TW201329221A - Thermally conductive material - Google Patents

Abstract

Provided is a thermally conductive material with excellent thermal conductivity, adhesion properties, heat resistance, and electrical insulating properties; an adhesive sheet having a thermally conductive material layer comprising the thermally conductive material; and a lighting device that uses the thermally conductive material. The thermally conductive material contains sheet shaped particles and adhesive resin as required components and is characterized in that it contains spherical particles at a volume of less than or equal to 500 parts by mass per one part by mass of sheet shaped particles and that the combined volume of sheet shaped particles and spherical particles is 1-600 parts by mass per 100 parts by mass of adhesive resin (solid content). The adhesive sheet, on at least one surface thereof, has a thermally conductive material layer comprising the thermally conductive material. The lighting device has a substrate (2) upon which is mounted a light emitting element (1), and a condenser (4), and is characterized in that the thermally conductive material layer (3) comprising the thermally conductive material is interposed between the substrate (2) and the condenser (4).

Description

Thermally conductive material

The present invention is directed to thermally conductive materials. More specifically, the present invention relates to, for example, a thermally conductive material that can be used to bond a wiring board to a member that requires heat dissipation such as a heat sink or a casing, or an adhesive sheet having a thermally conductive material layer made of the thermally conductive material, And an illumination device using the aforementioned thermally conductive material.

A sheet made of a resin composition in which a flexible resin is blended with a thermally conductive filler such as alumina or cerium oxide, and the surface of the heat generating body or the heat radiating body using the sheet is not smooth. Following these surfaces, the thermally conductive material used for the sheet is required to be soft.

In the case of a flexible heat conductive material, an anthracene is used as a base material, and a heat conductive material filled with a semiconductor heat conductive filler (for example, JP-A-2003-197833), an alumina powder, a zinc oxide powder, and the like are used. A heat conductive material of an anthrone gel and a hydrocarbyl alkoxy decane is proposed (for example, Japanese Laid-Open Patent Publication No. 2011-084621).

However, since the fluorenone and the fluorenone gel are not only low in adhesion, and the low molecular weight siloxane compound contained in these is a cause of contact failure in electronic parts and the like, the use thereof is limited in practical use.

Therefore, in recent years, it has been desired to develop a thermally conductive material excellent in thermal conductivity, adhesion, heat resistance, and electrical insulation.

The present invention provides a thermally conductive material excellent in thermal conductivity, adhesiveness, heat resistance, and electrical insulating properties, an adhesive sheet having a thermally conductive material layer having the thermally conductive material, and the use of the above-mentioned prior art. For the purpose of lighting fixtures for thermally conductive materials.

The present invention relates to (1) a thermally conductive material containing a plate-like particle and an adhesive resin as an essential component, and is characterized in that each part of the plate-like particle contains 500 parts by mass or less of spherical particles, and each adhesive resin is contained. (solid content) 100% by mass of a thermally conductive material in which the total amount of the plate-like particles and the spherical particles is 1 to 600 parts by mass, and (2) the thermally conductive material according to the above (1), wherein the length and width of the plate-like particles The heat conductive material according to the above (1) or (2), wherein the thickness of the plate-like particles is 0.01 to 20 μm, the length in the plane direction is 0.1 to 100 μm, and (4) at least one side. An adhesive sheet having a thermally conductive material layer made of the thermally conductive material according to any one of the above (1) to (3), and (5) a substrate having a substrate on which a luminescent element is mounted, and an illumination device for a radiator. Characterized by the foregoing between the substrate and the aforementioned radiator (1) The lighting device for a thermally conductive material according to any one of the above aspects.

In the present invention, a thermally conductive material excellent in thermal conductivity, adhesiveness, heat resistance, and electrical insulating properties is provided. The adhesive sheet of the present invention is excellent in thermal conductivity, adhesiveness, heat resistance, and electrical insulation because of the heat conductive material layer having the above-described heat conductive material. In the lighting fixture of the present invention, the heat conductive material of the present invention is interposed between the substrate and the heat radiator, and the substrate and the heat sink having the light emitting element are excellent in adhesion and heat conductivity, and are also excellent in electrical insulating properties.

Best form for implementing the invention

In the heat conductive material of the present invention, the heat conductive material containing the plate-like particles and the adhesive resin as an essential component is contained in an amount of 500 parts by mass or less per 1 part by mass of the plate-like particles. The total amount of the plate-like particles and the spherical particles in an amount of 100 parts by mass of the adhesive resin (solid content) is 1 to 600 parts by mass.

In the heat conductive material of the present invention, the plate-like particles and the adhesive resin are contained as an essential component, and the spherical particles are contained in an amount of a specific amount or less, and a specific amount of the plate-like particles and the ball per adhesive resin (solid content) are contained. The total amount of the particles is in a specific range, and is excellent in thermal conductivity, adhesion, heat resistance, and electrical insulation.

One of the major features of the present invention is the use of plate-like particles in the thermally conductive material. In the thermally conductive material of the present invention, the use of the plate-like particles is used. The thermal conductive material layer formed by the thermally conductive material of the invention has a high thermal conductivity in the surface direction, and thus can exhibit thermal conductivity in the plane direction. Further, in the present invention, when the plate-like particles and the spherical particles are used in combination, the thermal conductivity of the thermally conductive material layer formed by using the thermally conductive material of the present invention increases in any of the thickness direction and the surface direction. It can exhibit an isotropic thermal conductivity.

Examples of the plate-like particles include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, and typical metals such as graphite, aluminum, zinc, and tin, iron, nickel, copper, manganese, silver, and platinum. a plate-like metal particle made of a metal such as a transition metal; made of alumina, ceria, titania, zirconia, magnesia, yttria, zinc oxide, iron oxide, tantalum nitride, titanium nitride, boron nitride, carbonization Bismuth, light calcium carbonate, heavy calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, kaolinite, pyrophyllite, montmorillonite, sericite, mica, magnesium Plate-like inorganic particles made of inorganic materials such as aluminum serpentine, bentonite, asbestos, zeolite, calcium citrate, magnesium silicate, diatomaceous earth, strontium sand, etc.; calcium taurate, laurel lysine Plate-like organic particles or the like made of an organic material, etc., but the present invention is not limited only to the examples. These plate-like particles may be used singly or in combination of two or more kinds. Among the plate-like particles, in terms of improving thermal conductivity, plate-like particles made of aluminum, silver, copper, or the like, plate-like particles made of boron nitride, and graphite are used. Plate-like particles, plate-like particles made of alumina, talc and mica, plate-like particles made of aluminum, silver, copper or alloys thereof, plate-like particles made of boron nitride, The plate-like particles made of graphite and the plate-like particles made of alumina are more preferable, and are made of aluminum. Plate-shaped particles made of silver, copper or alloys thereof, plate-like particles made of boron nitride, and plate-like particles made of graphite are more preferably made of boron nitride, aluminum, silver, copper or the like. The plate-like particles made of the alloy are more preferably, and plate-like particles made of boron nitride or aluminum are particularly preferable. These plate-like particles may be used singly or in combination of two or more kinds.

In the platy particles, surface treatment can be performed as necessary. The surface treatment may be, for example, a decane coupling treatment, a titanate treatment, an oxidation treatment, a coating resin treatment, an energy ray irradiation treatment, an electrochemical treatment, or the like, and a saturated fatty acid such as stearic acid or oleic acid or linoleic acid may be used. The unsaturated fatty acid is adsorbed to the plate-like particles or the like, but the present invention is not limited to the examples. In the surface treatment, it is preferable that the plate-like particles to be coated with the coating resin are excellent in thermal conductivity and thermal adhesion, and particularly excellent in insulation properties.

The resin used for coating the resin-coated plate-like particles, that is, the resin-coated particles, may be, for example, a propylene-based resin. However, the present invention is not limited to the examples. In the propylene-based resin, for example, an acrylic resin obtained by polymerizing a monomer component mainly composed of an acrylate is preferable, and trimethylolpropane triacrylate, acrylic acid, epoxidized polybutadiene, and A resin obtained by polymerizing a monomer component of vinyl benzene is more preferable.

The coating amount of the resin in the plate-like particles covered with the resin is 100 parts by mass per plate-like particle, and from the viewpoint of improving the electrical insulating property, it is preferably 1 part by mass or more, from the viewpoint of improving the dielectric breakdown voltage. More preferably, it is 3 parts by mass or more, and more preferably 5 parts by mass or more, and from the viewpoint of improving thermal conductivity, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less. More preferably, it is 30 parts by mass or less.

The aspect ratio of the plate-like particles is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more from the viewpoint of improving thermal conductivity, and it is time-dependent to suppress mixing of the adhesive resin and the plate-like particles. From the viewpoint of adhesion, it is preferably 100 or less, more preferably 90 or less, still more preferably 80 or less.

The aspect ratio of the plate-like particles is a value obtained by dividing the maximum length of the plate-like particles in the plane direction by the maximum thickness of the plate-like particles. In other words, the aspect ratio of the plate-like particles is obtained by the formula: [the aspect ratio of the plate-like particles] = [the maximum length of the surface direction of the plate-like particles] ÷ [the maximum thickness of the plate-like particles].

The maximum length and the maximum thickness of the plate-like particles in the plane direction are such that the plate-like particles are directly observed by a scanning electron microscope or the like, and the maximum length and the maximum thickness of the arbitrarily selected plate-like particles are measured, and the average number of the measured particles is averaged. The value is obtained. The number of the plate-like particles to be measured is not particularly limited, but from the viewpoint of improving the accuracy and facilitating the measurement, about 10 to 20 are preferable. The maximum length and the maximum thickness of the plate-like particles contained in the thermally conductive material layer can be determined by measuring the plate-like particles obtained by dissolving the thermally conductive material layer in a solvent such as an organic solvent.

In the present specification, the length and thickness of the plate-like particles in the plane direction are conveniently referred to as the maximum length and the maximum thickness of the surface directions of the respective plate-like particles.

The thickness of the plate-like particles is preferably from the viewpoint of improving thermal conductivity. 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more, and it is preferably 20 μm or less, more preferably 15 μm from the viewpoint of suppressing adhesion with time when mixing the adhesive resin and the plate-like particles. The following, more preferably 10 μm or less.

The length of the plate-like particle in the surface direction is preferably 0.1 μm or more, and more preferably 0.2 μm or more from the viewpoint of improving thermal conductivity, and the viewpoint of increasing the viscosity with time due to suppression of mixing of the adhesive resin and the plate-like particles. The upper portion is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less.

Examples of the spherical particles include spherical particles of a metal oxide such as cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, or titanium oxide; and metal hydroxides such as aluminum hydroxide or magnesium hydroxide. Spherical particles; spherical particles of metal nitrides such as boron nitride, aluminum nitride, tantalum nitride, and tantalum carbide; spherical particles of metal carbide such as tantalum carbide; carbon black, graphite, etc. Spherical particles made of inorganic powder; alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, typical metals such as aluminum, zinc, and tin, iron, nickel, copper, manganese, silver, platinum, etc. Metal particles such as a metal such as a transition metal, etc., but the present invention is not limited to this example. These spherical particles may be used alone or in combination of two or more kinds. Among the spherical particles, alumina, magnesia, aluminum hydroxide, magnesium hydroxide, aluminum nitride and niobium carbide are preferred, alumina, magnesia, aluminum nitride and niobium carbide are preferred, and alumina and magnesia are preferred. For even better.

The average particle diameter of the spherical particles is preferably from 0.01 to 200 from the viewpoint of improving the dispersion stability and thermal conductivity of the thermally conductive material of the present invention. Μm, more preferably 0.01 to 100 μm. The average particle diameter of the spherical particles is a value measured by a laser diffraction/scattering type particle size distribution measuring apparatus (product number: LA-920, manufactured by Horiba, Ltd.).

The heat conductive material of the present invention contains an amount of spherical particles of 500 parts by mass or less per 1 part by mass of the plate-like particles, that is, an amount of 0 to 500 parts by mass. The amount of the spherical particles in an amount of 1 part by mass per layer of the plate-like particles is 0 parts by mass or more, preferably 1 part by mass or more, more preferably 2 parts by mass or more, from the viewpoint of improving dispersion stability and thermal conductivity, thereby improving dispersion. From the viewpoint of the stability of the stability and the thermal conductivity, it is 500 parts by mass or less, preferably 450 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 350 parts by mass or less, still more preferably 300% by mass. The following.

The mass ratio of the plate-like particles to the spherical particles (plate-like particles/spherical particles) is preferably 0.3/100 or more, more preferably 0.6/100 or more, from the viewpoint of improving dispersion stability and thermal conductivity. It is preferably 1/100 or more, and is preferably 90/100 or less, more preferably 70/100 or less, still more preferably 50/100 or less, from the viewpoint of improving the stability of dispersion stability and thermal conductivity. Good for 30/100 or less.

The total amount of the plate-like particles and the spherical particles per 100 parts by mass of the adhesive resin (solid content) is 1 part by mass or more, preferably from the viewpoint of improving the dispersion stability and thermal conductivity of the thermally conductive material of the present invention. 3 parts by mass or more, more preferably 5 parts by mass or more, and 600 parts by mass or less, preferably 550 parts by mass or less, from the viewpoint of improving the stability of dispersion and thermal conductivity of the thermally conductive material of the present invention. More preferably, it is 530 parts by mass or less, more preferably 520 parts by mass or less, and even more preferably 500 masses. The following. In addition, the total amount of the plate-like particles and the spherical particles per 100 parts by mass of the adhesive resin (solid content) is preferably 10 parts by mass or more, more preferably from the viewpoint of improving the thermal conductivity of the thermally conductive material of the present invention. From the viewpoint of improving the adhesiveness and electrical insulating properties of the thermally conductive material of the present invention, it is preferably 550 parts by mass or less, more preferably 530 parts by mass or less, from 15 parts by mass or more, and more preferably 50 parts by mass or more. More preferably, it is 500 mass parts or less.

The total content of the plate-like particles and the spherical particles in the thermally conductive material of the present invention is preferably 0.5% by mass or more, more preferably 3% by mass or more, from the viewpoint of improving the thermal conductivity of the thermally conductive material of the present invention. More preferably, it is 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. From the viewpoint of improving the adhesion and electrical insulating properties of the thermally conductive material of the present invention, it is preferably 90% by mass. % or less, more preferably 85% by mass or less.

Examples of the adhesive resin include (meth)acrylic adhesive resin, anthrone-based adhesive resin, urethane-based adhesive resin, vinyl alkyl ether-based adhesive resin, and vinylpyrrolidone. The adhesive resin, the acrylamide-based adhesive resin, the cellulose-based adhesive resin, the rubber-based heat conductive material, and the like, but the present invention is not limited to this example. These adhesive resins may be used alone or in combination of two or more kinds within the range not inhibiting the object of the present invention.

Among the adhesive resins, it is excellent in adhesion and resistance to heavy load, and it can be used for various types of adherends. For the wide versatility, it is preferable to use (meth)acrylic adhesive resin. (meth)acrylic acid A (meth)acrylic adhesive resin obtained by polymerizing a monomer component containing an alkyl ester as a main component is more preferable.

The "monomer component having a (meth)acrylic acid alkyl ester as a main component" means that the content of the (meth)acrylic acid alkyl ester in the monomer component is 50% by mass or more. The content of the (meth)acrylic acid alkyl ester in the monomer component is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably from the viewpoint of improving the adhesion. It is 80% by mass or more. In addition, the upper limit of the content of the alkyl (meth)acrylate in the monomer component is preferably 100% by mass, but more preferably 97% by mass or less, and still more preferably from the viewpoint of improving heat resistance. 95% by mass or less.

Among the (meth)acrylic acid alkyl esters, alkyl esters are obtained from the viewpoint of obtaining a wide-ranging general-purpose (meth)acrylic adhesive resin which is excellent in adhesion and can be used for various adherends. The alkyl methacrylate having a carbon number of from 1 to 18 is preferred, and the alkyl acrylate having a carbon number of from 1 to 18 is more preferred. Examples of suitable alkyl (meth)acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (methyl). Acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl acrylate, n-heptyl (meth) acrylate, n-octyl (A Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-fluorenyl (methyl) Acrylate, isodecyl (meth) acrylate, n-fluorenyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, iso-four (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-stearyl sulfhydryl (meth) acrylate, isostearyl fluorenyl (Meth) acrylate, n-lauryl (meth) acrylate, etc., but the present invention is not limited only to the examples. These (meth) acrylates may be used alone or in combination of two or more. Among these (meth)acrylic acid alkyl esters, an alkyl acrylate having an alkyl ester having 1 to 18 carbon atoms is preferred from the viewpoint of improving adhesion, n-butyl acrylate, n- More preferably, octyl acrylate, isooctyl acrylate and 2-ethylhexyl acrylate are more preferably n-butyl acrylate and 2-ethylhexyl acrylate.

In the present specification, "(meth) acrylate" means "acrylate" and/or "methacrylate", and "(meth) propylene" means "propylene" and / or "methacryl" base".

The monomer component may contain a monomer other than the alkyl (meth)acrylate within the range not inhibiting the object of the present invention. Examples of the monomer other than the alkyl (meth)acrylate include a monomer having a carboxyl group, a monomer having a hydroxyl group, an acid phosphate monomer, a monomer having an epoxy group, and a monomer having a nitrogen atom. a monomer having two or more polymerizable double bonds, an aromatic monomer, a monomer having a halogen atom, a vinyl ester monomer, a vinyl ester monomer, etc., but the present invention is not limited only to the Illustrative. These monomers may be used alone or in combination of two or more. Among these monomers, a monomer having a carboxyl group and a monomer having a hydroxyl group are preferred.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, and anhydrous maleic acid. However, the present invention is not limited to the examples. These carboxyl group-containing monomers may be used alone or in combination of two or more. Among these carboxyl group-containing monomers, acrylic acid, methacrylic acid, itaconic acid, and anhydrous maleic acid are preferred, and acrylic acid and methacrylic acid are more preferred.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl group. The hydroxyalkyl group having a hydroxyalkyl group such as a acrylate or the like has a hydroxyalkyl (meth) acrylate having 2 to 4, but the present invention is not limited to this example. These monomers having a hydroxyl group may be used singly or in combination of two or more kinds.

Examples of the acidic phosphate ester-based monomer include 2-propenylmethoxyethyl acid phosphate and 2-methylpropenyloxyethyl acid phosphate. However, the present invention is not limited to this example. These acidic phosphate ester monomers may be used alone or in combination of two or more.

Examples of the monomer having an epoxy group include a (meth) acrylate having an epoxy group such as a glycidyl acrylate or a propylene methacrylate, but the present invention is not limited only to the Illustrative. These epoxy group-containing monomers may be used singly or in combination of two or more kinds.

Examples of the monomer having a nitrogen atom include (meth) acrylamide, dimethylaminoethyl acrylate, dimethylaminoethyl methyl group such as acrylamide or methacrylamide. Acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, quinone acrylate, A (meth) acrylate having a nitrogen atom or the like such as quinone imine methacrylate, but the present invention is not limited only to the exemplification. These monomers having a nitrogen atom may be used singly or in combination of two or more kinds.

Examples of the monomer having two or more polymerizable double bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, and triethylene glycol dimethacrylate. , tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, etc., but The invention is not limited only to this illustration. These monomers having two or more polymerizable double bonds may be used alone or in combination of two or more.

The aromatic monomer may, for example, be a styrene compound such as styrene or α-methylstyrene, but the present invention is not limited to the examples. These aromatic monomers may be used alone or in combination of two or more.

The monomer having a halogen atom may, for example, be halogenated ethylene such as vinyl chloride, but the present invention is not limited to the examples. The monomer having a halogen atom may be used alone or in combination of two or more.

The vinyl ester monomer may, for example, be a fatty acid such as vinyl acetate, but the present invention is not limited to the examples. The vinyl ester-based monomer may be used alone or in combination of two or more.

Examples of the vinyl ether monomer include butyl vinyl ether and cyclohexyl vinyl ether. However, the present invention is not limited to the examples. These vinyl ether-based monomers may be used singly or in combination of two or more kinds.

The content of the monomer other than the alkyl acrylate in the monomer component is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably from the viewpoint of improving the adhesion. 20% by mass or less. In addition, the lower limit of the content ratio of the monomer other than the alkyl acrylate in the monomer component is preferably 0% by mass, but more preferably 3% by mass or more, and still more preferably 5, from the viewpoint of improving heat resistance. More than % by mass.

When the monomer component is polymerized, a chain transfer agent may be used as necessary in view of increasing the molecular weight distribution or suppressing gelation. Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and 3-decyl group. N-octyl propionate, methoxybutyl 3-mercaptopropionate, stearic acid 3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptoproperate) Terephthalate esters such as esters, dipentaerythritol hexa(3-mercaptopropionate); ethyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, 1,2-didecyl Alkyl mercaptans such as alkanes; mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; phenyl mercaptan, m-toluene mercaptan, p-toluene mercaptan, 2-naphthyl mercaptan, etc. Aromatic thiols; sulfhydryl isocyanurates such as tris(3-mercaptopropoxy)ethyl]isocyanurate; 2-hydroxyethyl disulfide, tetraethyl thiuram Disulfides such as disulfides; dithiocarbamates such as benzyldiethylcarbamate; dimers such as α-methylstyrene dimer; tetrabromo A halogenated alkyl ester such as carbon is used, but the present invention is not limited to this example. These chain transfer agents may be used alone or in combination of two or more. Among these chain transfer agents, it is easy to obtain, excellent crosslinking prevention, and lowering of polymerization rate The compound having a mercapto group such as a mercaptocarboxylic acid, a mercaptocarboxylic acid ester, an alkyl mercaptan, a mercapto alcohol, an aromatic mercaptan or a mercapto isocyanurate is preferred.

The amount of the chain transfer agent is not particularly limited as long as it is appropriately set depending on the composition of the monomer component, the polymerization conditions such as the polymerization temperature, and the molecular weight of the intended polymer, but a polymerization having a weight average molecular weight of several thousands to several tens of thousands is obtained. The content of the material is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

Examples of the method for polymerizing the monomer component include a bulk polymerization method, a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method. However, the present invention is not limited to the examples.

The bulk polymerization can be carried out by irradiation or heating of an energy ray such as ultraviolet rays, electron beams, or radiation. In the case of bulk polymerization of a monomer component by irradiation of an energy ray, it is preferable to polymerize a monomer component by irradiating a monomer component with an energy ray in an inert gas atmosphere such as nitrogen or an atmosphere in which air is blocked.

When the monomer component is polymerized by a bulk polymerization method, a photopolymerization initiator can be used. The photopolymerization initiator may, for example, be an acetonyl polymerization initiator, a benzoin ether polymerization initiator, a benzyl ketal polymerization initiator, a mercaptophosphine oxide polymerization initiator, a benzoin system. A polymerization initiator, a benzophenone polymerization initiator, etc., but the present invention is not limited only to the examples. These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator may be appropriately set depending on the physical properties of the desired polymer, etc., but usually, in terms of 100 parts by mass of the monomer component, It is preferably 0.01 to 50 parts by mass, more preferably 0.03 to 20 parts by mass.

When the monomer component is polymerized by a solution polymerization method, examples of the solvent include an aromatic solvent such as benzene, toluene or xylene; an alcohol solvent such as isopropyl alcohol or n-butyl alcohol; and propylene glycol; An ether solvent such as methyl ether, dipropylene glycol methyl ether, ethyl cellosolve or butyl cellosolve; an ester solvent such as ethyl acetate, butyl acetate or cellosolve acetate; acetone, methyl ethyl ketone An organic solvent such as a ketone solvent such as methyl isobutyl ketone or diacetone alcohol or a guanamine solvent such as dimethylformamide, but the present invention is not limited to the examples. These solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of the monomer component, the concentration of the obtained polymer, and the like.

When the monomer component is polymerized by a solution polymerization method, a polymerization initiator can be used. The polymerization initiator may, for example, be 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), or tert-butyl. Peroxide-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, benzamidine peroxide, di-tert-butyl peroxide, etc., but the invention is not limited only to Illustrative. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator may be appropriately set in accordance with the physical properties of the polymer to be obtained, etc., but it is usually 0.001 to 20 parts by mass, more preferably 0.005, per 100 parts by mass of the monomer component. ~10 parts by mass.

The polymerization conditions in the case of polymerizing the monomer component are not particularly limited as long as they are appropriately set in accordance with the polymerization method. The polymerization temperature is preferably room temperature to 200 ° C, more preferably 40 to 140 ° C. Reaction time to polymerize monomer components It is sufficient to set the reaction to completion.

By polymerizing a monomer component by the above method, a (meth)acrylic-type adhesive resin can be obtained. The weight average molecular weight (Mw) of the (meth)acrylic adhesive resin is improved from the viewpoint of improving the adhesion of the thermally conductive material, the heat resistance, and the dispersion stability of the plate-like metal particles and the spherical particles used as necessary. It is preferably 300,000 or more, more preferably 400,000 or more, and still more preferably 500,000 or more. The upper limit of the weight average molecular weight of the (meth)acrylic adhesive resin is not particularly limited, but the adhesion and heat resistance of the thermally conductive material, and the dispersion stability of the plate-like metal particles and the spherical particles used as necessary are improved. The viewpoint is preferably 1.5 million or less, more preferably 1.2 million or less, still more preferably 1,000,000 or less, and still more preferably 900,000 or less.

In the present specification, the weight average molecular weight of the (meth)acrylic adhesive resin means a measurement apparatus for a gel permeation chromatography (GPC), which is manufactured by using TOSOH (stock), product number: HLC-8220GPC, and separation. Pipe column: TOSOH (stock) system, article number: TSKgel Super HZM-M, converted from standard polystyrene [TOSOH (stock) system].

The glass transition temperature of the (meth)acrylic adhesive resin can be easily adjusted by appropriately adjusting the type and amount of the monomer used in preparing the (meth)acrylic adhesive resin.

The glass transition temperature (Tg) of the (meth)acrylic adhesive resin is preferably -65 ° C or higher, more preferably -63 ° C or higher, and more preferably - from the viewpoint of improving the adhesion of the thermally conductive material. 60 ° C or more, from the viewpoint of improving the adhesion and heat resistance of the thermally conductive material, it is preferably -20 ° C Lower, more preferably -30 ° C or less, and even more preferably -40 ° C or less.

In the present specification, the glass transition temperature of the (meth)acrylic adhesive resin is a glass transition temperature of a homogeneous polymer using a monomer used as a raw material of the (meth)acrylic adhesive resin. In the formula: 1/Tg=Σ(Wm/Tgm)/100 (wherein, Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the homogeneity of the monomer m. The temperature at which the glass transition temperature (absolute temperature: K) of the polymer is based on the formula of Fox.

The glass transition temperature (Tg) of the main homogeneous polymer, for example, the glass transition temperature (Tg) of the homogeneous polymer of acrylic acid is 106 ° C, the glass transition temperature (Tg) of the homogeneous polymer of methacrylic acid is 130 ° C, methyl Glass transition temperature (Tg) of acrylate homogeneous polymer is 8 ° C, glass transition temperature (Tg) of homopolymer of ethyl acrylate is -22 ° C, glass transfer of homogeneous polymer of n-butyl acrylate The glass transition temperature (Tg) of a homogeneous polymer of 2-hydroxyhexyl acrylate having a temperature (Tg) of -54 ° C and 2-ethylhexyl acrylate is -70 ° C, and the glass transition temperature (Tg) of a homogeneous polymer of 2-hydroxyethyl acrylate The glass transition temperature (Tg) of a homogeneous polymer of -15 ° C, 2-hydroxyethyl methacrylate is 55 ° C, and the glass transition temperature (Tg) of a homogeneous polymer of 4-hydroxybutyl acrylate is -70 The glass transition temperature (Tg) of a homopolymer of °C and methyl methacrylate is 105 ° C, the glass transition temperature (Tg) of a homopolymer of vinyl acetate is 32 ° C, and the glass transition of a homogeneous polymer of acrylonitrile Temperature (Tg The glass transition temperature (Tg) of a homogeneous polymer of styrene at 125 ° C is 100 ° C.

The glass transition temperature of the (meth)acrylic adhesive resin is not particularly limited, and means a glass transition temperature determined based on the above formula. In the case where the glass transition temperature of the monomer or the polyfunctional monomer is unknown, the glass transition temperature of the monomer component is not more than 10% by mass, and only the glass transition temperature is used. Known monomers determine the glass transition temperature. In the case where the glass transition temperature of the monomer component is more than 10% by mass of the unidentified monomer, the glass transition temperature of the (meth)acrylic adhesive resin is analyzed by differential scanning calorimetry (DSC) and differential calorimetry. (DTA), thermomechanical analysis (TMA), etc. are obtained.

The glass transition temperature of the (meth)acrylic adhesive resin can be determined, and the composition of the monomer component which is a raw material of the (meth)acrylic adhesive resin can be determined.

The measuring device for the differential scanning heat may, for example, be manufactured by Seiko Instruments Inc., product number: DSC220C or the like. Further, when measuring the differential scanning heat, a method of drawing a differential scanning heat (DSC) curve, a method of obtaining a differential curve by a differential scanning heat (DSC) curve, a method of performing a smoothing process, and determining a peak temperature of the target The method and the like are not particularly limited. For example, in the case of using the above-described measuring device, data obtained by using the above measuring device may be used for drawing. At that time, an analytical software that can perform mathematical processing can be used. As the analysis software, for example, an analysis software (Seiko Instruments Inc., product number: EXSTAR6000] and the like, but the present invention is not limited only to the examples. The peak temperature obtained in this way includes an error of about 5 ° C from the top and bottom.

In "Adhesion and Adhesives Technology" 2nd edition, Germany, Carl Hanzer, 2002 Alphonsus Pocius "Dahlquist's adhesion criterion" reported that the room temperature modulus of the adhesive thermal conductivity material measured at a cycle number of 1 Hz was less than 0.3 MPa (10 ⁷ dyne/cm ² ). The adhesive resin used in the present invention satisfies the adhesion determination criterion, that is, the room temperature storage elastic modulus of the adhesive resin which satisfies the measurement of the number of cycles of 1 Hz, which is less than 0.3 MPa (10 ⁷ dyne). /cm ² ) is better. The storage modulus (G') at 25 ° C of the adhesive resin at a cycle number of 1 Hz is preferably 0.5 × 10 ⁶ Pa or less, more preferably 0.3 × 10 ⁶ Pa or less from the viewpoint of improving the adhesion.

In the heat conductive material of the present invention, when the plate-like particles, the spherical particles, a crosslinking agent to be described later, a crosslinking accelerator, an additive, or the like are used, the total amount is adjusted to 100% by mass. In the heat conductive material of the present invention, the content of the adhesive resin is 10% by mass or more, preferably 15% by mass or more, from the viewpoint of improving the adhesion and electrical insulating properties of the thermally conductive material of the present invention, thereby improving heat conduction. From the viewpoint of properties, it is 90% by mass or less, preferably 85% by mass or less.

The thermally conductive material of the present invention can be easily prepared by mixing an adhesive resin, plate-like particles, spherical particles, or the like. At this time, in the modulation of plate-like particles In view of the fact that the spherical particles or the like are uniformly dispersed thermally conductive materials, it is preferred to use an adhesive resin solution in which an adhesive resin is dissolved in an organic solvent.

The organic solvent used in the adhesive resin solution is not particularly limited as long as it can dissolve the adhesive resin. Examples of the organic solvent include, for example, an organic solvent used for polymerizing a monomer component by a solution polymerization method, and others such as gasoline, coal tar, petroleum ether, petroleum spirit, musk acid, and mineral spirits. Etc., but the invention is not limited only to the illustration. The concentration of the nonvolatile matter in the adhesive resin solution is not particularly limited, but is usually about 10 to 70% by mass.

When the above-mentioned adhesive resin has a crosslinkable group (functional group), the thermally conductive material of the present invention may contain a crosslinking agent as necessary. The crosslinking agent can cure the adhesive resin by crosslinking the adhesive resin having a crosslinkable group.

As the crosslinking agent, a compound having two or more functional groups reactive with a crosslinkable group possessed by the adhesive resin in one molecule can be used. Examples of the crosslinking agent include a polyisocyanate crosslinking agent, a polyfunctional epoxy crosslinking agent, and an anthrone crosslinking agent. However, the present invention is not limited to the examples.

Examples of the polyisocyanate crosslinking agent include aromatic polyisocyanate such as xylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and methylphenyl diisocyanate, and hexamethylene diisocyanate. An aliphatic or alicyclic polyisocyanate such as isophorone diisocyanate, a hydrogenated product of the above aromatic polyisocyanate, a dimer or a trimer of such a polyisocyanate, a polyisocyanate or a trimethylol group thereof An adduct such as a polyol such as propane, but the present invention is not limited only to this example. Show. These polyisocyanate-based crosslinking agents may be used singly or in combination of two or more kinds.

As the polyisocyanate, for example, Coronate L, Coronate L-55E, Coronate HX, Coronate HL, Coronate HL-S, Coronate 2234, Aquanate 200, Aquanate 210 [above, Japanese Polyurethane Industry Co., Ltd., Coronate and Aquanate are Registered trademark]; Desmodur N3400 [Sumitomo Bayer urethane (shares) (now Bayer AG), Desmodur is a registered trademark]; Duranate D-201 "Duranate TSE-100, Duranate TSS-100, Duranate 24A-100 ,Duranate E-405-80T [above, Asahi Kasei Chemicals Co., Ltd., Duranate is a registered trademark]; Takenate D-110N, Takenate D-120N, Takenate M-631N, MTERT-Olester NP1200 [above, Mitsui Chemical Polyamine The polyisocyanate may be used singly or in combination of two or more kinds, and the like may be easily used in the form of a formic acid ester (stock), Takenate, and Olester.

Examples of the polyfunctional epoxy-based crosslinking agent include ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, and double Phenolic A type epoxy resin, N, N, N', N'-tetraepoxypropyl-m-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl) Cyclohexane, N,N-diepoxypropylaniline, N,N-diepoxypropyltoluamide, etc., but the present invention is not limited only to the examples. These polyfunctional epoxy-based crosslinking agents may be used alone or in combination of two or more.

The anthrone-based crosslinking agent may, for example, be manufactured by Shin-Etsu Chemical Co., Ltd., product number: X-92-122, etc., but the present invention is not limited only to the examples. The anthrone-based crosslinking agent may be used alone or in combination of two or more types.

Among the crosslinking agents, a polyisocyanate 2-polymer, a polyisocyanate 3-mer, a polyisocyanate 2-functional prepolymer, and a polyisocyanate adduct are preferred, and a hexamethylene diisocyanate 2-mer is preferred. Isocyanurate body (trimer) of hexamethylene diisocyanate, adduct of methyl phenyl diisocyanate and trimethylolpropane, etc., isocyanate of hexamethylene diisocyanate The urea ester body is even better. The isocyanurate body of hexamethylene diisocyanate may, for example, be manufactured by Asahi Kasei Chemical Co., Ltd., trade name: Duranat (registered trademark) TSE-100, trade name: Duranat (registered trademark) TSS-100, and the like. However, the invention is not limited only to the illustration.

When the total amount of the crosslinking agent (functional group) of the adhesive resin is 1 equivalent, the amount of the crosslinking agent is usually preferably 0.03 to 1 equivalent, more preferably 0.05 to 0.5 equivalent.

In the present invention, a crosslinking accelerator can be used in an appropriate amount. Examples of the crosslinking accelerator include dibutyltin dilaurate, tin octylate, dibutyltin bis(2-ethylhexanoate), lead 2-ethylhexanoate, and 2-ethylhexanoate. Ester, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, zinc naphthalate, cobalt naphthalate, tin octylate, bismuth octanoate, tetra-n-butyltin, titanium diisopropoxide (Ethylacetamidine acetate), zirconium tetraacetone pyruvate, etc., but the present invention is not limited only to the examples. These crosslinking accelerators may be used alone or in combination of two or more.

The thermally conductive material of the present invention may contain, for example, a dispersing agent, an adhesion-imparting agent, an antioxidant, a plasticizer, a flame retardant, a flame retardant, an anti-settling agent, and the like in an appropriate amount within a range not inhibiting the object of the present invention. Tackifier Additives such as a thixotropic imparting agent, a surfactant, an antifoaming agent, an antistatic agent, a surface treating agent, an antiaging agent, an ultraviolet absorber, an ultraviolet stabilizer, and the like.

The non-volatile content of the thermally conductive material of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of improving productivity, and is preferably 80% by mass from the viewpoint of improving coatability. The following is more preferably 70% by mass or less. The non-volatile content of the thermally conductive material can be adjusted by adjusting the amount of the solvent contained in the thermally conductive material, the amount of the additive, and the like. The solvent may be the same as the organic solvent used in the above-mentioned adhesive resin solution.

The viscosity of the thermally conductive material of the present invention (measured by Toki Sangyo Co., Ltd., product number: TVB-10M, measured at a temperature of 25 ° C at a rotation number of 12 r/m) is preferable from the viewpoint of improving coatability. It is 100mPa. Above s, more preferably 500mPa. More than s, and more preferably 1000mPa. s or more, from the viewpoint of improving the coating property as described above, it is preferably 60,000 mPa. Below s, more preferably 40,000 mPa. s below, and more preferably 20,000 mPa. s below.

The adhesive sheet of the present invention is a layer of a thermally conductive material having at least one surface of a thermally conductive material. The adhesive sheet of the present invention can be obtained, for example, by forming a layer of a thermally conductive material on at least one surface of a substrate. Therefore, the adhesive sheet of the present invention may have a layer of a thermally conductive material only on one surface of the substrate, or may have a layer of a thermally conductive material on both surfaces of the substrate.

As a method of applying the thermally conductive material of the present invention to a substrate, for example, a knife coater, a slit die coater, and a lip coater can be used. , a roller coater, a curtain coater, a spray coater, a bar coater, a knurling wheel coater, a coating method such as a doctor blade, a coating method such as immersion, etc., but the present invention Not only limited to this illustration. When the thermally conductive material of the present invention is applied to a substrate, the thermally conductive material of the present invention may be directly applied to a substrate, or may be applied to a release paper or the like, and then the coated article may be transferred to a substrate. On the material. After coating the thermally conductive material of the present invention in this manner, a layer of thermally conductive material can be formed on the substrate by drying.

On the surface of the layer of the thermally conductive material formed on the substrate, for example, a release paper or a release film can be applied. In the case where the release paper is attached to the surface of the thermally conductive material layer in this manner, the layer of the thermally conductive material can be suitably protected. The release paper is peeled off from the surface of the layer of thermally conductive material when a thermally conductive material is used. When a layer of a thermally conductive material is formed on one surface of a substrate having a shape such as a sheet shape or a strip shape, a conventional release agent is applied to the back surface of the base material of the obtained adhesive sheet, and a release agent layer is formed in advance. The adhesive sheet is curled into a roll shape by causing the heat conductive material layer to be inside, and the surface of the heat conductive material layer can be protected or preserved by contact with the release agent layer on the back surface of the substrate.

Examples of the substrate include papers such as paper, kraft paper, crepe paper, and cellophane, resin substrates, woven fabrics, non-woven fabrics, fabrics such as fabrics, and conductive substrates. However, the present invention is not limited only to This example. Among the substrates, the thermally conductive material of the present invention can be suitably used, for example, for bonding a wiring board to a member requiring heat dissipation such as a heat sink or a casing, and preferably a resin substrate, a nonwoven fabric, and a conductive substrate.

As the resin used for the resin substrate, for example, polyethylene, poly Polyolefin resin such as propylene, polyester such as polyethylene terephthalate or polybutylene terephthalate, polystyrene, polyvinyl chloride, cellophane, acrylic resin, polyimine Polyphenylene sulfide, polyamine or the like, but the invention is not limited only to the examples. Examples of the resin substrate include a resin film and a sheet. The thickness of the resin film cannot be determined by the use of the heat conductive material of the present invention, but is usually about 1 to 100 μm, and is preferably 1 μm or more, and more preferably 2 μm from the viewpoint of improving electrical insulating properties and thermal conductivity. The above is more preferably 3 μm or more, and is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, still more preferably 20 μm or less, and further preferably from the viewpoint of improving electrical insulating properties and thermal conductivity. It is 10 μm or less, and particularly preferably 5 μm or less.

Examples of the nonwoven fabric include a spunbond nonwoven fabric, a melt blown nonwoven fabric, and a needle-punched nonwoven fabric. However, the present invention is not limited to the examples. Among these non-woven fabrics, a spunbonded nonwoven fabric is preferred. Examples of the fibers constituting the nonwoven fabric include polyolefin resins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polystyrene, and polychlorinated chlorine. Semi-synthetic synthesis of synthetic fibers such as synthetic fibers, rayon, copper ammonia, etc. of vinyl, cellophane, acrylic resin, polyimine, polyphenylene sulfide, polyamine, etc. Fiber or the like, but the invention is not limited only to this example. The thickness and the amount of the nonwoven fabric are arbitrary. However, as an example, the thickness is 3 to 50 μm, and the basis weight is 5 to 100 g/m ² . The thickness of the nonwoven fabric is preferably 3 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more from the viewpoint of improving electrical insulating properties and thermal conductivity, and is preferably 50 μm or less from the viewpoint of improving electrical insulating properties. More preferably, it is 45 μm or less, and still more preferably 40 μm or less. Further, the amount of the non-woven fabric is preferably 5 g/m ² or more, more preferably 10 g/m ² or more, still more preferably 15 g/m ² or more, from the viewpoint of improving thermal conductivity, and improving electrical insulation and heat conduction. From the viewpoint of properties, it is preferably 100 g/m ² or less, more preferably 80 g/m ² or less, still more preferably 60 g/m ² or less.

Examples of the conductive substrate include titanium foil, stainless steel foil, nickel foil, nickel-chromium alloy foil, copper foil, tantalum foil, aluminum foil, tin foil, lead foil, zinc foil, iron foil, molybdenum foil, zirconium foil, and gold foil. A metal foil such as a silver foil, a platinum foil, or a palladium foil, a graphite sheet, or the like, but the present invention is not limited to this example. The thickness of the conductive substrate is arbitrary, but is usually about 1 to 100 μm, and is preferably 1 μm or more, more preferably 2 _μm or more, and still more preferably 3 μm or more from the viewpoint of improving thermal conductivity, thereby improving electrical insulation. From the viewpoint of properties, it is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, still more preferably 20 μm or less, still more preferably 10 μm or less, and particularly preferably 5 μm or less.

The thermally conductive material of the present invention is applied to a substrate and then dried. Examples of the drying method include irradiation with hot air and far infrared rays.

The thickness of the thermally conductive material layer after drying the thermally conductive material of the present invention is not particularly limited, but is usually about 1 μm to 5 mm.

As described above, the thermally conductive material of the present invention has excellent electrical insulating properties due to excellent adhesion and thermal conductivity. For example, the thermally conductive material of the present invention can be applied to one side of a substrate or Forming a layer of thermally conductive material on both sides, or suitable for use as a thermal conductivity only with no substrate Adhesive sheet of material layer.

The overall thickness of the adhesive sheet of the present invention cannot be determined by the use of the adhesive sheet of the present invention, but is usually about 50 to 300 μm.

Further, the thermally conductive material of the present invention can be suitably used, for example, in a lighting fixture having a substrate on which a light-emitting element is mounted and a heat radiator. In this case, the thermally conductive material of the present invention may be provided between the substrate and the heat radiator. Hereinafter, an embodiment of the lighting fixture will be described based on the drawings.

Fig. 1 is a schematic explanatory view showing an embodiment of an illumination fixture having a thermally conductive material of the present invention between a substrate and the heat radiator. The lighting fixture shown in Fig. 1 includes a light-emitting element 1, a substrate 2, a thermally conductive material layer 3 made of a thermally conductive material, and a heat radiator 4. In the illuminating device, the thermal conductive material layer 3 having the thermally conductive material of the present invention between the substrate 2 and the heat radiator 4, and the adhesion and thermal conductivity of the substrate 2 and the heat radiator 4 in which the light-emitting element 1 is mounted Excellent and excellent in electrical insulation.

In FIG. 1, the light-emitting element 1 is disposed on one surface of the substrate 2. On the other surface of the substrate 2, the thermally conductive material layer 3 which is made of the thermally conductive material of the present invention is integrated with the radiator 4.

Examples of the light-emitting element 1 include an element such as a light-emitting diode (LED) and electroluminescence, but the present invention is not limited to this example. As the substrate 2, for example, a printed wiring board or the like can be mentioned. Further, the heat radiator 4 may be, for example, a heat sink or a casing, but the present invention is not limited to this example.

In the lighting fixture of the present invention, since the heat conductive material of the present invention is provided between the substrate and the heat radiator, the substrate and the heat sink having the light emitting element are excellent in adhesion and thermal conductivity, and are excellent in electrical insulation. .

Example

Next, the present invention will be described in more detail based on the examples, but the present invention is not limited only to the present embodiment.

Example 1

100 parts of ethyl acetate (parts by mass or less), 50.5 parts of n-butyl acrylate, and 2-ethylhexyl acrylate were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After 37.0 parts, 9.0 parts of vinyl acetate, 0.5 parts of 2-hydroxyethyl acrylate, and 3.0 parts of acrylic acid, 0.05 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin. Solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts (resin solid content: 100 parts) of the acrylic adhesive resin solution obtained above and a slurry of plate-like aluminum particles (the aspect ratio of the plate-shaped aluminum particles: 40, thickness: 0.25 μm, and the like) were mixed. Length in the plane direction: 10 μm) 3 parts (solid content of plate-like aluminum particles) and globular oxygen After 500 parts of the aluminum particles (average particle diameter: 10 μm), ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

By mixing 100 parts of the mixed solution obtained above with 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate, trade name: Coronate L-55E), a thermally conductive material was obtained. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 2

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and a slurry of plate-like aluminum particles (the aspect ratio of the plate-shaped aluminum particles: 33, the thickness: 0.3 μm, and the surface direction) were mixed. Length: 10 μm) 10 parts (solid content of the plate-like aluminum particles) and 500 parts of spherical alumina particles (average particle diameter: 30 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. Stir well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 3

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and a slurry of plate-like aluminum particles (the aspect ratio of the plate-shaped aluminum particles: 50, thickness: 0.4 μm, surface direction) were mixed. Length: 20 μm) 41 parts (solid content of the plate-like aluminum particles) and 43 parts of spherical alumina particles (average particle diameter: 30 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. Stir well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. Make The obtained thermally conductive material was applied to a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet of a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 4

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and a slurry of plate-like aluminum particles (the aspect ratio of the plate-like aluminum particles: 40, the thickness: 0.25 μm, and the surface direction) were mixed. Length: 10 μm) 12 parts (solid content of the plate-like aluminum particles) and 250 parts of spherical alumina particles (average particle diameter: 10 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. Stir well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. Thermally conductive material layer Adhesive sheet. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 5

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and a slurry of plate-like aluminum particles (the aspect ratio of the plate-shaped aluminum particles: 50, the thickness: 0.25 μm, and the surface direction) were mixed. Length: 12.5 μm) 10 parts (solid content of the plate-like aluminum particles) and 200 parts of spherical alumina particles (average particle diameter: 10 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. The mixture was thoroughly stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 6

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and a slurry of plate-like aluminum particles (the aspect ratio of the plate-like aluminum particles: 40, the thickness: 0.25 μm, and the surface direction) were mixed. Length: 10 μm) 3 parts (solid content of the plate-like aluminum particles) and 200 parts of spherical alumina particles (average particle diameter: 10 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. Stir well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 7

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and a slurry of plate-like aluminum particles (the aspect ratio of the plate-shaped aluminum particles: 55, the thickness: 0.4 μm, and the surface direction) were mixed. Length: 22 μm) 1 part (solid content of the plate-like aluminum particles) and 200 parts of spherical alumina particles (average particle diameter: 10 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. Stir well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 8

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by mixing 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) with a slurry of plate-like aluminum particles (plate-like aluminum particles) Aspect ratio: 50, thickness: 0.2 μm, length in the plane direction: 10 μm) 3 parts (solid content of plate-like aluminum particles) and spherical alumina particles (average particle diameter: 30 μm) 20 parts, making non-volatile Ethyl acetate was added so that the content rate of the fraction was 70% by mass, and the mixture solution was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 9

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and boron nitride particles (aspect ratio: 25, thickness: 0.4 μm, length in the plane direction: 10 μm) were mixed with 100 parts of the ball. 200 parts of alumina particles (average particle diameter: 20 μm) were added, and ethyl acetate was added so that the content of the nonvolatile content was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 10

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 20 parts of boron nitride particles (aspect ratio: 33.3, thickness: 0.3 μm, length in the plane direction: 10 μm) were mixed with the ball. 200 parts of alumina particles (average particle diameter: 10 μm) were added, and ethyl acetate was added so that the content of the nonvolatile content was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material is applied to a release paper [(share) Sun A. On the product No.: K-80HS, it was dried in an environment of 100 ° C for 5 minutes to obtain an adhesive sheet having a layer of a thermally conductive material having a thickness of about 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 11

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by mixing 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and boron nitride particles (aspect ratio: 40, thickness: 0.3 μm, length in the plane direction: 12 μm), 10 parts of the ball 200 parts of alumina particles (average particle diameter: 10 μm) were added, and ethyl acetate was added so that the content of the nonvolatile content was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. The adhesive sheet is used as a thin adhesive having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper. sheet.

Example 12

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 20 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 20 parts of graphite particles (aspect ratio: 25, thickness: 0.4 μm, length in the plane direction: 10 μm) and spherical oxidation were mixed. 200 parts of aluminum particles (average particle diameter: 10 μm) were added, and ethyl acetate was added so that the content rate of a nonvolatile content was 70 mass%, and it stirred well, and the mixed solution was obtained.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 13

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by mixing 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and graphite particles (aspect ratio: 25, thickness: 0.4 μm, length in the plane direction: 10 μm), 10 parts and spherical oxidation 200 parts of aluminum particles (average particle diameter: 10 μm) were added, and ethyl acetate was added so that the content rate of a nonvolatile content was 70 mass%, and it stirred well, and the mixed solution was obtained.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 14

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by mixing 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and graphite particles (aspect ratio: 25, thickness) : 0.4 μm, length in the surface direction: 10 μm) 5 parts and 200 parts of spherical alumina particles (average particle diameter: 10 μm), and ethyl acetate was added so that the content of the nonvolatile content was 70% by mass, and the mixture was thoroughly stirred. A mixed solution was obtained.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 15

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and talc (length ratio: 30, thickness: 1 μm, length in the plane direction: 30 μm) were mixed with 50 parts of spherical alumina particles. 250 parts of (average particle diameter: 30 μm), ethyl acetate was added so that the content rate of a nonvolatile content was 70 mass%, and it stirred well, and the mixed solution was obtained.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 16

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and talc (length ratio: 30, thickness: 1 μm, length in the plane direction: 30 μm) were mixed with 100 parts of spherical alumina particles. 250 parts of (average particle diameter: 30 μm), ethyl acetate was added so that the content rate of a nonvolatile content was 70 mass%, and it stirred well, and the mixed solution was obtained.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material is applied to a release paper [(share) Sun A. On the product No.: K-80HS, it was dried in an environment of 100 ° C for 5 minutes to obtain an adhesive sheet having a layer of a thermally conductive material having a thickness of about 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 17

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 100 parts of mica (length ratio: 40, thickness: 0.8 μm, length in the plane direction: 32 μm) and spherical alumina were mixed. 250 parts of the particles (average particle diameter: 20 μm) were added with ethyl acetate so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. The adhesive sheet is used as a thin adhesive having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper. sheet.

Example 18

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by mixing 200 parts (resin solid content: 100 parts) of the acrylic adhesive resin solution and 40 parts of boron nitride particles (aspect ratio: 10, thickness: 0.3 μm, length in the plane direction: 3 μm) and the ball 200 parts of alumina particles (average particle diameter: 20 μm) were added, and ethyl acetate was added so that the content of the nonvolatile content was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.40 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 19

By mixing 100 parts of the mixed solution obtained in Example 18 with isocyanide An acid-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) was used in an amount of 0.40 part to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes, and then formed into a thermally conductive material. The layer was bonded to a polyethylene terephthalate film having a thickness of 4 μm to form a thermally conductive material layer, and an adhesive sheet having a total thickness of about 100 μm was obtained. As the adhesive sheet, an adhesive sheet having a layer of a thermally conductive material on both sides of a polyethylene terephthalate film was used by peeling off the release paper.

Example 20

By mixing 100 parts of the mixed solution obtained in Example 13 and 0.40 part of an isocyanate-based crosslinking agent [manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate, trade name: Coronate L-55E], a thermally conductive material was obtained. . The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes, and then formed into a thermally conductive material. The layer was bonded to a polyethylene terephthalate film having a thickness of 4 μm to form a thermally conductive material layer, and an adhesive sheet having a total thickness of about 100 μm was obtained. As the adhesive sheet, an adhesive sheet having a layer of a thermally conductive material on both sides of a polyethylene terephthalate film was used by peeling off the release paper.

Example 21

By mixing 100 parts of the mixed solution obtained in Example 18 with 0.40 part of an isocyanate-based crosslinking agent [manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate, trade name: Coronate L-55E], a thermally conductive material was obtained. . The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes, and then formed into a thermally conductive material. The layer was bonded to an aluminum foil having a thickness of 12 μm to obtain an adhesive sheet having a layer of a thermally conductive material and having a total thickness of 100 μm. This adhesive sheet was used as an adhesive sheet having a layer of a thermally conductive material on both sides of the aluminum foil by peeling off the release paper.

Comparative example 1

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Then, by mixing 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 233 parts of spherical alumina particles (average particle diameter: 30 μm), the content of the nonvolatile matter was 70% by mass. Ethyl acetate was added in a manner and stirred well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material is applied to a release paper [(share) Sun A. On the product No.: K-80HS, it was dried in an environment of 100 ° C for 5 minutes to obtain an adhesive sheet having a layer of a thermally conductive material having a thickness of about 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative example 2

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Then, by mixing 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 43 parts of spherical alumina particles (average particle diameter: 30 μm), the content of the nonvolatile matter was 70% by mass. Ethyl acetate was added in a manner and stirred well to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative example 3

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 41 parts of plate-like aluminum particles (aspect ratio: 200, thickness: 1 μm, length in the surface direction: 200 μm) were mixed to make a nonvolatile matter. Ethyl acetate was added so that the content rate was 70% by mass, and the mixed solution was obtained by sufficiently stirring.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative example 4

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by mixing 200 parts of the acrylic adhesive resin solution ( The resin solid content: 100 parts) and 41 parts of plate-like aluminum particles (aspect ratio: 1, thickness: 10 μm, length in the surface direction: 10 μm), and ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass. And fully stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Next, the following physical properties were investigated using the thermally conductive material or the adhesive sheet obtained in each of the examples or the comparative examples. The results are shown in Table 1.

[Distributed stability]

The mixed solution obtained in each of the examples or the comparative examples was placed in a test tube, placed in an environment having a temperature of 23 ° C and a relative humidity of 50%, and the mixed solution was visually observed to disperse the stability according to the following evaluation criteria. Based on the evaluation of thermal conductivity.

[Evaluation Benchmark]

○: No sedimentation of the mixed solution was observed even after being left for 12 hours or more.

△: Settling of the mixed solution was observed for less than 3 hours for 3 hours or more.

×: Settling of the mixed solution was observed for less than 3 hours.

[thermal conductivity] (1) Hotline method

A test piece was produced by cutting the adhesive sheet in a size of 50 mm × 120 mm.

On the other hand, yttrium, quartz glass, and zirconia are used as standard materials, and the thermal conductivity is such that a thermal conductivity meter (Kyoto Electronics Co., Ltd., product number: QTM500) is used, and the temperature is 23 ° C, and the relative humidity is When measured in an environment of 50%, the thermal conductivity of bismuth is 0.24 W/mK, the thermal conductivity of quartz glass is 1.41 W/mK, and the thermal conductivity of zirconia is 3.3 W/mK.

Next, the test piece was pasted on each standard material, and the thermal conductivity was measured in the same manner as described above, and the deviation between the thermal conductivity of the standard material and the test piece was plotted, and the thermal conductivity was determined by interpolation, based on the following evaluation criteria. Evaluate thermal conductivity.

[Evaluation Benchmark]

○: Thermal conductivity is 0.8 W/mK or more

△: Thermal conductivity is 0.4 W/mK or less and less than 0.8 W/mK

×: The thermal conductivity is less than 0.4 W/mK

(2) Periodic heating method (thermal conductivity in the thickness direction)

The thermal diffusivity of the test piece was measured by a method based on ISO 22007-3 (period heating method) in an environment of a temperature of 23 ° C and a relative humidity of 50%. Further, the specific heat of the test piece was measured in accordance with JIS K7123, and the specific gravity was measured in accordance with JIS K7112.

Based on the measurement results of the thermal diffusivity, the specific heat and the specific gravity of the test piece measured as described above, the thermal conductivity was determined by the formula: [thermal conductivity] = [thermal diffusivity] × [specific heat] × [specific gravity], and the following The thermal conductivity is evaluated based on the evaluation criteria.

[Evaluation Benchmark]

○: Thermal conductivity is 0.8 W/mK or more

△: Thermal conductivity is 0.4 W/mK or less and less than 0.8 W/mK

×: The thermal conductivity is less than 0.4 W/mK

(3) Thermal conductivity in the plane direction

The thermal conductivity of the surface direction can be estimated by, for example, Omura Takahiro, the other two, "the method of estimating the thermal conductivity of the in-plane direction of the fiber-based heat-insulating material by the periodic heating method and the unsteady heat method", Nichias Technical Times No. 330 It is measured by a conventional method such as the method described in Nichias (shares), 2002, No. 2, and 1-6.

In the present embodiment and the comparative example, the thermal conductivity in the plane direction is based on the thermal conductivity (λ _h ) obtained by the above-described hot line method and the thermal conductivity (λ _y ) obtained by the periodic heating method. : [thermal conductivity (λ _x ) in the plane direction = [thermal conductivity (λ _h ) obtained by the hot wire method] ² ÷ [thermal conductivity (λ _y ) obtained by the periodic heating method], and the following The evaluation benchmark is based on an assessment.

[Evaluation Benchmark]

◎: The thermal conductivity in the plane direction is 1.5 W/mK or more.

○: The thermal conductivity in the plane direction is 1.0 W/mK or more and less than 1.5 W/mK.

△: The thermal conductivity in the plane direction is 0.4 W/mK or more and less than 1.0 W/mK.

×: The thermal conductivity in the plane direction is less than 0.4 W/mK or more.

[adhesiveness]

A polyester film having a thickness of 25 μm was attached to one side of the adhesive sheet to prepare a test tape having a width of 25 mm and a length of 50 mm. The test piece obtained as described above was placed on a stainless steel plate to which a polishing treatment was applied in advance, and a roller having a mass of 2 kg was reciprocated once to integrate the two to prepare a test piece. After the test piece was cured for 20 minutes in an environment of a temperature of 23 ° C and a relative humidity of 50%, a QC tensile tester (Tester industry) was used in the environment. (Feed) The adhesive sheet was peeled off at a tensile speed of 300 mm/min from the test piece, and the adhesive force was measured at the same time, and the adhesion was evaluated based on the following evaluation criteria.

[Evaluation Benchmark]

○: Adhesive strength is 5N/25mm or more

△: The adhesive force is 1N/25mm or more and less than 5N/25mm

×: Adhesion is less than 1N/25mm, or agglutination occurs

[heat resistance] (1) Heat-resistant shear maintenance

A polyester film having a thickness of 25 μm was attached to one side of the adhesive sheet to prepare a test tape having a width of 25 mm and a length of 25 mm. The test piece obtained above was placed on a stainless steel plate to which a polishing treatment was applied in advance, and the roller was rubbed once with a mass of 2 kg to integrate the two to prepare a test piece. After the test piece was cured for 20 minutes in an environment at a temperature of 120 ° C, a load of 1 kg in a vertical direction was applied to the test piece in the environment, and the test was carried out by using a maintenance tester (manufactured by Tester Industries Co., Ltd.). The time from the start of the test until the test piece was peeled off from the stainless steel plate was evaluated based on the following evaluation criteria.

[Evaluation Benchmark]

○: The time until the test piece was peeled off from the stainless steel plate was 720 minutes or longer.

△: The time until the test piece was peeled off from the stainless steel plate was 10 minutes or more and less than 720 minutes.

×: The time until the test piece was peeled off from the stainless steel plate was less than 10 minutes.

(2) Resistance to heavy load stripping

An aluminum foil having a thickness of 40 μm was attached to one side of the adhesive sheet to prepare a test tape having a width of 25 mm and a length of 50 mm. The test piece obtained above was placed on an aluminum plate, and a 2 kg roller was reciprocated once, and the test piece was produced by integrating the two. After the test piece was cured in an environment of a temperature of 23 ° C and a relative humidity of 50% for 24 hours, a test piece was placed in a vertical direction with a load of 100 g in a vertical direction in an environment of 120 ° C for 2 hours, and the test was started from the test to the test. The time until the sheet was peeled off from the aluminum sheet was evaluated based on the following evaluation criteria.

[Evaluation Benchmark]

○: The time until the test piece was peeled off from the aluminum plate was 120 minutes or more

△: The time until the test piece was peeled off from the aluminum plate was 50 minutes or more and less than 120 minutes.

×: The time until the test piece was peeled off from the aluminum plate was less than 50 minutes.

(3) T-peel strength

The peeling paper of one side of the test piece cut|disconnected by 4 cm of the longitudinal direction and 4 cm of the horizontal direction was peeled, and it adhered to the aluminum plate, and the peeling paper of the back surface was peeled, and the stainless steel plate of 5 cm of longitudinal direction and 5 cm of width was attached [ mass 50 g, SUS304. Glow annealing (BA) treatment plate], allowed to stand at room temperature for 24 hours. Next, the test piece was placed in a vertical direction in an environment of 120 ° C, and the holding time until the stainless steel plate was peeled off from the test piece was measured, and the evaluation was based on the following evaluation criteria.

[Evaluation Benchmark]

○: Maintenance time is 24 hours or more

△: The maintenance time is less than 1 hour and less than 24 hours.

×: The maintenance time is less than 1 hour.

[Electrical insulation] (1) Volume resistance

The volume resistivity of the adhesive sheet was measured using JIS C2151 as the standard in an environment of 23 ± 5 ° C and a relative humidity of 50 ± 10% using an insulation meter [Dak (DKK), product number: SME-8331E]. The assessment is based on the following evaluation criteria.

[Evaluation Benchmark]

○: The volume resistivity is 1 × 10 ¹⁴ Ω ‧ cm or more

△: The volume resistivity is 1 × 10 ¹⁰ Ω ‧ cm or more and less than 1 × 10 ¹⁴ Ω ‧ cm

×: The volume resistivity is less than 1 × 10 ¹⁰ Ω ‧ cm

(2) Insulation breakdown voltage

As a measurement tester for the dielectric breakdown voltage, a Tama electric test (strand) system and a pressure tester TP-516UZ were used. The IEC60243-1 was used as the standard, and the external temperature method (short-time method) was used, and the measurement temperature was 23 ° C. The oxime oil was used as the surrounding medium, and the cylindrical electrode (application surface) having a diameter of 25 mm and the entire aluminum foil (detection surface) were used as test electrodes, and the dielectric breakdown voltage was measured at a detection current of 10 mA, and evaluated based on the following evaluation criteria.

[Evaluation Benchmark]

◎: The dielectric breakdown voltage is 20kV/mm or more

○: The dielectric breakdown voltage is 10kV/mm or more and less than 20kV/mm.

△: The dielectric breakdown voltage is 1 kV/mm or more and less than 10 kV/mm.

×: The dielectric breakdown voltage is less than 1kV/mm.

[Total assessment]

In each physical property, the evaluation of ◎ is 20 points, the evaluation of ○ is 10 points, the evaluation of △ is 5 points, and the evaluation of × is -10 points. By summing up the points of each physical property, the total point is obtained. Number (highest point: 120 points).

From the results shown in Table 1, the thermal conductivity materials obtained in the respective comparative examples were evaluated with ×, and the points in the total evaluation were 45 points or less. The thermally conductive materials obtained in the respective examples were not only only There is no evaluation of ×, and the total evaluation is 70 points or more, and it is found that the total of heat conductivity, adhesion, heat resistance, and electrical insulation is excellent.

Manufacturing example 1

After adding 184.0 g of a slurry of a plate-like aluminum particle (nonvolatile content: 65.2% by mass) in a separable flask having a volume of 1 liter, 589.4 g of mineral olein was added to the flask, and the slurry was obtained by stirring. material. Nitrogen gas was introduced into the flask while stirring the obtained slurry, and after the nitrogen atmosphere was obtained, the contents of the flask were heated to 80 ° C, and the atmosphere in the flask was maintained in a nitrogen atmosphere.

Next, 0.92 g of acrylic acid, oxidized 1,2-polybutadiene 9.0 g, and trimethylolpropane triacrylate (0.44 g, divinylbenzene) diluted with mineral spirits to 50% by mass were added to the flask. 4.2 g and 0.68 g of azobisisobutyronitrile were reacted at 80 ° C for 6 hours, and the reaction was terminated by cooling the contents of the flask to room temperature. After completion of the reaction, the contents of the flask were taken out, and the impurities were removed by filtration, and washed with mineral oil to obtain a slurry containing aluminum particles covered with the resin.

The content of the non-volatile content in the slurry obtained as described above was 55.7 mass%, and the amount of the resin in the aluminum particles covered with the resin was investigated based on the following method. The coverage of the plate-like aluminum particles per 100 g of the resin was 13.8 g. (Reaction rate: 80%). After washing a part of the slurry with hexane and filtering, Mineral oil was added to prepare a slurry having a content of plate-like aluminum particles of 50.0% by mass.

[Method for Measuring the Covering Amount of Resin]

After removing a part of the slurry and drying it, the aluminum is dissolved in aqua regia [concentrated hydrochloric acid: concentrated nitric acid (capacity ratio) = 3:1], and the residual resin is filtered, washed with water, dried, and the mass is measured. Find the coverage of the resin.

Further, the amount of the plate-like aluminum particles is determined by subtracting the amount of coating of the resin from the mass of the aluminum particles covered with the resin.

Example 22

100 parts of the mixed solution obtained in Example 5 and 0.30 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were mixed to obtain a thermally conductive material. . The obtained thermally conductive material was applied to a release paper (developed by Sun A., product number: K-80HS), and dried for 5 minutes in an environment of 100 ° C to form a layer and thickness of the thermally conductive material. The polyethylene terephthalate film having a thickness of about 4 μm was bonded to obtain an adhesive sheet having a heat conductive material layer and having a total thickness of 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 23

In Example 22, a polyethylene terephthalate film having a thickness of about 4 μm was used instead of a polyethylene terephthalate film having a thickness of about 12 μm, and an adhesive sheet having a layer of a thermally conductive material was adjusted. An adhesive sheet was obtained in the same manner as in Example 22 except that the thickness was 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 24

In Example 22, a film made of polyethylene terephthalate having a thickness of about 4 μm was used, and a film made of polyimide having a thickness of about 12.5 μm was used, and the thickness of the adhesive sheet having the layer of the heat conductive material was adjusted. An adhesive sheet was obtained in the same manner as in Example 22 except 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 25

In Example 22, a polyethylene terephthalate film having a thickness of about 4 μm was used, and a film of a polyphenylene sulfide having a thickness of about 5 μm was used to adjust the thickness of the adhesive sheet having a layer of the heat conductive material. An adhesive sheet was obtained in the same manner as in Example 22 except that the thickness was 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 26

In Example 22, a polyethylene terephthalate film having a thickness of about 4 μm was used, and a polyimide film having a thickness of about 9 μm was used, and the thickness of the adhesive sheet having the heat conductive material layer was adjusted to be 100 μm. An adhesive sheet was obtained in the same manner as in Example 22. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 27

In Example 22, a polyethylene terephthalate film having a thickness of about 4 μm was used, and a polyester nonwoven fabric having a thickness of about 36 μm (pound amount: 23 g/m ² ) was used to adjust a layer having a thermally conductive material. An adhesive sheet was obtained in the same manner as in Example 22 except that the thickness of the adhesive sheet was 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 28

In Example 22, a polyethylene terephthalate film having a thickness of about 4 μm was used, and a non-woven fabric made of rayon having a thickness of about 36 μm (pound amount: 14 g/m ² ) was used to adjust a layer having a thermally conductive material. An adhesive sheet was obtained in the same manner as in Example 22 except that the thickness of the adhesive sheet was 100 μm. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 29

After preparing the acrylic adhesive resin solution in the same manner as in Example 1, 200 parts of the acrylic adhesive resin solution (solid content: 100 parts) and the slurry of the resin-coated plate-like aluminum particles obtained in Production Example 1 were mixed. Body (length ratio of plate-like aluminum particles: 50, thickness: 0.25 μm, length in the plane direction: 12.5 μm) 10 parts (solid content of aluminum particles covered with resin) and spherical alumina particles (average particle diameter: 200 parts of 10 μm) was added with ethyl acetate so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 30

In the example 29, the amount of the slurry of the plate-like aluminum particles covered with the resin (the aspect ratio of the plate-shaped aluminum particles: 50, the thickness: 0.25 μm, and the length in the plane direction: 12.5 μm) was changed from 10 parts. For 15 parts, an adhesive sheet was obtained by the same operation as in Example 29. The adhesive sheet is used as the two sides without the substrate by peeling off the release paper An adhesive sheet having a layer of thermally conductive material thereon.

Example 31

In the example 29, the amount of the slurry of the plate-like aluminum particles covered with the resin (the aspect ratio of the plate-shaped aluminum particles: 50, the thickness: 0.25 μm, and the length in the plane direction: 12.5 μm) was changed from 10 parts. For 20 parts, an adhesive sheet was obtained by the same operation as in Example 29. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 32

In Example 22, 100 parts of the mixed solution obtained in Example 30 was used instead of 100 parts of the mixed solution obtained in Example 5 (a slurry of plate-like aluminum particles covered with a resin (the aspect ratio of the plate-like aluminum particles: 50, thickness: 0.25 μm, length in the surface direction: 12.5 μm): 15 parts), an adhesive sheet was obtained in the same manner as in Example 22. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both surfaces of a resin substrate by peeling off the release paper.

Example 33

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, by using 200 parts of the acrylic adhesive resin solution (tree Lipid solid component: 100 parts) Slurry with plate-like aluminum particles (length ratio of plate-like aluminum particles: 40, thickness: 0.25 μm, length in the plane direction: 10 μm) 7 parts (solid content of plate-like aluminum particles) In the above, ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass, and the mixed solution was obtained by sufficiently stirring.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 34

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, in this case, 200 parts (resin solid content: 100 parts) of the acrylic adhesive resin solution and 10 parts of boron nitride particles (aspect ratio: 40, thickness: 0.3 μm, length in the plane direction: 12 μm) were used. Ethyl acetate was added so that the content rate of a nonvolatile content was 70 mass %, and it stirred well, and the mixed solution was obtained.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 35

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, in this case, 200 parts (resin solid content: 100 parts) of the acrylic adhesive resin solution and 10 parts of graphite particles (aspect ratio: 25, thickness: 0.4 μm, length in the plane direction: 10 μm) were made to be nonvolatile. Ethyl acetate was added so that the content rate of the fraction was 70% by mass, and the mixture solution was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied to a release paper (developed by Sun A., product number: K-80HS), and dried by 5 minutes in an environment of 100 ° C. In the bell, an adhesive sheet having a thickness of about 100 μm and a layer of a thermally conductive material was formed. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 36

The acrylic adhesive resin solution was prepared in the same manner as in Example 1. The acrylic adhesive resin contained in the obtained acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -51.2 °C.

Next, the non-volatile matter was obtained by using 50 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and 50 parts of talc particles (aspect ratio: 30, thickness: 1 μm, length in the surface direction: 30 μm). Ethyl acetate was added so that the content rate was 70% by mass, and the mixture solution was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Example 37

100 parts of ethyl acetate, 50.5 parts of n-butyl acrylate, 37.0 parts of 2-ethylhexyl acrylate, and vinyl acetate 9.0 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After adding 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.06 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic pressure-sensitive adhesive resin contained in the acrylic pressure-sensitive adhesive solution has a weight average molecular weight of 500,000 and a glass transition temperature of -51.2 °C.

Next, in place of the acrylic adhesive resin solution used in Example 11, the acrylic adhesive resin solution obtained as described above was used, and the isocyanate crosslinking agent (manufactured by Japan Polyurethane Co., Ltd.) was used. An adhesive sheet was obtained in the same manner as in Example 11 except that the amount of the isocyanate and the trade name: Coronate L-55E was 0.30 parts.

Example 38

100 parts of ethyl acetate, 50.5 parts of n-butyl acrylate, 37.0 parts of 2-ethylhexyl acrylate, and vinyl acetate 9.0 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After adding 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.03 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Again, here The acrylic acid-based adhesive resin contained in the olefinic adhesive resin solution had a weight average molecular weight of 1,000,000 and a glass transition temperature of -51.2 °C.

Next, in place of the acrylic adhesive resin solution used in Example 11, the acrylic adhesive resin solution obtained as described above was used, and the isocyanate crosslinking agent (manufactured by Japan Polyurethane Co., Ltd.) was used. An adhesive sheet was obtained in the same manner as in Example 11 except that the amount of the isocyanate and the trade name: Coronate L-55E was 0.20 parts.

Example 39

100 parts of ethyl acetate, 87.5 parts of n-butyl acrylate, 9.0 parts of vinyl acetate, and 2-hydroxyethyl acrylate 0.5 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After 3.0 parts of acrylic acid and 0.05 parts of acrylic acid, 0.05 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 700,000 and a glass transition temperature of -45.2 °C.

Then, an adhesive sheet was obtained in the same manner as in Example 11 except that the acrylic pressure-sensitive adhesive solution used in Example 11 was used instead of the acrylic pressure-sensitive adhesive solution obtained above.

Example 40

With cooling tube, nitrogen inlet tube, thermometer, dropping funnel and stirring 100 parts of ethyl acetate, 15.5 parts of n-butyl acrylate, 80.0 parts of 2-ethylhexyl acrylate, 1.0 part of vinyl acetate, 0.5 parts of 2-hydroxyethyl acrylate, and acrylic acid were added to the reaction vessel of the mixer. After 3.0 parts, 0.05 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 700,000 and a glass transition temperature of -63.8 °C.

Then, an adhesive sheet was obtained in the same manner as in Example 11 except that the acrylic pressure-sensitive adhesive solution used in Example 11 was used instead of the acrylic pressure-sensitive adhesive solution obtained above.

Example 41

100 parts of ethyl acetate, 50.5 parts of n-butyl acrylate, 37.0 parts of 2-ethylhexyl acrylate, and vinyl acetate 9.0 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After adding 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.06 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic pressure-sensitive adhesive resin contained in the acrylic pressure-sensitive adhesive solution has a weight average molecular weight of 500,000 and a glass transition temperature of -51.2 °C.

Next, in place of the acrylic adhesive resin solution used in Example 33, the acrylic adhesive resin solution obtained as described above was used and changed. An adhesive sheet was obtained in the same manner as in Example 33 except that the amount of the isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) was 0.30 parts.

Example 42

100 parts of ethyl acetate, 50.5 parts of n-butyl acrylate, 37.0 parts of 2-ethylhexyl acrylate, and vinyl acetate 9.0 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After adding 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.03 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 1,000,000 and a glass transition temperature of -51.2 °C.

Next, in place of the acrylic adhesive resin solution used in Example 33, the acrylic adhesive resin solution obtained as described above was used, and the isocyanate crosslinking agent (manufactured by Japan Polyurethane Co., Ltd.) was used. An adhesive sheet was obtained in the same manner as in Example 33 except that the amount of the isocyanate and the trade name: Coronate L-55E was 0.20 parts.

Example 43

100 parts of ethyl acetate, 87.5 parts of n-butyl acrylate, 9.0 parts of vinyl acetate, and 2-hydroxyethyl acrylate 0.5 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After 3.0 parts of acrylic acid and 0.05 parts of acrylic acid, 0.05 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 700,000 and a glass transition temperature of -45.2 °C.

Then, an adhesive sheet was obtained in the same manner as in Example 33 except that the acrylic pressure-sensitive adhesive solution used in Example 33 was used instead of the acrylic pressure-sensitive adhesive solution obtained above.

Example 44

100 parts of ethyl acetate, 15.5 parts of n-butyl acrylate, 80.0 parts of 2-ethylhexyl acrylate, and vinyl acetate 1.0 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After adding 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.05 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution had a weight average molecular weight of 700,000 and a glass transition temperature of -63.8 °C.

Then, an adhesive sheet was obtained in the same manner as in Example 33 except that the acrylic adhesive resin solution used in Example 33 was used instead of the acrylic adhesive resin solution obtained above.

Comparative Example 5

In Example 29, the amount of the slurry of the plate-like aluminum particles covered with the resin (the aspect ratio of the plate-like aluminum particles: 50, the thickness: 0.25 μm, and the length in the plane direction: 12.5 μm) was changed from 10 parts to 10 parts. An adhesive sheet was obtained in the same manner as in Example 29 except 0.1 part. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative Example 6

In Example 29, the amount of the slurry of the plate-like aluminum particles covered with the resin (the aspect ratio of the plate-like aluminum particles: 50, the thickness: 0.25 μm, and the length in the plane direction: 12.5 μm) was changed from 10 parts to 10 parts. An adhesive sheet was obtained in the same manner as in Example 29 except for 210 parts. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative Example 7

100 parts of ethyl acetate, 50.5 parts of n-butyl acrylate, 37.0 parts of 2-ethylhexyl acrylate, and vinyl acetate 9.0 were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.1 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Again, here propylene The acrylic adhesive resin contained in the acid-based adhesive resin solution had a weight average molecular weight of 250,000 and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and boron nitride particles (aspect ratio: 40, thickness: 0.3 μm, length in the plane direction: 12 μm) and 10 parts of the ball were obtained. In 200 parts of the alumina particles (average particle diameter: 10 μm), ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the obtained mixed solution was mixed with 0.44 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate, trade name: Coronate L-55E) to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative Example 8

100 parts of ethyl acetate, 96.5 parts of 2-ethylhexyl acrylate, 0.5 parts of 2-hydroxyethyl acrylate, and 3.0 parts of acrylic acid were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. Thereafter, 0.03 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. Acquired propylene The content of non-volatiles in the acid-based adhesive resin solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 700,000 and a glass transition temperature of -66.7 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and boron nitride particles (aspect ratio: 40, thickness: 0.3 μm, length in the plane direction: 12 μm) and 10 parts of the ball were obtained. In 200 parts of the alumina particles (average particle diameter: 10 μm), ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative Example 9

In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer, 100 parts of ethyl acetate and n-butyl acrylate were added. 50.5 parts of ester, 37.0 parts of 2-ethylhexyl acrylate, 9.0 parts of vinyl acetate, 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.01 parts of azoisobutyronitrile was added, and 60 ° C in a nitrogen atmosphere. The reaction was carried out for 8 hours to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 1.8 million and a glass transition temperature of -51.2 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and boron nitride particles (aspect ratio: 40, thickness: 0.3 μm, length in the plane direction: 12 μm) and 10 parts of the ball were obtained. In 200 parts of the alumina particles (average particle diameter: 10 μm), ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred. However, since agglomerates were generated during stirring, the termination was followed. Operation.

Comparative Example 10

100 parts of ethyl acetate, 50.5 parts of n-butyl acrylate, 37.0 parts of methyl methacrylate, and 9 parts of vinyl acetate were placed in a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and a stirrer. After 0.5 parts of 2-hydroxyethyl acrylate and 3.0 parts of acrylic acid, 0.05 part of azoisobutyronitrile was added, and the reaction was carried out at 80 ° C for 5 hours in a nitrogen atmosphere to obtain an acrylic adhesive resin solution. The content of nonvolatiles in the obtained acrylic pressure-sensitive adhesive solution was 50% by mass. Further, the acrylic adhesive resin contained in the acrylic adhesive resin solution has a weight average molecular weight of 700,000 and a glass transition temperature of -1.3 °C.

Next, 200 parts of the acrylic adhesive resin solution (resin solid content: 100 parts) and boron nitride particles (aspect ratio: 40, thickness: 0.3 μm, length in the plane direction: 12 μm) and 10 parts of the ball were obtained. In 200 parts of the alumina particles (average particle diameter: 10 μm), ethyl acetate was added so that the content of the nonvolatile matter was 70% by mass, and the mixture was sufficiently stirred to obtain a mixed solution.

100 parts of the mixed solution obtained by mixing and 0.22 parts of an isocyanate-based crosslinking agent (manufactured by Nippon Polycarbonate Co., Ltd., polyisocyanate, trade name: Coronate L-55E) were used to obtain a thermally conductive material. The obtained thermally conductive material was applied onto a release paper (developed by Sun A., product number: K-80HS), and dried in an environment of 100 ° C for 5 minutes to obtain a thickness of about 100 μm. An adhesive sheet having a layer of thermally conductive material. This adhesive sheet is used as an adhesive sheet having a layer of a thermally conductive material on both sides of the substrate without peeling off the release paper.

Comparative Example 11

In place of the acrylic adhesive resin solution used in Example 33, an acrylic adhesive resin solution obtained in the same manner as in Comparative Example 7 and an isocyanate crosslinking agent [Japan Polyurethane Industrial Co., Ltd.) were used. An adhesive sheet was obtained in the same manner as in Example 33 except that the amount of the product, the polyisocyanate, and the trade name: Coronate L-55E was changed to 0.44 parts.

Comparative Example 12

An adhesive sheet was produced in the same manner as in Example 33 except that the acrylic adhesive resin solution used in Example 33 was used instead of the acrylic adhesive resin solution obtained in the same manner as in Comparative Example 9. However, when the acrylic adhesive resin solution is mixed with the boron nitride particles and the spherical alumina particles, agglomerates are generated when the mixture is stirred, and the subsequent operation is terminated.

Comparative Example 13

An adhesive sheet was obtained in the same manner as in Example 33 except that the acrylic adhesive resin solution used in Example 33 was used instead of the acrylic adhesive resin solution obtained in the same manner as in Comparative Example 8.

Comparative Example 14

An adhesive sheet was obtained in the same manner as in Example 33 except that the acrylic adhesive resin solution used in Example 33 was used instead of the acrylic adhesive resin solution obtained in the same manner as in Comparative Example 10.

Next, physical properties were investigated in the same manner as described above using the thermally conductive material or the adhesive sheet obtained in each of the examples or the comparative examples. The results are shown in Table 2.

The results shown in Table 2 were evaluated for the heat conductive material obtained in each of the comparative examples, and the total point of the evaluation was 25 points or less. The heat conductive materials obtained in the respective examples were not only ineffective. The evaluation of ×, the total point of the evaluation is 60 points or more, and it is known that the thermal conductivity, the adhesion, the heat resistance, and the electrical insulation have an excellent performance. Further, it was found that the thermally conductive materials obtained in Examples 33 to 36 and Examples 41 to 44 exhibited remarkably excellent heat conductivity and heat resistance (T-peel strength) in the respective surface directions.

From the above results, it is known that the thermally conductive material obtained in each of the examples and the adhesive sheet of the thermally conductive material layer having the thermally conductive material are applied to, for example, a wiring board, a heat sink, a casing, and the like. When the exothermic members are joined. Examples of the product in which the wiring board is bonded to a member requiring heat dissipation include, for example, a substrate having a substrate on which a light-emitting element is mounted, and an illumination device for a heat radiator.

Moreover, the adhesive sheet of the present invention can be used not only in place of the fixing tool in which the conventional component is fixed by a fixing device such as a screw or a screw, but also the adhesive sheet of the present invention can be used together with the fixing device. The fixing device is further fixed in a strong layer. The article using the adhesive sheet fixing member of the present invention as described above, for example, as shown in Fig. 1, serves as a filling gap (air layer) existing between the substrate 2 and the heat radiator 4, thereby preventing not only heat conduction due to the presence of the air layer. The adhesive sheet of the present invention is excellent in industrial applicability because it can be made thinner and longer in life, and the steps are shortened when the machine is manufactured.

Industrial utilization

The heat conductive material of the present invention is expected to be used in an adhesive sheet, a light-emitting diode (LED), an illumination device using electroluminescence, a backlight illumination device, a battery such as a solar cell or a lithium ion battery, and an IC. For power control devices such as computer parts and components such as CPUs, power supply circuits such as inverters, touch panels, and electromagnetic shielding.

1‧‧‧Lighting elements

2‧‧‧Substrate

3‧‧‧ Thermal Conductive Material Layer

4‧‧‧ radiator

Fig. 1 is a schematic explanatory view showing an embodiment of a lighting fixture of the thermally conductive material of the present invention between a substrate constituting the illuminating device and a heat radiator.

1‧‧‧Lighting elements

2‧‧‧Substrate

3‧‧‧ Thermal Conductive Material Layer

4‧‧‧ radiator

Claims (5)

A thermally conductive material which contains a plate-like particle and an adhesive resin as an essential component, and is characterized in that it contains spherical particles in an amount of 500 parts by mass or less per 1 part by mass of the plate-like particles, and each adhesive property The total amount of the plate-like particles and the spherical particles of 100 parts by mass of the resin (solid content) is 1 to 600 parts by mass. The thermally conductive material according to claim 1, wherein the plate-like particles have an aspect ratio of 10 to 100. The thermally conductive material according to claim 1 or 2, wherein the plate-like particles have a thickness of 0.01 to 20 μm and a length in the plane direction of 0.1 to 100 μm. An adhesive sheet characterized by having a thermally conductive material layer comprising at least one of the thermally conductive materials according to any one of claims 1 to 3. A lighting device comprising a substrate on which a light-emitting element is mounted and a heat-emitting device, wherein the heat conductive material according to any one of claims 1 to 3 is interposed between the substrate and the heat radiator. .