WO2014192886A1 - 熱伝導性粘着シート - Google Patents
熱伝導性粘着シート Download PDFInfo
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- WO2014192886A1 WO2014192886A1 PCT/JP2014/064316 JP2014064316W WO2014192886A1 WO 2014192886 A1 WO2014192886 A1 WO 2014192886A1 JP 2014064316 W JP2014064316 W JP 2014064316W WO 2014192886 A1 WO2014192886 A1 WO 2014192886A1
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- pressure
- sensitive adhesive
- meth
- adhesive layer
- adhesive sheet
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
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- 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
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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
- C09J2301/10—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
- C09J2301/122—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 only on one side of the carrier, e.g. single-sided adhesive tape
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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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2301/30—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
- C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Definitions
- the present invention relates to a heat conductive adhesive sheet. More specifically, the present invention relates to a thermally conductive adhesive sheet that is thermally connected to members on both sides of the sheet but is not physically bonded to one member.
- thermo conductivity is required for heat conductive members (such as adhesive sheets) used in electronic devices.
- heat conductive members such as adhesive sheets
- a pressure-sensitive adhesive sheet having thermal conductivity a double-sided pressure-sensitive adhesive sheet in which particles (for example, aluminum hydroxide, alumina, etc.) are added to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is known (see Patent Document 1).
- both surfaces of the PSA sheet are adhered and fixed to adherends (members and parts such as electric and electronic devices). It has the disadvantage that it cannot be removed freely.
- adherends members and parts such as electric and electronic devices.
- the substrate-less double-sided pressure-sensitive adhesive sheet has low self-supporting properties, there are problems that the pressure-sensitive adhesive sheet is easily wrinkled when the adherend is attached, and that the surface smoothness is inferior.
- the inventors of the present invention have a heat conductive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing heat conductive particles.
- the members on both sides of the sheet can be thermally connected, exhibiting excellent thermal conductivity, the member on one surface side is stuck and fixed, and the member on the other surface side is physically
- the present invention has been completed by finding that the members and the like can be moved and removed when necessary without being fixed.
- the present invention is a heat conductive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing heat conductive particles, wherein one surface is an adhesive surface and the other surface is a non-adhesive surface.
- the heat conductive adhesive sheet characterized by this is provided.
- the heat conductive adhesive sheet may have a non-adhesive layer only on one surface of the adhesive layer.
- the ratio of the thickness of the non-adhesive layer to the thickness of the adhesive layer is preferably 0.04 to 0.6.
- the heat resistance value of the said heat conductive adhesive sheet is 6 K * cm ⁇ 2 > / W or less.
- the total thickness of the heat conductive adhesive sheet is preferably 50 to 500 ⁇ m.
- the initial elastic modulus of the heat conductive adhesive sheet is preferably 0.5 to 2000 MPa.
- the arithmetic average surface roughness Ra on the non-adhesive surface side of the heat conductive adhesive sheet is preferably 0.001 to 1.0 ⁇ m.
- non-adhesive surface is preferably black.
- the heat conductive adhesive sheet can be used for thin electric / electronic devices.
- the heat conductive pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer containing heat conductive particles, and one surface is an adhesive surface and the other surface is a non-adhesive surface.
- the members can be thermally connected to each other, and excellent thermal conductivity is exhibited (for example, the heat of the adherend side adherend is conducted to the non-adhesive side member).
- the adherend is stuck and fixed, and the member or the like is not stuck and fixed on the non-adhesive surface, and the member or the like can be moved or removed when necessary.
- one surface is a non-adhesive surface, it is hard to produce a wrinkle in an adhesive sheet at the time of adherend adherend.
- the non-adhesive surface of the pressure-sensitive adhesive sheet can be smoothed, a member that is in contact with the non-adhesive surface can be smoothly moved or removed, and the pressure-sensitive adhesive sheet is displaced from the adherend even if the member is moved. Or wrinkles on the adhesive sheet.
- FIG. 1 is a schematic cross-sectional view showing an example of the heat conductive pressure-sensitive adhesive sheet of the present invention.
- FIG. 2 is a schematic cross-sectional view showing another example of the heat conductive pressure-sensitive adhesive sheet of the present invention.
- FIG. 3 is a schematic diagram showing a thermal characteristic evaluation apparatus.
- the heat conductive pressure-sensitive adhesive sheet of the present invention is a heat conductive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing heat conductive particles, and one surface is an adhesive surface and the other surface is a non-adhesive surface. It has become.
- adheresive sheet includes “adhesive tape”.
- composition coating liquid etc.
- non-adhesive layer does not include a release liner (separator) that is peeled off when the heat conductive adhesive sheet is used.
- one surface is an adhesive surface and the other surface is a non-adhesive surface.
- stacked the non-adhesion layer only on the one surface of the adhesive layer containing the said heat conductive particle are mentioned, for example.
- the non-adhesive layer include a base material.
- FIG. 1 is a schematic sectional view showing an example of the heat conductive pressure-sensitive adhesive sheet of the present invention.
- FIG. 2 is a schematic sectional view showing another example of the heat conductive pressure-sensitive adhesive sheet of the present invention.
- 1 is a heat conductive adhesive sheet
- 10 is an adhesive layer (thermal conductive adhesive layer)
- 20 is a non-adhesive layer (base material).
- 21 and 23 are plastic films
- 22 is a metal foil.
- Non-adhesive layer examples include a substrate.
- a substrate for example, fiber-type base materials, such as cloth, a nonwoven fabric, felt, a net; Paper-type base materials, such as various paper; Aluminum, gold
- Metal base materials such as metal foils or metal plates such as; plastic base materials such as films and sheets made of various resins; foams such as foam sheets; graphite; and laminates thereof.
- a substrate having at least a plastic film is preferable from the viewpoint of strength, toughness, and electrical insulation.
- the substrate may be a single layer or multiple layers.
- the material constituting the plastic substrate is not particularly limited.
- polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer
- Polystyrene resins such as polystyrene; polycarbonate; polyethersulfone; and the like.
- the said material can be used individually or in combination of 2 or more types.
- polyester such as polyethylene terephthalate (PET), and polyimide are preferable because of the good balance of strength, handleability (handling property), cost, dimensional stability, anchoring force, More preferred is polyethylene terephthalate.
- the base material is preferably a polyester film or a polyimide film, and more preferably a polyethylene terephthalate film.
- examples of the multilayer substrate among the substrates having at least a plastic film include a laminate of two or more plastic films, a laminate of a plastic film and a metal foil, and the like.
- a laminate having a plastic film / metal foil layer structure and a plastic film / metal foil / plastic film layer structure is preferable in terms of thermal conductivity and the like.
- a polyester film such as a polyethylene terephthalate film and a polyimide film are preferable, and a polyethylene terephthalate film is particularly preferable.
- metal foil used for the said laminated body aluminum foil, copper foil, etc. are preferable from points, such as heat conductivity.
- the base material may be subjected to a surface treatment as necessary.
- a surface treatment include, for example, conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc., in order to improve adhesion to the adhesive layer.
- a peeling treatment on the back surface of the base material in the case of protecting the adhesive surface can be mentioned.
- means for imparting heat radiation to the heat conductive adhesive sheet or improving heat radiation may be taken.
- heat radiability is imparted to or improved in a heat-conductive adhesive sheet, for example, when used in electrical and electronic equipment, the heat of the heated electronic components is efficiently radiated (diffused) to the entire interior of the electrical equipment or the surrounding space. It is possible to suppress or prevent the deterioration of the performance of the electric / electronic device due to heat.
- Examples of methods for imparting and improving thermal radiation to the heat conductive adhesive sheet include: (i) making the color (color) of the non-adhesive surface (the outermost surface of the non-adhesive layer) a dark color system; There is a method of providing a heat radiation layer as the outermost layer of the adhesive layer.
- the color of the non-adhesive surface is preferably black, dark gray, brown, red, dark red, dark green, dark blue, dark blue, dark purple, etc. Particularly preferred is black.
- L * (lightness) is 35 or less (0 to 35).
- a * and b * are both preferably in the range of -30 to 30, for example, in the range of -20 to 20.
- the L * , a * , and b * defined in the L * a * b * color system can be measured using, for example, a color difference meter (manufactured by Konica Minolta, apparatus name “CR-200”). it can.
- the L * a * b * color system is standardized by the International Commission on Illumination (CIE) in 1976, and is specified in JIS Z8781-4: 2013 in the Japanese Industrial Standards.
- the above (i) include using a base material colored or painted in the above color as the base material.
- a plastic film such as a polyester film or a polyimide film colored or painted in the above-mentioned dark color as a base material, and particularly based on a polyester film (polyethylene terephthalate film or the like) colored or painted in black. It is particularly preferable to use it as a material.
- the heat radiation material used for forming the heat radiation layer is a material having a high radiation rate (for example, 0.6 to 1, preferably 0.7 to 1, more preferably 0.8 to 1).
- a high radiation rate for example, carbon materials, ceramics, tin oxide-antimony oxide semiconductors, metals, and the like can be given.
- a thermal radiation material can be used individually by 1 type or in combination of 2 or more types.
- a method for measuring emissivity the method defined in JIS A 1423: 1983 can be used.
- the heat radiation layer can be formed by laminating directly or through another layer on the outer surface side of the substrate.
- the base material surface is coated and printed with a paint or ink containing a heat radiating material, or the base material surface is coated with a coating film or printed layer containing a heat radiating material on a tape base.
- a heat radiation layer can be provided by sticking an adhesive tape or sheet provided on the back side of the material.
- the paint and ink containing the heat radiation material a commercially available heat radiation paint or the like can be used.
- seat, etc. can be used.
- the color of a heat radiation layer does not necessarily need to be a dark color system.
- the thickness of the non-adhesive layer (such as a substrate) is not particularly limited, but the lower limit is preferably 2 ⁇ m, more preferably from the viewpoints of handleability, thermal conductivity, anti-wrinkle resistance, and smoothness. It is 5 ⁇ m, more preferably 9 ⁇ m. Moreover, the upper limit becomes like this. Preferably it is 100 micrometers, More preferably, it is 50 micrometers, More preferably, it is 40 micrometers.
- the pressure-sensitive adhesive layer of the heat conductive pressure-sensitive adhesive sheet exhibits adhesiveness.
- Such an adhesive layer is formed of an adhesive composition.
- the acrylic pressure-sensitive adhesive layer described later is formed from an acrylic pressure-sensitive adhesive composition.
- an adhesive which comprises the said adhesive layer For example, a urethane adhesive, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a polyester adhesive, a polyamide adhesive, epoxy Based pressure-sensitive adhesives, vinyl alkyl ether pressure-sensitive adhesives, fluorine-based pressure-sensitive adhesives, and the like.
- an acrylic pressure-sensitive adhesive is preferable from the viewpoint of weather resistance, heat resistance, function, cost, and ease of designing a pressure-sensitive adhesive according to the purpose of use. That is, it is preferable that the heat conductive adhesive sheet of this invention has an acrylic adhesive layer.
- the acrylic pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer.
- the acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth) acryloyl group in the molecule) as a constituent monomer component.
- the acrylic polymer is preferably a polymer containing (meth) acrylic acid alkyl ester as a constituent monomer component.
- an acrylic polymer can be used individually or in combination of 2 or more types.
- (meth) acrylic-acid alkylester For example, (meth) acrylic-acid methyl, (meth) acrylic-acid ethyl, (meth) acrylic-acid propyl, (meth) acrylic-acid isopropyl, (meth) acrylic Acid butyl, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth)
- a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms (particularly 2 to 12 carbon atoms) is preferred, and more preferably 4 to 9 carbon atoms.
- (Meth) acrylic acid alkyl ester having an alkyl group of The said (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more types.
- the ratio of the (meth) acrylic acid alkyl ester to the total monomer components (100% by weight) constituting the acrylic polymer is not particularly limited, but is preferably 60% by weight or more (eg, 60 to 99% by weight). More preferably, it is 70% by weight or more (for example, 70 to 98% by weight), and further preferably 80% or more (for example, 80 to 98% by weight).
- the acrylic polymer may be a polymer containing only the (meth) acrylic acid alkyl ester as a constituent monomer component, but it is possible to impart functions according to necessity, various properties of the adhesive, From the point of controlling the structure of the acrylic polymer and the like more appropriately, the monomer component may be a polymer containing a copolymerizable monomer together with the (meth) acrylic acid alkyl ester. In addition, a copolymerizable monomer can be used individually or in combination of 2 or more types.
- a polar group-containing monomer may be mentioned. Although it does not specifically limit as said polar group containing monomer, For example, a carboxyl group containing monomer, a hydroxyl group containing monomer, a nitrogen containing monomer, a sulfonic acid group containing monomer, a phosphoric acid group containing monomer etc. are mentioned. In addition, a polar group containing monomer can be used individually or in combination of 2 or more types.
- the carboxyl group-containing monomer is a monomer having one or more carboxyl groups in one molecule, but may be in the form of an anhydride. Although it does not specifically limit as said carboxyl group containing monomer, For example, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, maleic anhydride, itaconic anhydride etc. are mentioned. In addition, a carboxyl group-containing monomer can be used individually or in combination of 2 or more types.
- the acrylic polymer preferably does not substantially contain a carboxyl group-containing monomer as a constituent monomer component.
- substantially free of a carboxyl group-containing monomer means that the monomer component constituting the acrylic polymer contains no carboxyl group-containing monomer or all the monomer components (100 wt. %) Of the carboxyl group-containing monomer is 0.1% by weight or less.
- the acrylic pressure-sensitive adhesive layer contains thermally conductive particles described later, if a carboxyl group-containing monomer is included as a monomer component that the acrylic polymer constitutes, depending on the thermally conductive particles, a polar group-containing monomer may be used. It may be difficult to obtain the effect of improving the adhesiveness due to the inclusion, and the fluidity of the acrylic pressure-sensitive adhesive composition, which is a composition forming the acrylic pressure-sensitive adhesive layer, is reduced. Formation of the agent layer may be difficult. The cause of these problems has not been sufficiently clarified, but the carboxyl group of the carboxyl group-containing monomer reacts with the functional group (for example, hydroxyl group) of the thermally conductive particles, so that the acrylic pressure-sensitive adhesive composition is more than necessary. This is presumably because it becomes harder or the pressure-sensitive adhesive layer becomes harder than necessary, and the wettability of the pressure-sensitive adhesive layer decreases.
- a carboxyl group-containing monomer is included as a monomer component that the acrylic polymer constitutes, depending on
- a hydroxyl group-containing monomer When a hydroxyl group-containing monomer is included as the copolymerizable monomer, the dispersibility of the heat conductive particles is improved, and good wettability to the adherend is easily obtained with the acrylic pressure-sensitive adhesive layer.
- the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate Etc.
- hydroxyl-containing monomer can be used individually or in combination of 2 or more types.
- nitrogen-containing monomer When a nitrogen-containing monomer is contained as a copolymerizable monomer, appropriate polarity is imparted, and it becomes easy to obtain good adhesive properties such as adhesiveness and adhesive reliability at the initial stage of application with an acrylic pressure-sensitive adhesive layer.
- the nitrogen-containing monomer include N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (1-hydroxypropyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, etc.
- N-hydroxyalkyl (meth) acrylamides N-hydroxyalkyl (meth) acrylamides; cyclic (meth) acrylamides such as N- (meth) acryloylmorpholine and N-acryloylpyrrolidine; acyclic (meth) acrylamides such as (meth) acrylamide and N-substituted (meth) acrylamide Is mentioned.
- N-substituted (meth) acrylamide examples include N-alkyl (meth) acrylamides such as N-ethyl (meth) acrylamide and Nn-butyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, N, N-di (t And N, N-dialkyl (meth) acrylamide such as (butyl) (meth) acrylamide.
- N-alkyl (meth) acrylamides such as N-ethyl (meth) acrylamide and Nn-butyl (meth) acrylamide
- nitrogen-containing monomer examples include N-vinyl-2-pyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl- N-vinyl cyclic amides such as 1,3-oxazin-2-one and N-vinyl-3,5-morpholinedione; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N Monomers having amino groups such as dimethylaminopropyl (meth) acrylate; monomers having a maleimide skeleton such as N-cyclohexylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide N-2-ethylhexylitaconimide, N-lauryl Takon'
- the nitrogen-containing monomer is preferably N-hydroxyalkyl (meth) acrylamide, N-vinyl cyclic amide, cyclic (meth) acrylamide, or N-substituted (meth) acrylamide, more preferably N- (2-hydroxyethyl).
- the ratio of the nitrogen-containing monomer to the total monomer component (100% by weight) constituting the acrylic polymer is not particularly limited, but the lower limit is preferably 1% by weight or more, more preferably 2% by weight or more. It is. Further, the upper limit is preferably 10% by weight or less, more preferably 7% by weight or less.
- 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, (meth) And acryloyloxynaphthalene sulfonic acid.
- a sulfonic acid group containing monomer can be used individually or in combination of 2 or more types.
- phosphate group-containing monomer examples include 2-hydroxyethyl acryloyl phosphate.
- a phosphate group containing monomer can be used individually or in combination of 2 or more types.
- the blending ratio of the polar group-containing monomer in the monomer component constituting the acrylic polymer is not particularly limited. For example, 0.1% with respect to the total amount (100% by weight) of the monomer component constituting the acrylic polymer. It is preferably at least 0.5% by weight, more preferably at least 0.5% by weight, even more preferably at least 1% by weight, even more preferably at least 2% by weight, even more preferably at least 3% by weight, particularly preferably at least 5% by weight. Further, the blending ratio of the polar group-containing monomer is not particularly limited. For example, it is preferably 40% by weight or less, more preferably 30% by weight with respect to the total amount of monomer components (100% by weight) constituting the acrylic polymer.
- the blending ratio of the polar group-containing monomer in the monomer component is not particularly limited. For example, it is preferably 0.1 to 40% by weight with respect to the total amount of monomer component (100% by weight) constituting the acrylic polymer. . When the blending ratio is within the above range, the cohesive force of the pressure-sensitive adhesive layer becomes appropriate, and high holding power and pressure-sensitive adhesive force can be obtained.
- examples of the copolymerizable monomer include monomers having an alkoxy group.
- a monomer having an alkoxy group is included as a copolymerizable monomer, the wettability of the acrylic pressure-sensitive adhesive layer can be improved, and heat from the adherend (heat generation source) can be efficiently conducted. it can.
- examples of the monomer having an alkoxy group include 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate. Can be mentioned.
- the monomer which has an alkoxy group can be used individually or in combination of 2 or more types.
- the ratio of the monomer having the alkoxy group to the total monomer component (100% by weight) constituting the acrylic polymer is not particularly limited, but the lower limit is preferably 3% by weight, more preferably 5% by weight. Moreover, it is preferable that the upper limit is 20 weight%, More preferably, it is 15 weight%.
- examples of the copolymerizable monomer include polyfunctional monomers. According to such a polyfunctional monomer, a crosslinked structure can be introduced into the acrylic polymer, and the cohesive force of the pressure-sensitive adhesive layer can be adjusted.
- examples of the polyfunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol.
- the said polyfunctional monomer can be used individually or in combination of 2 or more types.
- the ratio of the polyfunctional monomer to the total monomer component (100% by weight) constituting the acrylic polymer is not particularly limited, but the lower limit thereof is preferably 0.01% by weight, more preferably 0.02%.
- the upper limit is preferably 2% by weight, and more preferably 1% by weight.
- the ratio of the polyfunctional monomer is 0.01% by weight or more, it is preferable because a high cohesive force can be obtained and a high holding power can be easily obtained.
- the ratio of the polyfunctional monomer is 2% by weight or less, the cohesive force becomes too high, and the occurrence of a problem that the adhesiveness is lowered can be suppressed.
- examples of the copolymerizable monomer include monomers having an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether; monomers having a cyano group such as acrylonitrile and methacrylonitrile; styrene, ⁇ -methylstyrene, and the like.
- Styrene monomers such as ethylene, propylene, isoprene, butadiene and isobutylene; monomers having isocyanate groups such as 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate Monomers; vinyl ether monomers such as vinyl ether; (meth) acrylic acid esters having a heterocycle such as tetrahydrofurfuryl (meth) acrylate; fluorine (meth) acrylate Monomers having a halogen atom such as a salt; Monomers having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; Monomers having a siloxane bond such as silicone (meth) acrylate; Cyclopentyl (meth) acrylate , (Meth) acrylates having alicyclic hydrocarbon
- the glass transition temperature (Tg) of the acrylic polymer is not particularly limited, but it is easy to obtain a low-elasticity acrylic pressure-sensitive adhesive layer, and it is easy to obtain an acrylic pressure-sensitive adhesive layer having good step absorbability.
- the upper limit is preferably ⁇ 10 ° C., more preferably ⁇ 20 ° C.
- the lower limit is preferably ⁇ 70 ° C., more preferably ⁇ 65 ° C.
- the Tg of the acrylic polymer can be prepared by selecting the composition and blending amount of the constituent monomer components.
- the Tg of the acrylic polymer refers to a value obtained from the Fox equation based on the Tg of the homopolymer of each monomer constituting the monomer component and the weight fraction (copolymerization composition) of the monomer.
- the value of Tg of the homopolymer can be obtained from various known materials (such as “Adhesion Technology Handbook” of Nikkan Kogyo Shimbun).
- the acrylic polymer can be obtained by polymerizing the monomer component.
- a polymerization method for example, solution polymerization, emulsion polymerization, block polymerization, photopolymerization (active energy ray polymerization) etc. are mentioned.
- a polymerization method using heat or active energy rays for example, ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutral beam, electron beams, ultraviolet rays, etc.
- a polymerization method using a heat or active energy ray using a polymerization initiator such as a photopolymerization initiator is preferred.
- a polymerization initiator can be used individually or in combination of 2 or more types.
- the polymerization method is preferably a polymerization method using an active energy ray (particularly, ultraviolet rays) using a photopolymerization initiator because the polymerization time can be shortened.
- the pressure-sensitive adhesive layer is preferably an active energy ray-curable pressure-sensitive adhesive layer.
- the photopolymerization initiator is not particularly limited.
- benzoin ether photopolymerization initiator acetophenone photopolymerization initiator, ⁇ -ketol photopolymerization initiator, aromatic sulfonyl chloride photopolymerization initiator, photo Examples thereof include active oxime photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators.
- a photoinitiator can be used individually or in combination of 2 or more types.
- benzoin ether photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, Anisole methyl ether etc. are mentioned.
- acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4- (t-butyl). ) Dichloroacetophenone and the like.
- Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. It is done.
- Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
- Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
- Examples of the benzoin photopolymerization initiator include benzoin.
- Examples of the benzyl photopolymerization initiator include benzyl.
- benzophenone photopolymerization initiator examples include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
- ketal photopolymerization initiator examples include benzyl methyl ketal.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, decylthioxanthone, and the like.
- the usage-amount of the said photoinitiator is not specifically limited, It is preferable that the minimum is 0.01 weight part with respect to 100 weight part of monomer components which comprise the said acrylic polymer, More preferably, it is 0.
- the upper limit is preferably 5 parts by weight, and more preferably 3 parts by weight.
- the irradiation energy and irradiation time of active energy rays are not particularly limited. It is only necessary that the photopolymerization initiator is activated to cause the monomer component to react.
- thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2-methylpropionic acid) dimethyl, , 4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazoline) -2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, 2,2 Azo polymerization initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate; Peroxide polymerization initiators such as xoxide, t-butyl permaleate, t-butyl hydroper
- the amount of the thermal polymerization initiator used is not particularly limited, but can be selected, for example, in a range that can be conventionally used as a polymerization initiator.
- the monomer component and the thermal polymerization initiator are dissolved in an appropriate solvent (for example, an organic solvent such as toluene or ethyl acetate), for example, 20 to 100 ° C. (preferably 40 to 80 ° C.). ) To obtain an acrylic polymer.
- an appropriate solvent for example, an organic solvent such as toluene or ethyl acetate
- the heat conductive pressure-sensitive adhesive sheet of the present invention contains heat conductive particles in the pressure-sensitive adhesive layer, so that good heat conductivity can be obtained, the pressure-sensitive adhesive sheet can hardly be burned, and the flame can be hardly spread by the pressure-sensitive adhesive sheet. . That is, excellent thermal conductivity and flame retardancy are obtained.
- Thermally conductive particles can be used alone or in combination of two or more.
- thermally conductive particles examples include metal hydroxides and hydrated metal compounds.
- the hydrated metal compound has a decomposition start temperature in the range of 150 to 500 ° C., and has a general formula M m1 O n1 .XH 2 O (where M is a metal and m1, n1 is 1 or more determined by the valence of the metal) Or a double salt containing the compound.
- metal hydroxide and the hydrated metal compound is not particularly limited, for example, aluminum hydroxide [Al 2 O 3 ⁇ 3H 2 O; or Al (OH) 3], boehmite [Al 2 O 3 ⁇ H 2 O; or AlOOH], magnesium hydroxide [MgO.H 2 O; or Mg (OH) 2 ], calcium hydroxide [CaO.H 2 O; or Ca (OH) 2 ], zinc hydroxide [Zn (OH 2 ), silicic acid [H 4 SiO 4 ; or H 2 SiO 3 ; or H 2 Si 2 O 5 ], iron hydroxide [Fe 2 O 3 .H 2 O or 2FeO (OH)], copper hydroxide [Cu (OH) 2 ], barium hydroxide [BaO ⁇ H 2 O; or BaO ⁇ 9H 2 O], zirconium oxide hydrate [ZrO ⁇ nH 2 O], tin oxide hydrate [SnO ⁇ H 2 O], basic magnesium carbonate [3MgCO
- Hijilite H-100-ME average particle size 75 ⁇ m
- Hijilite H-10 average particle size 55 ⁇ m
- Hijilite H-31 average particle size 18 ⁇ m
- Hijilite H-32 average particle size 8 ⁇ m
- Hijilite H-42 average particle size 1 ⁇ m
- Hijilite H-43M average particle size 0.8 ⁇ m
- B103ST average particle size 8 ⁇ m
- magnesium hydroxide examples include, for example, trade name “KISUMA A 5A” (average particle diameter 1 ⁇ m) (manufactured by Kyowa Chemical Industry Co., Ltd.), trade name “ECOMAG Z-10” (average particle diameter 1.4 ⁇ m, Tateho Chemical Industry Co., Ltd.).
- examples of the heat conductive particles include metal nitrides such as boron nitride, aluminum nitride, silicon nitride, and gallium nitride; aluminum oxide (alumina), magnesium oxide, titanium oxide, zinc oxide, tin oxide, copper oxide, Examples thereof include metal oxides such as nickel oxide and antimonic acid doped tin oxide.
- metal nitrides such as boron nitride, aluminum nitride, silicon nitride, and gallium nitride
- magnesium oxide titanium oxide
- zinc oxide titanium oxide
- tin oxide copper oxide
- metal oxides such as nickel oxide and antimonic acid doped tin oxide.
- heat conductive particles As such heat conductive particles, general commercial products can be used.
- Examples of commercially available boron nitride include trade name “HP-40” (manufactured by Mizushima Alloy Iron Co., Ltd.) and trade name “PT620” (manufactured by Momentive).
- Examples of commercially available aluminum oxide include trade name “AS-50” (manufactured by Showa Denko KK), trade name “AL-13KT” (average particle size 96 ⁇ m) (manufactured by Showa Denko KK), and the like.
- the thermal conductive particles metal hydroxide, hydrated metal compound, and metal oxide are preferable from the viewpoint of thermal conductivity, flame retardancy, and cost, and aluminum hydroxide, alumina, and magnesium oxide are more preferable.
- the thermally conductive particles are preferably at least one particle selected from the group consisting of metal hydroxides, hydrated metal compounds, and metal oxides, and more preferably from aluminum hydroxide, alumina, and magnesium oxide. At least one particle selected from the group consisting of: As the heat conductive particles, aluminum hydroxide is particularly preferable.
- the shape of the heat conductive particles is not particularly limited, and may be a bulk shape, a needle shape, a plate shape, or a layer shape.
- the bulk shape includes, for example, a spherical shape, a rectangular parallelepiped shape, a crushed shape, or a deformed shape thereof.
- the average particle size of the heat conductive particles is not particularly limited, but is preferably 0.1 to 1000 ⁇ m.
- the lower limit is more preferably 0.2 ⁇ m, still more preferably 0.5 ⁇ m.
- the upper limit is more preferably 200 ⁇ m, still more preferably 100 ⁇ m, and particularly preferably 50 ⁇ m.
- the 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 total content of the heat conductive particles in the pressure-sensitive adhesive layer is not particularly limited, but is preferably 25% by volume or more and 75% by volume or less with respect to the total volume (100% by volume) of the pressure-sensitive adhesive layer.
- the lower limit is more preferably 30% by volume.
- the upper limit is 70 volume% more preferably, More preferably, it is 60 volume%.
- the content ratio of the heat conductive particles is 25% by volume or more, good heat conductivity and good flame retardancy are easily obtained, which is preferable.
- it is preferable for the content ratio of the heat conductive particles to be 75% by volume or less, since a decrease in flexibility can be suppressed and a decrease in adhesive force and holding force can be suppressed.
- the unit “volume%” used in the content (content ratio) can be converted to the unit “weight%” using the density of the heat conductive particles.
- the flame retardancy effect cannot be obtained. That is, it has been recognized that it is difficult to achieve both flame retardancy and adhesiveness using the above heat conductive particles.
- the average particle size of the heat conductive particles contained in the pressure-sensitive adhesive layer is small (for example, in the case of 0.1 to 10 ⁇ m)
- the present inventors improve the flame retardancy and also have a high adhesive strength. We found that there was little decline.
- the thermal conductive particles having an average particle size of 10 ⁇ m or less particularly 8 ⁇ m or less
- the adhesive strength of the adhesive layer is that of the adhesive layer having the same composition except that the thermal conductive particles are not included. It may be higher than the force, and in addition, it has excellent flame retardancy.
- the average particle size of the heat conductive particles is 10 ⁇ m or less (for example, 0.1 to 10 ⁇ m) from the viewpoint that both flame retardancy and adhesiveness can be achieved and coating properties are excellent. Is preferred. Especially, even if the heat conductive particles are added, the adhesive strength is less likely to be lowered, and from the viewpoint that the adhesive force may be higher than the pressure sensitive adhesive layer not containing the heat conductive particles, 8 ⁇ m or less. (For example, 0.1 to 8 ⁇ m) is preferable, and 1 ⁇ m or less (for example, 0.1 to 1 ⁇ m) is more preferable.
- the content of the heat conductive particles having an average particle size of 10 ⁇ m or less is preferably, for example, 20 to 330 parts by weight with respect to 100 parts by weight of the base polymer such as an acrylic polymer in the pressure-sensitive adhesive layer, and the lower limit is more preferable. Is 50 parts by weight, more preferably 60 parts by weight, particularly preferably 100 parts by weight. When the content is 20 parts by weight or more, excellent flame retardancy is obtained.
- the adhesive force is high, and repulsion resistance (bent according to the shape of the adherend) (For example, it is difficult to be peeled off from the adherend even if it is attached by being bent at 90 ° or 180 °) and the adhesive property (tack) at the time of attachment is excellent.
- the thickness of the pressure-sensitive adhesive layer is uniform, and the surface of the pressure-sensitive adhesive layer is smooth and free from defects such as fading.
- the coating property (characteristic that allows easy application of a pressure-sensitive adhesive layer with a uniform thickness and a smooth surface) Also excellent.
- the heat conductive particles are excellent in flame retardancy and adhesiveness
- the heat conductive particles having an average particle size of 10 ⁇ m or less preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less
- the heat conductive particles may be used in combination of two or more heat conductive particles having different average particle diameters.
- two or more kinds of the above heat conductive particles having different average particle diameters are used in combination, for example, it is preferable to use a combination of particles having an average particle diameter of 5 ⁇ m or more and particles having an average particle diameter of less than 5 ⁇ m.
- the said heat conductive particle can be filled more densely in an adhesive layer.
- the blending ratio (weight ratio) of particles having an average particle diameter of 5 ⁇ m or more and particles having an average particle diameter of less than 5 ⁇ m is preferably 1:10 to 10: 1, more preferably. Is from 1: 5 to 5: 1, more preferably from 1: 2 to 2: 1.
- the heat conductive particles may be, for example, a combination of heat conductive particles (particle group A) having an average particle size of 10 ⁇ m or more and heat conductive particles (particle group B) having an average particle size of less than 10 ⁇ m.
- the pressure-sensitive adhesive composition is more likely to have a finely packed structure.
- the fluidity is increased and the viscosity is decreased, so that the adhesion to the adherend may be further improved (adhesion force is further increased).
- the thickness of the pressure-sensitive adhesive layer tends to be uniform.
- the mixing ratio (weight ratio) of the particle group A and the particle group B is preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3.
- the average particle diameter of the particle group A is, for example, 10 to 100 ⁇ m, and the lower limit thereof is preferably 12 ⁇ m, more preferably 15 ⁇ m. Moreover, the upper limit becomes like this. Preferably it is 50 micrometers, More preferably, it is 30 micrometers, More preferably, it is 25 micrometers.
- the average particle size of the particle group B is, for example, 0.1 ⁇ m or more and less than 10 ⁇ m, and the lower limit thereof is preferably 0.3 ⁇ m, more preferably 0.5 ⁇ m. Moreover, the upper limit becomes like this. Preferably it is 8 micrometers, More preferably, it is 5 micrometers, More preferably, it is 3 micrometers.
- a dispersant may be further contained in order to stably disperse the heat conductive particles without agglomeration within a range not impairing the effects of the present invention.
- the dispersant is not particularly limited, but, for example, a phosphate ester is preferably used.
- Phosphoric acid esters include polyoxyethylene alkyl (or alkylallyl) ether or polyoxyethylene alkyl aryl ether phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid diester, phosphoric acid triester Or a derivative thereof.
- the said dispersing agent can be used individually or in combination of 2 or more types.
- the content of the dispersant is not particularly limited. For example, 0.01% with respect to 100 parts by weight of the base polymer in the pressure-sensitive adhesive layer (for example, the acrylic polymer in the case of the acrylic pressure-sensitive adhesive layer). It is preferably ⁇ 10 parts by weight.
- the lower limit is more preferably 0.05 parts by weight, still more preferably 0.1 parts by weight.
- the upper limit is more preferably 5 parts by weight, still more preferably 3 parts by weight.
- a general commercial product can be used as the dispersant.
- a trade name “Plisurf A212E” (Daiichi Kogyo Seiyaku Co., Ltd.)
- a trade name “Plisurf A210G” (Daiichi Kogyo Seiyaku Co., Ltd.)
- Name “Plisurf A212C” (Daiichi Kogyo Seiyaku Co., Ltd.)
- Trade Name “Plisurf A210F” (Daiichi Kogyo Seiyaku Co., Ltd.)
- Trade Name “Phosphanol RE610” (Toho Chemical Co., Ltd.)
- Examples include “Fanol RS710” (manufactured by Toho Chemical Co., Ltd.), trade name “Phosphanol RS610” (manufactured by Toho Chemical Co., Ltd.), and the like.
- the pressure-sensitive adhesive layer may further contain a fluorinated surfactant.
- a fluorinated surfactant By using the fluorosurfactant, the degree of adhesion and frictional resistance between the base polymer and the thermally conductive particles may be reduced, and the stress dispersibility may be improved. Therefore, in the heat conductive adhesive sheet of this invention, higher adhesiveness may be obtained.
- the fluorine-based surfactant is not particularly limited, but for example, a fluorine-based surfactant having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group in the molecule is preferable.
- a fluorine-based surfactant having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group in the molecule is preferable.
- the above-mentioned fluorine-containing surfactant is a fluorine-based nonionic surfactant having a C 2-3 alkylene group and a fluorinated hydrocarbon group in the molecule. It is preferable that In addition, the said fluorosurfactant can be used individually or in combination of 2 or more types.
- the fluorinated hydrocarbon group is not particularly limited, but is preferably a perfluoro group, for example.
- the perfluoro group may be monovalent or divalent or higher.
- the fluorinated hydrocarbon group may have a double bond or a triple bond, and may be a straight chain or a branched structure or a cyclic structure.
- the number of carbon atoms of the fluorinated hydrocarbon group is not particularly limited, but is preferably 1 or 2 or more, more preferably 3 to 30, and still more preferably 4 to 20.
- 1 type of the said fluorinated hydrocarbon group may be introduce
- the oxy C 2-3 alkylene group is represented by the formula: —R—O— (where R is a linear or branched alkylene group having 2 or 3 carbon atoms).
- the oxy C 2-3 alkylene group is not particularly limited, and examples thereof include oxyethylene group (—CH 2 CH 2 O—), oxypropylene group [—CH 2 CH (CH 3 ) O—] and the like.
- the oxy C 2-3 alkylene group may be any form such as an alcohol having a hydrogen atom bonded to a terminal oxygen atom, an ether bonded to another hydrocarbon group, or an ester bonded to another hydrocarbon group via a carbonyl group. But you can.
- the form which has this structure in a part of cyclic structure such as cyclic ethers and lactones, may be sufficient.
- One kind of the oxy C 2-3 alkylene group may be introduced into the fluorine-based surfactant molecule, or two or more kinds thereof may be introduced.
- the fluorosurfactant is not particularly limited, and is obtained, for example, by polymerizing a monomer component containing a monomer having an oxy C 2-3 alkylene group and a monomer having a fluorinated hydrocarbon group.
- a copolymer is mentioned.
- the fluorosurfactant is a copolymer, it may be, for example, a block copolymer or a graft copolymer.
- the block copolymer (copolymer having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group in the main chain) is not particularly limited, but examples thereof include polyoxyethylene perfluoroalkyl ether, polyoxyethylene peroxy ether, and the like. Fluoroalkylate, polyoxypropylene perfluoroalkyl ether, polyoxyisopropylene perfluoroalkyl ether, polyoxyethylene sorbitan perfluoroalkylate, polyoxyethylene polyoxypropylene block copolymer perfluoroalkylate, polyoxyethylene glycol perfluoroalkyl Chelate etc. are mentioned.
- the graft copolymer (a copolymer having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group in the side chain) is not particularly limited, but for example, a vinyl compound having at least a polyoxyalkylene group and fluorine And a copolymer obtained by polymerizing a monomer component containing a vinyl compound having a functionalized hydrocarbon group, and an acrylic copolymer is particularly preferable.
- the vinyl compound having a polyoxyalkylene group include polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and polyoxyethylene polyoxypropylene (meth) acrylate. Is mentioned.
- vinyl compound having a fluorinated hydrocarbon group examples include perfluoroalkyl (meth) acrylates such as perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, and perfluoropentyl (meth) acrylate.
- perfluoroalkyl (meth) acrylates such as perfluorobutyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, and perfluoropentyl (meth) acrylate.
- (Meth) acrylic acid ester containing a fluorinated hydrocarbon is mentioned.
- the above-mentioned fluorosurfactant contains an alicyclic hydrocarbon group, an aromatic group in the molecule within a range that does not impair dispersibility in the acrylic polymer. It may have various functional groups such as an aromatic hydrocarbon group, a carboxyl group, a sulfonic acid group, a cyano group, an amide group, and an amino group.
- the fluorosurfactant is a vinyl copolymer
- the monomer component can be copolymerized with a vinyl compound having a polyoxyalkylene group and a vinyl compound having a fluorinated hydrocarbon group as a monomer component. May be used.
- Such copolymerizable monomers can be used alone or in combination of two or more.
- Examples of the copolymerizable monomer component include (meth) acrylic acid C 1-20 alkyl esters such as undecyl (meth) acrylate and dodecyl (meth) acrylate; alicyclic carbonization such as cyclopentyl (meth) acrylate.
- a (meth) acrylic acid ester having a hydrogen group; a (meth) acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth) acrylate is preferably used.
- carboxyl group-containing monomers such as maleic acid and crotonic acid; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins and dienes such as ethylene and butadiene Vinyl ethers such as vinyl alkyl ethers; amide group-containing monomers such as acrylamide; amino group-containing monomers such as (meth) acryloylmorpholine; glycidyl group-containing monomers such as methyl glycidyl (meth) acrylate; 2 -Isocyanate group-containing monomers such as methacryloyloxyethyl isocyanate; and polyfunctional copolymerizable monomers (polyfunctional monomers) such as dipentaerythritol hexa (meth) acrylate and divinylbenzene.
- sulfonic acid group-containing monomers such as sodium vinyl s
- the weight average molecular weight of the fluorosurfactant is not particularly limited. For example, when it is less than 20000 (for example, 500 or more and less than 20000), the base polymer such as the acrylic polymer and the thermally conductive particles The effect of reducing the adhesion and frictional resistance between them is high. Further, when a fluorosurfactant having a weight average molecular weight of 20,000 or more (for example, 20,000 to 100,000, preferably 22,000 to 80,000, more preferably 24,000 to 60,000) is used in combination, In addition, the stability of the mixed bubbles is increased.
- the amount of use (solid content) of the fluorosurfactant is not particularly limited.
- the amount of use (solid content) of the fluorosurfactant is not particularly limited.
- the lower limit is preferably 0.02 parts by weight, and more preferably 0.03 parts by weight.
- the upper limit is preferably 3 parts by weight, and more preferably 2 parts by weight.
- the pressure-sensitive adhesive layer is present in a stable amount without agglomeration of the metal hydroxide and / or the hydrated metal compound with a smaller content than when the dispersant or the fluorosurfactant is used alone.
- the dispersant and the fluorosurfactant may be used in combination.
- the blending ratio is not particularly limited, but the ratio (weight ratio) of the dispersant to the fluorosurfactant is 1:20 to 20: 0.01 is preferable, more preferably 1:10 to 10: 0.01, and still more preferably 1: 5 to 5: 0.01.
- fluorosurfactant having an oxy C 2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of less than 20,000 include a trade name “Futgent 251” (manufactured by Neos Co., Ltd.), The name “FTX-218” (manufactured by Neos Co., Ltd.), the product name “Megafuck F-477” (manufactured by DIC), the product name “Megafuck F-470” (manufactured by DIC), and the product name “Surflon S-381” (AGC Seimi Chemical Co., Ltd.), trade name “Surflon S-383” (AGC Seimi Chemical Co., Ltd.), trade name “Surflon S-393” (AGC Seimi Chemical Co., Ltd.), trade name “Surflon KH-20” ( AGC Seimi Chemical Co., Ltd.) and trade name “Surflon KH-40” (manufact
- fluorosurfactant having an oxy C2-3 alkylene group and a fluorinated hydrocarbon group and having a weight average molecular weight of 20000 or more
- the trade name “F-top EF-352” Mitsubishi Materials Electronics Chemicals
- Product name, “F-top EF-801” manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.
- product name “Unidyne TG-656” manufactured by Daikin Industries, Ltd.
- the pressure-sensitive adhesive layer may further contain a crosslinking agent.
- a crosslinking agent a known and commonly used crosslinking agent can be used.
- epoxy crosslinking agent isocyanate crosslinking agent, silicone crosslinking agent, oxazoline crosslinking agent, aziridine crosslinking agent, silane crosslinking agent, alkyl
- isocyanate crosslinking agents and epoxy crosslinking agents are preferred.
- Examples of the isocyanate crosslinking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenyl.
- Examples include methane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
- a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule, specifically, 2-isocyanatoethyl (meth) acrylate or the like can also be used.
- epoxy-based crosslinking agent examples include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, and triglyceride ether.
- the content of the crosslinking agent is not particularly limited, but is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the base polymer such as the acrylic polymer in the pressure-sensitive adhesive layer.
- the upper limit is more preferably 3 parts by weight, still more preferably 2 parts by weight. When the content is 5 parts by weight or less, good flexibility is obtained, and when the content is 0.01 parts by weight or more, high cohesiveness is obtained.
- the pressure-sensitive adhesive layer may further contain a tackifier resin from the viewpoint of further improving the tackiness.
- a tackifier resin is included.
- the tackifying resin is not particularly limited.
- an acrylic polymer is obtained by copolymerizing monomer components by irradiating ultraviolet rays, a hydrogenated type adhesive is used because it is difficult to inhibit polymerization even when used together. It is preferable to use an imparting resin.
- hydrogenated tackifying resins include derivatives obtained by hydrogenating tackifying resins such as rosin resins, petroleum resins, terpene resins, coumarone-indene resins, styrene resins, alkylphenol resins, xylene resins ( And hydrogenated rosin resins, hydrogenated petroleum resins, hydrogenated terpene resins, and the like. Among these, a hydrogenated rosin resin is preferable.
- the hydrogenated rosin-based tackifying resin include modified rosin obtained by modifying unmodified rosin (raw rosin) such as gum rosin, wood rosin and tall oil rosin by hydrogenation.
- the softening point of the tackifying resin is not particularly limited, but is preferably 80 to 200 ° C., and more preferably 90 to 200 ° C. When the softening point of the tackifying resin is within the range, the cohesive force is further improved.
- the content of the tackifying resin is not particularly limited, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the base polymer such as the acrylic polymer in the pressure-sensitive adhesive layer.
- the lower limit is more preferably 2 parts by weight, still more preferably 3 parts by weight.
- the upper limit is more preferably 40 parts by weight, still more preferably 30 parts by weight.
- tackifying resin a general commercial product can be used.
- a trade name “Super Ester A-100” softening point 95 to 105 ° C., manufactured by Arakawa Chemical Industries
- a trade name “Super Ester A-125” Hydrogenated rosin resins such as “Softening point 120 to 130 ° C., Arakawa Chemical Industries, Ltd.” can be used.
- the pressure-sensitive adhesive layer may further contain an acrylic oligomer from the viewpoint of further improving the adhesiveness.
- the acrylic oligomer is a polymer having a glass transition temperature (Tg) higher than that of the acrylic polymer and a small weight average molecular weight, functions as a tackifier resin, and inhibits polymerization during polymerization using ultraviolet rays. It has the advantage of being difficult to wake up.
- the pressure-sensitive adhesive layer further improves silane coupling from the point that adhesion and durability are further improved and the affinity between the heat conductive particles and the base polymer such as the acrylic polymer is further improved.
- An agent may be included.
- silane coupling agent known ones can be appropriately used.
- silane coupling agents such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, Amino group-containing silane coupling agents such as 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine; (methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
- Acrylic group-containing silane coupling Grayed agents such Inshianeto group-containing silane coupling agents such as 3-isocyanate propyl triethoxysilane and the like.
- the silane coupling agent may be used alone or in combination of two or more.
- the content of the silane coupling agent is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the base polymer such as the acrylic polymer in the pressure-sensitive adhesive layer.
- the lower limit is more preferably 0.02 parts by weight, still more preferably 0.05 parts by weight.
- the upper limit is more preferably 5 parts by weight, still more preferably 2 parts by weight.
- the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer containing bubbles.
- the pressure-sensitive adhesive layer containing bubbles can impart thickness and cushioning properties to the pressure-sensitive adhesive layer, and the performance of filling the unevenness of the adherend surface, that is, the unevenness absorbability (unevenness followability) is improved.
- the adhesive layer includes a base polymer such as the acrylic polymer, the thermally conductive particles, the dispersant, the fluorosurfactant, the crosslinking agent, the tackifier resin, the acrylic oligomer, and the silane cup.
- a base polymer such as the acrylic polymer, the thermally conductive particles, the dispersant, the fluorosurfactant, the crosslinking agent, the tackifier resin, the acrylic oligomer, and the silane cup.
- other additives may be included depending on the application.
- a plasticizer, a filler, anti-aging agent, a coloring agent (a pigment, dye, etc.) etc. are mentioned, for example.
- the thickness of the pressure-sensitive adhesive layer is, for example, 25 to 400 ⁇ m, and the lower limit thereof is preferably 45 ⁇ m, more preferably 50 ⁇ m, still more preferably 75 ⁇ m, and particularly preferably 100 ⁇ m. Moreover, the upper limit becomes like this. Preferably it is 250 micrometers, More preferably, it is 200 micrometers, More preferably, it is 150 micrometers. By setting it as the above thickness, sufficient adhesive force and holding force can be obtained.
- the pressure-sensitive adhesive layer can be formed from a pressure-sensitive adhesive composition in which a base polymer such as the acrylic polymer, the heat conductive particles, and the dispersant added as necessary are mixed.
- a monomer component for forming a base polymer such as the acrylic polymer, the polymerization initiator (for example, photopolymerization initiator, thermal polymerization initiator, etc.), an appropriate solvent (toluene or ethyl acetate). Etc.) are mixed to prepare a monomer solution, and a polymer solution containing a base polymer such as an acrylic polymer in which monomer components are copolymerized by performing a polymerization reaction according to the type of the polymerization initiator on the monomer solution.
- the heat conductive particles and, if necessary, the dispersing agent are blended into the polymer solution to prepare a pressure-sensitive adhesive composition having a viscosity suitable for coating.
- a monomer mixture for forming a base polymer such as an acrylic polymer, a photopolymerization initiator, etc. is mixed to prepare a monomer mixture, and the monomer mixture is mixed with the monomer mixture.
- the thermally conductive particles are added to the syrup as needed.
- the above-mentioned dispersant and the like may be blended to prepare a composition having a viscosity suitable for coating, and the pressure-sensitive adhesive layer may be formed using the composition.
- the pressure-sensitive adhesive composition preferably has an appropriate viscosity from the viewpoint of excellent coatability.
- the viscosity of the pressure-sensitive adhesive composition is preferably, for example, 0.5 to 50 Pa ⁇ s, and the lower limit is more preferably 1 Pa ⁇ s, and even more preferably 5 Pa ⁇ s.
- the upper limit is more preferably 40 Pa ⁇ s.
- the viscosity means a rotor: No. using a BH viscometer as a viscometer. The viscosity measured under the conditions of 5 rotors, rotation speed: 10 rpm, measurement temperature: 30 ° C.
- the viscosity of the pressure-sensitive adhesive composition is, for example, a method of blending various polymer components such as acrylic rubber and a thickening additive, a monomer component for forming an acrylic polymer (for example, forming an acrylic polymer ( It can be adjusted by a method of partially polymerizing a monomer component such as (meth) acrylic acid ester, etc.) to obtain a partial polymer.
- the pressure-sensitive adhesive layer surface (adhesive surface) of the heat conductive pressure-sensitive adhesive sheet of the present invention may be protected by a release liner until use.
- the release liner is used as a protective material for the pressure-sensitive adhesive layer, and is peeled off when the pressure-sensitive adhesive sheet is attached to an adherend. Note that the release liner is not necessarily provided.
- a conventional release paper or the like can be used.
- a fluoropolymer for example, polytetrafluoro Low adhesion substrates made of ethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.
- a low adhesive substrate made of a polymer for example, an olefin resin such as polyethylene or polypropylene
- an olefin resin such as polyethylene or polypropylene
- a release liner having a release treatment layer formed on at least one surface of a release liner base material can be suitably used.
- release liner base materials include polyester films (polyethylene terephthalate film, etc.), olefin resin films (polyethylene film, polypropylene film, etc.), polyvinyl chloride films, polyimide films, polyamide films (nylon films), rayon films.
- plastic base film synthetic resin film
- papers quality paper, Japanese paper, kraft paper, glassine paper, synthetic paper, topcoat paper, etc.
- the release treatment agent constituting the release treatment layer is not particularly limited, and for example, a silicone release treatment agent, a fluorine release treatment agent, a long-chain alkyl release treatment agent, or the like can be used.
- the release treatment agents can be used alone or in combination of two or more.
- the thickness of the release liner, the formation method, etc. are not particularly limited.
- the method for producing the heat conductive pressure-sensitive adhesive sheet of the present invention varies depending on the composition of the pressure-sensitive adhesive composition and the like, and is not particularly limited.
- a known forming method can be used. For example, the following (1) to ( 4) and the like.
- (1) A pressure-sensitive adhesive composition containing a monomer component that forms a base polymer such as the acrylic polymer, a partially polymerized product of the monomer component, the thermally conductive particles, and, if necessary, the dispersant described above is non-adhesive.
- a composition layer is formed by coating (coating) on a layer (such as a substrate), and the composition layer is cured (for example, cured by irradiation with active energy rays such as heat curing or ultraviolet rays) to form an adhesive layer.
- a layer such as a substrate
- the composition layer is cured (for example, cured by irradiation with active energy rays such as heat curing or ultraviolet rays) to form an adhesive layer.
- Monomer component for forming a base polymer such as the acrylic polymer, a partial polymer of the monomer component, the thermally conductive particles, and the dispersant as necessary.
- the pressure-sensitive adhesive composition is applied (coated) on a separator to form a composition layer, and the composition layer is cured (for example, cured by irradiation with active energy rays such as heat curing or ultraviolet light).
- a method for producing an adhesive sheet by transferring the adhesive layer onto a non-adhesive layer (such as a substrate) (3) a base polymer (including a polymer solution) such as the above acrylic polymer, the thermally conductive particles, If necessary, the pressure-sensitive adhesive composition in which the above-mentioned dispersant or the like is uniformly dissolved and dispersed is applied (coated) on a non-tacky layer (base material, etc.) and dried to form a pressure-sensitive adhesive layer. 4.
- a non-adhesive layer such as a substrate
- a base polymer including a polymer solution
- the pressure-sensitive adhesive composition in which the above-mentioned dispersant or the like is uniformly dissolved and dispersed is applied (coated) on a non-tacky layer (base material, etc.) and dried to form a pressure-sensitive adhesive layer.
- Method for producing pressure-sensitive adhesive sheet (4) A pressure-sensitive adhesive in which the base polymer (including polymer solution) such as the above-mentioned acrylic polymer, the above-mentioned heat conductive particles, and, if necessary, the above-mentioned dispersant are uniformly dissolved and dispersed
- a method of producing a pressure-sensitive adhesive sheet by coating (coating) a composition on a separator and drying to form a pressure-sensitive adhesive layer, and then transferring the pressure-sensitive adhesive layer onto a non-pressure-sensitive layer (such as a substrate).
- the curing method in the above (1) to (4) it is possible to form a pressure-sensitive adhesive layer that is homogeneous and has a smooth surface even when a thin pressure-sensitive adhesive layer containing heat conductive particles is formed in terms of excellent productivity.
- a method of curing with active energy rays (particularly a method of curing with ultraviolet rays) is preferable.
- hardening with active energy rays may be inhibited by oxygen in the air, for example, when hardening, oxygen is obtained by bonding a separator on the pressure-sensitive adhesive layer or hardening in a nitrogen atmosphere. Is preferably blocked.
- a bubble-containing pressure-sensitive adhesive composition obtained by introducing and mixing bubbles (bubble-forming gas) into the pressure-sensitive adhesive composition containing the thermally conductive particles, It can apply
- a known coating method can be adopted, and is not particularly limited. For example, roll coating, kiss roll coating, gravure coating, reverse coating , Roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater, and the like.
- the thickness (total thickness) of the heat conductive pressure-sensitive adhesive sheet of the present invention is, for example, 50 to 500 ⁇ m in order to cope with the recent miniaturization of mobile devices and home appliances.
- the lower limit is preferably 80 ⁇ m, more preferably 100 ⁇ m, and still more preferably 140 ⁇ m.
- the upper limit is preferably 300 ⁇ m, more preferably 250 ⁇ m, and still more preferably 240 ⁇ m.
- the thickness (total thickness) of the heat conductive adhesive sheet does not include the thickness of the release liner.
- the ratio of the thickness of the non-adhesive layer (such as a substrate) to the total thickness of the adhesive sheet (the former / the latter) is, for example, 0.03 to 0.6.
- the lower limit is preferably 0.04, more preferably 0.05, and the upper limit is preferably 0.5, more preferably 0.3, and still more preferably 0.2.
- the ratio of the thickness of the non-adhesive layer (such as a substrate) and the thickness of the adhesive layer is in the above range, more excellent thermal conductivity, anti-sticking wrinkle resistance, and smoothness can be obtained.
- 180 ° Peel Adhesive Force (180 ° Peeling Adhesive Force) of Adhesive Surface of Thermal Conductive Adhesive Sheet of the Present Invention (23 ° C., 50% RH, Tensile Speed 300 mm / min, Peeling Condition of Peeling Angle 180 °, SUS304 Steel Plate ) Is preferably 2N / 20 mm or more (for example, 2 to 20 N / 20 mm), more preferably 2.5 N / 20 mm or more (for example, 2.5 to 20 N / 20 mm).
- the heat conductive adhesive sheet of the present invention preferably has a heat resistance value of 6 K ⁇ cm 2 / W or less.
- the upper limit is more preferably 5K ⁇ cm 2 / W, even more preferably 4.5K ⁇ cm 2 / W.
- the lower limit is, for example, 1 K ⁇ cm 2 / W, and usually 3 K ⁇ cm 2 / W. When the thermal resistance value is within this range, more excellent thermal conductivity can be obtained.
- the heat conductive adhesive sheet of the present invention preferably has a thermal conductivity of 0.3 W / m ⁇ K or more.
- the lower limit is more preferably 0.4 W / m ⁇ K, and still more preferably 0.45 W / m ⁇ K.
- the upper limit is 2.0 W / m * K, for example, and is 1.5 W / m * K normally. When the thermal conductivity is within this range, more excellent thermal conductivity can be obtained.
- the thermal resistance value and the thermal conductivity can be evaluated by, for example, a method described in “(1) Thermal resistance value and thermal conductivity” in (Evaluation) described later.
- the heat conductive pressure-sensitive adhesive sheet of the present invention preferably has VTM-0 or V-0 flame retardancy in the flame retardancy test of UL94 standard.
- the heat conductive pressure-sensitive adhesive sheet of the present invention preferably has an initial elastic modulus in the range of 0.5 to 2000 MPa.
- the lower limit is more preferably 5 MPa, still more preferably 50 MPa.
- the upper limit is more preferably 1000 MPa, and further preferably 500 MPa. When the initial elastic modulus is in this range, better sticking wrinkle resistance can be obtained.
- the arithmetic average surface roughness Ra on the non-stick surface side is preferably in the range of 0.001 to 1.0 ⁇ m.
- the lower limit is more preferably 0.05 ⁇ m, still more preferably 0.01 ⁇ m.
- the upper limit is more preferably 0.5 ⁇ m, and still more preferably 0.2 ⁇ m.
- the heat conductive adhesive sheet of the present invention preferably has a holding power (80 ° C., 100 gf) of 0.5 mm or less.
- the holding force is more preferably 0.3 mm or less, and still more preferably 0.15 mm or less.
- the heat conductive pressure-sensitive adhesive sheet of the present invention is excellent in heat conductivity, anti-wrinkle resistance, and smoothness. Therefore, mobile devices (for example, mobile phones, smartphones, portable information terminals, etc.), home appliances (for example, digital cameras, It can be suitably used in applications such as fixing components (electrical / electronic device components) used in electronic devices such as video movies, personal computers, hard disks, LED lighting, and lithium ion batteries. In recent years, as electric and electronic devices have become smaller and more dense, the heat generated inside when using electric and electronic devices has become difficult to cool down to the outside of the device. There is a risk of fire inside the electronic device.
- the heat conductive pressure-sensitive adhesive sheet of the present invention has excellent heat conductivity, the electric / electronic inside a small / thin (for example, 1 to 20 mm) electric / electronic device in which heat can be trapped easily. It is suitable for the fixing use of equipment components.
- Example 1 As monomer components, 82 parts by weight of 2-ethylhexyl acrylate, 12 parts by weight of 2-methoxyethyl acrylate, 5 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 1 part by weight of hydroxyethyl acrylamide (HEAA) are mixed.
- NDP N-vinyl-2-pyrrolidone
- HEAA hydroxyethyl acrylamide
- dipentaerythritol hexaacrylate (trade name “KAYARAD DPHA-40H”, manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and trade name “Plysurf A212E” (as a dispersant) 1 part by weight of Daiichi Kogyo Seiyaku Co., Ltd.) was added.
- heat conductive particles 100 parts by weight of aluminum hydroxide powder trade name “Hijilite H-31” (shape: crushed, average particle size: 18 ⁇ m, Showa Denko KK), aluminum hydroxide powder A trade name “Hijilite H-42” (shape: crushed, average particle size: 1 ⁇ m, Showa Denko KK) 100 parts by weight was added to obtain a composition.
- a composition layer is formed by applying the above composition to the release treatment surface of a release liner made of polyethylene terephthalate (trade name “Diafoil MRF38” (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.)). On this composition layer, the same release liner as described above was laminated such that the release treatment surface was on the composition layer side.
- the release liner on one side of the pressure-sensitive adhesive layer is peeled off, and the surface of the pressure-sensitive adhesive layer and a polyethylene terephthalate film (base material) (trade name “Lumirror S10 # 12”, manufactured by Toray Industries, Inc., thickness 12 ⁇ m)
- base material a polyethylene terephthalate film (base material) (trade name “Lumirror S10 # 12”, manufactured by Toray Industries, Inc., thickness 12 ⁇ m)
- the total thickness (excluding the release liner) of the single-sided PSA sheet was 187 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 2 The release liner / adhesive layer / base material was the same as in Example 1 except that a polyethylene terephthalate film (trade name “Lumirror S10 # 25”, manufactured by Toray Industries, Inc., thickness 25 ⁇ m) was used as the base material.
- a single-sided pressure-sensitive adhesive sheet having a configuration was produced.
- the total thickness of the single-sided PSA sheet (thickness excluding the release liner) was 200 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 3 Except that the thickness of the pressure-sensitive adhesive layer was 150 ⁇ m and a polyethylene terephthalate film (trade name “Lumirror S10 # 38”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m) was used as the base material, A single-sided pressure-sensitive adhesive sheet having a configuration of release liner / pressure-sensitive adhesive layer / base material was produced. The total thickness (excluding the release liner) of the single-sided PSA sheet was 188 ⁇ m. The content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 4 Except that the thickness of the pressure-sensitive adhesive layer was 150 ⁇ m, and a polyethylene terephthalate film (trade name “Lumirror S10 # 50”, manufactured by Toray Industries, Inc., thickness 50 ⁇ m) was used as the base material, A single-sided pressure-sensitive adhesive sheet having a configuration of release liner / pressure-sensitive adhesive layer / base material was produced. The total thickness of the single-sided PSA sheet (thickness excluding the release liner) was 200 ⁇ m. The content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 5 Two polyethylene terephthalate films (trade name “Diafoil M110-9”, manufactured by Mitsubishi Chemical Co., Ltd., thickness 9 ⁇ m) and aluminum foil (thickness 7 ⁇ m) are bonded together with an adhesive, and then polyethylene terephthalate film / aluminum foil / polyethylene terephthalate film.
- a substrate having a three-layer structure was prepared. The thickness of the substrate is 30 ⁇ m.
- An adhesive sheet was prepared.
- the total thickness (excluding the release liner) of the single-sided PSA sheet was 205 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 6 Polyethylene terephthalate film (trade name “Lumirror S10 # 25”, manufactured by Toray Industries, Inc., thickness 25 ⁇ m) (trade name “Diafoil M110-9”, manufactured by Mitsubishi Chemical Corporation, thickness 9 ⁇ m) and one aluminum foil (thickness 7 ⁇ m) ) Were bonded with an adhesive to prepare a base material having a three-layer structure of polyethylene terephthalate film / aluminum foil / polyethylene terephthalate film. The thickness of the substrate is 47 ⁇ m.
- An adhesive sheet was prepared.
- the adhesive layer was provided in the 9-micrometer-thick polyethylene terephthalate film side among the said base materials.
- the total thickness (excluding the release liner) of the single-sided PSA sheet was 197 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 7 Polyethylene terephthalate film (trade name “Lumirror S10 # 38”, manufactured by Toray Industries, Inc., thickness 38 ⁇ m) (trade name “Diafoil M110-9”, manufactured by Mitsubishi Chemical Corporation, thickness 9 ⁇ m) and one aluminum foil (thickness 7 ⁇ m) ) Were bonded with an adhesive to prepare a base material having a three-layer structure of polyethylene terephthalate film / aluminum foil / polyethylene terephthalate film. The thickness of the substrate is 60 ⁇ m.
- An adhesive sheet was prepared.
- the adhesive layer was provided in the 9-micrometer-thick polyethylene terephthalate film side among the said base materials.
- the total thickness (excluding the release liner) of the single-sided PSA sheet was 185 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 8 The configuration of the release liner / adhesive layer / base material was the same as in Example 1 except that a polyethylene terephthalate film (trade name “Lumirror 2DC61”, manufactured by Toray Industries, Inc., thickness 2 ⁇ m) was used as the base material.
- a single-sided PSA sheet was prepared.
- the total thickness (excluding the release liner) of the single-sided PSA sheet was 177 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 9 Exfoliation was carried out in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was 38 ⁇ m, and an aluminum foil (trade name “BESPA”, manufactured by Sumi Light Aluminum Foil Co., Ltd., thickness 12 ⁇ m) was used as the base material.
- BESPA aluminum foil
- a single-sided pressure-sensitive adhesive sheet with a base material having a liner / pressure-sensitive adhesive layer / base material structure was produced.
- a black single-sided tape (thermal radiation layer) (trade name “UTS-10BAF”, manufactured by Nitto Denko Corporation, thickness 10 ⁇ m) is bonded onto the aluminum foil of the above-mentioned single-sided pressure-sensitive adhesive sheet with a substrate, and a release liner / adhesive
- a single-sided PSA sheet having a configuration of layer / base material layer / heat radiation layer was produced.
- the total thickness (excluding the release liner) of the single-sided PSA sheet was 60 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 10 Release liner / adhesive layer / base material in the same manner as in Example 9 except that a black single-sided tape (trade name “UTS-20BAF”, manufactured by Nitto Denko Corporation, thickness 20 ⁇ m) was used as the heat radiation layer.
- a single-sided PSA sheet having a layer / heat radiation layer configuration was prepared.
- the total thickness (thickness excluding the release liner) of the single-sided PSA sheet was 70 ⁇ m.
- the content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- Example 1 In the same manner as in Example 1, a laminate having a configuration of release liner / adhesive layer (thickness: 175 ⁇ m) / release liner was obtained. This was made into the double-sided adhesive sheet. The total thickness (thickness excluding the release liner) of the double-sided PSA sheet was 175 ⁇ m. The content ratio (particle volume ratio) of the heat conductive particles in the pressure-sensitive adhesive layer was 42.9% by volume.
- FIG. 3A is a schematic front view of the thermal characteristic evaluation apparatus
- FIG. 3B is a schematic side view of the thermal characteristic evaluation apparatus. Note that the release liner was removed during the measurement.
- a pair of aluminum blocks (A5052, thermal conductivity: 140 W / m ⁇ K) (sometimes referred to as “rods”) L formed so as to form a cube having one side of 20 mm.
- the pressure-sensitive adhesive sheet 1 (width: 20 mm, length: 20 mm) was sandwiched between them, and a pair of blocks L were bonded together with the pressure-sensitive adhesive sheet 1.
- the heating element H is disposed on the upper block L
- the radiator C is disposed below the block L on the lower side.
- the pair of blocks L bonded together with the pressure-sensitive adhesive sheet 1 is positioned between a pair of pressure adjusting screws T that penetrates the heating element H and the radiator C.
- a load cell R is disposed between the pressure adjusting screw T and the heating element H, and is configured to measure the pressure when the pressure adjusting screw T is tightened. The pressure applied to the pressure-sensitive adhesive sheet 1 was used.
- the pressure adjusting screw T was tightened so that the pressure applied to the pressure-sensitive adhesive sheet 1 was 25 N / cm 2 (250 kPa).
- three probes P (diameter 1 mm) of a contact-type displacement meter were installed so as to penetrate the lower block L and the adhesive sheet 1 from the radiator C side. At this time, the upper end portion of the probe P is in contact with the lower surface of the upper block L, and the distance between the upper and lower blocks L (the thickness of the adhesive sheet 1) can be measured.
- a temperature sensor D was attached to the heating element H and the upper and lower blocks L.
- the temperature sensor D was attached to one place of the heating element H, and the temperature sensors D were attached to the five places of each block L at intervals of 5 mm in the vertical direction.
- the pressure adjusting screw T was tightened, pressure was applied to the adhesive sheet 1, the temperature of the heating element H was set to 80 ° C., and cooling water of 20 ° C. was circulated through the radiator C. .
- the temperature of the upper and lower blocks L is measured by each temperature sensor D, and the thermal conductivity (W / m ⁇ K) and temperature gradient of the upper and lower blocks L are measured.
- Holding power It carried out according to evaluation of the holding power of JISZ1528 by making the adhesive sheet obtained by said Example and the comparative example into an evaluation sample.
- a sample with a backing material was obtained using “Lumirror S-10 # 25” manufactured by Toray Industries, Inc. on one side (adhesive side) of the adhesive sheet.
- a sample with a backing material is pasted by reciprocating a 2 kg roller so as to have an area of 10 mm ⁇ 20 mm, and after curing at room temperature of 23 ° C. for 30 minutes, a load of 100 g is applied in an atmosphere of 80 ° C. for 1 hour, The amount of displacement from the initial stage of application was confirmed, and the value was set as the holding power (mm).
- the thermally conductive adhesive sheet of the present invention can thermally connect between members on both sides of the sheet, exhibits excellent thermal conductivity, and adherends such as members are adhered and fixed on the adhesive surface, and is non-adhesive On the surface, members and the like are not attached and fixed, and can be moved and removed when necessary, and thus, for example, it is useful as a heat conductive adhesive sheet for thin electric / electronic devices.
- Adhesive layer 20
- Non-adhesive layer (base material) 21
- Plastic Film 1 Adhesive Sheet (Thermal Conductive Adhesive Sheet) 2
- Thermometer 3 Contact displacement meter C
- Heating element (heat block) L block (rod) P probe R load cell T pressure adjusting screw
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Abstract
Description
また、本発明の他の目的は、上記特性に加え、被着体貼り付け時にシートに皺が生じにくい熱伝導性粘着シートを提供することにある。
さらに、本発明の別の目的は、上記特性に加え、シート表面が平滑で、シートの片方の面に接している部材や部品を動かしたり取り外したりする際、その操作を円滑に行うことができる熱伝導性粘着シートを提供することにある。
非粘着層として、例えば、基材などが挙げられる。前記基材としては、特に限定されないが、例えば、布、不織布、フェルト、ネット等の繊維系基材;各種の紙等の紙系基材;アルミニウム、金、銀、銅、亜鉛、ニッケル、合金等の金属箔又は金属板等の金属系基材;各種樹脂によるフィルムやシート等のプラスチック基材;発泡シート等の発泡体;グラファイト;これらの積層体などが挙げられる。これらのなかでも、強度や強靱性、電気絶縁性の点より、少なくともプラスチックフィルムを有する基材が好ましい。基材は単層であっても複層であってもよい。
熱伝導性粘着シートの粘着剤層は接着性を発揮する。このような粘着剤層は粘着剤組成物により形成される。例えば、後述のアクリル系粘着剤層はアクリル系粘着剤組成物により形成される。
本発明の熱伝導性粘着シートは、粘着剤層に熱伝導性粒子を含有しているので、良好な熱伝導性が得られるとともに、粘着シートを燃えにくくでき、粘着シートで炎を広がりにくくできる。すなわち、優れた熱伝導性と難燃性が得られる。熱伝導性粒子は、単独で又は2種以上組み合わせて用いることができる。
上記粘着剤層には、本発明の効果を損なわない範囲で、上記熱伝導性粒子を凝集させることなく安定して分散させるために、さらに分散剤が含まれていてもよい。
上記粘着剤層には、さらに、フッ素系界面活性剤が含まれていてもよい。上記フッ素系界面活性剤を用いることにより、ベースポリマーと熱導電性粒子との密着度や摩擦抵抗が低減され、応力分散性が向上する場合がある。そのため、本発明の熱伝導性粘着シートにおいて、より高い粘着性が得られる場合がある。
上記粘着剤層には、粘着剤層の凝集力を調整できるという観点から、さらに架橋剤が含まれていてもよい。上記架橋剤は、公知慣用の架橋剤を使用することができ、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤などを挙げることができる。中でも、イソシアネート系架橋剤、エポキシ系架橋剤が好ましい。
上記粘着剤層には、粘着性が一層向上するという観点から、さらに粘着付与樹脂が含まれていてもよい。特に、上記アクリル系ポリマー等のベースポリマーを構成するモノマー成分にカルボキシル基含有モノマーが含まれない場合は、粘着剤層の厚みが薄いと、高い粘着力が得られにくいため、粘着付与樹脂が含まれることが好ましい。上記粘着付与樹脂としては、特に限定されないが、紫外線を照射して、モノマー成分を共重合してアクリル系ポリマーを得る場合、併用しても重合阻害が起こりにくいという理由から、水素添加型の粘着付与樹脂を用いることが好ましい。水素添加型の粘着付与樹脂としては、例えば、ロジン系樹脂、石油系樹脂、テルペン系樹脂、クマロン・インデン系樹脂、スチレン系樹脂、アルキルフェノール樹脂、キシレン樹脂などの粘着付与樹脂に水素添加した誘導体(水素添加型ロジン系樹脂、水素添加型石油系樹脂、水素添加型テルペン系樹脂など)が挙げられる。中でも、水素添加型ロジン系樹脂が好ましい。上記水素添加型ロジン系粘着付与樹脂としては、例えば、ガムロジン、ウッドロジン、トール油ロジンなどの未変性ロジン(生ロジン)を水添化により変性した変性ロジンなどが挙げられる。
上記粘着剤層には、粘着性が一層向上するという観点から、さらにアクリル系オリゴマーが含まれていてもよい。上記アクリル系オリゴマーは、上記アクリル系ポリマーよりもガラス転移温度(Tg)が高く、重量平均分子量が小さい重合体であり、粘着付与樹脂として機能し、かつ紫外線を用いた重合の際に重合阻害を起こしにくいという利点を有する。
上記粘着剤層には、粘着力、耐久力がより向上するという点や、上記熱伝導性粒子と上記アクリル系ポリマー等のベースポリマーとの親和性をより向上させるという点から、さらにシランカップリング剤が含まれていてもよい。
上記粘着剤層は、気泡を含有する粘着剤層であってもよい。上記気泡を含有する粘着剤層は、粘着剤層に厚みとクッション性を付与することができ、被着体表面の凹凸を埋める性能、即ち凹凸吸収性(凹凸追従性)が向上する。
上記粘着剤層には、上記アクリル系ポリマー等のベースポリマー、上記熱伝導性粒子、上記分散剤、上記フッ素系界面活性剤、上記架橋剤、上記粘着付与樹脂、上記アクリル系オリゴマー、上記シランカップリング剤の他に、用途に応じて、その他の添加剤が含まれていてもよい。上記その他の添加剤としては、例えば、可塑剤、充填剤、老化防止剤、着色剤(顔料や染料など)などが挙げられる。
本発明の熱伝導性粘着シートの粘着剤層表面(粘着面)は、使用時までは剥離ライナーにより保護されていてもよい。剥離ライナーは粘着剤層の保護材として用いられており、粘着シートを被着体に貼付する際に剥がされる。なお、剥離ライナーは、必ずしも設けられていなくてもよい。
(1)上記アクリル系ポリマー等のベースポリマーを形成するモノマー成分、該モノマー成分の部分重合物、前記熱伝導性粒子、必要に応じて、上記分散剤などを含む粘着剤組成物を、非粘着層(基材など)上に塗布(塗工)して組成物層を形成し、該組成物層を硬化(例えば、熱硬化や紫外線などの活性エネルギー線照射による硬化)させて粘着剤層を形成して粘着シートを製造する方法
(2)上記アクリル系ポリマー等のベースポリマーを形成するモノマー成分、該モノマー成分の部分重合物、前記熱伝導性粒子、必要に応じて、上記分散剤などを含む粘着剤組成物を、セパレータ上に塗布(塗工)して組成物層を形成し、該組成物層を硬化(例えば、熱硬化や紫外線などの活性エネルギー線照射による硬化)させて粘着剤層を形成した後、該粘着剤層を非粘着層(基材など)上に転写して粘着シートを製造する方法
(3)上記アクリル系ポリマー等のベースポリマー(ポリマー溶液などを含む)、前記熱伝導性粒子、必要に応じて、上記分散剤などを均一に溶解、分散させた粘着剤組成物を、非粘着層(基材など)上に塗布(塗工)し、乾燥させて粘着剤層を形成して粘着シートを製造する方法
(4)上記アクリル系ポリマー等のベースポリマー(ポリマー溶液などを含む)、前記熱伝導性粒子、必要に応じて、上記分散剤などを均一に溶解、分散させた粘着剤組成物を、セパレータ上に塗布(塗工)し、乾燥させて粘着剤層を形成した後、該粘着剤層を非粘着層(基材など)上に転写して粘着シートを製造する方法
モノマー成分として、アクリル酸2-エチルヘキシル82重量部、アクリル酸2-メトキシエチル12重量部、N-ビニル-2-ピロリドン(NVP)5重量部、ヒドロキシエチルアクリルアミド(HEAA)1重量部とが混合されたモノマー混合物に、光重合開始剤として商品名「イルガキュアー651」(2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、BASFジャパン社製)0.05重量部および商品名「イルガキュアー184」(1-ヒドロキシシクロヘキシルフェニルケトン、BASFジャパン社製)0.05重量部を配合した後、粘度(BH粘度計No.5ローター、10rpm、測定温度30℃)が約20Pa・sになるまで紫外線を照射して、モノマー成分の一部が重合した混合物(モノマー混合物の部分重合物、シロップ)を作製した。
上記シロップ100重量部に、多官能モノマーとしてジペンタエリスリトールヘキサアクリレート(商品名「KAYARAD DPHA-40H」、日本化薬社製)0.05重量部と、分散剤として商品名「プライサーフA212E」(第一工業製薬社製)1重量部とを添加した。さらに、熱伝導性粒子として、水酸化アルミニウム粉末である商品名「ハイジライトH-31」(形状:破砕状、平均粒径:18μm、昭和電工社製)100重量部と、水酸化アルミニウム粉末である商品名「ハイジライトH-42」(形状:破砕状、平均粒径:1μm、昭和電工社製)100重量部とを添加し、組成物を得た。
片面に剥離処理が施されているポリエチレンテレフタレート製の剥離ライナー(商品名「ダイアホイルMRF38」(三菱化学ポリエステルフィルム社製)の剥離処理面に、上記組成物を塗布して組成物層を設け、この組成物層の上に、上記と同様の剥離ライナーを剥離処理面が組成物層側となるように積層した。
次に、照度約5mW/cm2の紫外線を、積層体の両面から3分間照射し、組成物層を硬化させて、厚み175μmの粘着剤層を形成し、剥離ライナー/粘着剤層/剥離ライナーの構成を有する積層体を得た。なお、粘着剤層に含まれるアクリル系ポリマーのガラス転移温度は、-62.8℃であった。また、粘着剤層に含まれるアクリル系ポリマーの重量は、上記シロップを構成するモノマーと、多官能モノマーの合計量に相当する。
次いで、上記粘着剤層の片面の剥離ライナーを剥離し、上記粘着剤層の表面と、ポリエチレンテレフタレートフィルム(基材)(商品名「ルミラーS10#12」、東レ株式会社製、厚み12μm)とを貼り合わせて、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、187μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
基材として、ポリエチレンテレフタレートフィルム(商品名「ルミラーS10#25」、東レ株式会社製、厚み25μm)を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、200μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
粘着剤層の厚みを150μmとし、且つ基材として、ポリエチレンテレフタレートフィルム(商品名「ルミラーS10#38」、東レ株式会社製、厚み38μm)を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、188μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
粘着剤層の厚みを150μmとし、且つ基材として、ポリエチレンテレフタレートフィルム(商品名「ルミラーS10#50」、東レ株式会社製、厚み50μm)を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、200μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
ポリエチレンテレフタレートフィルム(商品名「ダイアホイル M110-9」、三菱化学株式会社製、厚み9μm)2枚とアルミ箔(厚み7μm)を接着剤で貼り合わせて、ポリエチレンテレフタレートフィルム/アルミ箔/ポリエチレンテレフタレートフィルムの3層構造の基材を作製した。基材の厚みは30μmである。
粘着剤層の厚みを175μmとし、且つ基材として、上記3層構造の基材を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、205μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
ポリエチレンテレフタレートフィルム(商品名「ルミラーS10#25」、東レ株式会社製、厚み25μm)(商品名「ダイアホイル M110-9」、三菱化学株式会社製、厚み9μm)各1枚とアルミ箔(厚み7μm)を接着剤で貼り合わせて、ポリエチレンテレフタレートフィルム/アルミ箔/ポリエチレンテレフタレートフィルムの3層構造の基材を作製した。基材の厚みは47μmである。
粘着剤層の厚みを150μmとし、且つ基材として、上記3層構造の基材を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。なお、前記基材のうち厚み9μmのポリエチレンテレフタレートフィルム側に粘着剤層を設けた。片面粘着シートの総厚(剥離ライナーを除く厚み)は、197μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
ポリエチレンテレフタレートフィルム(商品名「ルミラーS10#38」、東レ株式会社製、厚み38μm)(商品名「ダイアホイル M110-9」、三菱化学株式会社製、厚み9μm)各1枚とアルミ箔(厚み7μm)を接着剤で貼り合わせて、ポリエチレンテレフタレートフィルム/アルミ箔/ポリエチレンテレフタレートフィルムの3層構造の基材を作製した。基材の厚みは60μmである。
粘着剤層の厚みを125μmとし、且つ基材として、上記3層構造の基材を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。なお、前記基材のうち厚み9μmのポリエチレンテレフタレートフィルム側に粘着剤層を設けた。片面粘着シートの総厚(剥離ライナーを除く厚み)は、185μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
基材として、ポリエチレンテレフタレートフィルム(商品名「ルミラー2DC61」、東レ株式会社製、厚み2μm)を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、177μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
粘着剤層の厚みを38μmとし、且つ基材として、アルミニウム箔(商品名「BESPA」、住軽アルミニウム箔株式会社製、厚み12μm)を用いたこと以外は、実施例1と同様にして、剥離ライナー/粘着剤層/基材の構成を有する基材付き片面粘着シートを作製した。さらに上記、基材付き片面粘着シートのアルミニウム箔上に黒色片面テープ(熱輻射層)(商品名「UTS-10BAF」、日東電工株式会社製、厚み10μm)を貼り合せて、剥離ライナー/粘着剤層/基材層/熱輻射層の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、60μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
熱輻射層として、黒色片面テープ(商品名「UTS-20BAF」、日東電工株式会社製、厚み20μm)を用いたこと以外は、実施例9と同様にして、剥離ライナー/粘着剤層/基材層/熱輻射層の構成を有する片面粘着シートを作製した。片面粘着シートの総厚(剥離ライナーを除く厚み)は、70μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
実施例1と同様にして、剥離ライナー/粘着剤層(厚み175μm)/剥離ライナーの構成を有する積層体を得た。これを両面粘着シートとした。両面粘着シートの総厚(剥離ライナーを除く厚み)は、175μmであった。粘着剤層における熱伝導性粒子の含有割合(粒子体積比率)は42.9体積%であった。
実施例、比較例で得られた粘着シートについて、下記の測定又は評価を行った。その結果を表1に示す。
上記の実施例、比較例で得られた粘着シートについて、厚み方向における熱伝導率を、図3に示す熱特性評価装置を用いて実施した。図3の(a)は熱特性評価装置の正面概略図であり、図3の(b)は熱特性評価装置の側面概略図である。なお、測定の際に剥離ライナーは除かれている。
具体的には、1辺が20mmの立方体となるように形成されたアルミニウム製(A5052、熱伝導率:140W/m・K)の一対のブロック(「ロッド」と称する場合もある。)L間に、粘着シート1(幅:20mm、長さ:20mm)を挟み込み、一対のブロックLを粘着シート1で貼り合わせた。
そして、一対のブロックLが上下となるように発熱体(ヒーターブロック)Hと放熱体(冷却水が内部を循環するように構成された冷却ベース板)Cとの間に配置した。具体的には、上側のブロックLの上に発熱体Hを配置し、下側にブロックLの下に放熱体Cを配置した。
このとき、粘着シート1で貼り合わされた一対のブロックLは、発熱体Hおよび放熱体Cを貫通する一対の圧力調整用ネジTの間に位置している。なお、圧力調整用ネジTと発熱体Hとの間にはロードセルRが配置されており、圧力調整用ネジTを締め込んだときの圧力が測定されるように構成されており、かかる圧力を粘着シート1に加わる圧力として用いた。
具体的には、この試験において、圧力調整用ネジTを、粘着シート1に加わる圧力が25N/cm2(250kPa)となるように締め込んだ。
また、下側のブロックLおよび粘着シート1を放熱体C側から貫通するように接触式変位計の3本のプローブP(直径1mm)を設置した。このとき、プローブPの上端部は、上側のブロックLの下面に接触した状態になっており、上下のブロックL間の間隔(粘着シート1の厚み)を測定可能に構成されている。
発熱体Hおよび上下のブロックLには温度センサーDを取り付けた。具体的には、発熱体Hの1箇所に温度センサーDを取り付け、各ブロックLの5箇所に上下方向に5mm間隔で温度センサーDをそれぞれ取り付けた。
測定はまず初めに、圧力調整用ネジTを締め込んで、粘着シート1に圧力を加え、発熱体Hの温度を80℃に設定するともに、放熱体Cに20℃の冷却水を循環させた。
そして、発熱体Hおよび上下のブロックLの温度が安定した後、上下のブロックLの温度を各温度センサーDで測定し、上下のブロックLの熱伝導率(W/m・K)と温度勾配から粘着シート1を通過する熱流束を算出するとともに、上下のブロックLと粘着シート1との界面の温度を算出した。そして、これらを用いて圧力における熱伝導率(W/m・K)および熱抵抗(K・cm2/W)を、下記の熱伝導率方程式(フーリエの法則)を用いて算出した。
Q=-λgradT
R=L/λ
Q:単位面積あたりの熱流速
gradT:温度勾配
L:シートの厚み
λ:熱伝導率
R:熱抵抗
上記の実施例、比較例で得られた各粘着シートを20mm×100mmの大きさに切出し、サンプルとした。SUS304BA板を被着体として、サンプルの基材面より2kgローラー1往復にて貼り合わせた。貼り合せ方向に対して垂直方向に発生した基材面のシワの発生個数を下記の基準で評価した。
○:10mm以上におよぶシワが20カ所未満
△:10mm以上におよぶシワが20カ所以上50カ所未満
×:10mm以上におよぶシワが50カ所以上
上記の実施例、比較例で得られた粘着シートを評価サンプルとして初期長さ10mm、断面積1.2~5.0mm2となるよう切断し、測定温度23℃、チャック間距離10mm、引張速度300mm/minで引張試験を行い、サンプルの伸びの変化量(mm)を測定した。その結果、得られたS-S曲線の初期の立ち上がりの部分に接線を引き、その接線が100%伸びに相当するときの引張強度を評価サンプルの断面積で割り、引張弾性率(MPa)とした。
上記の実施例、比較例で得られた粘着シートをスライドガラスに貼り合わせた後、基材表面(比較例1では粘着面)の表面粗さについて、光学式プロファイラーNT9100(Veeco社製)を使用して、Measurement Type:VSI(Infinite Scan)、Objective:2.5X、FOV:1.0X、Modulation Threshold:0.1%の条件で、n=3で測定した。測定後、Terms Removal:Tilt Only(Plane Fit)、Window Filtering:Noneにてデータ解析を行い、算術平均表面粗さRa(μm)を求めた。
上記の実施例、比較例で得られた粘着シートを評価サンプルとして、JIS Z1528の保持力の評価に準じて行った。粘着シートの片面(粘着面)に東レ社製「ルミラーS-10#25」を用いて裏打ち材つきのサンプルを得た。裏打ち材つきサンプルを10mm×20mmの面積になるように2kgローラー1往復にて貼付けを行い、30分間23℃の室温にて養生したのち、80℃の雰囲気下100gの荷重を1時間印加し、貼付け初期からのズレ量を確認して保持力(mm)の値とした。
上記の実施例、比較例で得られた各粘着シートを評価サンプルとして20mm×100mmの大きさに切出し、剥離ライナーを剥がして、露出した粘着面をSUS304BA板(被着体A)に2kgローラー1往復(速度:5mm/秒)にて貼り合わせた。次いで、基材面(比較例1では他方の剥離ライナーを剥がして露出した粘着面)をSUS304BA板(被着体B)上に設置し、2kgローラー1往復(速度:5mm/秒)にて押圧した。これを80℃で2時間加温し、1時間室温で放冷した後、サンプルを被着体Bとの界面で、引き剥がし角度180°にて10mm/秒の速度で剥離し、被着体Bに糊残りがしているかどうかを目視観察し、以下の基準で評価した。
○:糊残りなし
×:糊残りあり
20 非粘着層(基材)
21 プラスチックフィルム
22 金属箔
23 プラスチックフィルム
1 粘着シート(熱伝導性粘着シート)
2 温度計
3 接触式変位計
C 放熱体
D 温度センサー
H 発熱体(ヒートブロック)
L ブロック(ロッド)
P プローブ
R ロードセル
T 圧力調整用ネジ
Claims (9)
- 熱伝導性粒子を含有している粘着剤層を有する熱伝導性粘着シートであって、一方の面が粘着面であり、他方の面が非粘着面となっていることを特徴とする熱伝導性粘着シート。
- 前記粘着剤層の一方の面にのみ非粘着層を有する請求項1記載の熱伝導性粘着シート。
- 前記非粘着層の厚みと粘着剤層の厚みの比(前者/後者)が、0.04~0.6である請求項2記載の熱伝導性粘着シート。
- 熱抵抗値が6K・cm2/W以下である請求項1~3の何れか1項に記載の熱伝導性粘着シート。
- 総厚みが50~500μmである請求項1~4の何れか1項に記載の熱伝導性粘着シート。
- 初期弾性率が0.5~2000MPaである請求項1~5の何れか1項に記載の熱伝導性粘着シート。
- 非粘着面側の算術平均表面粗さRaが0.001~1.0μmである請求項1~6の何れか1項に記載の熱伝導性粘着シート。
- 非粘着面が黒色である請求項1~7の何れか1項に記載の熱伝導性粘着シート。
- 薄型電気・電子機器用に用いる請求項1~8の何れか1項に記載の熱伝導性粘着シート。
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US20160152872A1 (en) | 2016-06-02 |
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JP2015164996A (ja) | 2015-09-17 |
US11149171B2 (en) | 2021-10-19 |
JP6378533B2 (ja) | 2018-08-22 |
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