CN101454419B - Thermally conductive pressure-sensitive adhesive composition and thermally conductive pressure-sensitive adhesive sheet-like molded body - Google Patents

Thermally conductive pressure-sensitive adhesive composition and thermally conductive pressure-sensitive adhesive sheet-like molded body Download PDF

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Publication number
CN101454419B
CN101454419B CN2007800193816A CN200780019381A CN101454419B CN 101454419 B CN101454419 B CN 101454419B CN 2007800193816 A CN2007800193816 A CN 2007800193816A CN 200780019381 A CN200780019381 A CN 200780019381A CN 101454419 B CN101454419 B CN 101454419B
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sensitive adhesive
thermally conductive
conductive pressure
acrylic
sheet
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CN101454419A (en
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酒谷光郎
熊本拓朗
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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
    • C09J121/00—Adhesives based on unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Abstract

Disclosed is a thermally conductive pressure-sensitive adhesive composition (F) obtained by adding a flame-retardant thermally conductive inorganic compound (B) and an expanded graphite powder (E) into an adhesive and/or cohesive composition (S) mainly containing at least one material selected from rubbers, elastomers and resins. Preferably, the composition (S) contains a (meth) acrylate polymer (A1) as a main component; and more preferably, it further contains a (meth) acrylate monomer (A2m). The thermally conductive pressure-sensitive adhesive composition (F) has an excellent balance among flame retardance, hardness and thermal conductivity, and is suitably used as a thermally conductive pressure-sensitive adhesive sheet-like molded body (G) by being molded into a sheet-like shape.

Description

The thermally conductive pressure-sensitive adhesive goods of thermally conductive pressure-sensitive adhesive composition and sheet-form
Technical field
The thermally conductive pressure-sensitive adhesive goods of the sheet-form that the present invention relates to a kind of thermally conductive pressure-sensitive adhesive composition and make by described contact adhesive composition.
Background technology
In recent years, follow for example raising that requires of plasma display (PDP) and unicircuit (IC) chip performance of electronic unit, the heating of these parts increases.Therefore, lasting needs are avoided because the dysfunction that temperature raises and causes.Usually adopt a kind of like this method, wherein by providing the heating part (for example electronic component) that contains heat dissipation element (for example heat sink, heat-dissipating metal sheet or radiator element) to dispel the heat.In order to realize heat transfer expeditiously, use various thermally-conductive sheet from the heating part to heat dissipation element.Usually under the situation that generate heat part and heat dissipation element are fixed together, need pressure-sensitive adhesive sheets.
The patent disclosure of Japanese unexamined (hereinafter being called " JP-A ") but H6-088061 discloses a kind of comprising by the polymkeric substance of the polar monomer preparation of acrylic or methacrylic acid alkyl ester and copolymerization and the heat-conduction electric insulation and the pressure sensitive adhesive of heat-conduction electric insulation particle (heat conductive filler).More particularly, heat-conduction electric insulation and pressure sensitive adhesive for example are prepared as follows, in the different monooctyl ester slurry of polyacrylic acid, mix in vinylformic acid, aluminum oxide and the linking agent (for example tripropylene glycol diacrylate), and with the mixture photopolymerization.
JP-A H10-324853 discloses a kind of thermally conductive pressure-sensitive adhesive, and this tackiness agent comprises the acrylic or methacrylic acid alkyl ester as main component but do not comprise the monomeric monomer mixture that contains polar group, Photoepolymerizationinitiater initiater and the photopolymerization preparation of the mixture formed as the polyfunctional acrylate or the methacrylic ester of linking agent by containing.
Above-mentioned pressure sensitive adhesive is difficult to reach balance between hardness and pressure-sensitive-adhesive.In addition, need photopolymerisation device, therefore, this pressure sensitive adhesive cost height.
JP-A 2002-322449 proposes to comprise alkyl acrylate or alkyl methacrylate and has the multipolymer of vinyl monomer of particular configuration and the thermally conductive pressure-sensitive adhesive of heat conduction particle.The vinyl monomer that uses is specific, preferably includes acrylate or the methacrylic ester or the 2-hydroxyl-3-phenoxy propyl acrylate of phosphoric acid group.But, must use a large amount of specific vinyl monomers, to obtain required pressure sensitive adhesive, therefore, the technical costs height of proposition.In addition, this tackiness agent still is difficult to reach balance between hardness and pressure-sensitive-adhesive.
In order to solve the specific acrylate following aforementioned prior art problems, the applicant in JP-A2002-285121, to propose to comprise to be dissolved in the solvent or the thermally conductive pressure-sensitive adhesive composition of methacrylate polymers.Solved the problems referred to above to a great extent, still, still continued to have the thermal conductivity that improves more, and between thermal conductivity, hardness and flame retardant resistance, have better equilibrated thermally conductive pressure-sensitive adhesive composition and thermally conductive pressure-sensitive adhesive sheet material.
Summary of the invention
Problem to be solved by this invention
Consider foregoing problems, major objective of the present invention is for providing a kind of thermally conductive pressure-sensitive adhesive composition with abundant isostatic flame retardant resistance, hardness and thermal conductivity; Thermally conductive pressure-sensitive adhesive goods with sheet-form with this useful performance.
The technical scheme that addresses this problem
The inventor provides thermally conductive pressure-sensitive adhesive composition by various researchs, and finds the thermally conductive pressure-sensitive adhesive composition by comprising flame-retarded heat-conducting mineral compound and expanded graphite powder and the thermally conductive pressure-sensitive adhesive goods of the sheet-form made by described binder composition can be realized above-mentioned target.Finished the present invention based on this discovery.
Therefore, the invention provides the thermally conductive pressure-sensitive adhesive goods (G) of thermally conductive pressure-sensitive adhesive composition of in following paragraph (1)-(12), describing (F) and the sheet-form of in following paragraph (13)-(18), describing.
(1) a kind of thermally conductive pressure-sensitive adhesive composition (F), described composition comprises and contains at least a tackiness agent and/or the Autoadhesive composition (S) that is selected from the material of rubber, elastomerics and resin as main component, and is combined with flame-retarded heat-conducting mineral compound (B) and expanded graphite powder (E) in the described composition.
(2) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (1), the average primary particle diameter of wherein said expanded graphite powder (E) is 5-500 μ m.
(3) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (1), wherein said expanded graphite powder (E) derives from the method that may further comprise the steps: will be through acid-treated graphite at 500-1, thermal treatment under 200 ℃ the temperature, thereby be expanded to specific volume is 100-300ml/g, subsequently described expanded graphite is clayed into power.
(4) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (1), wherein said flame-retarded heat-conducting mineral compound (B) is an aluminium hydroxide.
(5) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (1), wherein said tackiness agent and/or Autoadhesive composition (S) comprise acrylic or methacrylic acid ester polymer (A1) as main component.
(6) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (5), wherein said tackiness agent and/or Autoadhesive composition (S) also comprise acrylic or methacrylic acid ester monomer (A2m).
(7) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (6), wherein said tackiness agent and/or Autoadhesive composition (S) also comprise organo-peroxide thermal polymerization (C2).
(8) thermally conductive pressure-sensitive adhesive composition (F) of above (5), described composition comprises:
100 parts by weight of acrylic or methacrylate polymers (A1),
25-100 parts by weight of acrylic or methacrylate monomer (A2m),
The expanded graphite powder of 5-100 weight part (E),
The flame-retarded heat-conducting mineral compound (B) of 100-450 weight part and
0.1-10 the organo-peroxide thermal polymerization (C2) of weight part.
(9) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (8), the second-order transition temperature that can form that wherein said acrylic or methacrylic acid ester polymer (A1) comprises 80-99.9% weight is not higher than-20 ℃ the unit (a1) of acrylic or methacrylic acid ester monomer of homopolymer and the monomeric unit (a2) with organic acidic group of 20-0.1% weight.
(10) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (8), wherein to measure by gel permeation chromatography (GPC), the weight-average molecular weight (Mw) of described acrylic or methacrylic acid ester polymer (A1) is 100,000-400,000.
(11) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (8), wherein said acrylic or methacrylic acid ester monomer (A2m) can form the acrylic or methacrylic acid ester monomer mixture (A2m ') that second-order transition temperature is not higher than the monomer with organic acidic group (a6m) of-20 ℃ the acrylic or methacrylic acid ester monomer (a5m) of homopolymer and 30-0.1% weight for what comprise 70-99.9% weight.
(12) at the thermally conductive pressure-sensitive adhesive composition (F) described in above (8), described composition also comprises the heat decomposable organic blowing agent (D) of 0.01-0.8 weight part.
(13) a kind of thermally conductive pressure-sensitive adhesive goods (G) of sheet-form, described goods will be by will each described thermally conductive pressure-sensitive adhesive composition (F) machine-shaping being that sheet-form is made in above (1)-(5).
(14) at the thermally conductive pressure-sensitive adhesive goods (G) of the sheet-form described in above (13), described goods are made by the described thermally conductive pressure-sensitive adhesive composition of curtain coating (F).
(15). a kind of thermally conductive pressure-sensitive adhesive goods (G) of sheet-form, described goods are made by a kind of like this method, wherein will in above (6)-(8), be shaped to sheet material by each described thermally conductive pressure-sensitive adhesive composition (F), and heat described sheet material, thereby make acrylic or methacrylic acid ester monomer (A2m) polymerization.
(16). a kind of thermally conductive pressure-sensitive adhesive goods (G) of foam sheet form, described goods are made by a kind of like this method, and wherein the thermally conductive pressure-sensitive adhesive composition (F) with above-mentioned (12) is shaped to sheet material, and heats described sheet material.
(17) at the thermally conductive pressure-sensitive adhesive goods (G) of the sheet-form described in above (16), wherein said foam sheet has the abscess that mean diameter is 50 μ m-550 μ m.
(18) at the thermally conductive pressure-sensitive adhesive goods (G) of the sheet-form described in above (16) or (17), the rate of expansion of wherein said foam sheet when foaming is 1.01-1.5 times.
Beneficial effect
The goods of thermally conductive pressure-sensitive adhesive sheet-form of the present invention have good and abundant isostatic flame retardant resistance, hardness and thermal conductivity.
Implement best mode of the present invention
Thermally conductive pressure-sensitive adhesive composition of the present invention (F) comprises and contains at least a tackiness agent and/or the Autoadhesive composition (S) that is selected from the material of rubber, elastomerics and resin as main component, and is combined with flame-retarded heat-conducting mineral compound (B) and expanded graphite powder (E) in the described composition.Term used herein " main component " is meant that the total content of the material that is selected from rubber, elastomerics and resin is at least 50% of described composition (S) gross weight.
(I) composition (S)
The main component of forming above-mentioned composition (S) is at least a material that is selected from rubber, elastomerics and resin.Described composition (S) is necessary for tackiness agent and/or Autoadhesive, and therefore, the material that is selected from rubber, elastomerics and resin is preferably selected from those materials into tackiness agent and/or Autoadhesive.But, also can use rubber, elastomerics and the resin of non-tackiness agent and/or non-Autoadhesive, condition be with bonding-and/or autoadhesion-imparting agent be used in combination.
About the specific examples of rubber, elastomerics and resin, that can mention has natural rubber and other conjugated diolefin polymers, for example polybutadiene rubber and a polyisoprene rubber; Isoprene-isobutylene rubber; Aromatic vinyl-conjugated diene copolymer, for example styrene-butadiene copolymer, styrene-isoprene copolymer rubber, styrene butadiene-isoprene copolymer rubber, styrene-isoprene block copolymer and styrene isoprene styrene block copolymer (SIS); The hydrogenated products of aromatic vinyl-conjugated diene copolymer, for example hydrogenated products of styrene-butadiene copolymer; Vinyl cyanide-conjugated diene copolymer, for example acrylonitrile butadiene copolymer rubber and vinyl cyanide-isoprene copolymer rubber; The hydrogenated products of vinyl cyanide-conjugated diene copolymer, for example hydrogenated products of acrylonitrile butadiene copolymer; Vinyl cyanide-aromatic vinyl-conjugated diene copolymer; The hydrogenated products of vinyl cyanide-aromatic vinyl-conjugated diene copolymer; The mixture of vinyl cyanide-conjugated diene copolymer and polyvinyl halide; Acrylic polymers and methacrylic polymer, for example polyacrylic acid, polymethyl acrylic acid, polymethyl acrylate, polymethylmethacrylate, polyethyl acrylate, polyethyl methacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, polyacrylic acid 2-ethylhexyl, polymethyl acrylic acid 2-ethylhexyl, poly-(vinylformic acid-n-butyl acrylate), poly-(vinylformic acid-2-EHA), poly-(vinylformic acid-n-butyl acrylate-2-EHA), poly-(methacrylic acid-n-butyl acrylate), poly-(methacrylic acid-2-EHA), poly-(methacrylic acid-n-butyl acrylate-2-EHA), poly-(vinylformic acid-methacrylic acid-n-butyl acrylate), poly-(vinylformic acid-methacrylic acid-2-EHA), poly-(vinylformic acid-methacrylic acid-n-butyl acrylate-2-EHA), polyacrylic acid stearyl and polymethyl acrylic acid stearyl; Many halogenohydrins rubber; Polyalkylene oxide, for example polyethylene oxide and poly(propylene oxide); Ethylene-propylene-diene copolymer (EPDM); Silicon rubber; Silicone resin; Contain viton; Fluorine resin; Alpha-olefinic polymer, for example polyethylene, ethene-alpha-olefin copolymer, for example ethylene-propylene copolymer and ethylene-butene copolymer, polypropylene, poly-1-butylene and poly--1-octene; Polyvinyl halide resin, for example polyvinyl chloride (PVC) RESINS and polyvinyl bromide resin; Polyvinylene halogenide resin, for example polyvinylidene dichloride resin and poly-inclined to one side sym-dibromoethane resin; Resins, epoxy; Resol; Polyphenylene oxide resin; Polymeric amide, for example nylon-6, nylon-6,6 and nylon-6,12; Urethane; Polyester; Polyvinyl acetate; With poly-(ethylene-vinyl alcohol).
Wherein, consider good bonding and self adhesion, optimization styrene-isoprene block copolymer, styrene isoprene styrene block copolymer (SIS), polyethyl acrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, polyacrylic acid 2-ethylhexyl, polymethyl acrylic acid 2-ethylhexyl, poly-(vinylformic acid-n-butyl acrylate), poly-(vinylformic acid-2-EHA), poly-(vinylformic acid-n-butyl acrylate-2-EHA); Poly-(methacrylic acid-n-butyl acrylate); Poly-(methacrylic acid-2-EHA), poly-(methacrylic acid-n-butyl acrylate-2-EHA), poly-(vinylformic acid-methacrylic acid-n-butyl acrylate), poly-(vinylformic acid-methacrylic acid-2-EHA), poly-(vinylformic acid-methacrylic acid-n-butyl acrylate-2-EHA).
The more preferably positive butyl ester of polyacrylic acid, Vinalac 5920, polyacrylic acid 2-ethylhexyl, polymethyl acrylic acid 2-ethylhexyl, poly-(vinylformic acid-n-butyl acrylate), poly-(vinylformic acid-2-EHA), poly-(vinylformic acid-n-butyl acrylate-2-EHA), poly-(methacrylic acid-n-butyl acrylate), poly-(methacrylic acid-2-EHA), poly-(methacrylic acid-n-butyl acrylate-2-EHA), poly-(vinylformic acid-methacrylic acid-n-butyl acrylate), poly-(vinylformic acid-methacrylic acid-2-EHA), poly-(vinylformic acid-methacrylic acid-n-butyl acrylate-2-EHA).
Most preferably poly-(vinylformic acid-methacrylic acid-2-EHA).
Above-mentioned rubber, elastomerics and resin can use separately or use with the form of wherein at least two kinds combination.
Preferred described tackiness agent and/or Autoadhesive composition (S) comprise acrylic or methacrylic acid ester polymer (Al) as main component.More preferably described tackiness agent and/or Autoadhesive composition (S) comprise acrylic or methacrylic acid ester polymer (Al) as main component, and also comprise acrylic or methacrylic acid ester monomer (A2m).
Optional mix tackiness agent and/or Autoadhesive composition (S) bonding-and/or autoadhesion-imparting agent is optional from known those materials, and for example comprises petroleum resin, terpine resin, resol and Gum Rosin.Wherein, preferred petroleum resin.These are bonding-and/or autoadhesion-imparting agent can use separately or use with the form of wherein at least two kinds combination.
About the specific examples of petroleum resin, that can mention has C5 petroleum resin by amylene, pentadiene and isoprene preparation; C9 petroleum resin by indenes, methyl indenes, Vinyl toluene, vinylbenzene, alpha-methyl styrene and the preparation of Beta-methyl vinylbenzene; C5-C9 multipolymer petroleum resin by above-mentioned monomer preparation; Petroleum resin by cyclopentadiene and Dicyclopentadiene (DCPD) preparation; The hydrogenated products of these petroleum resin; For example by maleic anhydride, toxilic acid, fumaric acid, vinylformic acid, methacrylic acid or phenol modified petroleum resin with above-mentioned petroleum resin modified preparation.
About the specific examples of terpine resin, can mention α-terpine resin, β-terpine resin are arranged and by the aromatic modified terpine resin of terpenes (for example α-terpine resin or β-terpenes) with aromatic monomer (for example vinylbenzene) copolymerization.
Resol comprises those materials of the condenses of phenolic compound and formaldehyde.Described phenolic compound for example comprises phenol, meta-cresol, 3,5-xylenol, to alkylphenol and Resorcinol.About the specific examples of resol, the resole of basic catalyst by the addition reaction preparation of phenolic compound and formaldehyde used in having of can mentioning; Use the lacquer resins of an acidic catalyst by the condensation reaction preparation of phenolic compound and formaldehyde; With the addition reaction of using an acidic catalyst by rosin and phenolic compound, the rosin-phenolic resin of the preparation of thermopolymerization subsequently.
About the specific examples of Gum Rosin, that can mention has gum resin, wood rosin and a starex; By the disproportionation of above-mentioned Gum Rosin or the stable Gum Rosin and the polymeric Gum Rosin of hydrogenation preparation; For example by maleic anhydride, toxilic acid, fumaric acid, vinylformic acid, methacrylic acid or phenol modified rosin resin with above-mentioned Gum Rosin modification preparation; Esterification products with these Gum Rosins.
The alcohol that is used to prepare the esterification products of Gum Rosin preferably includes polyvalent alcohol.About the specific examples of polyvalent alcohol, that can mention has dibasic alcohol, for example ethylene glycol, glycol ether, propylene glycol and a neopentyl glycol; Trivalent alcohol, for example glycerine, trimethylolethane and TriMethylolPropane(TMP); Tetravalent alcohol, for example tetramethylolmethane and Glycerol dimer; And hexavalent alcohol, for example dipentaerythritol.These alcohol can use separately or use with the form of wherein at least two kinds combination.
Do not limit bonding-and/or the softening temperature of autoadhesion-imparting agent especially, and described reagent can select in wide region suitably, from 200 ℃ or lower high softening-point as for those materials that under the room temperature are liquid.
(I)-1 acrylic or methacrylic acid ester polymer (Al)
The main component of forming tackiness agent and/or Autoadhesive composition (S) is preferably acrylic or methacrylic acid ester polymer (Al).More preferably described tackiness agent and/or Autoadhesive composition (S) also comprise acrylic or methacrylic acid ester monomer (A2m).
Acrylic or methacrylic acid ester polymer (Al) and acrylic or methacrylic acid ester monomer (A2m) are described in detail in detail now.
Do not limit acrylic or methacrylic acid ester polymer (Al) especially, but the second-order transition temperature that can form that preferably comprises 80-99.9% weight is not higher than-20 ℃ the unit (a1) of acrylic or methacrylic acid ester monomer of homopolymer and the monomeric unit (a2) with organic acidic group of 20-0.1% weight.
The term of Shi Yonging " acrylic or methacrylic acid esters " is meant acrylate and/or methacrylic ester in this manual.
Do not limit and obtain monomeric unit (a1) and can form the acrylic or methacrylic acid ester monomer (a1m) that second-order transition temperature is not higher than-20 ℃ homopolymer.About the specific examples of acrylic or methacrylic acid ester monomer (a1m), that can mention has an ethyl propenoate (24 ℃) (annotate: the temperature in the bracket is the second-order transition temperature of its homopolymer), propyl acrylate (37 ℃), butyl acrylate (54 ℃), sec-butyl acrylate (22 ℃), vinylformic acid heptyl ester (60 ℃), Ethyl acrylate (61 ℃), Octyl acrylate (65 ℃), 2-EHA (50 ℃), vinylformic acid 2-methoxyl group ethyl ester (50 ℃), vinylformic acid 3-methoxyl group propyl ester (75 ℃), vinylformic acid 3-methoxyl group butyl ester (56 ℃), vinylformic acid 2-oxyethyl group methyl esters (50 ℃), Octyl methacrylate (25 ℃) and decyl-octyl methacrylate (49 ℃).
These acrylic or methacrylic acid ester monomers (a1m) can use separately or use with the form of wherein at least two kinds combination.
The consumption of preferred these acrylic or methacrylic acid ester monomers (a1m) makes that the content of the monomeric unit (a1) in resulting acrylic or methacrylic acid ester copolymer (Al) is 80-99.9% weight, more preferably 85-99.5% weight.When the amount of acrylic or methacrylic acid ester monomer (a1m) is in this scope, the thermally conductive pressure-sensitive adhesive of resulting sheet-form and/or Autoadhesive goods (G) room temperature or near have the binding property or the self adhesion of raising during temperature.
Do not limit to such an extent that give the monomer with organic acidic group of unit (a2) especially, and for example comprise the have organic acid group monomer of (for example carbonyl, anhydride group or sulfonic acid group).Also can use the have organic acid group monomer of (for example sulfenic acid group,-sulfinic acid group or phosphate group).
About having the monomeric specific examples of organic acidic group, that can mention has α, β-olefinic unsaturated monocarboxylic acid, for example vinylformic acid, methacrylic acid and a Ba Dousuan; α, the unsaturated polycarboxylic acid of β-olefinic, for example methylene-succinic acid, toxilic acid and fumaric acid; And α, the partial ester of the unsaturated polycarboxylic acid of β-olefinic, for example methylene-succinic acid methyl esters, toxilic acid butyl ester and fumaric acid propyl ester.Also can use and have the monomer that for example can be converted into the organic group of carboxyl by hydrolysis.This monomer for example comprises maleic anhydride and itaconic anhydride.
About having the monomeric specific examples of sulfonic acid group, that can mention has α, β-unsaturated sulfonic acid, for example allyl sulphonic acid, methallyl sulfonic acid, vinyl sulfonic acid, a styrene sulfonic acid and acrylamide-2-methyl propane sulfonic acid; With these sour salt.
In having the above-mentioned monomer of organic acidic group, preferably has the monomer of carboxyl.Preferred especially acrylic or methacrylic acid.Not expensive and easy commercially available the getting of these monomers, and have and good copolymerization of other monomers and good productivity.
Monomer (a2m) with organic acidic group can use separately or use with the form of wherein at least two kinds combination.
The amount that is used for the monomer (a2m) that polymeric has organic acidic group makes that preferably the content at the monomeric unit (a2) of resulting acrylic or methacrylic acid ester polymer (Al) is 20%-0.1% weight, more preferably 15%-0.5% weight.When the monomeric amount with organic acidic group was in this scope, the viscosity of polyblend can remain on suitable value in polymerization process.
As mentioned above, because simple and easy, preferably by having the monomeric polymerization of organic acidic group, the monomeric unit (a2) that will have organic acidic group is introduced in the acrylic or methacrylic acid ester polymer.Perhaps, after preparing polymkeric substance,, also organic acid group can be introduced in the acrylic or methacrylic acid ester polymer by known high polymers reaction.
Acrylic or methacrylic acid ester polymer (Al) can comprise the unit (a3) of the monomer derived from the functional group with non-organic acid group (a3m) that is not more than 10% weight.The functional group of non-organic acid group for example comprises hydroxyl, amino, amido, epoxy group(ing) and sulfydryl.
About having the monomeric specific examples of hydroxyl, that can mention has acrylic or methacrylic acid hydroxy alkyl ester, for example Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate and a Rocryl 410.
About having amino monomeric specific examples, that can mention has vinylformic acid N, N-dimethylamino methyl esters, methacrylic acid N, N-dimethylamino methyl esters, a vinylformic acid N, N-dimethylamino ethyl ester, methacrylic acid N, N-dimethylamino ethyl ester and amino-benzene ethene.
About having the monomeric specific examples of amido, that can mention has α, the unsaturated carboxylic acid amides monomer of β-olefinic, for example acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide and a N,N-DMAA.
About having the monomeric specific examples of epoxy group(ing), that can mention has glycidyl acrylate, glycidyl methacrylate and an allyl glycidyl ether.
Monomer (a3m) with functional group of non-organic acid group can use separately or use with the form of wherein at least two kinds combination.
The amount that is used for the monomeric unit (a3) of the acrylic or methacrylic acid ester polymer (A1) that the amount of the monomer (a3m) that polymeric has the functional group of non-organic acid group preferably obtains is not more than 10% weight.When the amount of described monomeric unit was not more than 10% weight, the viscosity of polyblend can remain on suitable value in polymerization process.
Except can form second-order transition temperature be not higher than-20 ℃ homopolymer the acrylic or methacrylic acid ester monomer unit (a1), have the monomeric unit (a2) of organic acidic group and have the monomeric unit (a3) of functional group of non-organic acid group, acrylic or methacrylic acid ester polymer (A1) also can comprise derived from can with the unit (a4) of the monomer (a4m) that is used to form unit (a1), (a2) and these monomer copolymerizations (a3).Monomer (a4m) can use separately or use with the form of wherein at least two kinds combination.
Preferably be not more than 10% weight of acrylic or methacrylic acid ester polymer (A1), more preferably no more than 5% weight derived from the amount of the unit (a4) of monomer (a4m).
Do not limit monomer (a4m) especially, and for example comprise and non-ly can form the acrylic or methacrylic acid ester monomer of acrylic or methacrylic acid ester monomer (a1m) that second-order transition temperature is not higher than-20 ℃ homopolymer; α, the full ester of the unsaturated polycarboxylic acid of β-olefinic; Alkenyl aromatic monomer; Conjugate diene monomer; Non-conjugated diene monomers; Vinyl cyanide monomers; Carboxylicesters with unsaturated alcohol; And olefinic monomer.
Can form the specific examples of acrylic or methacrylic acid ester monomer of acrylic or methacrylic acid ester monomer (a1m) that second-order transition temperature is not higher than-20 ℃ homopolymer about non-, that can mention has methyl acrylate (10 ℃), methyl methacrylate (105 ℃), Jia Jibingxisuanyizhi (63 ℃), propyl methacrylate (25 ℃) and a butyl methacrylate (20 ℃).Annotate: the temperature in the bracket is meant the second-order transition temperature of each monomeric homopolymer.
About α, the specific examples of the full ester of the unsaturated polycarboxylic acid of β-olefinic, that can mention has dimethyl fumarate, DEF, dimethyl maleate, ethyl maleate and a dimethyl itaconate.
About the specific examples of alkenyl aromatic monomer, that can mention has vinylbenzene, alpha-methyl styrene, methyl-alpha-methyl styrene, Vinyl toluene and a Vinylstyrene.
About the specific examples of conjugate diene monomer, that can mention has 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, chlorbutadiene and a cyclopentadiene.
About the specific examples of non-conjugated diene monomers, that can mention has 1,4-hexadiene, Dicyclopentadiene (DCPD) and ethylidene norbornene.
About the specific examples of vinyl cyanide monomers, that can mention has vinyl cyanide, methacrylonitrile, α-Lv Bingxijing and a α-ethyl acrylonitrile.
About with the specific examples of the carboxylicesters of unsaturated alcohol, that can mention has a vinyl-acetic ester.
About the specific examples of olefinic monomer, that can mention has ethene, propylene, butylene and an amylene.
Measure by gel permeation chromatography (GPC), the weight-average molecular weight (Mw) of preferred acrylic or methacrylic acid ester polymer (Al) is 100,000-400,000, more preferably 150,000-300,000.
Acrylic or methacrylic acid ester polymer (Al) be preferably especially by the optional monomer of the functional group that can form acrylic or methacrylic acid ester monomer (a1m), monomer (a2m) that second-order transition temperature is not higher than-20 ℃ homopolymer, have the non-organic acid group with organic acidic group and can with the multipolymer of the optional monomer preparation of these monomer copolymerizations.
Do not limit polymerization process especially, and can be in for example solution polymerization, letex polymerization, suspension polymerization and the mass polymerization any.Wherein, preferred solution polymerization.Be particularly useful as solution polymerization polymerisation medium carboxylicesters (for example ethyl acetate or ethyl lactate) or aromatic solvent (for example benzene, toluene or dimethylbenzene) arranged.
Monomer can be in batches or in the disposable adding aggregation container.The monomer of preferred disposable all amounts of adding.
Do not limit the method that polymerization causes especially, still, the preferred method of thermal polymerization of using that adopt as polymerization starter (C1).Do not limit thermal polymerization especially, and can be in superoxide and the azo-compound any.
About the specific examples of peroxidic polymerization initiators, that can mention has hydroperoxide, for example a tertbutyl peroxide; Superoxide, for example benzoyl peroxide and cyclohexanone peroxide; And persulphate, for example Potassium Persulphate, Sodium Persulfate and ammonium persulphate.These superoxide can be used as redox catalyst, that is, suitably be used in combination with reductive agent.
About the specific examples of azo-compound polymerization starter, can mention have 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 2,2 '-azo two-(2-methylbutyronitrile).
Do not limit the amount of polymerization starter (C1) especially, but calculate based on the monomer of 100 weight parts, polymerization starter (C1) is preferably the 0.01-50 weight part.
Do not limit other conditions of monomer polymerization, for example polymerization temperature, polymerization pressure and agitation condition.
After polymerization is finished, if desired, the polymkeric substance for preparing is separated from polymerisation medium.Do not limit separation method especially.For example under the situation of solution polymerization, can adopt wherein polymeric solution to be placed decompression down, remove, obtain the method for acrylic or methacrylic acid ester polymer (Al) so that polymerisation medium is steamed.
(I)-2 acrylic or methacrylic acid ester monomer (A2m)
Except acrylic or methacrylic acid ester polymer (Al) as the main component, preferred adhesive or Autoadhesive composition (S) also comprise acrylic or methacrylic acid ester monomer (A2m).When thermally conductive pressure-sensitive adhesive composition (F) machine-shaping was the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form, the acrylic or methacrylic acid ester monomer (A2m) that is included in tackiness agent or the Autoadhesive composition (S) was polymerized to the acrylic or methacrylic acid ester polymer.
Do not limit acrylic or methacrylic acid ester monomer (A2m) especially, condition is that it is the ester of acrylic or methacrylic acid.Preferred acrylic or methacrylic acid ester monomer (A2m) is for can form the acrylic or methacrylic acid ester monomer (a5m) that second-order transition temperature is not higher than-20 ℃ homopolymer.
About forming the specific examples of acrylic or methacrylic acid ester monomer (a5m) that second-order transition temperature is not higher than-20 ℃ homopolymer, those materials that above-mentioned example about the acrylic or methacrylic acid ester monomer (a1m) that is used to prepare acrylic or methacrylic acid ester polymer (Al) is arranged that can mention.Acrylic or methacrylic acid ester monomer (a5m) can use separately or use with the form of wherein at least two kinds combination.
About acrylic or methacrylic acid ester monomer (A2m), can use with can with the acrylic or methacrylic acid ester monomer (a5m) of monomeric mixture (A2m ') form of its copolymerization.
Particularly preferred monomer mixture (A2m ') comprises that the second-order transition temperature that can form of 70-99.9% weight is not higher than-20 ℃ the acrylic or methacrylic acid ester monomer (a5m) of homopolymer and the monomer with organic acidic group (a6m) of 30-0.1% weight.The amount of acrylic or methacrylic acid ester monomer (a5m) is preferably 70-99.9% weight in monomer mixture (A2m '), more preferably 75-99% weight.When the content of acrylic or methacrylic acid ester monomer (a5m) was in this scope, the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form had the pressure-sensitive-adhesive of raising and flexible.
About the specific examples of monomer (a6m) with organic acidic group, that can mention has above-mentioned those materials of quoting about the specific examples of the monomer (a2m) that is used to prepare acrylic or methacrylic acid ester polymer (Al).Monomer (a6m) with organic acidic group can use separately or use with the form of wherein at least two kinds combination.
The content that has the monomer (a6m) of organic acidic group in monomer mixture (A2m ') is preferably 30-0.1% weight, more preferably 25-1% weight.When the content of the monomer with organic acidic group (a6m) was in this scope, the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form had the enough hardness and the pressure-sensitive-adhesive of raising under high temperature (100 ℃).
Except the monomer with organic acidic group (a6m) of the acrylic or methacrylic acid ester monomer (a5m) of 70-99.9% weight and 30-0.1% weight, monomer mixture (A2m ') also can comprise its amount be at most 20% weight can with one or more monomers (a7m) of its copolymerization.
About can with can form second-order transition temperature be not higher than-20 ℃ homopolymer acrylic or methacrylic acid ester monomer (a5m) and have the specific examples of monomer (a7m) of monomer (a6m) copolymerization of organic acidic group, those materials that the specific examples relevant for above-mentioned monomer (a3) that is used to prepare acrylic or methacrylic acid ester polymer (Al) and monomer (a4) that can mention is quoted and those materials of quoting about following polyfunctional monomeric specific examples.
But the monomer (a7m) about copolymerization can use polyfunctional monomer as mentioned above, promptly has the monomer of at least two polymerisable unsaturated functional groups.By the copolymerization of polyfunctional monomer, can in multipolymer, introduce intramolecularly and/or intermolecular cross-linking, thereby can improve the interior poly-of pressure sensitive adhesive.
Specific examples about polyfunctional monomer, that can mention has polyfunctional acrylate and a methacrylic ester, for example 1,6-hexylene glycol acrylate, 1,6-hexylene glycol methacrylic ester, 1, the 2-glycol diacrylate, 1, the 2-ethylene glycol dimethacrylate, 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate, Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, two-Viscoat 295, two-trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate, dipentaerythritol acrylate and Dipentaerythritol hexamethyl acrylate; The triazine that replaces, for example 2, two (the trichloromethyl)-6-p-methoxystyrenes of 4--5-triazine; With the unsaturated aromatic ketone of olefinic, for example 4-acryloxy benzophenone.
Calculate based on 100 parts by weight of acrylic or methacrylate polymers (Al), the amount of acrylic or methacrylic acid ester monomer (A2m) is generally the 25-100 weight part, is preferably the 30-50 weight part.When the amount of acrylic or methacrylic acid ester monomer (A2m) was greater than or less than this scope, the pressure-sensitive-adhesive retentivity was poor once in a while for the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form.
(II) expanded graphite powder (E)
Do not limit the expanded graphite powder (E) of mixing thermally conductive pressure-sensitive adhesive composition of the present invention (E) especially.Preferred expanded graphite (E) derives from the method that may further comprise the steps: at 500-1, thermal treatment is 100-300ml/g through acid-treated graphite thereby be expanded to specific volume under 200 ℃ the temperature, subsequently described expanded graphite is clayed into power.More specifically, described expanded graphite (E) derives from the method that may further comprise the steps: use strong acid treatment graphite, cure through acid-treated graphite, reuse the graphite of strong acid treatment through curing, at 500-1, thermal treatment is through acid-treated graphite, to remove disacidify under 200 ℃ the temperature, and be that specific volume is 100-300ml/g with graphite expansion, subsequently described expanded graphite is clayed into power.Thermal treatment temp is 800-1 more preferably, 000 ℃.
The average primary particle diameter of preferred expanded graphite powder (E) is 5-500 μ m, and more preferably 30-300 μ m is preferably 50-200 μ m especially.When the median size of expanded graphite powder (E) during less than 5 μ m, resulting thermally conductive pressure-sensitive adhesive composition (F) easily has too high viscosity, but and the common variation of processing forming.In contrast, when the median size of expanded graphite powder (E) during greater than 500 μ m, powdered graphite easily is present in the lip-deep large-sized zone of thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form, therefore, when being used for when bonding, between adhesive article and tackiness agent, form little slit usually, and thermal conductivity and self adhesion reduction.
Calculate based on 100 parts by weight of acrylic or methacrylate polymers (Al), the consumption of expanded graphite powder (E) is preferably the 5-100 weight part, and more preferably the 10-50 weight part is preferably the 20-40 weight part especially.When the amount of expanded graphite powder (E) during less than 5 weight parts, thermally conductive pressure-sensitive adhesive sheet articles (G) the thermal conductance rate variance of resulting material form.In contrast, when the amount of expanded graphite powder (E) during greater than 100 weight parts, along with the increase of quantity of graphite, the thermal conductivity of the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form only improves lesser extent, so the cost height.
(III) flame-retarded heat-conducting mineral compound (B)
Do not limit flame-retarded heat-conducting mineral compound (B) especially, and about its specific examples, that can mention has aluminium hydroxide, magnesium hydroxide, calcium hydroxide, two hydrated gypsum, zinc borate, kaolin, calcium aluminate, lime carbonate, aluminium carbonate and a dawsonite.These flame-retarded heat-conducting mineral compound (B) can use separately or use with the form of wherein at least two kinds combination.
Do not limit the shape of flame-retarded heat-conducting mineral compound (B) especially, and can be in sphere, needle-like, fibers form, squamous, the branch form peace plate form any, or not moulding.
In flame-retarded heat-conducting mineral compound (B), preferred especially aluminium hydroxide.The thermally conductive pressure-sensitive adhesive goods (G) of thermally conductive pressure-sensitive adhesive composition that aluminium hydroxide obtains (F) and sheet-form have improved especially flame retardant resistance.
The particle diameter of aluminium hydroxide is generally 0.2-150 μ m, is preferably 0.7-100 μ m, is preferably 1-80 μ m especially.Have the be easy to get thermally conductive pressure-sensitive adhesive goods (G) of sheet-form of the high thermally conductive pressure-sensitive adhesive composition of viscosity (F) and hardness height and product having shape-following-up performance difference of the aluminium hydroxide of small particle size too.In contrast, the flexible meeting of thermally conductive pressure-sensitive adhesive goods (G) with sheet-form that the aluminium hydroxide of too big particle diameter obtains is too big, and pressure-sensitive-adhesive is desirably not high, poor adhesion and thermal distortion at high temperature at high temperature.
Calculate based on 100 parts by weight of acrylic or methacrylate polymers (Al), the amount of flame-retarded heat-conducting mineral compound (B) is preferably the 100-450 weight part, and more preferably the 150-300 weight part is preferably the 200-250 weight part especially.When the amount of compound (B) during less than 100 weight parts, the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form are at high temperature poor adhesion and thermal conductance rate variance easily.In contrast, when the amount of compound (B) during greater than 450 weight parts, the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form easily hardness height and product having shape-following-up performance are poor.
(IV) other compositions
(IV)-1 organo-peroxide thermal polymerization (C2)
In the step of thermally conductive pressure-sensitive adhesive goods (G) that with binder composition (F) machine-shaping is sheet-form, be included in acrylic or methacrylic acid ester monomer (A2m) polymerization in the composition (S) in the binder composition (F).In order to promote polymerization, except the composition (S) that comprises acrylic or methacrylic acid ester polymer (Al) and acrylic or methacrylic acid ester monomer (A2m), preferred adhesive composition (F) also comprises organo-peroxide thermal polymerization (C2).
In the presence of acrylic or methacrylic acid ester polymer (Al), expanded graphite powder (E), flame-retarded heat-conducting mineral compound (B), organo-peroxide thermal polymerization (C2) and following heat decomposable organic blowing agent (D), carry out the polymerization of acrylic or methacrylic acid ester monomer (A2m).Except the condition of initiated polymerization, do not limit the polymerizing condition of acrylic or methacrylic acid ester monomer (A2m) especially.
Organo-peroxide thermal polymerization (C2) is preferably used as polymerization starter.If use Photoepolymerizationinitiater initiater to replace organo-peroxide thermal polymerization (C2), then thermally conductive pressure-sensitive adhesive goods (G) highly adhesive of resulting sheet-form is poor.If use the azo thermal polymerization to replace organo-peroxide thermal polymerization (C2), then when decomposing, produce nitrogen usually, and the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form easily contain undesirable abscess at goods.
About the specific examples of organo-peroxide thermal polymerization (C2), that can mention has hydroperoxide, for example a tertbutyl peroxide; And superoxide, for example benzoyl peroxide, cyclohexanone peroxide, 1, two (the t-butyl peroxy ketonic oxygen base) hexanes of 6-are (under the suitable situation, hereafter is " tBCH ") and 1, two (t-butyl peroxy)-3 of 1-, 3,5-trimethylcyclohexanone (under the suitable situation, hereafter is " TMCH ").Preferred organo-peroxide thermal polymerization (C2) makes and do not produce the volatile matter that sends noxious odor when thermolysis.In addition, 1 minute half life temperature of preferred organo-peroxide thermal polymerization (C2) is 120 ℃-170 ℃.
Calculate based on 100 parts by weight of acrylic or methacrylate polymers (Al), the amount of organo-peroxide thermal polymerization (C2) is preferably the 0.1-10 weight part, and more preferably the 0.2-5 weight part is preferably the 0.5-2 weight part especially.
The transformation efficiency of preferred acrylic or methacrylic acid ester monomer (A2m) is at least 95% weight.Under the situation of low-conversion too, because unreacted monomer, the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form easily produce undesirable smell.
The thermally conductive pressure-sensitive adhesive composition (F) that comprises organo-peroxide thermal polymerization (C2) preferably comprises:
100 parts by weight of acrylic or methacrylate polymers (Al),
25-100 parts by weight of acrylic or methacrylate monomer (A2m),
The expanded graphite powder of 5-100 weight part (E),
The flame-retarded heat-conducting mineral compound (B) of 100-450 weight part and
0.1-10 the organo-peroxide thermal polymerization (C2) of weight part.
The thermally conductive pressure-sensitive adhesive composition (F) that comprises organo-peroxide thermal polymerization (C2) more preferably comprises:
100 parts by weight of acrylic or methacrylate polymers (Al),
20-200 parts by weight of acrylic or methacrylate monomer (A2m),
The expanded graphite powder of 5-100 weight part (E),
The flame-retarded heat-conducting mineral compound (B) of 100-450 weight part,
0.1-10 the organo-peroxide thermal polymerization (C2) of weight part and
0.01-0.8 the heat decomposable organic blowing agent (D) of weight part.
(IV)-2 heat decomposable organic blowing agent (D)
Decomposition-the kick off temperature of preferred heat decomposable organic blowing agent (D) is 80 ℃-200 ℃.Heat decomposable organic blowing agent (D) for example comprises 4, two (benzenesulfonyl hydrazides) (under the suitable situation, hereafter is " OBSH ") of 4-oxo.Also can use decomposition-kick off temperature to be higher than 200 ℃ heat decomposable organic blowing agent (for example Cellmic C 121) as heat decomposable organic blowing agent (D), condition is to mix with a certain amount of frothing aid, makes that the decomposition-kick off temperature of resulting mixture is 100 ℃-200 ℃.
Specific examples about frothing aid, mixture, sodium stearate, sodium laurate, Sodium pentadecanecarboxylate, potassium stearate, potassium laurate and the potassium palmitate of mixture, zinc palmitate, palmitinic acid and the zinc oxide of mixture, zinc laurate, lauric acid and the zinc oxide that Zinic stearas, stearic acid and zinc oxide (that is zinc oxide) are arranged that can mention.
Calculate based on 100 parts by weight of acrylic or methacrylate polymers (Al), the amount of heat decomposable organic blowing agent (D) is preferably the 0.01-0.8 weight part, more preferably the 0.05-0.6 weight part is preferably the 0.1-0.4 weight part especially, most preferably is the 0.1-0.3 weight part.When the amount of organic whipping agent (D) is in this scope, the mean diameter of the abscess of the thermally conductive pressure-sensitive adhesive goods (G) of resulting sheet-form can be controlled in required numerical value, therefore, the adhesive article of sheet-form (G) has product having shape-following-up performance and pressure sensitive adhesion retentivity good and abundant isostatic hardness and pressure-sensitive-adhesive and excellence.
(IV)-3 outside linking agent
Outside linking agent can be mixed in the thermally conductive pressure-sensitive adhesive composition of the present invention (F), with the force of cohesion that improves pressure sensitive adhesive and improve thermotolerance.By mixing outside linking agent, can in the polymer composition of the composition that gets self-contained acrylic or methacrylic acid ester polymer (Al) and acrylic or methacrylic acid ester monomer (A2m), form crosslinking structure.
About the specific examples of outside linking agent, that can mention has polyfunctional isocyanate crosslinking, for example tolylene diisocyanate, TriMethylolPropane(TMP) vulcabond and a ditan triisocyanate; Epoxy crosslinking agent, for example diglycidyl ether, polyoxyethylene glycol diglycidyl ether and trimethylolpropane tris glycidyl ether; The melamine resin linking agent; Amino resin crosslinking agent; The metal-salt linking agent; The metal-chelating crosslinker agent; And peroxide cross-linking agent.
By in the polymer composition of the composition that gets self-contained acrylic or methacrylic acid ester polymer (Al) and acrylic or methacrylic acid ester monomer (A2m), mixing outside linking agent, with postheat treatment or use radiotreatment, in resulting multipolymer, form intramolecularly and/or intermolecular cross-linking.
Thermally conductive pressure-sensitive adhesive composition of the present invention (F) comprises acrylic or methacrylic acid ester polymer (Al), acrylic or methacrylic acid ester monomer (A2m), expanded graphite powder (E), flame-retarded heat-conducting mineral compound (B), organo-peroxide thermal polymerization (C2) and the heat decomposable organic blowing agent (D) of aforementioned proportion, and if desired, also comprise known additives, for example pigment, other fillers, fire retardant, antioxidant and thickening material, condition is to realize the present invention.
Pigment comprises organic and mineral dye widely, the carbon black and the titanium dioxide of for example unexpansive powdered graphite (E).Other fillers comprise various mineral compound, for example clay.Also can use for example carbon nanotube of soccerballene (Fullerene) and nano particle.
Fire retardant for example comprises that phosphoric acid gathers ammonium, zinc borate, tin compound, organo phosphorous compounds, red phosphorus compound and organic silicon fibre retardant.
Because many antioxidants influence radical polymerization, therefore do not use antioxidant usually, still, if desired, can use various antioxidants, for example polyphenol antioxidation agent, quinhydrones antioxidant and hindered amine antioxidant.
Thickening material for example comprises acrylic polymers particle, finely divided inorganic compound particle, and for example finely divided silica dioxide granule and reactive inorganic compound be magnesium oxide for example.
(V) the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form
The thermally conductive pressure-sensitive adhesive goods (G) of sheet-form of the present invention are by being that sheet-form prepares with thermally conductive pressure-sensitive adhesive composition (F) machine-shaping.
When the content of the acrylic or methacrylic acid ester monomer (A2m) in thermally conductive pressure-sensitive adhesive composition (F) was not more than 5% weight, owing to there is not the polymerization of monomer (A2m), described binder composition (F) fully machine-shaping was a sheet-form.
The thermally conductive pressure-sensitive adhesive goods (G) of sheet-form can be the single sheet material that is only formed by thermally conductive pressure-sensitive adhesive composition (F), or for comprise ground and by binder composition (F) form on the side of ground the layer or by the both sides of binder composition (F) at ground on form the layer composite sheet.
Do not limit the thickness of the layer of thermally conductive pressure-sensitive adhesive sheet material or thermally conductive pressure-sensitive adhesive composition (F) especially, but be generally 50 μ m-3mm.If thickness is less than 50 μ m, then when the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form and heating part and heat radiation part are bonding, between the goods (G) of sheet-form and heating part or heat radiation part, easily produce bubble, the result reduces thermal conductivity.In contrast, if thickness greater than 3mm, then the thermotolerance of the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form is easily too big, and does not easily desirably reduce thermal diffusivity.
Be not defined for the ground of the composite sheet of the binder layer for preparing one or more layers binder composition (F) that comprises ground and on the one or both sides of ground, form.
About the specific examples of ground, that can mention has a paper tinsel of being made by the metal or alloy with good thermal conductivity (for example aluminium, copper, stainless steel or beryllium-copper); Has the sheet material that the polymkeric substance (for example heat conduction organosilicon) of good thermal conductivity is made; Wherein mix the heat-conducting plastic film of heat conductive filler; Supatex fabric; Woven fiber glass; And honeycomb structure.About the specific examples of plastics film, that can mention has a film of being made by thermally stable polymer (for example polyimide, polyethylene terephthalate, Polyethylene Naphthalate, tetrafluoroethylene, polyetherketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfones, polyphenylene sulfide, polyamidoimide, polyester-imide and aromatic poly).
Not limiting thermally conductive pressure-sensitive adhesive composition (F) machine-shaping especially is the method for sheet-form.The preferred examples of processing molding method is included in for example casting method of curtain coating binder composition (F) on the separated polyester film of separate-type paper of working sheet; With the calendering process of thermally conductive pressure-sensitive adhesive composition (F) by pressure roller, if desired, after binder composition (F) being clipped between two separated working sheets of separate-type paper; With the extrusion method that thermally conductive pressure-sensitive adhesive composition (F) is extruded by the forcing machine with controlled fissured punch die.
Preferably when thermally conductive pressure-sensitive adhesive composition (F) machine-shaping is sheet material, suppress, have the sheet material of uniform thickness with preparation.Applied pressure is not more than 10MPa usually, preferably is not more than 1MPa.If apply the pressure above 10MPa, then abscess easily subsides.According to the kind and the amount of press time and polymerization starter, can suitably select the press time, but consider productive rate, the preferred press time is in 1 hour.
The thermally conductive pressure-sensitive adhesive goods (G) of required sheet-form can followingly make: when binder composition forms sheet material or afterwards, and heating thermally conductive pressure-sensitive adhesive composition (F).For example by using warm air or using electric heater or Infrared heaters to heat.The selection of preferred Heating temperature makes organo-peroxide thermal polymerization (C2) and heat decomposable organic blowing agent (D) decomposition efficiency good, and the thermolysis of the polymerization of acrylic or methacrylic acid ester monomer (A2m) and heat decomposable organic blowing agent (D) is carried out simultaneously.According to concrete organo-peroxide thermal polymerization (C2) and heat decomposable organic blowing agent (D), change suitable temperature, but be preferably 100 ℃-200 ℃.
Preferably when the binder composition that will mix whipping agent (D) (F) machine-shaping is sheet-form or afterwards, under 100 ℃-200 ℃ temperature, by heating the thermally conductive pressure-sensitive adhesive foam article (G) that the thermally conductive pressure-sensitive adhesive composition (F) that has mixed heat decomposable organic blowing agent (D) prepares sheet-form, thereby form the sheet material of thermally conductive pressure-sensitive adhesive composition (F), realize the polymerization of acrylic or methacrylic acid ester monomer (A2m) and the thermolysis of heat decomposable organic blowing agent (D).
The thermally conductive pressure-sensitive adhesive goods (G) of sheet-form are preferably foam article.The mean diameter of preferred abscess is 50 μ m-550 μ m, and more preferably 100 μ m-500 μ m are preferably 150 μ m-450 μ m especially.When the mean diameter of abscess is in this scope, improved the pressure sensitive adhesion retentivity more.
Frothing percentage (that is, the rate of expansion when foaming) is preferably 1.01-1.5, and more preferably 1.05-1.4 is preferably 1.1-1.3 especially.When frothing percentage is in this scope, improved the pressure sensitive adhesion retentivity more.
Can directly go up the thermally conductive pressure-sensitive adhesive goods (G) that form sheet-form at ground (for example heat dissipation element), described ground can be the part of electronic installation or parts.
Embodiment
By following examples the present invention is described in more detail.Unless otherwise indicated, part and per-cent otherwise in each embodiment are weight part and weight percent.
Estimate the performance of the thermally conductive pressure-sensitive adhesive goods (G) of acrylic or methacrylic acid ester copolymer, thermally conductive pressure-sensitive adhesive composition (F) and sheet-form by the following method.
(1) weight-average molecular weight (Mw) of acrylic or methacrylic acid ester polymer (Al) and number-average molecular weight (Mn)
By gel permeation chromatography, use tetrahydrofuran (THF) as the expansion solvent, and measure these molecular weight according to the standard substance polystyrene.
(2) mean diameter of the abscess of the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form
The surface of the thermally conductive pressure-sensitive adhesive foam article (G) by laser capture microdissection sem observation sheet-form.100 abscesses are measured, and calculating mean value.
Rate of expansion when (3) the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form foam
The volume of the thermally conductive pressure-sensitive adhesive foam article (G) of the sheet-form of analytical unit weight.The volume of the non-foam goods of thermally conductive pressure-sensitive adhesive (G) of the sheet-form with same composition of analytical unit weight.By with the volume of the foam article of unit weight volume, the rate of expansion when obtaining foaming divided by the non-foam goods of unit weight.
(4) hardness of the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form
According to Standard of Rubber Industry Society, Japan (SRIS), Asker method, the hardness of the adhesive article (G) of mensuration sheet-form.The hardness test machine that uses is ASKER CL-150LJ, derives from Kobunshi Keiki Co., Ltd..
6 samples of thermally conductive pressure-sensitive adhesive goods (G) of sheet-form that are of a size of wide 30mm, long 60mm and thick 1mm separately are superimposed, with the preparation test sample that sample is aging, that is, sample placed 23 ℃ thermostatic chamber at least 48 hours.Sample with return after wet machine (サ Application プ Le) contact 20 seconds mensuration hardness.Replication 5 times calculates average hardness value.
(5) thermal conductivity of the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form
The adhesive article (G) of sheet-form is cut into 300mm * 160mm * 1mm size, with the preparation test sample.Sample is aging, that is, place 23 ℃ thermostatic chamber at least 48 hours.
By unstable state hot line relative method, use Rapid Thermal conductance test machine (" QTM-500 " derives from IPROS Corporation) to measure thermal conductivity.The reference plate that is used for comparison has known thermal conductivity, uses organosilicon sponge (0.1W/mK), silicon rubber (0.2W/mK), quartzy (1.4W/mK) and zirconium white (3.4W/mK).
(6) the pressure sensitive adhesion retentivity of the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form
With size is that the sample of 25mm * 25mm * 1mm is superimposed on aluminium sheet, and uses the pressure roller of 2kg compressed together.Make sheet glass bonding by the opposite side that is compressed on aluminium sheet.The sample of preparation was like this left standstill 1 hour.Sample is fixed on the wall of vertical laying state.Allow sheet glass hang the weight of 500g.The sample that bears a heavy burden is placed in the thermostatic chamber of 100 ℃ of atmosphere.Measure the hold-time of bearing a heavy burden, the timed interval of this time for dropping to weight from sheet glass from the placement sample.The heavy burden hold-time is long more, and the pressure sensitive adhesion retentivity of the adhesive article of sheet-form (G) is good more.
(7) flame retardant resistance
Measure the flame retardant resistance of the thermally conductive pressure-sensitive adhesive goods (G) of sheet-form by UL standard " UL94:The Standard for Flammability of PlasticMaterials for Parts in Devices and Appliances (flame-retardancy standards of device or the used plastic material of equipment unit) ".The sheet material sample is placed in the cylinder, and applied flame 10 seconds.After flaming combustion, apply flame 10 seconds immediately once more.According to the level evaluation flame retardant resistance of in following table 1, quoting.For each adhesive article (G) of sheet-form, 5 samples are carried out the flame retardant resistance test, according to the adhesive article (G) of sheet-form being classified in the standard shown in the following table 1.
The flame retardant resistance classification UL94?V-0 UL94?V-1 VL94?V-2
The longest flaming combustion time * 1 ≤ 10 seconds ≤ 30 seconds ≤ 30 seconds
Flaming combustion time and the summation * 2 of flaming combustion time for the first time for the second time ≤ 50 seconds ≤ 250 seconds ≤ 250 seconds
The longest flaming combustion time adds the maximum value * 3 of the summation of time of persistence after lighting for the second time ≤ 30 seconds ≤ 60 seconds ≤ 60 seconds
Have or not molten drop and the molten drop cotton of whether igniting Deny * 4 Deny * 4 Be
Flaming combustion and flameless combustion are until retaining clip Deny * 4 Deny * 4 Deny * 4
Annotate:
*1 goods for each adhesive sheet form, the maximum value of the flaming combustion time that 5 samples are recorded.
*The summation of the 2 flaming combustion times first time that after for the first time applying flame, record and the flaming combustion time second time of after applying flame for the second time, recording.This summation is the goods for each adhesive sheet form, to the summation of 5 sample testing values.
*The 3 flaming combustion times second time that record after applying flame for the second time added the maximum value of the summation of time of persistence.This summation is the adhesive article for each sheet-form, to the summation of 5 sample values.
*4 adhesive articles for each sheet-form are not observed this phenomenon to 5 all samples.
Embodiment 1
In reaction vessel, pack into the acrylic acid monomer mixture that comprises 94% 2-EHA and 6%, 0.03 part 2 of 100 weight parts, 2-Diisopropyl azodicarboxylate and 700 weight part ethyl acetate.With the content uniform dissolution.With the atmosphere in the nitrogen alternate container, subsequently in 80 ℃ of following polymerizations 6 hours.Polymerisation conversion is 97%.With resulting polymer product drying under reduced pressure,, obtain heavy-gravity solid propenoic acid or methacrylate polymers (Al) (1) with the evaporation of acetic acid ethyl ester.The Mw of acrylic or methacrylic acid ester polymer (Al) (1) is 270,000, and the Mw/Mn ratio is 3.1.
At the mortar of the shredder following composition of packing into immediately.
100 parts by weight of acrylic or methacrylate polymers (Al) (1),
(repeating oxygen ethylene chain number is 23, " NK Ester for the 2-EHA that comprises 91.3% weight of 32 weight parts, the methacrylic acid of 6.1% weight and 2.6% weight polyethylene glycol dimethacrylate TM23G ", derive from Shin-Nakamura Chemical Co., acrylic or methacrylic acid ester monomer mixture (A2m ') Ltd.),
1.0 1 of weight part, two (t-butyl peroxy ketonic oxygen base)-hexane (hereafter is " tBCH ") (the organo-peroxide thermal polymerizations (C2) of 6-; 1 minute half life temperature: 150 ℃),
0.2 part 4,4 '-two (benzenesulfonyl hydrazides) (hereafter is " OBSH ") (the heat decomposable organic blowing agents (D) of oxo; " Neocel lborn TM1000S ", derive from Eiwa ChemicalInd.Co., Ltd.),
The expanded graphite powder of 30 weight parts (E) " EC-100 " derives from ITO Kokuen Co., Ltd. and
The aluminium hydroxide of 220 weight parts (flame-retarded heat-conducting mineral compound (B); " BF TM-083 ", derives from Nippon Light Metal Co., Ltd.; Median size: 8 μ m).
Under room temperature, the various composition thorough mixing that will pack into by shredder together.With the mixture degassing, decompression is simultaneously stirred, and obtains heavy-gravity liquid thermal conductivity contact adhesive composition (F) (1) subsequently.
The polyester film that will contain parting agent is placed on the bottom of the mould of long 400mm, wide 400mm and dark 2mm.Fill mould with above-mentioned thermally conductive pressure-sensitive adhesive composition (F) (1).The surface of the exposure of the binder composition (F) (1) of filling covers with the polyester film that contains parting agent.The binder composition (F) (1) that is clipped between the polyester film that contains parting agent is taken out from mould, and in remaining on 155 ℃ air oven, handled 30 minutes, to realize polymerization and foaming.Therefore, obtain being clipped in the thermally conductive pressure-sensitive adhesive foam article (G) (1) of the sheet-form between the polyester film that contains parting agent.
Measure to such an extent that the polymerisation conversion of acrylic or methacrylic acid ester monomer mixture (A2m ') is 99.9% by unreacted monomeric in the adhesive article (G) (1) of foam sheet form.Estimate the performance of the binder foam goods (G) (1) of sheet-form.The results are shown in table 2.
For relatively, repeat above-mentioned steps, wherein do not mix OBSH (heat decomposable organic blowing agent (D)), and other all conditions keep identical.Therefore, obtain being clipped in the non-foam goods of thermally conductive pressure-sensitive adhesive (G) (1 ') of the sheet-form between the polyester film that contains parting agent.
Estimate the performance of the binder foam goods (G) (1) of sheet-form.The results are shown in table 2.
Comparing embodiment 1
Repeat the step described in the embodiment 1, wherein do not mix expanded graphite powder (E), and other all conditions keep identical.Therefore, obtain being clipped in the thermally conductive pressure-sensitive adhesive foam article (G) (2) of the sheet-form between the polyester film that contains parting agent and be clipped in the non-foam goods of thermally conductive pressure-sensitive adhesive foam (G) (2 ') of the sheet-form between the polyester film that contains parting agent.
The performance of the binder foam goods (G) (2) of evaluation sheet-form and the non-foam goods of tackiness agent (G) (2 ') of sheet-form.The results are shown in table 2.
Comparing embodiment 2
Repeat the step described in the embodiment 1, (SYZR-501 derives from SANYO Trading Co., Ltd.) replace the EC-100 (expanded graphite powder (E)) of 30 weight parts, and other all conditions keeps identical wherein to use the expansible black lead of 30 weight parts.This expansible black lead is not an expanded graphite, and by with the preparation of acid treatment graphite, still, will not heat-treat through acid-treated graphite.Therefore, obtain being clipped in the thermally conductive pressure-sensitive adhesive foam article (G) (3) of the sheet-form between the polyester film that contains parting agent and the non-foam goods of thermally conductive pressure-sensitive adhesive foam (G) (3 ') of sheet-form.
The performance of the binder foam goods (G) (3) of evaluation sheet-form and the non-foam goods of tackiness agent (G) (3 ') of sheet-form.The results are shown in table 2.
Comparing embodiment 3
Repetition is wherein used the graphite (" SPR of 30 weight parts in the step described in the embodiment 1 TM-9811 ", derive from ITO Kokuen Co., Ltd. is not an expanded graphite powder) replace the EC-100 (expanded graphite powder (E)) of 30 weight parts, and other all conditions keep identical.Therefore, obtain being clipped in of sheet-form and contain the thermally conductive pressure-sensitive adhesive foam article (G) (4) between the polyester film of parting agent and the non-foam goods of thermally conductive pressure-sensitive adhesive (G) (4 ') of sheet-form.
The performance of the binder foam goods (G) (4) of evaluation sheet-form and the goods (G) (4 ') of the non-foam sheet-form of tackiness agent.The results are shown in table 2.
Table 2
Figure DEST_PATH_GSB00000515159300021
The footnote of table 2
* 1A: the weight part that calculates based on 100 parts by weight of acrylic or methacrylate polymers (A1) (1)
B: the weight part that calculates based on the composition (S) of 100 weight parts
* 2 polyethylene glycol dimethacrylates
* 31, two (the t-butyl peroxy ketonic oxygen base) hexanes of 6-
*4 p, p '-oxygen base two (benzenesulfonyl hydrazides)
The result who is shown in table 2 is summarized as follows.
In embodiment 1, will comprise the thermally conductive pressure-sensitive adhesive composition (F) of following material:
100 parts by weight of acrylic or methacrylate polymers (Al) (1),
32 parts by weight of acrylic or mixed with methacrylate monomers thing (A2m '),
The expanded graphite powder of 30 weight parts (E),
The flame-retarded heat-conducting mineral compound (B) of 220 weight parts,
1.0 the organo-peroxide thermal polymerization (C2) of weight part and
0.2 the heat decomposable organic blowing agent (D) of part,
Machine-shaping is sheet material, and heating, thereby make acrylic or methacrylic acid ester monomer mixture (A2m ') polymerization, heat decomposable organic blowing agent (D) thermolysis obtains having mean diameter and is the thermally conductive pressure-sensitive adhesive foam article (G) (1) of sheet-form of the abscess of 200 μ m.The binder foam goods (G) (1) of sheet-form have enough hardness, and have good pressure sensitive adhesion retentivity and thermal conductivity.According to the UL-94 flame-retardancy standards, its flame retardant resistance is categorized as V-2.
For relatively, prepare the non-foam goods of thermally conductive pressure-sensitive adhesive (G) (1 ') of sheet-form.By the non-foam goods of tackiness agent (G) (1 ') of the binder foam goods (G) (1) of sheet-form and sheet-form as seen, thermal conductivity is roughly the same.That is to say that the difference between the thermal conductivity of the binder foam goods (G) (1) of sheet-form and the non-foam goods of tackiness agent (G) (1 ') of sheet-form is little, condition is that expanded graphite powder is mixed in two kinds of sheet materials.
In contrast, under the situation of not mixing expanded graphite powder (E), the binder foam of resulting sheet-form and non-foam goods have excellent flame-retardant performance, but thermal conductance rate variance (comparing embodiment 1).The non-constant of thermal conductivity of the binder foam goods of sheet-form particularly.
Using expanded graphite to replace under the situation of expanded graphite powder (E), the binder foam of resulting sheet-form and non-foam goods have excellent flame-retardant performance, but thermal conductance rate variance (comparing embodiment 2).Using graphite to replace under the situation of expanded graphite powder (E), the binder foam of resulting sheet-form and non-foam goods have excellent flame-retardant performance, but thermal conductance rate variance (comparing embodiment 3).The non-constant of thermal conductivity of the binder foam goods of sheet-form particularly.
Industrial usability
The thermally conductive pressure-sensitive adhesive goods (G) of sheet-form of the present invention have flame retardant resistance, hardness and thermal conductivity good and that be in admirable proportion.
Consider these useful performances, the thermally conductive pressure-sensitive adhesive goods of sheet-form are as having the thermally-conductive sheet of thermal conductive resin from heating part to thermal component, and this sheet material is applicable to electronic unit, for example plasma display (PDP).

Claims (17)

1. a thermally conductive pressure-sensitive adhesive composition (F), described composition comprises and contains at least a binder composition (S) that is selected from the material of rubber, elastomerics and resin as main component, and be combined with flame-retarded heat-conducting mineral compound (B) and expanded graphite powder (E) in the described composition
Described expanded graphite powder (E) derives from the method that may further comprise the steps: will be through acid-treated graphite at 500-1, and thermal treatment under 200 ℃ the temperature is 100-300ml/g thereby be expanded to specific volume, subsequently described expanded graphite is clayed into power.
2. the thermally conductive pressure-sensitive adhesive composition of claim 1 (F), the average primary particle diameter of wherein said expanded graphite powder (E) is 5-500 μ m.
3. the thermally conductive pressure-sensitive adhesive composition of claim 1 (F), wherein said flame-retarded heat-conducting mineral compound (B) is an aluminium hydroxide.
4. the thermally conductive pressure-sensitive adhesive composition of claim 1 (F), wherein said binder composition (S) comprises acrylic or methacrylic acid ester polymer (A1) as main component.
5. the thermally conductive pressure-sensitive adhesive composition of claim 4 (F), wherein said binder composition (S) also comprises acrylic or methacrylic acid ester monomer (A2m).
6. the thermally conductive pressure-sensitive adhesive composition of claim 5 (F), wherein said binder composition (S) also comprises organo-peroxide thermal polymerization (C2).
7. the thermally conductive pressure-sensitive adhesive composition of claim 4 (F), described composition comprises:
100 parts by weight of acrylic or methacrylate polymers (A1),
25-100 parts by weight of acrylic or methacrylate monomer (A2m),
The expanded graphite powder of 5-100 weight part (E),
The flame-retarded heat-conducting mineral compound (B) of 100-450 weight part and
0.1-10 the organo-peroxide thermal polymerization (C2) of weight part.
8. the second-order transition temperature that can form that the thermally conductive pressure-sensitive adhesive composition of claim 7 (F), wherein said acrylic or methacrylic acid ester polymer (A1) comprise 80-99.9% weight is not higher than-20 ℃ the unit (a1) of acrylic or methacrylic acid ester monomer of homopolymer and the monomeric unit (a2) with organic acidic group of 20-0.1% weight.
9. the thermally conductive pressure-sensitive adhesive composition of claim 7 (F) is wherein measured by gel permeation chromatography (GPC), and the weight-average molecular weight (Mw) of described acrylic or methacrylic acid ester polymer (A1) is 100,000-400,000.
10. the thermally conductive pressure-sensitive adhesive composition of claim 7 (F), wherein said acrylic or methacrylic acid ester monomer (A2m) can form the acrylic or methacrylic acid ester monomer mixture (A2m ') that second-order transition temperature is not higher than the monomer with organic acidic group (a6m) of-20 ℃ the acrylic or methacrylic acid ester monomer (a5m) of homopolymer and 30-0.1% weight for what comprise 70-99.9% weight.
11. the thermally conductive pressure-sensitive adhesive composition of claim 7 (F), described composition also comprise the heat decomposable organic blowing agent (D) of 0.01-0.8 weight part.
12. the thermally conductive pressure-sensitive adhesive goods (G) of a sheet-form, described goods are by being that sheet-form is made with each thermally conductive pressure-sensitive adhesive composition (F) machine-shaping among the claim 1-4.
13. the thermally conductive pressure-sensitive adhesive goods (G) of the sheet-form of claim 12, described goods are made by the described thermally conductive pressure-sensitive adhesive composition of curtain coating (F).
14. the thermally conductive pressure-sensitive adhesive goods (G) of a sheet-form, described goods are made by a kind of like this method, wherein each thermally conductive pressure-sensitive adhesive composition (F) among the claim 5-7 is shaped to sheet material, and heat described sheet material, thereby make acrylic or methacrylic acid ester monomer (A2m) polymerization.
15. the thermally conductive pressure-sensitive adhesive goods (G) of a foam sheet form, described goods are made by a kind of like this method, and wherein the thermally conductive pressure-sensitive adhesive composition (F) with claim 11 is shaped to sheet material, and heats described sheet material.
16. the thermally conductive pressure-sensitive adhesive goods (G) of the sheet-form of claim 15, wherein said foam sheet have the abscess that mean diameter is 50 μ m-550 μ m.
17. the thermally conductive pressure-sensitive adhesive goods (G) of the sheet-form of claim 15 or 16, the rate of expansion of wherein said foam sheet when foaming is 1.01-1.5 times.
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