide, polyester-imide, aromatic polyamine.
3. example
Thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) can be used as a part for electronic unit and use.Now, also can be molded directly within and provide as the part as electronic unit on the base material of radiator.As the object lesson of this electronic unit, can enumerate and there is field and cause machine or the parts that parts, fuel cell, solar cell, battery, mobile phone, PDA(Personal Digital Assistant), notebook computer, liquid crystal, surface conductance type electron emission display device (SED), plasma display panel (PDP) or unicircuit (IC) etc. around the power units such as parts around of heating part in the machine of generating (EL), photodiode (LED) light source, automobile have heating part.
Be explained, the using method in e-machine as thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), take situation about using in LED light source during as example, using method that can be below example.That is, be directly attached on LED light source; Be clipped between LED light source and exothermic material (scatterer, fan, Po Er paste element, heat pipe, graphite flake etc.); Be attached in the exothermic material (scatterer, fan, Po Er paste element, heat pipe, graphite flake etc.) that is connected in LED light source; Use basket as surrounding LED light source; Be attached on the basket that surrounds LED light source; Be embedded in the medium method in space of LED light source and basket.In addition, as the purposes example that possesses the LED light source of thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), can enumerate the back lighting device (TV, mobile phone, PC, notebook PC, PDA etc.) of the display unit with transmissive type liquid crystal panel; Lamps apparatus for vehicle; Industrial illumination; Illumination for business; General house illumination etc.
In addition, the example beyond LED light source as thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), can enumerate following example.That is, at 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; High briliancy light-emitting inorganic EL light source; CPU; MPU; In semiconductor element etc., also can use thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).
And then the using method of thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) is not limited to aforesaid way, the enterprising enforcement such as the basket of the device before also can being attached to beyond the device of example is used.Such as using in the device that also can possess at automobile etc.That is, can enumerate that to be attached at the basket of the device that automobile possesses inner; Be attached at the outside of the basket that automobile possesses; Connect the heating part (auto navigation/fuel cell/heat exchanger) and this basket be positioned at the basket inside that automobile possesses; Be attached to that to be connected in the heating panel of the heating part (auto navigation/fuel cell/heat exchanger) that is positioned at the basket inside that automobile possesses first-class.
Be explained, except automobile, also can utilize identical method to use thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G).As its object, for example, can enumerate PC; House; Televisor; Mobile phone; Vending Machine; Refrigerator; Solar cell; Surface-conduction-electron emission display (SED); OLED display; Inorganic EL indicating meter; Organic EL illuminating; Inorganic EL illumination; OLED display; Notebook personal computer; PDA; Fuel cell; Semiconductor device; Electric cooker; Washing machine; Drier; Combination has the optical semiconductor device of optical semiconductor and fluor; Various power units; Game machine; Electrical condenser etc.
And then thermal conductivity pressure-sensitive adhesive composite of the present invention (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) are not limited to above-mentioned using method, also can use by other method according to purposes.For example, for the homogenization of the heat such as carpet or heat pad, use; Sealing agent as LED light source/thermal source is used; Sealing agent as solar battery cell (too Yang Electricity pond セ Le) is used; Backboard as solar cell is used; Between the backboard of solar cell and top cover, use; Thermal insulation layer inner side in Vending Machine inside is used; Basket at organic EL illuminating is inner, uses together with siccative, moisture adsorbent; The heat-conducting layer of the basket inside of organic EL illuminating and on, use together with siccative, moisture adsorbent; The heat-conducting layer of the basket inside of organic EL illuminating, exothermic layer and on, use together with siccative, moisture adsorbent; At the heat-conducting layer of the basket inside of organic EL illuminating, the exothermic layer of epoxy system and on, use together with siccative, moisture adsorbent; For the cooling component of the device for human or animal is cooled off oneself, clothes, towel, sheet material etc., in the enterprising enforcement of the face contrary with health, use; In the pressing element of the anchoring device carrying in the image processing systems such as electronic photo duplicating machine, electrophotographic printer, use; Pressing element itself as the anchoring device carrying in the image processing systems such as electronic photo duplicating machine, electrophotographic printer is used; As the hot-fluid that loads the processing object of film forming apparatus, control and use with heat-conducting part; At the hot-fluid that loads the processing object of film forming apparatus, control and use with heat-conducting part; Between the skin of radioactive substance accommodating container and interior finish, use; In the box body that is provided with the solar panel that absorbs solar ray, use; Between CCFL reflective sheet backlight and aluminum chassis, use etc.
Finally, in the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) involved in the present invention, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), thermal conductivity pressure-sensitive adhesive composite (F) and the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), preferred thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
In addition, thermal conductivity pressure-sensitive adhesive composite (F) involved in the present invention, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), in the manufacture method of the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) and thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), blend compositions preferably also contains the polymerization starter below above 10 mass parts of 0.01 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except described in there is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) described expansion fossil ink powder (D).
In addition, in the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) involved in the present invention, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), thermal conductivity pressure-sensitive adhesive composite (F) and the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), described blend compositions preferably also contains the multi-functional monomer below above 15 mass parts of 0.1 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.
In addition, in the manufacture method of thermal conductivity pressure-sensitive adhesive composite (F) involved in the present invention, thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), thermal conductivity pressure-sensitive adhesive composite (F) and the manufacture method of thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), described blend compositions preferably also contains the phosphoric acid ester below above 100 mass parts of 20 mass parts with respect to (methyl) acrylic acid resin composition (A) 100 mass parts.
Embodiment
Below use embodiment that the present invention is described in more detail, but the present invention is not limited to embodiment.Be explained, " part " used herein or " % ", as long as be not particularly limited, are quality standard.
< mobility >
Mobility to the blend compositions obtaining through the 1st ~ 3rd mixed processes described later is evaluated.Specifically, make Kazakhstan bit (Hubelt) container that blend compositions is housed be inclined relative to horizontal 30 °, with the state of this blend compositions after 1 minute, evaluate.The results are shown in table 2.Situation using blend compositions along oblique flow is as " zero ", immobilising situation as " * ".Blend compositions has mobility person and is easy to this blend compositions to carry out sheet material.That is, the productivity of thermal conductivity pressure-sensitive adhesive sheet-like formed body improves.
< volume specific resistance (insulativity) >
Preparation is cut to the thermal conductivity pressure-sensitive adhesive sheet material of making by aftermentioned method the test film of 80mm * 80mm size.Installation test sheet in digital ultra-high resistance/small electric flowmeter (trade(brand)name " the エ ー デ ィ ー シ ー of 8340A ”, Co., Ltd. system), measures resistivity to two ends, the left and right inflow current of this test film.Voltage starts to be slowly reduced to the voltage that can measure, the resistivity under the voltage that mensuration can be measured from 500V.Be explained, the duration of charging is 1 minute.Carry out this mensuration 3 times, (the unit: Ω cm) of the volume specific resistance using its mean value as thermal conductivity pressure-sensitive adhesive sheet material.Show the result in table 2.If the result obtaining by this evaluation is 1.0 * 10 10more than Ω cm, can say that insulativity is excellent.
< cooling performance >
In the thermal conductivity pressure-sensitive adhesive sheet-like formed body of making by aftermentioned method, to being judged as insulativity excellence person by above-mentioned test, prepare to be cut into the big or small test film of 25mm * 25mm.Test film is attached on the aluminium sheet of 150mm * 150mm * thickness 3mm, test film be attached at aluminium sheet one side and become the face of opposition side on the fixing miniature ceramic heater (Sakaguchi Dennetsu Kabushiki Kaisha's system, trade(brand)name: MS-5,25mm * 25mm) of pincer pliers, this aluminium sheet is unsettled.Afterwards, miniature ceramic heater is connected in to slide transformer, utilizes thermometrograph to take the surface of the miniature ceramic heater in the time of 60 minutes with 60W heating.Top temperature is now shown in to table 2.This temperature is lower, represent more heats to be passed to aluminium sheet from miniature ceramic heater, so this temperature is lower, can say that the thermal resistance of thermal conductivity pressure-sensitive adhesive sheet-like formed body is lower.Be explained, this evaluation is carried out under 23 ℃ of atmosphere.
The making > of < thermal conductivity pressure-sensitive adhesive sheet-like formed body
(embodiment 1)
In reactor, put into 100 parts of the monomer mixtures that formed by 2-EHA 94% and vinylformic acid 6%, 2,700 parts of 0.03 part of 2 '-azobis isobutyronitrile and ethyl acetate are also dissolved equably, carry out after nitrogen replacement, at 80 ℃, carry out polyreaction 6 hours.Polymerisation conversion is 97%.Resulting polymers is carried out to drying under reduced pressure, make ethyl acetate evaporation, obtain (methyl) acrylic ester polymer (A1-1) of the sticking solid state of tool.The weight-average molecular weight (Mw) of (methyl) acrylic ester polymer (A1-1) is 270,000, weight-average molecular weight (Mw)/number-average molecular weight (Mn) is 3.1.Weight-average molecular weight (Mw) and number-average molecular weight (Mn) for by using tetrahydrofuran (THF) as the gel permeation chromatography of elutriant, utilize polystyrene standard to convert to try to achieve.
Then, utilize electronic balance weighing with the ratio of 60:35:5, to be mixed with 88 parts of 1.0 parts of multi-functional monomers, 2-EHAs (being slightly designated as " 2EHA " in table 2) and the organo-peroxide thermal polymerization (1 of pentaerythritol triacrylate, tetramethylol methane tetraacrylate and pentaerythritol diacrylate, two (the tert-butyl hydroperoxide ketonic oxygen base) hexanes (half life temperature was 150 ℃ in 1 minute) of 6-) 1.0 parts, they are mixed with 13 parts of above-mentioned (methyl) acrylic ester polymers (A1-1).During mixing, use thermostatic bath (Toki Sangyo Co., Ltd.'s system, trade(brand)name " PVC ス コ メ イ ト 150III ") and breathe out bit mixing machine that (the little flat making of Co., Ltd. is made, trade(brand)name " ACM-5LVT type ", capacity: 5L).The temperature of breathing out container of bits regulates and is set as 60 ℃, makes rotating speed scale is 3, stir 10 minutes.This operation is called to the 1st mixed processes.
Then, weigh 50 parts of phosphoric acid ester (aginomoto Off ァ インテク ノ Co., Ltd. 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) 500 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) 500 parts and zinc oxide (ア of Co., Ltd. system テ ッ Network system, パ Na テ ト ラ WZ-0511) are 2 parts, put in the container of bits of above-mentioned Kazakhstan, and the temperature of breathing out container of bits is regulated to be set as 60 ℃, to make rotating speed scale be 5, stirs 10 minutes.This operation is called to the 2nd mixed processes.
Then, weigh expansion fossil ink powder (itoite China ink Industrial Co., Ltd system, trade(brand)name " EC-500 ", median size: 30 μ m) 2 parts, put in the container of bits of above-mentioned Kazakhstan, make to breathe out and in container of bits, reach vacuum (0.1MPa(G)), while the temperature of breathing out container of bits is regulated, to be set as 60 ℃, rotating speed scale be 3, carry out vacuum defoamation stirs 10 minutes.This operation is called to the 3rd mixed processes.
Then, the blend compositions obtaining through the 1st ~ 3rd mixed processes is hung down on the PET film of having processed in the demoulding of thickness 75 μ m, the PET film that further other demouldings of cladding thickness 75 μ m have been processed on this blend compositions.This duplexer of the PET film clamping that blend compositions has been processed by the demoulding is divided between the roller of 0.65mm between the two by making, and makes sheet.Afterwards, this duplexer is put in baking oven, at 150 ℃, heated 15 minutes.By this heating process, make (methyl) acrylate monomer carry out polymerization and crosslinking reaction, obtain thermal conductivity pressure-sensitive adhesive sheet-like formed body (being only expressed as below " sheet material ") (G1).Being explained, when the remaining amount of monomer in sheet material (G1) is calculated the polymerisation conversion of (methyl) acrylate monomer, is 99.9%.
(embodiment 2 ~ 5 and comparative example 1 ~ 3)
Except according to changing shown in table 2 formula of each material, obtain similarly to Example 1 sheet material (G2～5, GC1～3).Evaluation result is shown in to table 2.
[table 2]
Figure 644111DEST_PATH_IMAGE002
As shown in table 2, the mobility of the blend compositions of related sheet material (the G1) ~ sheet material (G5) of embodiment before carrying out sheet material is all good, and after sheet material, the volume specific resistance of this sheet material is high, cooling performance is excellent.That is, known according to the present invention, the thermal conductivity pressure-sensitive adhesive sheet-like formed body that can provide balance to possess well insulativity and thermal conductivity.On the other hand, the above-mentioned performance inequality of related sheet material (the GC1) ~ sheet material (GC3) of comparative example.Specifically, as described below.The cooling performance of the sheet material (GC1) of the poor comparative example 1 of zinc oxide and expansion fossil China ink is poor.The volume specific resistance of the sheet material (GC3) of the comparative example 3 that the sheet material (GC2) of comparative example 2 that in addition, the content of expansion fossil China ink is many and the content of zinc oxide are many is low.Be explained, for the low comparative example 2 and comparative example 3 of volume specific resistance, due to unresolved problem of the present invention, therefore do not implement the test of cooling performance.

Claims (21)

1. thermal conductivity pressure-sensitive adhesive composite (F), it is for carrying out polyreaction and crosslinking reaction forms in blend compositions,
Described polyreaction is the polyreaction of (methyl) acrylate monomer (α 1), described crosslinking reaction comes from the crosslinking reaction of polymkeric substance of the structural unit of described (methyl) acrylate monomer (α 1) for (methyl) acrylic ester polymer (A1) and/or contain
(methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts,
The zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts,
Expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts,
Below above 1400 mass parts of 600 mass parts except described in there is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) described expansion fossil ink powder (D).
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, described blend compositions also contains the polymerization starter below above 10 mass parts of 0.01 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
4. according to the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 1 ~ 3 any one, wherein, described blend compositions also contains the multi-functional monomer below above 15 mass parts of 0.1 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
5. according to the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 1 ~ 4 any one, wherein, described blend compositions also contains the phosphoric acid ester below above 100 mass parts of 20 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
6. thermal conductivity pressure-sensitive adhesive sheet-like formed body (G), it,, for after blend compositions is shaped to sheet or when described blend compositions is shaped to sheet, carries out polyreaction and crosslinking reaction to form,
Described polyreaction is the polyreaction of (methyl) acrylate monomer (α 1), described crosslinking reaction is the crosslinking reaction of the polymkeric substance of described (methyl) acrylic ester polymer (A1) and/or the contain structural unit that comes from described (methyl) acrylate monomer (α 1)
(methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts,
The zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts,
Expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts,
Below above 1400 mass parts of 600 mass parts except described in there is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) described expansion fossil ink powder (D).
7. thermal conductivity pressure-sensitive adhesive sheet-like formed body according to claim 6 (G), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
8. according to the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 6 or 7, wherein, described blend compositions also contains the polymerization starter below above 10 mass parts of 0.01 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
9. according to the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 6 ~ 8 any one, wherein, described blend compositions also contains the multi-functional monomer below above 15 mass parts of 0.1 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
10. according to the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 6 ~ 9 any one, wherein, described blend compositions also contains the phosphoric acid ester below above 100 mass parts of 20 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
The manufacture method of 11. thermal conductivity pressure-sensitive adhesive composites (F), it comprises following operation: the operation of making blend compositions, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except described in there is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) described expansion fossil ink powder (D), and
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/or contain the structural unit that comes from described (methyl) acrylate monomer (α 1) in described blend compositions.
The manufacture method of 12. thermal conductivity pressure-sensitive adhesive composites according to claim 11 (F), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
13. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 11 or 12, wherein, described blend compositions also contains the polymerization starter below above 10 mass parts of 0.01 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
14. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 11 ~ 13 any one, wherein, described blend compositions also contains the multi-functional monomer below above 15 mass parts of 0.1 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
15. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive composite (F) described in claim 11 ~ 14 any one, wherein, described blend compositions also contains the phosphoric acid ester below above 100 mass parts of 20 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
The manufacture method of 16. thermal conductivity pressure-sensitive adhesive sheet-like formed bodies (G), it comprises following operation: the operation of making blend compositions, (methyl) acrylic acid resin composition (A) containing (methyl) acrylic ester polymer (A1) and (methyl) acrylate monomer (α 1) that described blend compositions contains 100 mass parts, the zinc oxide with needle-like portion (C) below above 40 mass parts of 0.5 mass parts, expansion fossil ink powder (D) below above 20 mass parts of 0.5 mass parts, below above 1400 mass parts of 600 mass parts except described in there is the zinc oxide (C) of needle-like portion and the insulativity thermal conductivity filler (B) described expansion fossil ink powder (D), and
After described blend compositions is shaped to sheet or when described blend compositions is shaped 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/or contain the structural unit that comes from described (methyl) acrylate monomer (α 1).
The manufacture method of 17. thermal conductivity pressure-sensitive adhesive sheet-like formed bodies according to claim 16 (G), wherein, described thermal conductivity filler (B) is aluminium hydroxide and/or aluminum oxide.
18. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 16 or 17, wherein, described blend compositions also contains the polymerization starter below above 10 mass parts of 0.01 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
19. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 16 ~ 18 any one, wherein, described blend compositions also contains the multi-functional monomer below above 15 mass parts of 0.1 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
20. according to the manufacture method of the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 16 ~ 19 any one, wherein, described blend compositions also contains the phosphoric acid ester below above 100 mass parts of 20 mass parts with respect to described (methyl) acrylic acid resin composition (A) 100 mass parts.
21. electronic units, it possesses radiator and fits in thermal conductivity pressure-sensitive adhesive composite (F) described in claim 1 ~ 5 any one of this radiator, or possesses radiator and fit in the thermal conductivity pressure-sensitive adhesive sheet-like formed body (G) described in claim 6 ~ 10 any one of this radiator.
CN201280023461.XA 2011-09-28 2012-09-06 Thermally conductive pressure-sensitive adhesive composition, thermally conductive pressure-sensitive adhesive sheet-like molded body, method for producing thermally conductive pressure-sensitive adhesive composition, method for producing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic component Pending CN103562334A (en)

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