CN104395424A - Thermally conductive adhesive composition - Google Patents

Thermally conductive adhesive composition Download PDF

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Publication number
CN104395424A
CN104395424A CN201380032607.1A CN201380032607A CN104395424A CN 104395424 A CN104395424 A CN 104395424A CN 201380032607 A CN201380032607 A CN 201380032607A CN 104395424 A CN104395424 A CN 104395424A
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China
Prior art keywords
thermal conductivity
methyl
adhesive sheet
monomer
binding compositions
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CN201380032607.1A
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Chinese (zh)
Inventor
古田宪司
寺田好夫
井口伸儿
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN104395424A publication Critical patent/CN104395424A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • H01L23/3735—Laminates or multilayers, e.g. direct bond copper ceramic substrates
    • 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
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (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

A thermally conductive adhesive composition comprising: an adhesive component containing high polymers and low polymers; and thermally conductive particles. The gel fraction measured in the adhesive component is 28%-59% by mass and the thermal conductivity thereof is at least 0.3 W/m*K.

Description

Thermal conductivity binding compositions
Technical field
The present invention relates to thermal conductivity binding compositions, specifically relate to the thermal conductivity binding compositions used in the industrial field of both requirement thermal conductivity and binding property.
Background technology
In the past, known in thermal conductivity binding compositions, by making the filler containing thermal conductivity in acrylic adhesive, thus make thermal conductivity improve compared with base binder.
Such as, thermal conductivity flame retardant resistance pressure-sensitive adhesive containing acrylic acid polymer and conducting filler (such as aluminum oxide) is proposed (for example, referring to following patent documentation 1.)。
The thermal conductivity flame retardant resistance pressure-sensitive adhesive recorded in following patent documentation 1 has sufficient thermal conductivity while maintenance high adhesion.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-294192 publication
Summary of the invention
Invent problem to be solved
But, for the thermal conductivity adhesive sheet obtained by thermal conductivity binding compositions is configured as sheet, require that the skew in its direction, face (shearing skew) obtains excellent thermal conductivity while reducing.
But there are the following problems for the thermal conductivity flame retardant resistance pressure-sensitive adhesive recorded in above-mentioned patent documentation 1: if reduce shear skew and reduce conducting filler containing proportional, then thermal conductivity reduces.
On the other hand, also there are the following problems for the thermal conductivity flame retardant resistance pressure-sensitive adhesive recorded in above-mentioned patent documentation 1: if obtain excellent thermal conductivity and increase conducting filler containing proportional, then shear skew and become large.
The object of the invention is to, excellent thermal conductivity is provided and reduces the thermal conductivity binding compositions shearing skew simultaneously.
For solving the method for problem
Thermal conductivity binding compositions of the present invention, it is characterized in that, have the adhesive composition containing superpolymer and oligopolymer and thermal conductivity particle, the gel fraction determined by following test of described adhesive composition is 28 ~ 59 quality %, and thermal conductivity is more than 0.3W/mK.
The gel fraction of adhesive composition: thermal conductivity binding compositions is about 1g floods 7 days in ethyl acetate 40g, afterwards, collect the insoluble composition of ethyl acetate of described thermal conductivity binding compositions, and make it dry, tried to achieve the gel fraction of described adhesive composition by following formula.
Gel fraction=(quality of the thermal conductivity binding compositions before the dry mass/dipping of the insoluble composition of ethyl acetate) × (quality of the quality/adhesive composition of thermal conductivity binding compositions) × 100
In addition, for thermal conductivity binding compositions of the present invention, the shearing skew determined preferably by following test was for less than 1.5mm/ hour.
Shear skew: after size thermal conductivity adhesive sheet being cut into 20mm × 10mm, by the lining material be made up of polyethylene terephthalate film fitting in thickness 25 μm perpendicular to the face of in the face of thickness direction of described thermal conductivity adhesive sheet, next, at 23 DEG C, under 50%RH environment, upper end 10mm × the 10mm perpendicular to the another side in the face of thickness direction of described thermal conductivity adhesive sheet part is fitted in the bottom of stainless steel plate, afterwards, leave standstill after within 30 minutes, making fit-state stable under the environment of 80 DEG C, the upper end of fixing described stainless steel plate, the weight of 300g is installed in the bottom of described thermal conductivity adhesive sheet, described thermal conductivity adhesive sheet is hung down under the condition of 80 DEG C, afterwards, measure under the environment of 80 DEG C placement after 1 hour described thermal conductivity adhesive sheet relative to described stainless steel plate side-play amount as shearing skew, wherein, described thermal conductivity adhesive sheet possesses the base material be made up of polyester film of thickness 12 μm, with be laminated in the two sides of described base material and 2 the thermal conductivity bonding coats obtained by sheet thermal conductivity binding compositions being configured as thickness 119 μm.
In addition, for thermal conductivity binding compositions of the present invention, the peeling adhesion force preferably by the peel angle 90 degree of following test determination is more than 5N/20mm.
Peeling adhesion force: thermal conductivity adhesive sheet is being machined to width 20mm and by described thermal conductivity adhering adhesive sheet after aluminium sheet, be determined at and be 90 degree relative to the peel angle of described aluminium sheet and peeling rate is that stripping strength when peeling off described thermal conductivity adhesive sheet under the condition of 300mm/ minute is as peeling adhesion force, wherein, described thermal conductivity adhesive sheet is possessed the base material be made up of polyester film of thickness 12 μm and is laminated in the two sides of described base material and 2 the thermal conductivity bonding coats obtained by sheet thermal conductivity binding compositions being configured as thickness 119 μm.
In addition, for thermal conductivity binding compositions of the present invention, preferably relative to described adhesive composition, being more than 1 quality % and being less than 40 quality % containing proportional of described oligopolymer.
In addition, for thermal conductivity binding compositions of the present invention, the weight-average molecular weight of preferred described oligopolymer is 5.0 × 10 2~ 1.0 × 10 5.
In addition, for thermal conductivity binding compositions of the present invention, preferably relative to described adhesive composition 100 mass parts, described thermal conductivity particle be less than 500 mass parts containing proportional.
In addition, for thermal conductivity binding compositions of the present invention, preferred thermal resistance value is less than 10cm 2k/W.
Invention effect
Thermal conductivity binding compositions of the present invention has adhesive composition containing superpolymer and oligopolymer and thermal conductivity particle, the gel fraction of adhesive composition is in specified range, thermal conductivity is more than particular value, therefore while excellent thermal conductivity, shear skew reduce.
Therefore, the various fields requiring high thermal conductivity and low sheraing skew can be suitable for.
Accompanying drawing explanation
Fig. 1 is the explanatory view of the manufacture method that the thermal conductivity adhesive sheet obtained by thermal conductivity binding compositions of the present invention is described,
Fig. 1 (a) represents the operation being coated with heat conductive adhesive raw material on basement membrane,
Fig. 1 (b) represents the operation configuring mulch film on the film of heat conductive adhesive raw material,
Fig. 1 (c) represents the operation making heat conductive adhesive raw material reaction,
Fig. 1 (d) represents the operation on two sides thermal conductivity bonding coat being laminated in base material.
Fig. 2 is the explanatory view of thermal property evaluating apparatus,
Fig. 2 (a) represents front elevation,
Fig. 2 (b) represents side elevational view.
Embodiment
Thermal conductivity binding compositions of the present invention contains adhesive composition and thermal conductivity particle.
In the present invention, adhesive composition contains superpolymer and oligopolymer.
The polymerization degree of superpolymer is such as more than 100, and be preferably more than 1000, and be such as less than 100000, described superpolymer is the polymkeric substance of monomer.
Such as, as monomer, as essential component, (methyl) alkyl acrylate system monomer can be enumerated, as any composition, can enumerate containing polar group monomer, polyfunctional monomer, can with the copolymerisable monomer of these monomer copolymerizations.
As (methyl) alkyl acrylate system monomer, there are alkyl methacrylate system monomer and/or alkyl acrylate system monomer, such as, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester etc., moieties is (methyl) alkyl acrylate of the alkyl of the C1-20 of straight-chain or branched.
In these (methyl) alkyl acrylate system monomers, particularly from the viewpoint of the balance easily obtaining adhesion properties, preferably enumerate (methyl) vinylformic acid C2-12 alkyl ester, more preferably enumerate (methyl) vinylformic acid C4-9 alkyl ester.
In monomer, with such as more than 60 quality %, be preferably more than 80 quality % and the ratio of such as below 99 quality % coordinates (methyl) alkyl acrylate system monomer.
As containing polar group monomer, such as can enumerate nitrogen containing monomer, hydroxyl monomer, containing sulfomonomer, the monomer having nitrogen and hydroxyl concurrently, the monomer having nitrogen and sulfo group concurrently, the monomer having hydroxyl and phosphate concurrently, carboxyl group-containing monomer etc.
As nitrogen containing monomer, can enumerate: such as, ring-type (methyl) acrylamides such as N-(methyl) acryloyl morpholine, N-(methyl) acryl tetramethyleneimine; Such as, (methyl) acrylamide, N-replace (methyl) acrylamide (such as, N-alkyl (methyl) acrylamide such as N-ethyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide; Such as, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, N-bis-(normal-butyl) (methyl) acrylamide, N, N, N-dialkyl group (methyl) acrylamides such as N-bis-(tertiary butyl) (methyl) acrylamide) etc. non-annularity (methyl) acrylamide; Such as, NVP (NVP), N-vinyl-2-piperidone, N-vinyl-3-morpholone mai, N-vinyl-2-hexanolactam, N-vinyl-1, the N-vinyl cyclic acid amides such as 3-oxazine-2-ketone, N-vinyl-3,5-morpholine diketone; Such as, (methyl) acrylate, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, the emulsion stabilities such as N-dimethylamino propyl ester; Such as, N-N-cyclohexylmaleimide, N-phenylmaleimide etc. are containing the monomer of maleimide skeleton; Such as, the clothing health imide series monomer such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-2-ethylhexyl clothing health imide, N-lauryl clothing health imide, N-cyclohexyl clothing health imide; Such as, the succimide system monomer such as N-(methyl) acryloyl-oxy methylene succimide, N-(methyl) acryl-6-oxygen base hexa-methylene succimide, N-(methyl) acryl-8-oxygen base hexa-methylene succimide; Such as, (methyl) acrylate, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, (methyl) acrylate system monomers such as N-dimethylamino ethyl ester, (methyl) tbutylaminoethylacrylate; Such as, 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-pseudoallyl-2-oxazoline and so on Han oxazolinyl monomer; Such as, (methyl) acryloylaziridine, (methyl) vinylformic acid-2-'-aziridino ethyl ester etc. are containing '-aziridino monomer etc.
As hydroxyl monomer, such as, can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxylauric ester etc.
As containing sulfomonomer, such as, can enumerate: styrene sulfonic acid, allyl sulphonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) propane sulfonic acid etc.
As the monomer having nitrogen and hydroxyl concurrently, such as, can enumerate: N-hydroxyalkyl (methyl) acrylamides such as N-(2-hydroxyethyl) (methyl) acrylamide (HEAA/HEMA), N-(2-hydroxypropyl) (methyl) acrylamide, N-(1-hydroxypropyl) (methyl) acrylamide, N-(3-hydroxypropyl) (methyl) acrylamide, N-(2-hydroxybutyl) (methyl) acrylamide, N-(3-hydroxybutyl) (methyl) acrylamide, N-(4-hydroxybutyl) (methyl) acrylamide.
As the monomer having nitrogen and sulfo group concurrently, such as, can enumerate 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid etc.
As the monomer having hydroxyl and phosphate concurrently, such as, can enumerate 2-hydroxyethyl (methyl) acryloyl phosphate etc.
As carboxyl group-containing monomer, such as, can enumerate: (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid etc.In addition, as carboxyl group-containing monomer, can enumerate: such as, the carboxylic acid anhydride such as maleic anhydride, itaconic anhydride; Such as, (methyl) vinylformic acid carboxyalkyl such as (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxybenzyl ester ester etc.
These are containing in polar group monomer, from the viewpoint of cementability and the confining force of giving thermal conductivity bonded combination object height, preferably enumerate the monomer of nitrogen containing monomer, nitrogenous and hydroxyl, more preferably enumerate NVP, HEAA/HEMA.
In monomer, coordinate containing polar group monomer with the ratio of such as more than 5 quality %, preferably 5 ~ 30 quality %, more preferably 5 ~ 25 quality %.If the mixing ratio containing polar group monomer in above-mentioned scope, then can give the good cementability of thermal conductivity binding compositions and confining force.
Polyfunctional monomer is the monomer with multiple ethylenically unsaturated hydrocarbons base, such as can enumerate: hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetra methylol propane three (methyl) acrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, epoxy acrylate, polyester acrylate, urethane acrylate, (methyl) vinylformic acid butanediol ester, 2 officials such as (methyl) vinylformic acid hexylene glycol ester can above polyfunctional monomer.
Preferably enumerating 4 officials such as Dipentaerythritol six (methyl) acrylate can above polyfunctional monomer.
In monomer, coordinate polyfunctional monomer with the ratio of such as below 2 quality %, preferably 0.01 ~ 2 quality %, more preferably 0.02 ~ 1 quality %.If the mixing ratio of polyfunctional monomer is in above-mentioned scope, then can improve the bonding force of thermal conductivity binding compositions.
As copolymerisable monomer, can enumerate: such as, (methyl) glycidyl acrylate, allyl glycidyl ether etc. is containing epoxy based monomers; Such as, (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) methoxyethyl glycol ester, (methyl) methoxyethyl polypropylene glycol ester etc. are containing Alkoxy monomeric; Such as, (methyl) alkali metal salts of acrylic acids such as (methyl) sodium acrylate; Such as, the cyano-containing such as vinyl cyanide, methacrylonitrile monomer; Such as, the styrenic monomers such as vinylbenzene, alpha-methyl styrene; Such as, the alpha-olefin such as ethene, propylene, isoprene, divinyl, iso-butylene; Such as, 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylic ester etc. are containing isocyanate group monomer; Such as, the vinyl ester such as vinyl-acetic ester, propionate system monomer; Such as, the vinyl ether system monomer such as alkyl vinyl ether; Such as, (methyl) tetrahydrofurfuryl acrylate etc. are containing (methyl) acrylate of heterocycle; Such as, the halogen atom-containing monomer such as (methyl) fluoroalkyl base ester; Such as, 3-(methyl) acryloxypropyl Trimethoxy silane, vinyltrimethoxy silane etc. are containing the monomer of alkoxysilyl; Such as, the monomer of the silicone-containing skeletons such as the silicone of (methyl) acryl is contained; Such as, (methyl) vinylformic acid ring propyl ester, (methyl) vinylformic acid ring butyl ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring heptyl ester, (methyl) vinylformic acid ring monooctyl ester, (methyl) vinylformic acid bornyl ester, (methyl) isobornyl acrylate etc. are containing (methyl) acrylate ((methyl) acrylate base ester of the cyclic alkyl of C3-20, preferably (methyl) vinylformic acid C5-7 cycloalkyl ester) of ester ring type alkyl; Such as, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, (methyl) vinylformic acid phenoxy group binaryglycol ester etc. are containing (methyl) acrylate etc. of aromatic hydrocarbyl.
In these copolymerisable monomers, preferably enumerate containing Alkoxy monomeric, more preferably enumerate (methyl) vinylformic acid 2-methoxy acrylate.By coordinating containing Alkoxy monomeric, thus the adaptation of thermal conductivity binding compositions relative to adherend can be improved, effectively can conduct the heat from adherend.
In monomer, such as, coordinate copolymerisable monomer with the ratio of below 30 quality %, preferably below 20 quality %.
These monomers can (only a kind) use separately, in addition, also can combine two or more to use.
Superpolymer obtains by making above-mentioned monomer polymerization (aftermentioned).
The weight-average molecular weight of superpolymer is such as more than 1.0 × 10 5, be preferably 1.0 × 10 6above, and be also such as 1.0 × 10 8below.The weight-average molecular weight of superpolymer is tried to achieve by the measuring method recorded in embodiment described later.
Superpolymer containing proportional relative to adhesive composition such as more than 10 quality % and below 99 quality %, be preferably 60 ~ 99 quality %, be more preferably 65 ~ 97.5 quality %, more preferably 70 ~ 95 quality %.
The polymerization degree of oligopolymer is such as less than 1000, is preferably less than 100, and is also such as more than 2, and described oligopolymer is the polymkeric substance of monomer.
As monomer, illustrative monomer in above-mentioned superpolymer can be enumerated.
In addition, as (methyl) acrylate containing ester ring type alkyl illustrative in (methyl) acrylate base ester system monomer, except above-mentioned illustration, also can enumerate (methyl) acrylate etc. containing ester ring type alkyl with caged scaffold.
Caged scaffold has the ester ring type structure of more than 3 rings, as have such caged scaffold ester ring type alkyl, such as, the tetrahydrochysene dicyclopentadiene base represented by following formula (a), the dihydro dicyclopentadiene base represented by following formula (b), the adamantyl represented by following formula (c), the tetrahydrochysene trimerization cyclopentadienyl represented by following formula (d), the In table dihydro trimerization cyclopentadienyl etc. represented by following formula (e) can be enumerated.
[changing 1]
In addition, in ester ring type alkyl, such as, part hydrogen atom can by replacements such as oxygen base alkyl such as oxygen base ethyls.
As (methyl) acrylate containing ester ring type alkyl with caged scaffold, such as, can enumerate: (methyl) vinylformic acid tetrahydrochysene dicyclopentadiene ester, (methyl) vinylformic acid tetrahydrochysene dicyclopentadiene base oxygen base ethyl ester, (methyl) vinylformic acid tetrahydrochysene three polycyclopentadiene ester, (methyl) vinylformic acid 1-adamantane esters, (methyl) vinylformic acid 2-methyl-2-adamantane esters, (methyl) vinylformic acid 2-ethyl-2-adamantane esters etc.
Monomer can be used alone or and the multiple kinds using kind different from each other.
As monomer, preferably enumerate (methyl) acrylate base ester system monomer ((methyl) acrylate containing ester ring type alkyl), (methyl) alkyl acrylate system monomer, containing polar group monomer.
When being used alone monomer, specifically, such as, being used alone of (methyl) acrylate base ester system monomer, being used alone of carboxyl group-containing monomer can be enumerated.
When monomer is the combination of the monomer of kind multiple kinds different from each other, specifically, can enumerate: the combination of (methyl) acrylate base ester system monomer and (methyl) alkyl acrylate system monomer, the combination of diverse 2 kinds of (methyl) acrylate base ester system monomers, (methyl) acrylate base ester system monomer and the combination containing polar group monomer (specifically, nitrogen containing monomer, hydroxyl monomer, carboxyl group-containing monomer).
As monomer, more preferably the combination of (methyl) acrylate base ester system monomer and (methyl) alkyl acrylate system monomer is enumerated, more preferably enumerate (methyl) vinylformic acid C5-7 cycloalkyl ester and the combination of (methyl) vinylformic acid C4-9 alkyl ester, preferably enumerate the combination of (methyl) cyclohexyl acrylate and (methyl) isobutyl acrylate further.
When combining (methyl) acrylate base ester system monomer with (methyl) alkyl acrylate system's monomer, (methyl) alkyl acrylate system monomer containing proportional be such as 10 ~ 400 mass parts relative to (methyl) acrylate base ester system monomer 100 mass parts, be preferably 30 ~ 200 mass parts.
Specifically, as polymkeric substance, such as can enumerate: the multipolymer of cyclohexyl methacrylate (CHMA) and Propenoic acid, 2-methyl, isobutyl ester (IBMA), the multipolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA), the multipolymer of isobornyl methacrylate (IBXMA) and methyl methacrylate (MMA), the multipolymer of cyclohexyl methacrylate (CHMA) and acryloyl morpholine (ACMO), cyclohexyl methacrylate (CHMA) and N, the multipolymer of N-acrylamide (DEAA), the multipolymer of vinylformic acid 1-adamantane esters (ADA) and methyl methacrylate (MMA), the multipolymer of methacrylic acid tetrahydrochysene dicyclopentadiene ester (DCPMA) and isobornyl methacrylate (IBXMA), the multipolymer of methacrylic acid tetrahydrochysene dicyclopentadiene ester (DCPMA) and methyl methacrylate (MMA), the multipolymer of methacrylic acid tetrahydrochysene dicyclopentadiene ester (DCPMA) and NVP (NVP), the multipolymer of methacrylic acid tetrahydrochysene dicyclopentadiene ester (DCPMA) and hydroxyethyl methacrylate (HEMA), the multipolymer of methacrylic acid tetrahydrochysene dicyclopentadiene ester (DCPMA) and vinylformic acid (AA), the homopolymer of methacrylic acid tetrahydrochysene dicyclopentadiene ester (DCPMA), the homopolymer of cyclohexyl methacrylate (CHMA), the homopolymer of isobornyl methacrylate (IBXMA), the homopolymer of isobornyl acrylate (IBXA), the homopolymer of vinylformic acid tetrahydrochysene dicyclopentadiene ester (DCPA), the homopolymer of methacrylic acid 1-adamantane esters (ADMA), the homopolymer of vinylformic acid 1-adamantane esters (ADA), the homopolymer etc. of methyl methacrylate (MMA).Preferably enumerate the multipolymer of CHMA and IBMA.
Oligopolymer can by by above-mentioned monomer by solution polymerization process, body (バ Le Network) polymerization, emulsion polymerization, suspension polymerization, body (Block shape) polymerization etc. and obtaining.Preferred employing mass polymerization.
In addition, oligopolymer by coordinating above-mentioned monomer and chain-transfer agent, can be obtained by above-mentioned polymerization under the existence of polymerization starter.
Chain-transfer agent is molecular weight in order to adjust oligopolymer and with monomer and use, specifically, can enumerates: such as, the mercaptan compound such as octyl mercaptan, lauryl mercaptan, tertiary lauryl mercaptan, 2 mercapto ethanol, thioglycerin; Such as, the Thiovanic acid compound such as Thiovanic acid; Such as, the Thiovanic acid ester cpds such as mercaptoacetate, the mercaptoacetate of neopentyl glycol, the mercaptoacetate of tetramethylolmethane of Methyl Thioglycolate, ethyl thioglycolate, Thiovanic acid propyl ester, Thiovanic acid butyl ester, the Thiovanic acid tert-butyl ester, 2-ethylhexyl mercaptoacetate, Thiovanic acid monooctyl ester, Thiovanic acid ester in the last of the ten Heavenly stems, Thiovanic acid dodecyl ester, ethylene glycol; Such as, alpha-methyl styrene dimer etc.
Chain-transfer agent may be used singly or in combination of two or more kinds.
Preferably enumerate Thiovanic acid.
The mixing ratio of chain-transfer agent is such as 0.1 ~ 20 mass parts relative to monomer 100 mass parts, is preferably 0.2 ~ 15 mass parts, is more preferably 0.3 ~ 10 mass parts.
As polymerization starter, the material identical with above-mentioned illustrative polymerization starter can be enumerated, preferably enumerate thermal polymerization, more preferably enumerate peroxidation system polymerization starter.
Polymerization starter can be used alone or and uses.
The mixing ratio of polymerization starter is such as 0.001 ~ 5 mass parts relative to monomer 100 mass parts, is preferably 0.01 ~ 3 mass parts.
When using thermal polymerization as polymerization starter, as polymerizing condition, Heating temperature is such as 50 ~ 200 DEG C, and heat-up time is such as 30 minutes ~ 10 hours.
In addition, oligopolymer can use commercially available product, such as, can use EBECRYL series (Daicelcytec Inc.) etc.
The weight-average molecular weight of oligopolymer is such as 5.0 × 10 2~ 1.0 × 10 5, be preferably 1.0 × 10 3~ 1.0 × 10 5, be more preferably 2.0 × 10 3~ 1.0 × 10 4.
If the weight-average molecular weight of oligopolymer is in above-mentioned scope, then can improves the peeling adhesion force (aftermentioned) of thermal conductivity binding compositions and shear skew (aftermentioned).
The weight-average molecular weight of oligopolymer is tried to achieve by the measuring method recorded in embodiment described later.
Oligopolymer containing proportional be such as 1 ~ 90 quality % relative to adhesive composition, be preferably more than 1 quality % and be less than 40 quality %, be more preferably 2.5 ~ 35 quality %, more preferably 5 ~ 30 quality %.
If containing of oligopolymer is proportional lower than the above-mentioned upper limit, then gel fraction (aftermentioned) can be set in desired scope, can reduce and shear skew.On the other hand, if oligopolymer containing proportional be more than above-mentioned lower limit, then gel fraction can be set as desired scope, can peeling adhesion force be improved.
Adhesive composition containing proportional be such as 1 ~ 50 quality % relative to thermal conductivity binding compositions, be preferably 10 ~ 40 quality %.
Thermal conductivity particle obtains by being formed as particle shape by thermally conductive materials, as such thermally conductive materials, such as, can enumerate hydrated metal compound.
Hydrated metal compound is that kick off temperature is in the scope of 150 ~ 500 DEG C and with formula M xo ynH 2o (M is atoms metal, x, y be according to the valence of metal determine more than 1 integer, n is the quantity of contained crystal water) compound that represents or the double salt comprising above-claimed cpd.
As hydrated metal compound, such as, can enumerate: aluminium hydroxide [Al 2o 33H 2o; Or Al (OH) 3], boehmite [Al 2o 3h 2o; Or AlOOH], magnesium hydroxide [MgOH 2o; Or Mg (OH) 2], calcium hydroxide [CaOH 2o; Or Ca (OH) 2], zinc hydroxide [Zn (OH) 2], silicic acid [H 4siO 4; Or H 2siO 3; Or H 2si 2o 5], ironic hydroxide [Fe 2o 3h 2o or 2FeO (OH)], copper hydroxide [Cu (OH) 2], hydrated barta [BaOH 2o; Or BaO9H 2o], Zirconium oxide hydrate [ZrOnH 2o], tin oxide hydrate [SnOH 2o], alkaline magnesium carbonate [3MgCO 3mg (OH) 23H 2o], hydrotalcite [6MgOAl 2o 3h 2o], dawsonite [Na 2cO 3al 2o 3nH 2o], borax [Na 2oB 2o 55H 2o], zinc borate [2ZnO3B 2o 53.5H 2o] etc.
In addition, as thermally conductive materials, except above-mentioned hydrated metal compound, such as, can enumerate: boron nitride, aluminium nitride, silicon nitride, gan, silicon carbide, silicon-dioxide, aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, stannic oxide, cupric oxide, nickel oxide, metaantimmonic acid doped stannum oxide (ア Application チ モ Application Suan ド ー プ acidifying ス ズ), calcium carbonate, barium titanate, potassium titanate, copper, silver, gold, nickel, aluminium, platinum, carbon (comprising diamond) etc.
As thermally conductive materials, consider from the reason of the thermal conductivity and flame retardant resistance of giving thermal conductivity bonded combination object height, preferably enumerate aluminium hydroxide.
Such as, as long as the shape particle shape (Powdered) of thermal conductivity particle is then not particularly limited, and can be bulk, needle-like, tabular, stratiform.Bulk such as comprises spherical, rectangular-shaped, broken shape or their special-shaped shape.
The size of thermal conductivity particle is not particularly limited, and such as, as 1 median size, such as, is 0.1 ~ 1000 μm, is preferably 0.5 ~ 200 μm, is more preferably 0.7 ~ 100 μm, more preferably 1 ~ 80 μm.1 particle diameter of thermal conductivity particle is the size-grade distribution based on being measured by the particle size distribution method in laser scattering method, with the form of the median size of volume reference, more specifically tries to achieve with the form of D50 value (in accumulation 50% diameter).
These thermal conductivity particles are commercially on sale, such as, as the thermal conductivity particle be made up of aluminium hydroxide, trade(brand)name " HIGILITE H-100-ME " (Showa electrician Inc.) can be enumerated, trade(brand)name " HIGILITE H-10 " (Showa electrician Inc.), trade(brand)name " HIGILITE H-32 " (Showa electrician Inc.), trade(brand)name " HIGILITE H-31 " (Showa electrician Inc.), trade(brand)name " HIGILITE H-42 " (Showa electrician Inc.), trade(brand)name " HIGILITEH-43M " (Showa electrician Inc.), trade(brand)name " B103ST " (Japanese light metal Inc.) etc., such as, as the thermal conductivity particle be made up of magnesium hydroxide, trade(brand)name " KISUMA5A " (consonance chemical industrial company system) etc. can be enumerated.
In addition, as the thermal conductivity particle be made up of boron nitride, trade(brand)name " HP-40 " (Shui Dao alloy iron Inc.) can be enumerated, trade(brand)name " PT620 " (MOMENTIVE Inc.) etc., such as, as the thermal conductivity particle be made up of aluminum oxide, trade(brand)name " AS-50 " (Showa electrician Inc.) can be enumerated, trade(brand)name " AS-10 " (Showa electrician Inc.) etc., such as, as the thermal conductivity particle be made up of metaantimmonic acid doped stannum oxide, trade(brand)name " SN-100S " (stone originates in industry Inc.) can be enumerated, trade(brand)name " SN-100P " (stone originates in industry Inc.), trade(brand)name " SN-100D (water-dispersion product) " (stone originates in industry Inc.) etc., such as, as the thermal conductivity particle be made up of titanium oxide, trade(brand)name " TTO series " (stone originates in industry Inc.) etc. can be enumerated, such as, as the thermal conductivity particle be made up of zinc oxide, trade(brand)name " SnO-310 " (Osaka, Sumitomo cement company system) can be enumerated, trade(brand)name " SnO-350 " (Osaka, Sumitomo cement company system), trade(brand)name " SnO-410 " (Osaka, Sumitomo cement company system) etc.
These thermal conductivity particles can be used alone or and use.
Thermal conductivity particle be such as less than 500 mass parts relative to adhesive composition 100 mass parts containing proportional, be preferably below 450 mass parts, be more preferably below 400 mass parts, more preferably below 350 mass parts, and be such as more than 1 mass parts, be preferably more than 10 mass parts, be more preferably more than 100 mass parts, more preferably more than 200 mass parts.
In addition, thermal conductivity particle containing proportional be such as more than 55 quality % relative to thermal conductivity binding compositions, be preferably more than 60 quality %, being more preferably more than 65 quality %, such as, is also below 90 quality %.
If the mixing ratio of thermal conductivity particle is in above-mentioned scope, then can give the thermal conductivity of thermal conductivity binding compositions excellence and excellent bonding (bonding) property.
Next, the method manufacturing thermal conductivity binding compositions is described.
When manufacturing thermal conductivity binding compositions, such as, coordinate superpolymer and oligopolymer, preparation adhesive composition, then the adhesive composition prepared and thermal conductivity particle are coordinated.In addition, also superpolymer, oligopolymer and thermal conductivity particle can be coordinated simultaneously.
In addition, also can by containing for the formation of the monomer of superpolymer monomer composition, coordinate with oligopolymer and thermal conductivity particle, make monomer polymerization.
Preferably by monomer composition, coordinate with oligopolymer and thermal conductivity particle after, make monomer polymerization.
When preparing monomer composition, first, in above-mentioned monomer, polymerization starter is coordinated.
As polymerization starter, such as, Photoepolymerizationinitiater initiater, thermal polymerization can be enumerated.
As Photoepolymerizationinitiater initiater, such as, can enumerate: benzoin ether system Photoepolymerizationinitiater initiater, methyl phenyl ketone system Photoepolymerizationinitiater initiater, α-one alcohol system Photoepolymerizationinitiater initiater, aromatic sulfonyl system Photoepolymerizationinitiater initiater, photolytic activity oxime system Photoepolymerizationinitiater initiater, bitter almond oil camphor system Photoepolymerizationinitiater initiater, benzil system Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, thioxanthone system Photoepolymerizationinitiater initiater etc.
As benzoin ether system Photoepolymerizationinitiater initiater, such as, can enumerate: benzoin methyl ether, benzoin ethyl ether, bitter almond oil camphor propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, phenylmethylether methyl ether etc.
As methyl phenyl ketone system Photoepolymerizationinitiater initiater, such as, can enumerate: 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 4-phenoxydichloroacetophenone, 4-(tertiary butyl) dichloroacetophenone etc.
As α-one alcohol system Photoepolymerizationinitiater initiater, such as, can enumerate: 2-methyl-2-hydroxypropiophenonepreparation, 1-[4-(2-hydroxyethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxycyclohexylphenylketone etc.
As aromatic sulfonyl system Photoepolymerizationinitiater initiater, such as, can enumerate 2-naphthalic sulfonic chloride etc.
As photolytic activity oxime system Photoepolymerizationinitiater initiater, such as, 1-phenyl-1,1-propanedione-2-(O-ethoxy carbonyl) oxime etc. can be enumerated.
As bitter almond oil camphor system Photoepolymerizationinitiater initiater, such as, bitter almond oil camphor etc. can be enumerated.
As benzil system Photoepolymerizationinitiater initiater, such as, benzil etc. can be enumerated.
As benzophenone series Photoepolymerizationinitiater initiater, such as, can enumerate: benzophenone, benzoyl phenylformic acid, 3,3 '-dimethyl-4-methoxy benzophenone, polyvinyl benzophenone etc.
As thioxanthone system Photoepolymerizationinitiater initiater, such as, can enumerate: thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropylthioxanthone, decyl thioxanthone etc.
As thermal polymerization, can enumerate: such as, 2, 2 '-azobis isobutyronitrile, 2, two-2-the methylbutyronitrile of 2 '-azo, 2, two (2 Methylpropionic acid) dimethyl ester of 2 '-azo, 4, two-4-the cyanopentanoic acid of 4 '-azo, the two isovaleronitrile of azo, 2, two (2-amidine propane) dihydrochloride of 2 '-azo, 2, two [2-(5-methyl-2-tetrahydroglyoxaline-2-base) propane] dihydrochloride of 2 '-azo, 2, two (the 2-methyl-prop amidine) dithionate of 2 '-azo, 2, two (the N of 2 '-azo, N '-dimethyleneisobutylamidine) hydrochloride, 2, the azo system polymerization starters such as two [N-(2-the carboxy ethyl)-2-methyl-prop amidine] hydrates of 2 '-azo, such as, the peroxidation system polymerization starter such as dibenzoyl peroxide, the peroxidation toxilic acid tert-butyl ester, the tertiary hexyl of peroxidation two (ジ-t-t-ヘ キ シ Le パ ー オ キ サ イ De), the tertiary hexyl-2-ethylhexanoate of peroxidation, tertbutyl peroxide, hydrogen peroxide, such as, the persulphate such as Potassium Persulphate, ammonium persulphate, such as, the reducto oxydative system polymerization starter etc. such as combination of the combination of persulphate and sodium bisulfite, superoxide and sodium ascorbate.
These polymerization starters both can (only a kind) use separately, in addition, also can combine two or more to use.
In these polymerization starters, from considerations such as the advantages that can shorten polymerization time, preferably enumerate Photoepolymerizationinitiater initiater.More preferably benzoin ether system Photoepolymerizationinitiater initiater, α-one alcohol system Photoepolymerizationinitiater initiater is enumerated.
When coordinating Photoepolymerizationinitiater initiater as polymerization starter, Photoepolymerizationinitiater initiater such as coordinates with such as 0.01 ~ 5 mass parts, the preferably ratio of 0.05 ~ 3 mass parts relative to monomer 100 mass parts.
In addition, when coordinating thermal polymerization as polymerization starter, thermal polymerization is not particularly limited, and coordinates with available ratio.
Next, when preparing monomer composition, as required, partial monosomy is polymerized.
When making partial monosomy be polymerized, when being combined with Photoepolymerizationinitiater initiater, to the mixture irradiation ultraviolet radiation of monomer and Photoepolymerizationinitiater initiater.When irradiation ultraviolet radiation, irradiate, until the viscosity of monomer composition (BH viscometer, No.5 rotor, 10rpm, mensuration temperature 30 DEG C) reaches such as 5 ~ 30Pas, preferably 10 ~ 20Pas with Photoepolymerizationinitiater initiater such irradiation energy that is excited.
In addition, when coordinating thermal polymerization, by the mixture of monomer and thermal polymerization such as more than the decomposition temperature of thermal polymerization, specifically under the polymerization temperature of about 20 ~ 100 DEG C, heat, until the viscosity of monomer composition (BH viscometer, No.5 rotor, 10rpm, mensuration temperature 30 DEG C) reaches such as 5 ~ 30Pas, preferably 10 ~ 20Pas in the same manner as coordinating the situation of Photoepolymerizationinitiater initiater.
It should be noted that, when making partial monosomy polymerization prepare monomer composition, first, (methyl) alkyl acrylate system monomer will be selected from, containing the monomer (the 1st monomer) in polar group monomer and copolymerisable monomer, coordinate with polymerization starter, partial monosomy (the 1st monomer) is made to be polymerized in the above described manner, afterwards, when the cooperation of the oligopolymer of the following stated, also can coordinate polyfunctional monomer (the 2nd monomer).
2nd monomer containing proportional be such as 0.001 ~ 10 mass parts relative to the 1st monomer 100 mass parts, be preferably 0.01 ~ 1 mass parts.
Thus, monomer composition is prepared.
It should be noted that, monomer composition, when partial monosomy has been polymerized, is prepared to the slurry with above-mentioned viscosity.
In the method, next, in the monomer composition configured, oligopolymer and thermal conductivity particle is coordinated.
That is, oligopolymer and thermal conductivity particle are engaged in monomer composition in the mode becoming above-mentioned mixing ratio.Preferably oligopolymer and thermal conductivity particle are engaged in monomer composition successively.
Thus, the heat conductive adhesive raw material of preparation containing monomer composition, oligopolymer and thermal conductivity particle.
It should be noted that, also can be as required, the additives such as dispersion agent (such as, nonionic surfactant etc.), tackifier, silane coupling agent, softening agent, packing material, age resister, tinting material are coordinated in the proper ratio in oligopolymer, monomer composition and/or heat conductive adhesive raw material.
It should be noted that, oligopolymer, thermal conductivity particle and/or additive etc. to be dispersed or dissolved in the state in organic solvent equal solvent, can be engaged in monomer composition and/or heat conductive adhesive raw material.
The viscosity (BM viscometer, No.4 rotor, 12rpm, mensuration temperature 23 DEG C) of the heat conductive adhesive raw material of gained is such as below 50Pas, is preferably 5 ~ 40Pas, is more preferably 10 ~ 35Pas.
It should be noted that, in heat conductive adhesive raw material, also can contain bubble.Use containing alveolate heat conductive adhesive raw material, make thermal conductivity adhesive sheet as described later, thus, can also by thermal conductivity adhesive sheet producing foamed body.
Fig. 1 is the explanatory view of the manufacture method that the thermal conductivity adhesive sheet obtained by thermal conductivity binding compositions of the present invention is described, Fig. 1 (a) represents the operation being coated with heat conductive adhesive raw material on basement membrane, Fig. 1 (b) represents the operation configuring mulch film on the film of heat conductive adhesive raw material, Fig. 1 (c) represents the operation making heat conductive adhesive raw material reaction, and Fig. 1 (d) represents the operation on two sides thermal conductivity bonding coat being laminated in base material.
Next, the manufacture method of thermal conductivity adhesive sheet is described.
As shown in Fig. 1 (a), when manufacturing thermal conductivity adhesive sheet 6, first, at the face coating heat conductive adhesive raw material 2 implementing lift-off processing of basement membrane 1.
Basement membrane 1 comprises release liner, specifically, can enumerate: such as, polyester film (polyethylene terephthalate film etc.); Such as, the fluorine mesentery be made up of fluorine based polymer (such as tetrafluoroethylene, polychlorotrifluoroethylene, fluorinated ethylene propylene, poly(vinylidene fluoride), tetrafluoraoethylene-hexafluoropropylene copolymer, chlorine vinyl fluoride-vinylidene fluoride copolymer etc.); Such as, the ethylene series resin molding be made up of ethylene series resin (polyethylene, polypropylene etc.); Such as, plastics system base material film (synthetic resin film) such as polychloroethylene film, polyimide film, polyamide membrane (nylon membrane), artificial cortina; Such as, the stationeries such as paper are coated with without wood pulp paper, Japan paper, kraft paper, glassine paper, synthetic paper, face; Such as, by the complex body etc. of their multiple stratifications.
It should be noted that, when heat conductive adhesive raw material 2 is containing Photoepolymerizationinitiater initiater, not hinder ultraviolet to the mode of the irradiation of heat conductive adhesive raw material 2, use the basement membrane 1 of transmitting UV.
As method heat conductive adhesive raw material 2 being coated basement membrane 1, such as, can enumerate: the extrusion coating methods etc. that roller coat, roller lick formula coating, intaglio plate coating, oppositely coating, roller brush, spraying, dipping roller coat, rod paintings, scraper for coating, airblade coating, curtain painting, die lip are coated with, utilize mould painting machine etc.
The applied thickness of heat conductive adhesive raw material 2 is such as 10 ~ 10000 μm, is preferably 50 ~ 5000 μm, is more preferably 100 ~ 3000 μm.
In the method, next, as shown in Fig. 1 (b), the film of heat conductive adhesive raw material 2 configures mulch film 3.When mulch film 3 is configured on film, be configured to make the mode implementing the face contact film of lift-off processing of mulch film 3.
As mulch film 3, such as, can enumerate the film identical with above-mentioned basement membrane 1.In addition, when heat conductive adhesive raw material 2 is containing Photoepolymerizationinitiater initiater, not hinder ultraviolet to the mode of the irradiation of heat conductive adhesive raw material 2, the mulch film 3 of transmitting UV is used.
In the method, afterwards, as shown in Fig. 1 (c), the monomer polymerization in heat conductive adhesive raw material 2 is made.
When making the monomer polymerization in heat conductive adhesive raw material 2, as mentioned above, when being combined with Photoepolymerizationinitiater initiater, to thermal conductivity binder materials 2 irradiation ultraviolet radiation, when being combined with thermal polymerization, heating heat conductive adhesive raw material 2.
It should be noted that, when make oligopolymer, thermal conductivity particle and/or additive be dispersed or dissolved in solvent coordinate again for heat conductive adhesive raw material 2, as mentioned above coating heat conductive adhesive raw material 2, makes it dry, thus can remove desolventizing.
Thus, heat conductive adhesive raw material 2 becomes thermal conductivity binding compositions, thermal conductivity binding compositions has been formed as stacked overleaf basement membrane 1 and on surface the stacked thermal conductivity bonding coat 4 of mulch film 3.
Afterwards, as shown in Fig. 1 (d), thermal conductivity bonding coat 4 is laminated in the two sides of base material 5.
Specifically, first, as shown in the dotted line of Fig. 1 (c) and arrow, mulch film 3 is peeled off from adhesive coating 4, afterwards, with reference to Fig. 1 (d), thermal conductivity bonding coat 4 is adhered to respectively surface and the back side of base material 5.
As base material 5, the material identical with above-mentioned basement membrane 1 can be enumerated.The thickness of base material 5 is such as 1 ~ 1000 μm, is preferably 5 ~ 500 μm.
Thus, the thermal conductivity adhesive sheet 6 of the thermal conductivity bonding coat 4 possessing base material 5 and be laminated in its two sides is obtained.
It should be noted that, be laminated with basement membrane 1 on the surface of the thermal conductivity bonding coat 4 of the face side of thermal conductivity adhesive sheet 6, be laminated with basement membrane 1 at the back side of the thermal conductivity bonding coat 4 of the rear side of thermal conductivity adhesive sheet 6.When using thermal conductivity adhesive sheet 6, each basement membrane 1 is peeled off from thermal conductivity bonding coat 4.
The thickness of the thermal conductivity adhesive sheet 6 of gained is (except the thickness of 2 basement membranes 1.) be such as 10 ~ 10000 μm, be preferably 50 ~ 5000 μm, be more preferably 100 ~ 3000 μm.
If the total thickness of thermal conductivity adhesive sheet 6 is more than above-mentioned lower limit, then can obtain sufficient bonding force and confining force.In addition, if the total thickness of thermal conductivity adhesive sheet 6 is below the above-mentioned upper limit, then sufficient thermal conductivity can be obtained.
About the thermal conductivity binding compositions of the thermal conductivity bonding coat 4 of formation thermal conductivity adhesive sheet 6, be 28 ~ 59 quality % by the gel fraction of the adhesive composition of following test determination, be preferably 28.5 ~ 52 quality %, be more preferably 29 ~ 50 quality %, more preferably 29.5 ~ 45 quality %, are particularly preferably 30 ~ 40 quality %.
The gel fraction of adhesive composition: thermal conductivity binding compositions is about 1g floods 7 days in ethyl acetate 40g, afterwards, collects the insoluble composition of ethyl acetate of thermal conductivity binding compositions, and makes it dry, is tried to achieve the gel fraction of adhesive composition by following formula.
Gel fraction=(quality of the thermal conductivity binding compositions before the dry mass/dipping of the insoluble composition of ethyl acetate) × (quality of the quality/adhesive composition of thermal conductivity binding compositions) × 100
If the gel fraction of adhesive composition is below the above-mentioned upper limit, then can reduces and shear skew, and peeling adhesion force can be made to improve.Therefore, the cementability of thermal conductivity adhesive sheet 6 can be made to improve.
On the other hand, if the gel fraction of adhesive composition is more than above-mentioned lower limit, then can reduces and shear skew, therefore can improve the cementability of thermal conductivity adhesive sheet 6.
In addition, the thermal conductivity of thermal conductivity adhesive sheet 6 (is measured by the method recorded in embodiment described later.) be more than 0.3W/mK, be preferably more than 0.4W/mK, be more preferably more than 0.5W/mK, and be also such as below 10W/mK.
If the thermal conductivity of thermal conductivity adhesive sheet 6 is more than above-mentioned lower limit, then may be used for the purposes of requirement thermal conductivity.
In addition, the shearing skew of thermal conductivity adhesive sheet 6 (is measured by the method recorded in embodiment described later.) be such as less than 1.5mm/ hour, be preferably less than 1.2mm/ hour, more preferably less than 1.0mm/ hour, be particularly preferably less than 0.8mm/ hour, most preferably be less than 0.5mm/ hour, and be also more than 0mm/ hour.
If the shearing skew of thermal conductivity adhesive sheet 6 is for below the above-mentioned upper limit, then can improve the confining force to adherend in direction, face, therefore, it is possible to be suitable for the field requiring above-mentioned characteristic.
In addition, the peeling adhesion force of the peel angle 90 degree of thermal conductivity adhesive sheet 6 (is measured by the method recorded in embodiment described later.) be such as more than 5N/20mm, be preferably more than 7N/20mm, be more preferably more than 10N/20mm, more preferably more than 15N/20mm, be particularly preferably more than 20N/20mm, and be also such as below 100N/20mm, be preferably below 50N/20mm.
If the peeling adhesion force that peel angle is 90 degree is more than above-mentioned lower limit, then can improve the bonding force to adherend of thickness direction, therefore, it is possible to be suitable for the field requiring above-mentioned characteristic.
In addition, the thermal resistance of thermal conductivity adhesive sheet 6 (is measured by the method recorded in embodiment described later.) be such as less than 12cm 2k/W, is preferably less than 10cm 2k/W, and be also such as 2cm 2more than K/W.If the thermal resistance of thermal conductivity adhesive sheet is less than the above-mentioned upper limit, then can give full play to the function as thermal conductivity adhesive sheet.
And, the thermal conductivity adhesive sheet 6 possessing the thermal conductivity bonding coat 4 formed by thermal conductivity binding compositions has adhesive composition containing superpolymer and oligopolymer and thermal conductivity particle, the gel fraction of adhesive composition is in specified range, thermal conductivity is more than particular value, therefore excellent thermal conductivity, and reduce shearing skew.
Therefore, the excellent thermal conductivity of thermal conductivity adhesive sheet 6, therefore, it is possible to be suitable for the purposes such as semiconductor device, hard disk, LED matrix (televisor, illumination, indicating meter etc.), EL device (OLED display, organic EL illuminating etc.), electrical condenser, battery (lithium ion battery etc.), power module, particularly require high thermal conductivity and the purposes of LED matrix both low sheraing skew.
That is, above-mentioned LED matrix possess install in perpendicular or parallel mode relative to the thermal component such as scatterer, frame, as the LED of generating component.And the LED of LED matrix is adhered to scatterer, frame by thermal conductivity adhesive sheet 6.
For such LED matrix, even if the heat caused by the luminescence of LED is being conducted to scatterer, frame simultaneously effectively by thermal conductivity adhesive sheet 6, thermal conductivity adhesive sheet 6 is subject to the Strong shear power in direction, face, also can reduce LED and scatterer, the shearing of frame offsets, they are firmly bonding.
In the embodiment of Fig. 1 (d), the thermal conductivity bonding coat 4 be made up of thermal conductivity binding compositions is laminated in the two sides of base material 5, produce the thermal conductivity adhesive sheet 6 possessing 2 thermal conductivity bonding coats 4 and 1 base material 5 thus, but, such as shown in Fig. 1 (c), also can make and not possess base material 5 and the thermal conductivity adhesive sheet 6 comprising the thermal conductivity bonding coat 4 clamped by basement membrane 1 and mulch film 3 (release liner).
In addition, the thermal conductivity of this thermal conductivity bonding coat 4 and excellent in flame retardance, therefore, it is possible to be suitable for the purposes such as semiconductor device, hard disk, LED matrix (televisor, illumination, indicating meter etc.), EL device (OLED display, organic EL illuminating etc.), electrical condenser (condenser etc.), battery (lithium ion battery etc.), power module.
Embodiment
Below, based on each embodiment and each comparative example, the present invention will be described, but the present invention is by their any restriction.
Embodiment 1
(preparation of oligopolymer)
Cyclohexyl methacrylate (CHMA) 60 mass parts, Propenoic acid, 2-methyl, isobutyl ester (IBMA) 40 mass parts and Thiovanic acid 4 mass parts as chain-transfer agent are dropped into and possesses in 4 mouthfuls of flasks of agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel.Then, 70 DEG C, stir 1 hour under nitrogen atmosphere after, be warming up to 90 DEG C, mix the tertiary hexyl of peroxidation-2-ethyl (trade(brand)name " Perhexyl O ", You Inc.) 0.005 mass parts as polymerization starter and the tertiary hexyl of peroxidation two (trade(brand)name " Perhexyl D ", You Inc.) 0.01 mass parts.Further, stir after 1 hour at 100 DEG C, be warming up to 150 DEG C with 1 hour, and stir 1 hour at 150 DEG C.Next, be warming up to 170 DEG C with 1 hour, and stir 60 minutes at 170 DEG C.Next, reduce pressure under the state of 170 DEG C, stir 1 hour, removing residual monomer, obtains oligopolymer.
The weight-average molecular weight of the oligopolymer of gained is 3400.
(preparation of monomer composition)
As the 1st monomer, coordinate 2-EHA 85 mass parts, vinylformic acid 2-methoxy acrylate 9 mass parts, NVP (NVP) 7 mass parts and hydroxyethyl acrylamide (HEAA) 1 mass parts, they are mixed, obtains the mixture of monomer.
In the mixture of gained, coordinate as 2 of Photoepolymerizationinitiater initiater, 2-dimethoxy-1,2-diphenylethane-1-ketone (trade(brand)name " Irgacure 651 ", Ciba Japan Inc.) 0.05 mass parts and 1-hydroxycyclohexylphenylketone (trade(brand)name " Irgacure 184 ", Ciba Japan Inc.) 0.05 mass parts.
Next, to mixture irradiation ultraviolet radiation, be polymerized to viscosity (BH viscometer, No.5 rotor, 10rpm, mensuration temperature 30 DEG C) and reach about 20Pas, prepare the partial polymer (slurry) of the monomer that partial monosomy has been polymerized.
In partial polymer 97.5 mass parts of the monomer prepared, coordinate oligopolymer (weight-average molecular weight 3400) 2.5 mass parts, dipentaerythritol acrylate (trade(brand)name " KAYARAD DPHA-40H ", Japanese chemical drug Inc.) 0.05 mass parts as the 2nd monomer and trade(brand)name " Plysurf A212E " (nonionic surfactant, the first industrial pharmaceutical Inc.) 1 mass parts as dispersion agent and mix, preparing monomer composition.
Coordinate monomer composition 100 mass parts and aluminum hydroxide particles (trade(brand)name " HIGILITE H-32 ", shape: broken shape, 1 median size: 8 μm, Showa electrician Inc.) 250 mass parts of gained, mix, prepare heat conductive adhesive raw material.
Reach the mode of 119 μm with the thickness after dry and solidification, the heat conductive adhesive raw material prepared is coated 2 release liners (trade(brand)name " Diafoil MRF38 ", polyester film Inc. of Mitsubishi Chemical) of the polyethylene terephthalate of lift-off processing implement to one side lift-off processing face between (with reference to Fig. 1 (b).)。
Specifically, first, heat conductive adhesive raw material is coated on the release liner as basement membrane (with reference to Fig. 1 (a).), then, the stacked release liner being used as mulch film on the film of heat conductive adhesive raw material.(with reference to Fig. 1 (b).)。
Next, to heat conductive adhesive raw material, from both sides (two release liners), (illumination is about 5mW/cm to irradiation ultraviolet radiation 2) 3 minutes.
Thus, make the monomer polymerization in heat conductive adhesive raw material, form the thermal conductivity bonding coat (with reference to Fig. 1 (c)) of the thickness 119 μm be made up of thermal conductivity binding compositions.
Afterwards, the release liner (mulch film) of side is peeled off from thermal conductivity bonding coat, thermal conductivity bonding coat is fitted in the two sides that thickness is the polyethylene terephthalate film (trade(brand)name " Lumirror S-10 ", TORAY Inc.) of 12 μm.
Thus, produce possess polyethylene terephthalate film and be arranged at the thermal conductivity bonding coat on its two sides and total thickness (except the thickness of release liner (basement membrane).That is, the thickness 12 μm of polyethylene terephthalate film and the thickness 119 μm of each heat conductive adhesive layer.Identical below.) be the thermal conductivity adhesive sheet of 250 μm.It should be noted that, be laminated with basement membrane respectively on the surface of thermal conductivity adhesive sheet and the back side.
Embodiment 2
The cooperation number of partial polymer (slurry) is changed to 95 mass parts, and the cooperation number of oligopolymer is changed to 5 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Embodiment 3
The cooperation number of partial polymer (slurry) is changed to 90 mass parts, and the cooperation number of oligopolymer is changed to 10 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Embodiment 4
The cooperation number of partial polymer (slurry) is changed to 80 mass parts, and the cooperation number of oligopolymer is changed to 20 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Embodiment 5
The cooperation number of partial polymer (slurry) is changed to 75 mass parts, and the cooperation number of oligopolymer is changed to 25 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Embodiment 6
The cooperation number of partial polymer (slurry) is changed to 70 mass parts, and the cooperation number of oligopolymer is changed to 30 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Embodiment 7
The cooperation number of partial polymer (slurry) is changed to 65 mass parts, and the cooperation number of oligopolymer is changed to 35 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Comparative example 1
The cooperation number of partial polymer (slurry) is changed to 60 mass parts, and the cooperation number of oligopolymer is changed to 40 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Comparative example 2
The cooperation number of partial polymer (slurry) is changed to 100 mass parts, and does not coordinate oligopolymer, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Comparative example 3
The cooperation number of partial polymer (slurry) is changed to 100 mass parts, and do not coordinate oligopolymer, in addition, the cooperation number of the dipentaerythritol acrylate as the 2nd monomer is changed to 0.01 mass parts, in addition, aluminum hydroxide particles is not coordinated, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Comparative example 4
The cooperation number of partial polymer (slurry) is changed to 100 mass parts, and do not coordinate oligopolymer, in addition, the cooperation number of the dipentaerythritol acrylate as the 2nd monomer is changed to 0.08 mass parts, in addition, aluminum hydroxide particles is not coordinated, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
Comparative example 5
The cooperation number of partial polymer (slurry) is changed to 100 mass parts, and does not coordinate oligopolymer, in addition, the cooperation number of aluminum hydroxide particles is changed to 500 mass parts, in addition, process similarly to Example 1, make thermal conductivity adhesive sheet.
(evaluation)
(1) mensuration of weight-average molecular weight
The weight-average molecular weight of oligopolymer and superpolymer (not containing the adhesive composition of oligopolymer and thermal conductivity particle) uses GPC device (device name: HLC-8220GPC, Dong Cao Inc.) measure respectively and try to achieve.Condition determination is as follows, is converted obtain weight-average molecular weight by polystyrene standard.
Sample concentration: 0.2mass% (tetrahydrofuran (THF) (THF) solution)
Sample injection rate: 10 μ l
Elutriant: THF
Flow velocity: 0.6ml/min
Measure temperature: 40 DEG C
Post:
Sample column; TSKguardcolumn SuperHZ-H (1)+TSKgel SuperHZM-H (2)
Reference column; TSKgel SuperH-RC (1)
Detector: differential refractometer (RI)
(2) gel fraction (adhesive composition)
Collect thermal conductivity binding compositions and be about 1g, by its accurate weighing.Afterwards, the thermal conductivity binding compositions after accurate weighing is flooded 7 days in ethyl acetate 40g, afterwards, the insoluble composition of ethyl acetate of thermal conductivity binding compositions all reclaims, and by its at 130 DEG C dry 2 hours, tries to achieve dry mass.
In addition, by calculating the quality of the adhesive composition in the thermal conductivity binding compositions after trying to achieve accurate weighing.
Then, by following formula, try to achieve the gel fraction of adhesive composition.
Gel fraction=(quality of the thermal conductivity binding compositions before the dry mass/dipping of the insoluble composition of ethyl acetate) × (quality of the quality/adhesive composition of thermal conductivity binding compositions) × 100 of adhesive composition
(3) skew (confining force) is sheared
After thermal conductivity adhesive sheet being cut into the size of 20mm × 10mm, the basement membrane of side is peeled off from thermal conductivity bonding coat, the release surface of thermal conductivity adhesive sheet is pasted on 25 μm of thick PET film (lining material).
Next, the basement membrane of opposite side is peeled off from thermal conductivity bonding coat, 23 DEG C, under 50%RH environment, upper end 10mm × the 20mm of the release surface of thermal conductivity adhesive sheet is placed in the bottom of stainless steel (SUS304BA) plate, reciprocal 1 time of the roller of use 2kg, adheres to stainless steel plate by thermal conductivity adhesive sheet thus.
Afterwards, under 80 DEG C of environment, leave standstill 30 minutes and after making adhesion (bonding) in stable condition (maintenance), the upper end of fixing stainless steel plate, the weight of 300g is installed in the bottom of thermal conductivity adhesive sheet and PET film (lining material), thermal conductivity adhesive sheet is hung down under the condition of 80 DEG C.Then, under 80 DEG C of environment, measure placement after 1 hour thermal conductivity adhesive sheet relative to stainless steel plate side-play amount (miles of relative movement) as shear skew.
(4) peeling adhesion force (90 degree of stripping tests)
The basement membrane of the side of thermal conductivity adhesive sheet is peeled off from thermal conductivity bonding coat, makes the release surface of thermal conductivity adhesive sheet fit in the PET film (lining material) of thickness 25 μm, be cut into width 20mm, length 150mm.
From thermal conductivity adhesive sheet, the basement membrane of opposite side is peeled off, 23 DEG C, under 50%RH atmosphere, the release surface of thermal conductivity adhesive sheet is pasted on aluminium sheet (#1050), makes 2kg roller on a pet film reciprocal 1 time, thermal conductivity adhesive sheet is pressed on aluminium sheet.
At 23 DEG C, maintenance is after 30 minutes, use universal tensile testing machine " TCM-1kNB " (Minebea Inc.), under the condition of peel angle 90 degree, draw speed 300mm/ minute, measure 90 degree of peeling adhesion forces (stripping strength) when being peeled off from aluminium sheet by thermal conductivity adhesive sheet according to JIS Z 0237.
(5) thermal conductivity and thermal resistance
The mensuration of thermal conductivity and thermal resistance uses the thermal property evaluating apparatus shown in Fig. 2 to implement.
Specifically, a pair block of cubical aluminum (A5052, thermal conductivity: 140W/mK) of length of side 20mm is being formed as (sometimes also referred to as barred body.) sandwich between L each embodiment and each comparative example thermal conductivity adhesive sheet 6 (20mm × 20mm, peel off both sides basement membrane after adhesive sheet), a pair block L thermal conductivity adhesive sheet 6 is fitted.
Then, the mode of presenting lower placement with a pair block L configures this pair block between heating element (heat block) H and radiator (cooling base formed in the mode of internal recycling with water coolant) C.Specifically, above the block L of upside, configure heating element H, at the below of downside block L configuration radiator C.
Now, with thermal conductivity adhesive sheet 6 fit a pair block L between a pair pressure adjusting screw T running through heating element H and radiator C.It should be noted that, be configured with load cell R between pressure adjusting screw T and heating element H, it is formed in the mode that can measure pressure when screwing pressure adjusting screw T, uses this pressure as the pressure putting on thermal conductivity adhesive sheet 6.
Specifically, in this experiment, pressure adjusting screw T is screwed until the pressure putting on thermal conductivity adhesive sheet 6 reaches 25N/cm 2(250kPa).
In addition, 3 probes P (diameter 1mm) of contact displacement meter are set in the mode of the block L and thermal conductivity adhesive sheet 6 that run through downside from radiator C side.Now, form as follows: the state that the upper end of probe P contacts in the lower surface of the block L with upside, the interval (thickness of thermal conductivity adhesive sheet 6) between upper and lower block L can be measured.
Mounting temperature sensor D on heating element H and upper and lower block L.Specifically, at the 1 place mounting temperature sensor D of heating element H, at 5 places of each block L in the vertical direction with 5mm interval mounting temperature sensor D respectively.
Be determined as follows and carry out: first, pressure adjusting screw T is screwed, pressure is applied to thermal conductivity adhesive sheet 6, the temperature of heating element H is set in 80 DEG C, and make the water coolant of circulation 20 DEG C in radiator C.
Then, after the temperature-stable of heating element H and upper and lower block L, the temperature of upper and lower block L is measured with each temperature sensor D, calculate the heat flux (Hot a fluid stream) by thermal conductivity adhesive sheet 6 by the thermal conductivity (W/mK) of upper and lower block L and thermograde, and calculate the temperature at the interface of upper and lower block L and thermal conductivity adhesive sheet 6.Then, use these parameters, utilize following thermal conductivity equation (Fourier's law) to calculate thermal conductivity (W/mK) under this pressure and thermal resistance (cm 2k/W).
Q＝-λgradT
R＝L/λ
Q: the heat flux of per unit area
GradT: thermograde
L: the thickness of sheet
λ: thermal conductivity
R: thermal resistance
The cooperation prescription of the thermal conductivity binding compositions of each embodiment and each comparative example and evaluation are shown in table 1.
Table 1
It should be noted that, foregoing invention provides as illustrative embodiment of the present invention, but they are only illustration, and also non-exclusively explains.The apparent variation of the present invention of those skilled in the art is also contained in the scope of the claim of patent.
Utilizability in industry
Thermal conductivity adhesive sheet is used for the purposes such as semiconductor device, hard disk, LED matrix (televisor, illumination, indicating meter etc.), EL device (OLED display, organic EL illuminating etc.), electrical condenser, battery (lithium ion battery etc.), power module.

Claims (7)

1. a thermal conductivity binding compositions, is characterized in that,
There is the adhesive composition containing superpolymer and oligopolymer and thermal conductivity particle,
The gel fraction determined by following test of described adhesive composition is 28 ~ 59 quality %,
Thermal conductivity is more than 0.3W/mK,
The gel fraction of adhesive composition: thermal conductivity binding compositions is about 1g floods 7 days in ethyl acetate 40g, afterwards, collect the insoluble composition of ethyl acetate of described thermal conductivity binding compositions, and make it dry, the gel fraction of described adhesive composition is tried to achieve by following formula
Gel fraction=(quality of the thermal conductivity binding compositions before the dry mass/dipping of the insoluble composition of ethyl acetate) × (quality of the quality/adhesive composition of thermal conductivity binding compositions) × 100.
2. thermal conductivity binding compositions according to claim 1, is characterized in that,
The shearing skew determined by following test is less than 1.5mm/ hour,
Shear skew: after size thermal conductivity adhesive sheet being cut into 20mm × 10mm, by the lining material be made up of polyethylene terephthalate film fitting in thickness 25 μm perpendicular to the face of in the face of thickness direction of described thermal conductivity adhesive sheet, then, at 23 DEG C, under 50%RH environment, upper end 10mm × the 10mm perpendicular to the another side in the face of thickness direction of described thermal conductivity adhesive sheet part is fitted in the bottom of stainless steel plate, afterwards, leave standstill after within 30 minutes, making fit-state stable under the environment of 80 DEG C, the upper end of fixing described stainless steel plate, the weight of 300g is installed in the bottom of described thermal conductivity adhesive sheet, described thermal conductivity adhesive sheet is hung down under the condition of 80 DEG C, afterwards, measure under the environment of 80 DEG C placement after 1 hour described thermal conductivity adhesive sheet relative to described stainless steel plate side-play amount as shearing skew, wherein, described thermal conductivity adhesive sheet possesses the base material be made up of polyester film of thickness 12 μm, with be laminated in the two sides of described base material and 2 the thermal conductivity bonding coats obtained by sheet thermal conductivity binding compositions being configured as thickness 119 μm.
3. thermal conductivity binding compositions according to claim 1, is characterized in that,
Be more than 5N/20mm by the peeling adhesion force of the peel angle 90 degree of following test determination,
Peeling adhesion force: thermal conductivity adhesive sheet is being machined to width 20mm and by described thermal conductivity adhering adhesive sheet after aluminium sheet, be determined at and be 90 degree relative to the peel angle of described aluminium sheet and peeling rate is that stripping strength when peeling off described thermal conductivity adhesive sheet under the condition of 300mm/ minute is as peeling adhesion force, wherein, described thermal conductivity adhesive sheet is possessed the base material be made up of polyester film of thickness 12 μm and is laminated in the two sides of described base material and 2 the thermal conductivity bonding coats obtained by sheet thermal conductivity binding compositions being configured as thickness 119 μm.
4. thermal conductivity binding compositions according to claim 1, is characterized in that,
Relative to described adhesive composition, being more than 1 quality % and being less than 40 quality % containing proportional of described oligopolymer.
5. thermal conductivity binding compositions according to claim 1, is characterized in that,
The weight-average molecular weight of described oligopolymer is 5.0 × 10 2~ 1.0 × 10 5.
6. thermal conductivity binding compositions according to claim 1, is characterized in that,
Relative to described adhesive composition 100 mass parts, described thermal conductivity particle be less than 500 mass parts containing proportional.
7. thermal conductivity binding compositions according to claim 1, is characterized in that,
Thermal resistance value is less than 10cm 2k/W.
CN201380032607.1A 2012-06-21 2013-06-12 Thermally conductive adhesive composition Pending CN104395424A (en)

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