WO2011096287A1 - 熱伝導性両面粘着シート - Google Patents
熱伝導性両面粘着シート Download PDFInfo
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- WO2011096287A1 WO2011096287A1 PCT/JP2011/051161 JP2011051161W WO2011096287A1 WO 2011096287 A1 WO2011096287 A1 WO 2011096287A1 JP 2011051161 W JP2011051161 W JP 2011051161W WO 2011096287 A1 WO2011096287 A1 WO 2011096287A1
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- sensitive adhesive
- pressure
- adhesive layer
- weight
- meth
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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
- 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
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
- C09J2301/1242—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape the opposite adhesive layers being different
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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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
- 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
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Definitions
- the present invention relates to a double-sided pressure-sensitive adhesive sheet having improved thermal conductivity.
- heat generators such as machines and electronic parts that generate heat have a risk of performance degradation or damage when heat is accumulated inside. Therefore, heat is adhered to the surface to dissipate heat to the outside. By doing so, performance is maintained and damage is prevented.
- the heat-conductive double-sided pressure-sensitive adhesive sheet contains a heat conductive substance in a pressure-sensitive adhesive layer composed of a resin composition.
- the thermal conductivity is improved as compared with the case where the agent layer is formed.
- the adhesive force does not peel off from the adherend due to the force when peeling the release film. It is necessary to have.
- heat treatment such as solder reflow may be performed on the adherend to which the thermally conductive double-sided adhesive sheet is attached, it is necessary to have an adhesive force that does not peel off from the adherend due to the influence of the heat treatment. There is.
- the attachment position between adherends may be misaligned, or bubbles may be mixed between the thermally conductive double-sided adhesive sheet and the adherend. is there.
- Patent Document 1 discloses a heat-conductive double-sided pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer composed of a heat-conductive pressure-sensitive adhesive composition configured to have such an adhesive force.
- the heat conductive double-sided pressure-sensitive adhesive sheet as in Patent Document 1 has a pressure-sensitive adhesive layer formed from a single heat-conductive pressure-sensitive adhesive composition, and has the same adhesive force on both sides.
- the adhesive strength to the adherend is reduced by heating, and the release film on the other surface is peeled off. There is a risk of unintentional peeling from the adherend due to the force of.
- the heat conductive double-sided pressure-sensitive adhesive sheet as described above has low workability when the adherends are bonded or peeled off.
- an object of the present invention is to provide a heat conductive double-sided pressure-sensitive adhesive sheet that can improve workability when adhering adherends to each other or peeling them.
- the heat conductive double-sided pressure-sensitive adhesive sheet comprises a heat conductive double-sided adhesive sheet comprising a pressure-sensitive adhesive layer formed by forming a heat conductive pressure-sensitive adhesive composition containing a heat conductive material and an acrylic polymer component into a sheet shape.
- a pressure-sensitive adhesive layer is laminated.
- the adhesive force applied to the adherend adhered to one surface of the pressure-sensitive adhesive layer is different from the adhesive force applied to the adherend adhered to the other surface.
- the adherend is adhered to the other surface in a state where the adherend is adhered to the one surface. Even when the release film is peeled off, it is possible to prevent unintentional peeling from the adherend. Moreover, it can peel from the adherend affixed on the other surface more easily than the adherend affixed on the one surface. Thereby, workability
- the adhesive strength of one surface cannot be peeled from the adherend
- the adhesive strength of the other surface can be configured to be easily peelable from the adherend. It is possible to select and use which adherend is to be attached to which surface in accordance with the type of wearing body and the use environment.
- the combination of the adhesive strengths of the strong pressure-sensitive adhesive layer and the weak pressure-sensitive adhesive layer can be easily changed. Specifically, for one strong pressure-sensitive adhesive layer (or weak pressure-sensitive adhesive layer), a plurality of weak pressure-sensitive adhesive layers (or strong pressure-sensitive adhesive layers) having different adhesive forces can be selected and laminated, The combination of adhesive strength can be easily changed.
- the strong pressure-sensitive adhesive layer contains less than 150 parts by weight of a heat conductive material with respect to 100 parts by weight of the acrylic polymer component, and the weak pressure-sensitive adhesive layer has a heat resistance of 100 parts by weight of the acrylic polymer component. It is preferable to contain 150 parts by weight or more of a conductive substance.
- the adhesive force with respect to the SUS304 steel plate of the said weak adhesive layer is less than 5.0 N / 20mm, and the adhesive force with respect to the SUS304 steel plate of the said strong adhesive layer is 5.0 N / 20mm or more. preferable.
- the thermally conductive substance is composed of one or two or more substances selected from the group consisting of boron nitride, aluminum hydroxide, and aluminum oxide.
- the thermal conductivity of the strong adhesive layer and the weak adhesive layer is preferably 0.5 W / m ⁇ K or more.
- the heat conductive double-sided pressure-sensitive adhesive sheet according to the present invention comprises a pressure-sensitive adhesive layer in which a heat conductive pressure-sensitive adhesive composition containing a heat conductive material and an acrylic polymer component is formed into a sheet shape.
- a heat conductive pressure-sensitive adhesive composition containing a heat conductive material and an acrylic polymer component
- the heat conductive pressure-sensitive adhesive composition itself is formed into a sheet shape and a pressure-sensitive adhesive layer is formed, or the heat conductive pressure-sensitive adhesive composition is formed into a sheet shape on a support such as a resin film.
- a support such as a resin film.
- Examples thereof include a laminate in which an adhesive layer is formed.
- the heat-conductive double-sided pressure-sensitive adhesive sheet according to the present invention is different in adhesive force to an adherend adhered to one surface of the adhesive layer and adhesive force to an adherend adhered to the other surface. It is configured as follows. Specifically, the pressure-sensitive adhesive layer is formed using two types of thermally conductive pressure-sensitive adhesive compositions configured to have different adhesive forces when formed into a sheet-like pressure-sensitive adhesive layer It is. In the following description, of the two types of thermally conductive pressure-sensitive adhesive compositions, the one that is configured to increase the adhesive strength when it becomes the pressure-sensitive adhesive layer, so that the strong adhesive composition and the adhesive strength become weaker The one configured in the above is referred to as a weak pressure-sensitive adhesive composition.
- the adhesive strength of the adhesive layer formed by each of the adhesive compositions can be adjusted by adjusting the blending amount of the heat conductive substance.
- the thermal conductivity thermal conductivity
- the adhesive strength of the pressure-sensitive adhesive layer can be adjusted, for example, by adjusting the type and molecular weight of the acrylic polymer constituting each pressure-sensitive adhesive composition, or by adjusting the gel fraction of the acrylic polymer. is there.
- the adhesive strength to the SUS304 steel plate is 5.0 N / 20 mm or more, preferably 6.0 N / 20 mm or more, more preferably on one surface (strong adhesion surface). 7.0 N / 20 mm or more, and usually 20 N / 20 mm or less. Further, the other surface (weakly adhesive surface) is configured to be more than 0 N / 20 mm and less than 5.0 N / 20 mm, preferably 4.5 N / 20 mm or less, more preferably 4.3 N / 20 mm or less.
- the “adhesive strength to SUS304 steel plate” is measured by the method described in Examples described later.
- the acrylic polymer component is not particularly limited, and commonly used acrylic polymers can be used.
- the acrylic polymer may be composed of a (meth) acrylic monomer represented by the following general formula (1) as a monomer unit.
- R 1 is hydrogen or a methyl group, and R 2 is an alkyl group having 2 to 14 carbon atoms
- R 1 is hydrogen or a methyl group.
- R 2 is an alkyl group having 2 to 14 carbon atoms, preferably having 3 to 12 carbon atoms, and more preferably 4 to 9 carbon atoms.
- the alkyl group of R 2 can be either linear or branched, and preferably has a branched chain because of its low glass transition point.
- Examples of the (meth) acrylic monomer represented by the general formula (1) include ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, Isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (Meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth)
- the (meth) acrylic monomer represented by the general formula (1) may be used alone or in combination of two or more.
- the total content of the (meth) acrylic monomer is 50 to 98% by weight, preferably 60 to 98% by weight, and preferably 70 to 90% by weight with respect to the whole monomer constituting the acrylic polymer. % Is more preferable.
- the content of the (meth) acrylic monomer By setting the content of the (meth) acrylic monomer to 50% by weight or more, it has good adhesiveness.
- the acrylic polymer preferably contains a polar group-containing monomer such as a hydroxyl group-containing monomer or a carboxyl group-containing monomer as a monomer unit.
- the content of the polar group-containing monomer is preferably from 0.1 to 20% by weight, more preferably from 0.2 to 10% by weight, more preferably from 0.1 to 20% by weight, based on the whole monomer constituting the acrylic polymer. More preferably, it is 2 to 7% by weight.
- the content of the polar group-containing monomer is within the above range, the cohesive force is more fully exhibited. Moreover, it will have favorable adhesiveness by content of the said polar group containing monomer being 20 weight% or less.
- the above hydroxyl group-containing monomer refers to a polymerizable monomer having one or more hydroxyl groups in the monomer structure.
- 4-hydroxybutyl (meth) 4-hydroxy
- the above carboxyl group-containing monomer means a polymerizable monomer having one or more carboxyl groups in the monomer structure.
- the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Of these, acrylic acid and methacrylic acid are preferably used.
- monomers other than the above-mentioned monomers can be used within a range that does not impair the effects of the present invention.
- monomers other than the above monomers include polymerizable monomers for adjusting the glass transition point and peelability of the acrylic polymer.
- a cohesive strength / heat resistance improving component As the other polymerizable monomer used in the acrylic polymer of the present invention, a cohesive strength / heat resistance improving component, an adhesive strength improving component, or a component having a functional group acting as a crosslinking base can be appropriately used.
- the cohesive strength / heat resistance improving component include sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, and the like.
- the adhesive strength improving component include amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, epoxy group-containing monomers, and vinyl ether monomers.
- a monomer or the like in which R 2 is an alkyl group having 1 or 15 carbon atoms can be used as appropriate. These monomer compounds may be used alone or in admixture of two or more.
- sulfonic acid group-containing monomer examples include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth).
- Examples of the phosphate group-containing monomer include 2-hydroxyethyl acryloyl phosphate.
- Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- vinyl ester monomer examples include vinyl acetate, vinyl propionate, vinyl laurate, vinyl pyrrolidone and the like.
- aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and the like.
- amide group-containing monomers examples include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diethylmethacrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, diacetone (meth) ) Acrylamide, N-vinylacetamide, N, N′-methylenebis (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-vinylcaprolactam, N-vinyl-2-pyrrolidone and the like.
- amino group-containing monomers examples include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- (meth) acryloylmorpholine, and the like. It is done.
- Examples of the imide group-containing monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, and itaconimide.
- epoxy group-containing monomer examples include glycidyl (meth) acrylate and allyl glycidyl ether.
- vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and the like.
- Examples of the (meth) acrylic monomer having an alkyl group having 1 or 15 carbon atoms include methyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl (meth) acrylate. It is done.
- the monomer constituting the acrylic polymer may contain other copolymerizable monomers as necessary in order to enhance characteristics such as cohesive force.
- copolymerizable monomers include vinyl compounds, (meth) acrylic acid esters of cyclic alcohols, and (meth) acrylic acid esters of polyhydric alcohols.
- vinyl compound include vinyl acetate, styrene, vinyl toluene, and the like.
- cyclic alcohol (meth) acrylic acid esters include cyclopentyl di (meth) acrylate and isobornyl (meth) acrylate.
- (Meth) acrylic acid esters of polyhydric alcohols include neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol Examples include methanetri (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
- the other copolymerizable monomers may be used singly or in combination of two or more, but the total content is 0 with respect to the whole monomer constituting the acrylic polymer. It is preferably ⁇ 50% by weight, more preferably 0 to 35% by weight, even more preferably 0 to 25% by weight.
- the acrylic polymer preferably has a weight average molecular weight of 600,000 or more, more preferably 700,000 to 3,000,000, and even more preferably 800,000 to 2,500,000.
- the weight average molecular weight is 600,000 or more, it has good durability.
- the weight average molecular weight is preferably 3 million or less.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
- the glass transition temperature (Tg) of the above acrylic polymer is desirably ⁇ 5 ° C. or less, preferably ⁇ 10 ° C. or less, for the reason that it is easy to balance the adhesiveness of the adhesive layer.
- the glass transition temperature is ⁇ 5 ° C. or less, the acrylic polymer has good fluidity and sufficient wettability with respect to the adherend, and has good adhesive strength.
- the glass transition temperature (Tg) of the acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and composition ratio to be used.
- Such an acrylic polymer can be produced by a known production method such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations. Further, the obtained acrylic polymer may be a homopolymer or a copolymer, and when it is a copolymer, it may be any of a random copolymer, a block copolymer, a graft copolymer, and the like. .
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out under an inert gas stream such as nitrogen, as a polymerization initiator, for example, azobisisobutyronitrile 0.01 to 0.2 parts per 100 parts by weight of the total amount of monomers Addition of parts by weight is usually carried out at about 50 to 70 ° C. for about 8 to 30 hours.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited, and can be appropriately selected and used.
- Examples of the polymerization initiator used in the present invention include azo initiators, persulfates, peroxide initiators, and redox initiators in which a peroxide and a reducing agent are combined. It is not limited.
- Examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl- 2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2, And 2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.).
- persulfate examples include potassium persulfate and ammonium persulfate.
- peroxide initiators include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butyl peroxyneo.
- Decanoate t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethyl hexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane, t-butyl hydroperoxide, peroxy
- Examples thereof include hydrogen oxide.
- the redox initiator include a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, and the like.
- the above polymerization initiators may be used alone or in combination of two or more.
- the content of the polymerization initiator as a whole is preferably about 0.005 to 1 part by weight and more preferably about 0.02 to 0.5 part by weight with respect to 100 parts by weight of the monomer.
- a chain transfer agent may be used in the polymerization.
- a chain transfer agent By using a chain transfer agent, the molecular weight of the acrylic polymer can be appropriately adjusted.
- chain transfer agents examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- chain transfer agents may be used alone or in combination of two or more.
- the content of the chain transfer agent as a whole is usually about 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the monomer.
- an emulsifier used for emulsion polymerization an anionic emulsifier, a nonionic emulsifier, or the like can be used.
- anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and the like.
- nonionic emulsifier examples include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, and the like. These emulsifiers may be used alone or in combination of two or more.
- reactive emulsifiers as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, for example, Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE10N (manufactured by ADEKA) and the like can be used.
- Reactive emulsifiers are preferred because they are incorporated into the polymer chain after polymerization and thus improve water resistance.
- the amount of the emulsifier used is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the monomer, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
- a crosslinking agent as a component constituting the acrylic polymer in the heat conductive pressure-sensitive adhesive composition.
- a crosslinking agent such as an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an aziridine crosslinking agent, or a metal chelate crosslinking agent may be used.
- aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate
- alicyclic isocyanates such as isophorone diisocyanate
- aliphatic isocyanates such as hexamethylene diisocyanate, and the like
- examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates, alicyclic isocyanates, aromatic diisocyanates, isocyanate adducts, adducts with various polyols, polyfunctionalized polyisocyanates, and the like. Can be used.
- examples of the lower aliphatic polyisocyanates include butylene diisocyanate and hexamethylene diisocyanate.
- examples of alicyclic isocyanates include cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate.
- Aromatic diisocyanates include 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, and the like.
- isocyanate adduct trimethylolpropane / tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., Product name Coronate HL), isocyanurate of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name Coronate HX), and the like.
- Examples of adducts with various polyols include polyether polyisocyanates, polyester polyisocyanates, and adducts of these with various polyols.
- Examples of the polyfunctionalized polyisocyanate include polyisocyanates polyfunctionalized with isocyanurate bonds, burette bonds, allophanate bonds, and the like.
- the above crosslinking agents may be used alone or in combination of two or more.
- the content of the entire crosslinking agent is preferably 0.02 to 5 parts by weight, more preferably 0.04 to 3 parts by weight, and 0.05 to 2 parts by weight with respect to 100 parts by weight of the acrylic polymer. More preferably.
- the addition amount of the crosslinking agent so that the gel fraction of the crosslinked thermally conductive pressure-sensitive adhesive composition is 40 to 90% by weight, and 50 to 85% by weight. It is more preferable to adjust to 55 to 80% by weight.
- the gel fraction By setting the gel fraction to 40% by weight or more, the cohesive force is improved and the durability is good. Moreover, it will have favorable adhesiveness by setting it as 90 weight% or less.
- the gel fraction (% by weight) was obtained by taking a dry weight W1 (g) sample from the crosslinked thermally conductive adhesive composition, immersing it in ethyl acetate, and then removing the insoluble content of the sample from ethyl acetate.
- the weight W2 (g) after taking out from the inside and drying can be measured, and (W2 / W1) ⁇ 100 can be calculated and obtained.
- the heat conductive substance can improve the heat conductivity of the heat conductive double-sided pressure-sensitive adhesive sheet by being contained in the pressure-sensitive adhesive layer.
- the thermal conductive material used in the present invention is not particularly limited, but boron nitride, aluminum nitride, silicon nitride, gallium nitride, aluminum hydroxide, magnesium hydroxide, silicon carbide, silicon dioxide, aluminum oxide, Titanium oxide, zinc oxide, tin oxide, copper oxide, nickel oxide, antimonic acid doped tin oxide, calcium carbonate, barium titanate, potassium titanate, copper, silver, gold, nickel, aluminum, platinum, carbon black, carbon tube ( Carbon nanotube), carbon fiber, diamond and the like.
- boron nitride, aluminum hydroxide, and aluminum oxide are preferably used because they have high thermal conductivity and electrical insulation. These heat conductive substances may be used alone or in combination of two or more.
- the shape of the heat conductive material used in the present invention is not particularly limited, and may be granular, needle shape, plate shape, or layer shape.
- the granular shape includes, for example, a spherical shape, a rectangular parallelepiped shape, a crushed shape, or a deformed shape thereof.
- the primary average particle diameter is 0.1 to 1000 ⁇ m, preferably 1 to 100 ⁇ m, more preferably 2 to 20 ⁇ m.
- the primary average particle diameter is a volume-based value obtained by the particle size distribution measurement method in the laser scattering method. Specifically, it is calculated
- the maximum length is 0.1 to 1000 ⁇ m, preferably 1 to 100 ⁇ m, more preferably 2 to 20 ⁇ m.
- the maximum length is 0.1 to 1000 ⁇ m or less, agglomeration between needle-shaped or plate-shaped thermally conductive substances is suppressed, and handling becomes easy.
- these aspect ratios in the case of acicular crystals, they are expressed as major axis length / minor axis length, or major axis length / thickness.
- the diagonal length is also expressed. / Expressed in thickness / long side length / thickness) is 1 to 10,000, preferably 10 to 1,000.
- heat conductive material commonly used materials can be used.
- boron nitride “HP-40” manufactured by Mizushima Alloy Iron Company, “PT620” manufactured by Momentive Company, etc.
- aluminum oxide “Hijilite H-32” and “Hijilite H-42” manufactured by Showa Denko Co., Ltd., as aluminum oxide “AS-50” manufactured by Showa Denko Co., Ltd., and as magnesium hydroxide, Kyowa.
- KISUMA 5A manufactured by Chemical Industries, Ltd.
- antimony-doped tin oxide such as “SN-100S”, “SN-100P”, “SN-100D (water dispersion)” manufactured by Ishihara Sangyo Co., Ltd.
- titanium oxide Uses “TTO series” manufactured by Ishihara Sangyo Co., Ltd., and “ZnO-310” “SnO-350” “SnO-410” manufactured by Sumitomo Osaka Cement Co., Ltd. It is possible.
- the amount of the thermally conductive material used is appropriately selected according to the adhesive strength when the thermally conductive adhesive composition is formed into a sheet to form an adhesive layer.
- the heat conductive material is preferably less than 150 parts by weight with respect to 100 parts by weight of the acrylic polymer, more preferably 10 to 150 parts by weight. The amount is preferably 50 to 130 parts by weight.
- the heat conductive material is preferably 150 parts by weight or more, more preferably 150 to 1000 parts by weight, with respect to 100 parts by weight of the acrylic polymer. More preferably, the amount is ⁇ 600 parts by weight.
- a silane coupling agent is used for the purpose of improving the affinity between the heat conductive substance and the acrylic polymer, or for improving the adhesive strength and durability of the adhesive layer.
- the silane coupling agent is not particularly limited, and a known silane coupling agent can be appropriately selected and used.
- silane coupling agent examples include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a (meth) acrylic group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.
- epoxy group-containing silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane and the like.
- amino group-containing silane coupling agents examples include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3- And dimethylbutylidene) propylamine.
- examples of the (meth) acryl group-containing silane coupling agent include 3-acryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.
- isocyanate group-containing silane coupling agent examples include 3-isocyanatopropyltriethoxysilane. Use of such a silane coupling agent is preferable for improving durability.
- the above silane coupling agents may be used alone or in combination of two or more.
- the total content of the silane coupling agent is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight with respect to 100 parts by weight of the acrylic polymer. 0.05 to 2 parts by weight is more preferable.
- the silane coupling agent in the above range the cohesive force and durability can be improved more reliably.
- the surface of a particulate-form heat conductive substance can fully be coat
- a tackifier resin can be used for the purpose of further improving the pressure-sensitive adhesive strength and durability of the pressure-sensitive adhesive layer.
- the tackifier resin is not particularly limited, and a known one can be appropriately selected and used. Examples of tackifying resins include rosin resins, terpene resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, alicyclic petroleum resins, xylene resins, and elastomers. Can do.
- the content of the tackifying resin is preferably 10 to 100 parts by weight, more preferably 20 to 80 parts by weight, and more preferably 30 to 50 parts by weight with respect to 100 parts by weight of the acrylic polymer. More preferably, it is any part by weight.
- the heat conductive pressure-sensitive adhesive composition includes those generally used as rubber or plastic compounding chemicals. It can add suitably in the range which does not impair an effect.
- rubber and plastic compounding chemicals include dispersants, antioxidants, antioxidants, processing aids, stabilizers, antifoaming agents, flame retardants, thickeners, and pigments.
- an acrylic polymer component composed of the components as described above, a heat conductive material, and other components are mixed in a solvent such as toluene and stirred to obtain a liquid heat conductive adhesive composition.
- a solvent such as toluene
- Two types specifically, a solution of a strong pressure-sensitive adhesive composition and a solution of a weak pressure-sensitive adhesive composition
- a dispersant may be contained in order to improve dispersibility.
- the two types of coating liquids are blended so that the content of the heat conductive material with respect to the acrylic polymer is different, and are configured so as to have different adhesive forces in the state of being formed into a sheet and forming an adhesive layer. ing. That is, a pressure-sensitive adhesive layer (strong pressure-sensitive adhesive layer) is formed by one coating liquid (strong pressure-sensitive adhesive composition solution), and a pressure-sensitive adhesive force is formed by the other coating liquid (weak pressure-sensitive adhesive composition solution). A weak adhesive layer (weak adhesive layer) will be formed.
- the two kinds of coating liquids are respectively applied onto a release film having one surface treated with a release agent (silicone or the like).
- a release agent silicone or the like.
- one coating liquid strong adhesion coating liquid
- the other coating liquid weak adhesive coating liquid
- a conventionally widely used method can be employed. For example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, extrusion coat method by die coater, etc. The method can be used.
- the thickness of the pressure-sensitive adhesive layer formed on the release film is preferably 0.5 to 250 ⁇ m, more preferably 2.5 to 100 ⁇ m, and even more preferably 5 to 50 ⁇ m.
- the thermal conductivity of the strong adhesive layer and the weak adhesive layer is preferably 0.5 W / m ⁇ K or more, and more preferably 0.6 W / m ⁇ K or more. When the thermal conductivity is 0.5 W / m ⁇ K or more, for example, even when it is used by being adhered to a heat sink or the like of a semiconductor module, sufficient thermal conductivity can be exhibited.
- the constituent material of the release film includes a plastic film, a porous material, and a thin body such as a laminate, and a plastic film is preferably used from the viewpoint of excellent surface smoothness.
- a plastic film include polyethylene, polypropylene, and polyethylene terephthalate.
- the porous material include paper, cloth, and non-woven fabric.
- the laminate include nets, foam sheets, metal foils, and laminates thereof.
- the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
- a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, A vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like can be used.
- the release film may be subjected to release treatment, antifouling treatment, and antistatic treatment as necessary.
- the release treatment and the antifouling treatment include those using a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent or silica powder.
- the antistatic treatment include a coating type, a kneading type, and a vapor deposition type.
- the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.
- the thickness of the release film is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- a release film with a strong pressure-sensitive adhesive layer and a release film with a weak pressure-sensitive adhesive layer are laminated so that the pressure-sensitive adhesive layers overlap each other.
- the adhesive strength of the surface on the strong adhesive layer side strong adhesive surface
- the adhesive strength of the surface on the weak adhesive layer side weak adhesive surface
- both sides are thermally conductive with release films attached to both sides.
- the thickness of the pressure-sensitive adhesive layer formed by laminating the strong pressure-sensitive adhesive layer and the weak pressure-sensitive adhesive layer is preferably 1 to 500 ⁇ m, more preferably 5 to 200 ⁇ m, and further preferably 10 to 100 ⁇ m. preferable.
- a support may be disposed between the strong pressure-sensitive adhesive layer and the weak pressure-sensitive adhesive layer.
- Examples of the support include a plastic substrate, a porous material, and a metal foil.
- Examples of the plastic substrate include polyethylene terephthalate (PET) and polyester film.
- Examples of the porous material include paper and non-woven fabric.
- the plastic substrate is not particularly limited as long as it can be formed into a sheet or film, and examples thereof include polyolefin film, polyester film, polyamide film, polyvinyl chloride film, polyvinylidene chloride film, and polycarbonate film. It is done.
- the thickness of the film is usually about 4 to 100 ⁇ m, preferably about 4 to 25 ⁇ m.
- the polyolefin film include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and ethylene / vinyl acetate copolymer.
- polyester film examples include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.
- polyamide film examples include polyacrylate film, polystyrene film, nylon 6, nylon 6,6, and partially aromatic polyamide.
- the plastic substrate can be subjected to a release treatment, an antifouling treatment, an easy adhesion treatment, and an antistatic treatment as necessary.
- the release treatment and antifouling treatment include those using a silicone, fluorine, long chain alkyl or fatty acid amide release agent, silica powder, and the like.
- the easy adhesion treatment include acid treatment, alkali treatment, primer treatment, corona treatment, plasma treatment, and ultraviolet treatment.
- the antistatic treatment include a coating type, a kneading type, and a vapor deposition type.
- the heat conductive double-sided pressure-sensitive adhesive sheet configured as described above has different adhesive force to the adherend adhered to one surface of the adhesive layer and adhesive force to the adherend adhered to the other surface.
- the adherends affixed on both surfaces can be adhere
- the adhesive strength of one surface is configured to be strong enough not to be peeled from the adherend, the adhesive strength of the other surface is weak enough to be easily peelable from the adherend. According to the type of the adherend and the usage environment, it is possible to select and use which adherend is to be attached to which surface.
- Example 1 Preparation of acrylic polymer solution In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 70 parts by weight of butyl acrylate, 30 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, 0.05 parts of 4-hydroxybutyl acrylate After adding parts by weight, 0.1 part by weight of 2,2′-azobisisobutyronitrile (initiator) and 155 parts by weight of toluene, the system was sufficiently replaced with nitrogen gas. And it heated at 80 degreeC for 3 hours, and obtained the acrylic polymer solution whose solid content is 40.0 weight%.
- thermal conductive weak adhesive composition 100 parts by weight of the above acrylic polymer solution, 30 parts by weight of a tackifier (trade name “Bencel D-125”, manufactured by Arakawa Chemical Co., Ltd.), thermal conductivity 200 parts by weight of thermally conductive aluminum hydroxide powder (trade name “Hijilite H-32” manufactured by Showa Denko KK) as a substance, 1 part by weight of a dispersant (trade name “Plysurf A212E” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Then, 2 parts by weight of a polyfunctional isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”) was blended as a cross-linking agent, and a weak adhesive coating solution was prepared by stirring with a disper for 15 minutes.
- a tackifier trade name “Bencel D-125”, manufactured by Arakawa Chemical Co., Ltd.
- the ratio of the heat conductive substance in the strong pressure-sensitive adhesive layer after drying is 29% by volume, and the ratio of the heat conductive substance in the weak pressure-sensitive adhesive layer is 45% by volume.
- it is composed of a strong adhesive layer and a weak adhesive layer by laminating a release film with a strong adhesive layer and a release film with a weak adhesive layer so that the strong adhesive layer and the weak adhesive layer overlap.
- a pressure-sensitive adhesive sheet provided with the prepared pressure-sensitive adhesive layer was produced.
- a release film is stuck on both surfaces of the pressure-sensitive adhesive sheet.
- Example 2 An adhesive sheet was prepared under the same conditions as in Example 1 except that 400 parts by weight of thermally conductive aluminum hydroxide powder was used for 100 parts by weight of the acrylic polymer when preparing the weakly adhesive coating solution. The ratio of the heat conductive substance which occupies for the weak adhesive layer after drying is 45 volume%.
- Example 1 The pressure-sensitive adhesive coating solution of Example 1 was applied on a release film so that the thickness after drying was 100 ⁇ m, and dried at 70 ° C. for 15 minutes to produce a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer consisting only of a strong pressure-sensitive adhesive layer. did.
- Example 2 A weakly adhesive coating solution of Example 2 was applied on a release film so that the thickness after drying was 100 ⁇ m, and dried at 70 ° C. for 15 minutes to produce an adhesive sheet comprising an adhesive layer consisting of only a weak adhesive layer. did.
- Measurement 1 A PET film having a thickness of 25 ⁇ m was bonded to the surface on the weak adhesive layer side (weak adhesive surface) in the adhesive sheet of each example, and this was cut into a width of 20 mm and a length of 150 mm to prepare a measurement sample. Next, the release film was peeled off from the surface on the side of the strong adhesive layer (strong adhesive surface), and the measurement sample was attached to the SUS304 steel plate by a reciprocating 2 kg roller at 23 ° C. and 50% RH atmosphere. And the SUS304 steel plate with which this sample for evaluation was affixed was cured at 23 degreeC for 30 minutes. The SUS304 steel plate is polished with No.
- Measurement 2 A PET film having a thickness of 25 ⁇ m was bonded to the strong adhesive surface of the adhesive sheet of each example, and this was cut into a width of 20 mm and a length of 150 mm to obtain a measurement sample, and measurement of the adhesive strength of the weak adhesive surface was measured. The same conditions were used. The measurement results are shown in Table 1 below.
- Measurement 3 A PET film having a thickness of 25 ⁇ m was bonded to one side of the pressure-sensitive adhesive sheet of each comparative example, and this was cut into a width of 20 mm and a length of 150 mm to obtain a measurement sample, and the measurement of the adhesive strength of the other side was measured. 1 and the same conditions. The measurement results are shown in Table 1 below.
- Measurement 4 A PET film having a thickness of 25 ⁇ m was bonded to the other surface of the pressure-sensitive adhesive sheet of each comparative example, and this was cut into a width of 20 mm and a length of 150 mm to obtain a measurement sample. 1 and the same conditions. The measurement results are shown in Table 1 below.
- Measurement 1 The thermal conductivity of the strong pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of each example and each comparative example was measured. The thermal conductivity is obtained by obtaining the thermal diffusivity using the product name “ai-phase mobile” manufactured by Eye Phase Co., Ltd., and multiplying the thermal diffusivity by the heat capacity per unit volume of the pressure-sensitive adhesive sheet measured with a differential scanning calorimeter (DSC) Calculated by The measurement results are shown in Table 2 below.
- DSC differential scanning calorimeter
- Measurement 2 The measurement of the thermal conductivity of the weak pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of each example was performed in the same manner as Measurement 1. The measurement results are shown in Table 2 below.
- ⁇ Adhesive property evaluation> 1 Preparation of sample for evaluation After peeling off the release film attached to the strong adhesive surface in the adhesive sheet of each example and attaching the glass epoxy substrate to the strong adhesive surface, peel off the release film attached to the weak adhesive surface. A sample for evaluation was prepared by attaching a SUS304 rigid plate to the weakly adhesive surface. Moreover, after peeling off the peeling film stuck on one side of the pressure-sensitive adhesive sheet of each comparative example and sticking the glass epoxy substrate on one side, the peeling film stuck on the other side is peeled off and the other side A sample for evaluation was prepared by attaching a SUS304 rigid plate to the plate.
- the pressure-sensitive adhesive sheet of Comparative Example 1 is composed of only the strong pressure-sensitive adhesive layer, and thus the adhesive strength on both sides is strong. And could not be easily peeled off. Moreover, since the adhesive layer is comprised only from the weak adhesive layer, the adhesive sheet of the comparative example 2 has weak adhesive force of both surfaces, and the other surface peels in the state affixed on the glass epoxy board
- the adhesive sheets of Examples 1 and 2 have a strong adhesive surface with a stronger adhesive strength than that of the weak adhesive surface, the weakly adhesive surface is adhered to the glass epoxy substrate. Even when the release film on the surface was peeled off, the adhesive sheet was not peeled off from the glass epoxy substrate. Furthermore, since the adhesive strength of the weak adhesive surface was weak, the glass epoxy substrate and SUS304 could be easily peeled off. That is, the pressure-sensitive adhesive sheets of Examples 1 and 2 can improve the workability when adhering adherends to each other or peeling them.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
Description
なお、1次平均粒子径は、レーザー散乱法における粒度分布測定法によって求められる体積基準の値である。具体的には、レーザー散乱式粒度分布計により、D50値を測定することによって求められるものである。
1.アクリルポリマー溶液の調整
冷却管、窒素導入管、温度計および攪拌機を備えた反応容器に、アクリル酸ブチル70重量部、2エチルヘキシルアクリレート30重量部、アクリル酸3重量部、4ヒドロキシブチルアクリレート0.05重量部、2,2’-アゾビスイソブチロニトリル(開始剤)0.1重量部、トルエン155重量部を加えた後、系内を窒素ガスで十分に置換した。そして、80℃で3時間加熱して固形分が40.0重量%のアクリルポリマー溶液を得た。
上記アクリルポリマー溶液100重量部に、粘着付与材(荒川化学社製、商品名「ベンセルD-125」)30重量部、熱伝導性物質として熱伝導性水酸化アルミ粉末(昭和電工社製、商品名「ハイジライトH-32」、1次平均粒子径8μm)100重量部、分散剤(第一工業製薬社製、商品名「プライサーフA212E」)1重量部、架橋剤として多官能イソシアネート化合物(日本ポリウレタン工業社製、商品名「コロネートL」)2重量部を配合し、ディスパーにて15分間攪絆して強粘着コーティング液を調整した。
上記アクリルポリマー溶液100重量部に、粘着付与材(荒川化学社製、商品名「ベンセルD-125」)30重量部、熱伝導性物質として熱伝導性水酸化アルミ粉末(昭和電工社製、商品名「ハイジライトH-32」)200重量部、分散剤(第一工業製薬社製、商品名「プライサーフA212E」)1重量部、架橋剤として多官能イソシアネート化合物(日本ポリウレタン工業社製、商品名「コロネートL」)2重量部を配合し、ディスパーにて15分間攪絆して弱粘着コーティング液を調整した。
ポリエチレンテレフタレートの片面をシリコーン剥離剤で処理した剥離フィルムの剥離処理面に、得られた強粘着コーティング液を乾燥後の厚みが50μmとなるよう塗布し、70℃で15分間乾燥して剥離フィルム上に強粘着剤層を形成した。また、他の離型フィルムの剥離処理面に、得られた弱粘着コーティング液を乾燥後の厚みが50μmとなるよう塗布し、70℃で15分間乾燥して剥離フィルム上に弱粘着剤層を形成した。
乾燥後の強粘着剤層に占める熱伝導性物質の割合は、29体積%であり、弱粘着剤層に占める熱伝導性物質の割合は、45体積%である。
そして、強粘着剤層と弱粘着剤層とが重なり合うように、強粘着剤層付き剥離フィルムと弱粘着剤層付き剥離フィルムとを積層させて、強粘着剤層と弱粘着剤層とから構成された粘着剤層を備える粘着シートを作製した。該粘着シートの両面には、剥離フィルムが貼付いた状態となっている。
弱粘着コーティング液を調整するに際し、アクリルポリマー100重量部に対して、熱伝導性水酸化アルミ粉末を400重量部用いてしたこと以外は、実施例1と同一条件で粘着シートを作成した。乾燥後の弱粘着剤層に占める熱伝導性物質の割合は、45体積%である。
実施例1の強粘着コーティング液を乾燥後の厚みが100μmとなるように剥離フィルム上に塗布し、70℃で15分間乾燥して強粘着剤層のみからなる粘着剤層を備える粘着シートを作製した。
実施例2の弱粘着コーティング液を乾燥後の厚みが100μmとなるように剥離フィルム上に塗布し、70℃で15分間乾燥して弱粘着剤層のみからなる粘着剤層を備える粘着シートを作製した。
1.測定1
各実施例の粘着シートにおける弱粘着剤層側の面(弱粘着面)に、厚さ25μmのPETフィルムを貼り合わせ、これを幅20mm、長さ150mmに切断して測定用サンプルを作製した。
次に、強粘着剤層側の面(強粘着面)から剥離フィルムを剥がし、測定用サンプルを23℃、50%RH雰囲気下でSUS304鋼板に2kgローラー1往復により貼り付けた。そして、この評価用サンプルが貼り付けられたSUS304鋼板を23℃で30分間養生した。
なお、前記SUS304鋼板は、粘着シートを貼り付ける前に、その表面を360番の耐水研磨紙で研磨処理し、さらに、トルエンでの脱脂を十分に施した後に、23℃、50%RHの雰囲気下で30分乾燥後に用いた。
養生後、ミネベア株式会社製 万能引張試験機「TCM-1kNB」を用いて剥離試験を行ない、SUS304鋼板に対する強粘着面の粘着力の測定を行なった。剥離試験の条件としては、剥離角度180°、剥離速度300mm/分で試験を行った。測定結果は、下記表1に示す。
各実施例の粘着シートにおける強粘着面に、厚さ25μmのPETフィルムを貼り合わせ、これを幅20mm、長さ150mmに切断して測定用サンプルとし、弱粘着面の粘着力の測定を測定1と同一条件で行なった。測定結果は、下記表1に示す。
各比較例の粘着シートにおける一方の面に、厚さ25μmのPETフィルムを貼り合わせ、これを幅20mm、長さ150mmに切断して測定用サンプルとし、他方の面の粘着力の測定を、測定1と同一条件で行なった。測定結果は、下記表1に示す。
各比較例の粘着シートにおける他方の面に、厚さ25μmのPETフィルムを貼り合わせ、これを幅20mm、長さ150mmに切断して測定用サンプルとし、一方の面の粘着力の測定を、測定1と同一条件で行なった。測定結果は、下記表1に示す。
1.測定1
各実施例、各比較例の粘着シートにおける強粘着剤層の熱伝導率の測定を行なった。熱伝導率は、アイフェイズ社製 商品名「ai-phase mobile」により熱拡散率を求め、該熱拡散率に示差走査熱量計(DSC)で測定した粘着シートの単位体積あたりの熱容量を乗じることにより算出した。測定結果は、下記表2に示す。
1.評価用サンプルの作製
各実施例の粘着シートにおける強粘着面に貼付けられている剥離フィルムを剥がして強粘着面にガラスエポキシ基板を貼付けた後、弱粘着面に貼付けられている剥離フィルムを剥がして弱粘着面にSUS304剛板を貼付けて評価用サンプルを作製した。
また、各比較例の粘着シートの一方の面に貼付けられている剥離フィルムを剥がして一方の面にガラスエポキシ基板を貼付けた後、他方の面に貼付けられている剥離フィルムを剥がして他方の面にSUS304剛板を貼付けて評価用サンプルを作製した。
粘着シートがガラスエポキシ基板に貼付けられた状態で、弱粘着面または他方の面に貼付いている剥離フィルムを剥がした際に、ガラスエポキシ基板から粘着シートが剥がれてしまうか否かについて評価を行なった。
また、それぞれの評価用サンプルを80℃で24時間加熱処理した後、ガラスエポキシ基板をSUS304剛板から剥離させた際の状態についても評価を行なった。
剥離フィルムを剥がす際に、ガラスエポキシ基板から粘着シートが剥がれなかったものであって、ガラスエポキシ基板とSUS304剛板との剥離を容易に行なうことができたものを「○」、剥離フィルムを剥がす際に、ガラスエポキシ基板から粘着シートが剥がれてしまったり、ガラスエポキシ基板とSUS304剛板との剥離を容易に行なえなかったりした場合を「×」として評価した。評価結果は、下記表3に示す。
これらに対し、実施例1及び2の粘着シートは、強粘着面の粘着力が弱粘着面の粘着力よりも強くなっているため、強粘着面がガラスエポキシ基板に貼付けられた状態で弱粘着面の剥離フィルムを剥がす際にもガラスエポキシ基板から粘着シートが剥がれることがなかった。さらに、弱粘着面の粘着力が弱いものであるため、ガラスエポキシ基板とSUS304とを容易に剥離させることができた。つまり、実施例1及び2の粘着シートは、被着体同士を貼合せたり剥離させたりする際の作業性を向上させることが可能となった。
Claims (6)
- 熱伝導性物質とアクリルポリマー成分とが含有されている熱伝導性粘着剤組成物がシート状に成形されてなる粘着剤層を備える熱伝導性両面粘着シートであって、
被着体に対する一方の面の粘着力が他方の面の粘着力よりも強くなるように、前記一方の面を形成する強粘着剤層と前記他方の面を形成する弱粘着剤層とが積層されてなることを特徴とする熱伝導性両面粘着シート。 - 前記強粘着剤層は、アクリルポリマー成分100重量部に対し、熱伝導性物質を150重量部未満含有していると共に、前記弱粘着剤層は、アクリルポリマー成分100重量部に対し、熱伝導性物質を150重量部以上含有していることを特徴とする請求項1に記載の熱伝導性両面粘着シート。
- 前記弱粘着剤層のSUS304鋼板に対する粘着力は、5.0N/20mm未満であることを特徴とする請求項1又は2に記載の熱伝導性両面粘着シート。
- 前記強粘着剤層のSUS304鋼板に対する粘着力は、5.0N/20mm以上であることを特徴とする請求項1又は2に記載の熱伝導性両面粘着シート。
- 前記熱伝導性物質は、窒化ホウ素、水酸化アルミニウム、および酸化アルミニウムからなる群より選択される1つ又は2つ以上の物質から構成されてなることを特徴とする請求項1又は2に記載の熱伝導性両面粘着シート。
- 前記強粘着剤層及び弱粘着剤層の熱伝導率は、0.5W/m・K以上であることを特徴とする請求項1又は2に記載の熱伝導性両面粘着シート。
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CN2011800083649A CN102753637A (zh) | 2010-02-04 | 2011-01-24 | 导热性双面粘合片 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012046710A1 (ja) * | 2010-10-07 | 2012-04-12 | 株式会社日本触媒 | 熱伝導性粘着剤 |
JP2013177564A (ja) * | 2012-02-08 | 2013-09-09 | Nitto Denko Corp | 熱伝導性シート、熱伝導性シート形成用粒子集合物粉体、および、これらの製造方法 |
WO2014157378A1 (ja) * | 2013-03-28 | 2014-10-02 | デクセリアルズ株式会社 | 熱伝導性シート |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10316953A (ja) | 1997-05-16 | 1998-12-02 | Nitto Denko Corp | 剥離可能な熱伝導性感圧接着剤とその接着シ―ト類 |
JP2002194306A (ja) * | 2000-12-26 | 2002-07-10 | Sekisui Chem Co Ltd | 熱伝導性シート |
JP2003183500A (ja) * | 2001-12-21 | 2003-07-03 | Kitagawa Ind Co Ltd | 熱伝導シート及びその製造方法 |
JP2006137833A (ja) * | 2004-11-11 | 2006-06-01 | Kitagawa Ind Co Ltd | 片面粘着性シート及びその製造方法 |
WO2008038734A1 (fr) * | 2006-09-29 | 2008-04-03 | Denki Kagaku Kogyo Kabushiki Kaisha | Feuille adhésive acrylique extrêmement conductrice de la chaleur |
JP2009503241A (ja) * | 2005-08-05 | 2009-01-29 | スリーエム イノベイティブ プロパティズ カンパニー | 向上した機能を有する熱伝導性接着テープ |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5302629A (en) * | 1992-05-15 | 1994-04-12 | Berejka Anthony J | Hydrophilic acrylic pressure sensitive adhesives |
US20030017332A1 (en) * | 2000-01-13 | 2003-01-23 | Youichi Takizawa | Acrylic sheet and acrylic pressure-sensitive adhesive sheet |
JP2002302662A (ja) | 2001-04-05 | 2002-10-18 | Sekisui Chem Co Ltd | 熱伝導性電気絶縁感圧接着剤 |
EP1433799A3 (en) * | 2002-12-23 | 2004-07-14 | Ucb, S.A. | Star shaped acrylic block copolymer |
JP2006137823A (ja) * | 2004-11-11 | 2006-06-01 | Sumitomo Chemical Co Ltd | 接着方法 |
JP4804007B2 (ja) * | 2005-01-13 | 2011-10-26 | 日東電工株式会社 | 粘着製品 |
JP5425376B2 (ja) * | 2006-08-11 | 2014-02-26 | 日東電工株式会社 | 両面粘着テープ又はシート、および長尺帯状物の巻回体 |
JP4228026B2 (ja) * | 2007-02-28 | 2009-02-25 | 日東電工株式会社 | バックライトシステムおよび粘着剤付光学シート |
JP5291316B2 (ja) * | 2007-09-26 | 2013-09-18 | 日東電工株式会社 | 導電性粘着テープ |
JP5133114B2 (ja) * | 2008-03-31 | 2013-01-30 | 三洋化成工業株式会社 | 帯電防止性粘着剤 |
JP5577074B2 (ja) * | 2009-11-09 | 2014-08-20 | 日東電工株式会社 | 光学用粘着シート |
-
2010
- 2010-02-04 JP JP2010023330A patent/JP5651344B2/ja active Active
-
2011
- 2011-01-24 KR KR1020127022988A patent/KR101678257B1/ko active IP Right Grant
- 2011-01-24 EP EP11739636A patent/EP2532723A1/en not_active Withdrawn
- 2011-01-24 WO PCT/JP2011/051161 patent/WO2011096287A1/ja active Application Filing
- 2011-01-24 US US13/576,478 patent/US20120301716A1/en not_active Abandoned
- 2011-01-24 CN CN2011800083649A patent/CN102753637A/zh active Pending
- 2011-01-27 TW TW100103172A patent/TW201137078A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10316953A (ja) | 1997-05-16 | 1998-12-02 | Nitto Denko Corp | 剥離可能な熱伝導性感圧接着剤とその接着シ―ト類 |
JP2002194306A (ja) * | 2000-12-26 | 2002-07-10 | Sekisui Chem Co Ltd | 熱伝導性シート |
JP2003183500A (ja) * | 2001-12-21 | 2003-07-03 | Kitagawa Ind Co Ltd | 熱伝導シート及びその製造方法 |
JP2006137833A (ja) * | 2004-11-11 | 2006-06-01 | Kitagawa Ind Co Ltd | 片面粘着性シート及びその製造方法 |
JP2009503241A (ja) * | 2005-08-05 | 2009-01-29 | スリーエム イノベイティブ プロパティズ カンパニー | 向上した機能を有する熱伝導性接着テープ |
WO2008038734A1 (fr) * | 2006-09-29 | 2008-04-03 | Denki Kagaku Kogyo Kabushiki Kaisha | Feuille adhésive acrylique extrêmement conductrice de la chaleur |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012046710A1 (ja) * | 2010-10-07 | 2012-04-12 | 株式会社日本触媒 | 熱伝導性粘着剤 |
JP2013177564A (ja) * | 2012-02-08 | 2013-09-09 | Nitto Denko Corp | 熱伝導性シート、熱伝導性シート形成用粒子集合物粉体、および、これらの製造方法 |
WO2014157378A1 (ja) * | 2013-03-28 | 2014-10-02 | デクセリアルズ株式会社 | 熱伝導性シート |
JP2014189727A (ja) * | 2013-03-28 | 2014-10-06 | Dexerials Corp | 熱伝導性シート |
US10550296B2 (en) | 2013-03-28 | 2020-02-04 | Dexerials Corporation | Thermally conductive sheet |
WO2015037626A1 (ja) * | 2013-09-13 | 2015-03-19 | デクセリアルズ株式会社 | 熱伝導性シート |
JP2015079948A (ja) * | 2013-09-13 | 2015-04-23 | デクセリアルズ株式会社 | 熱伝導性シート |
US10040979B2 (en) | 2013-09-13 | 2018-08-07 | Dexerials Corporation | Thermally conductive sheet |
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JP5651344B2 (ja) | 2015-01-14 |
US20120301716A1 (en) | 2012-11-29 |
JP2011162582A (ja) | 2011-08-25 |
CN102753637A (zh) | 2012-10-24 |
KR20120130331A (ko) | 2012-11-30 |
EP2532723A1 (en) | 2012-12-12 |
TW201137078A (en) | 2011-11-01 |
KR101678257B1 (ko) | 2016-11-21 |
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