WO2018025538A1 - Insulating film - Google Patents

Insulating film Download PDF

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Publication number
WO2018025538A1
WO2018025538A1 PCT/JP2017/023544 JP2017023544W WO2018025538A1 WO 2018025538 A1 WO2018025538 A1 WO 2018025538A1 JP 2017023544 W JP2017023544 W JP 2017023544W WO 2018025538 A1 WO2018025538 A1 WO 2018025538A1
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WO
WIPO (PCT)
Prior art keywords
insulating film
particles
ceramic particles
film
resin
Prior art date
Application number
PCT/JP2017/023544
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French (fr)
Japanese (ja)
Inventor
史朗 石川
和彦 山▲崎▼
Original Assignee
三菱マテリアル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017057816A external-priority patent/JP2018026320A/en
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to US16/300,158 priority Critical patent/US11124673B2/en
Priority to CN201780031656.1A priority patent/CN109155165B/en
Priority to KR1020197001637A priority patent/KR102357814B1/en
Priority to EP17836645.6A priority patent/EP3493223A4/en
Publication of WO2018025538A1 publication Critical patent/WO2018025538A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/305—Polyamides or polyesteramides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306—Polyimides or polyesterimides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Definitions

  • the present invention relates to an insulating film.
  • This application claims priority based on Japanese Patent Application No. 2016-151222 filed in Japan on August 1, 2016 and Japanese Patent Application No. 2017-057816 filed on March 23, 2017 in Japan. , The contents of which are incorporated herein.
  • Insulating films are, for example, coating layers for metal wires used in coils and motors, protective films that protect the surface of electronic components such as semiconductor chips and LED elements and circuit boards, and circuit layers and substrates in metal-based circuit boards. It is used as an insulating material.
  • a film formed from a resin composition containing a resin and an inorganic filler is used.
  • the resin a resin having high heat resistance, chemical resistance, and mechanical strength such as polyimide and polyamideimide is used.
  • Non-patent Document 1 Non-patent Document 1
  • the withstand voltage V R of the insulating film, h the thickness of the insulating film, when the withstand voltage per thickness and V F, represented by the following formula (1).
  • V R V F ⁇ h
  • the thermal resistance R of the insulating film is expressed by the following equation (2), where h is the thickness of the insulating film and ⁇ is the thermal conductivity of the insulating film. R ⁇ h / ⁇ (2) From the expressions (1) and (2), the thermal resistance R of the insulating film can be expressed by the following expression (3).
  • Patent Documents 1 and 2 describe using nanoparticles as an inorganic filler in order to improve the withstand voltage of an insulating film.
  • Patent Document 1 discloses an insulating film using nanoparticles having an average maximum diameter of 500 nm or less as an inorganic filler.
  • Patent Document 2 discloses an insulating film including a polyamideimide resin and insulating fine particles having an average primary particle diameter of 200 nm or less.
  • an insulating film to which 5% by mass of insulating fine particles are added is described.
  • Patent Documents 3 and 4 describe an insulating film using both nanoparticles and microparticles as inorganic fillers in order to further improve the thermal conductivity.
  • Patent Document 3 discloses a resin composition for an electrically insulating material, which contains a microparticle-sized first inorganic filler and a nanoparticle-sized second inorganic filler made of a predetermined material as the inorganic filler.
  • Patent Document 4 discloses, as inorganic fillers, microparticle-sized thermally conductive inorganic spherical microfillers, plate-like, rod-like, fiber-like, or scale-like microfillers, and nanoparticle-sized thermally conductive inorganic nanofillers.
  • a resin composition filled with is disclosed.
  • the insulating film to which microparticles are added has a problem that the withstand voltage decreases.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide an insulating film having both high thermal conductivity and high voltage resistance, and excellent in heat resistance, chemical resistance, and mechanical properties.
  • an insulating film which is one embodiment of the present invention includes a resin including polyimide, polyamideimide, or a mixture thereof, and ceramic particles having a specific surface area of 10 m 2 / g or more. And the ceramic particles form aggregated particles, and the content of the ceramic particles is in the range of 5% by volume to 60% by volume.
  • the resin is made of polyimide, polyamideimide, or a mixture thereof, heat resistance, chemical resistance, and mechanical properties are improved.
  • the withstand voltage is improved, and the withstand voltage is not easily lowered even when a large amount of ceramic particles are added.
  • the fine ceramic particles form aggregated particles, heat is easily conducted between the primary particles of the ceramic particles, and a heat conduction network structure can be easily formed. Therefore, the thermal conductivity of the insulating film is improved.
  • the content of the ceramic particles is in the range of 5 vol% or more and 60 vol% or less, withstand voltage and without impairing the excellent heat resistance, chemical resistance, and mechanical properties of polyimide and polyamideimide It becomes possible to further improve the thermal conductivity.
  • a resin layer made of polyimide, polyamideimide, or a mixture thereof is provided on at least one surface of the insulating film.
  • the resin layer can be interposed, so that the insulating film and the object to be fixed are closely adhered and the insulating film and the object to be fixed are interposed.
  • the thermal resistance can be lowered.
  • an insulating film is used as a coating film for a coil or motor metal wire (enameled wire), a double-layered insulating film is formed between enameled wires wound in a coil shape.
  • the resin layer can be interposed between the two stacked insulating films, the two stacked insulating films can be strongly adhered to each other and the thermal resistance between the two stacked insulating films can be lowered. it can. Thus, the layer interface thermal resistance between enameled wires wound in a coil shape can be reduced.
  • an insulating film having both high thermal conductivity and voltage resistance, and excellent heat resistance, chemical resistance, and mechanical properties.
  • the insulating film which is one embodiment of the present invention will be described below.
  • the insulating film which is this embodiment can be used as an insulating film of a metal wire used for a coil or a motor like an enamel film of an enameled wire, for example. Further, it can be used as a protective film for protecting the surface of an electronic component or a circuit board. Further, in a metal base circuit board or the like, it can be used as an insulating film disposed between the circuit layer and the board. Moreover, it can use as an insulating material for circuit boards, such as a flexible printed circuit board, as a single sheet
  • the insulating film according to the present embodiment includes a resin made of polyimide, polyamideimide, or a mixture thereof, and ceramic particles having a specific surface area of 10 m 2 / g or more.
  • the ceramic particles form aggregated particles.
  • the content of the ceramic particles is in the range of 5% by volume to 60% by volume. The reason why the composition of the insulating film according to this embodiment is defined as described above will be described below.
  • the resin used in the insulating film of this embodiment is a base material for the insulating film. Since polyimide and polyamideimide have an imide bond, they have excellent heat resistance and mechanical properties. For this reason, in this embodiment, polyimide, polyamideimide, or a mixture thereof is used as the resin.
  • the polyamide-imide and the polyimide preferably have a mass average molecular weight of 100,000 or more, and more preferably in the range of 100,000 to 500,000.
  • An insulating film containing polyamide-imide or polyimide having a mass average molecular weight within the above range is further improved in heat resistance and mechanical properties.
  • the ceramic particles used in the insulating film of this embodiment have an effect of efficiently improving the performance value of the insulating film.
  • the specific surface area of the ceramic particles becomes too small, that is, if the particle size of the primary particles of the ceramic particles becomes too large, the voltage resistance of the insulating film may be lowered.
  • the specific surface area of the ceramic particles is set to 10 m 2 / g or more.
  • the specific surface area of the ceramic particles is preferably 50 m 2 / g or more.
  • the specific surface area of the ceramic particles becomes too large, that is, if the particle size of the primary particles of the ceramic particles becomes too small, the ceramic particles tend to form excessively large aggregated particles, and the surface roughness Ra of the insulating film becomes large. There is a risk. If the surface roughness Ra of the insulating film becomes excessively large, the contact area with the surface of the electronic component or circuit board becomes narrow, and the insulating film is easily peeled off from the electronic component or circuit board. There is a possibility that problems such as difficulty in dissipating the heat generated by the heat to the outside through the insulating film may occur. For this reason, the surface roughness Ra of the insulating film is preferably small. In order not to excessively increase the surface roughness Ra of the insulating film, the specific surface area of the ceramic particles is preferably 300 m 2 / g or less.
  • the specific surface area of the ceramic particles is the BET specific surface area measured by the BET method.
  • the specific surface area of the ceramic particles in the insulating film can be measured by heating the insulating film, pyrolyzing and removing the resin component, and collecting the remaining ceramic particles.
  • the ceramic particles preferably have a BET diameter calculated from the BET specific surface area and density using the following formula within a range of 1 nm to 200 nm.
  • An insulating film containing ceramic particles having a BET diameter in the above range is further improved in voltage resistance.
  • BET diameter 6 / (density ⁇ BET specific surface area)
  • Ceramic particles form agglomerated particles.
  • Aggregated particles may be agglomerates in which primary particles are relatively weakly connected, or may be aggregates in which primary particles are relatively strongly connected. Moreover, you may form the particle assembly which aggregated particles further aggregated.
  • the primary particles of the ceramic particles form aggregated particles and are dispersed in the insulating film, a network due to mutual contact between the ceramic particles is formed, and heat is easily conducted between the primary particles of the ceramic particles, The thermal conductivity of the insulating film is improved.
  • the agglomerated particles of the ceramic particles preferably have a shape having anisotropy in which the primary particles are connected by point contact. In this case, it is preferable that the primary particles of the ceramic particles are chemically strongly bonded.
  • the average particle size of the aggregated particles is preferably 5 times or more, and preferably in the range of 5 times to 100 times the BET diameter. Moreover, it is preferable that the average particle diameter of aggregated particles exists in the range of 20 nm or more and 500 nm or less. When the average particle diameter of the aggregated particles is in the above range, the thermal conductivity of the insulating film can be reliably improved.
  • the average particle size of the agglomerated particles is a value of Dv50 measured with a laser diffraction particle size distribution analyzer after subjecting ceramic particles to ultrasonic dispersion in a NMP solvent together with a dispersant.
  • Aggregated particles (ceramic particles) in the insulating film can be recovered by heating the insulating film to thermally decompose and remove the resin component.
  • the content of the ceramic particles in the insulating film is 5% by volume or more and 60% by volume or less. If the ceramic particle content is too low, the thermal conductivity of the insulating film may not be sufficiently improved. On the other hand, if the content of ceramic particles is too large, that is, the resin content is relatively reduced, the shape of the insulating film may not be stably maintained. In addition, ceramic particles tend to form excessively large agglomerated particles, which may increase the surface roughness Ra of the insulating film. In order to reliably improve the thermal conductivity of the insulating film, the content of the ceramic particles is preferably 10% by volume or more. In order to reliably improve the stability of the shape of the insulating film and to reduce the surface roughness Ra, the content of the ceramic particles is preferably 50% by volume or less.
  • Ceramic particles examples include silica (silicon dioxide) particles, alumina (aluminum oxide) particles, boron nitride particles, titanium oxide particles, alumina-doped silica particles, and alumina hydrate particles.
  • a ceramic particle may be used individually by 1 type, and may be used in combination of 2 or more type. Among these ceramic particles, alumina particles are preferable because of their high thermal conductivity.
  • Ceramic particles commercially available products may be used. Commercially available products include silica particles such as AE50, AE130, AE200, AE300, AE380, AE90E (all manufactured by Nippon Aerosil Co., Ltd.), T400 (manufactured by Wacker), SFP-20M (Denka Corporation), Alu65 (Japan) Alumina particles such as Aerosil Co., Ltd., boron nitride particles such as AP-170S (Maruka Corp.), titanium oxide particles such as AEROXIDE (R) TiO 2 P90 (Nippon Aerosil Co., Ltd.), MOX170 (Nippon Aerosil Co., Ltd.) Alumina-doped silica particles such as those manufactured by Sasol, and alumina hydrate particles manufactured by Sasol can be used.
  • silica particles such as AE50, AE130, AE200, AE300, AE380, AE90E (all manufactured by Nippon Aerosil Co.,
  • the insulating film according to this embodiment may be provided with a resin layer on at least one surface.
  • the resin layer is preferably made of polyimide, polyamideimide, or a mixture thereof.
  • the resin layer has a high affinity with the resin that is the base material of the insulating film, and does not contain ceramic particles in the layer, and thus is easily deformed as compared with the insulating film. For this reason, for example, when fixing an insulating film and an object to be fixed (for example, a heating element such as an electronic component or a circuit board, or a conductor such as a metal foil of a copper foil for a circuit), a resin layer may be interposed. As a result, the insulating film and the object to be fixed can be strongly adhered.
  • a two-layered insulating film is formed between metal wires wound in a coil shape (enameled wire). Since the resin layer can be interposed between the two stacked insulating films, the two stacked insulating films can be strongly adhered to each other. This improves the peel strength of the two-layered insulating film. Further, since the thermal resistance between the two stacked insulating films can be lowered, the layer interface thermal resistance between enameled wires wound in a coil shape can be reduced.
  • the thickness of the resin layer is preferably in the range of 0.1 ⁇ m to 2 ⁇ m.
  • the thickness of the resin layer is in the above range, the adhesion between the insulating film and the object to be fixed and the two stacked insulating films can be surely increased, and between the insulating film and the solid object and 2 The thermal resistance between the stacked insulating films can be reliably lowered. If the thickness of the resin layer becomes too thin, the adhesion between the insulating film, the object to be fixed, and the two stacked insulating films may be reduced. On the other hand, if the resin layer is too thick, the thermal resistance may be increased.
  • the insulating film according to the present embodiment includes, for example, ceramic particles in which polyimide, polyamideimide, or a precursor thereof is dissolved in a solvent, a specific surface area is 10 m 2 / g or more, and aggregated particles are formed. It can be produced by preparing a dispersed ceramic particle-dispersed resin solution and then forming the ceramic particle-dispersed resin solution into a film using the ceramic particle-dispersed resin solution.
  • the solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP), diglyme, triglyme, ⁇ -butyrolactone, dimethyl sulfoxide (DMSO), and mixtures thereof.
  • the ceramic particle-dispersed resin solution may be prepared by a method in which a ceramic solution is mixed with a resin solution in which polyimide or polyamideimide or a precursor thereof is dissolved in a solvent, and the ceramic particles are dispersed in the resin solution. it can.
  • the ceramic particle-dispersed resin solution is prepared by mixing a ceramic particle dispersion in which ceramic particles are dispersed in a solvent and polyimide or polyamideimide or a precursor thereof, and mixing the polyimide or polyamideimide in the ceramic particle dispersion. Or it can prepare by the method of dissolving these precursors.
  • the ceramic particle dispersion resin solution is obtained by mixing a resin solution in which polyimide or polyamideimide or a precursor thereof is dissolved in a solvent and a ceramic particle dispersion in which ceramic particles are dispersed in the solvent. Can also be prepared.
  • an electrodeposition method and a coating method can be used as a method for forming the insulating film on the substrate.
  • the electrodeposition method uses an electrodeposition solution prepared by adding water to a ceramic particle-dispersed resin solution to generate an electrodeposition product on a substrate by an electrodeposition coating method, and then heats the electrodeposition product. Then, the insulating film is produced by drying and curing.
  • the coating method is to apply a ceramic particle-dispersed resin solution on a substrate to form a coating film, then dry the coating film to form a dry film, and then heat and cure to form an insulating film. It is a manufacturing method.
  • a film or sheet-like insulating film is formed by, for example, applying a ceramic particle-dispersed resin solution on a release film to form a coating film, and then drying the coating film and then peeling the dry film from the release film. Thereafter, the dried film can be obtained by heat treatment and curing.
  • the insulating film provided with the resin layer can be manufactured as follows, for example.
  • a resin material for forming the resin layer and a solvent are mixed, and the resin material is dissolved to prepare a resin solution.
  • this resin solution is applied to the insulating film to form a coating layer.
  • the coating layer is heated and dried.
  • solvents for dissolving the resin material include aprotic polarities such as N-methyl-2-pyrrolidone (NMP), diglyme, triglyme, ⁇ -butyrolactone, dimethyl sulfoxide (DMSO), etc. Mention may be made of solvents and mixtures thereof.
  • a dipping method As a method for applying the resin solution to the insulating film, a dipping method, a spin coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
  • the resin is made of polyimide, polyamideimide, or a mixture thereof, heat resistance and mechanical properties are improved. Moreover, since it contains the fine ceramic particle
  • the insulating film of this embodiment can be configured to include a resin layer made of polyimide, polyamideimide, or a mixture thereof on at least one surface.
  • the resin layer can be interposed, so that the insulating film and the object to be fixed are closely adhered, and the insulating film and the object to be fixed are interposed.
  • the thermal resistance can be lowered.
  • an insulating film is used as a coating film for a coil or motor metal wire (enameled wire), a double-layered insulating film is formed between enameled wires wound in a coil shape.
  • the resin layer can be interposed between the two stacked insulating films, the two stacked insulating films can be strongly adhered to each other and the thermal resistance between the two stacked insulating films can be lowered. it can. Thereby, the layer interface thermal resistance between the enamel wires wound in a coil shape can be reduced.
  • Ceramic particles described in Table 1 below were prepared.
  • the specific surface area described in Table 1 is a BET specific surface area measured by the BET method.
  • the average particle size of the agglomerated particles is a value of Dv50 measured by a laser diffraction particle size distribution analyzer after ultrasonic dispersion in an NMP (N-methyl-2-pyrrolidone) solvent together with a dispersant.
  • a ceramic particle dispersion was prepared by sonication.
  • a ceramic particle dispersion resin solution was prepared by adding the ceramic particle dispersion to 3.3 g of the polyamideimide solution so that the ceramic particle concentration becomes a value described in Table 2 below.
  • the ceramic particle concentration is the volume content of ceramic particles relative to the total volume of polyamideimide and ceramic particles.
  • ⁇ Preparation of insulating film by electrodeposition method> Using the prepared electrodeposition solution, a DC voltage of 100 V is applied by the electrodeposition method, and electrodeposition is performed on the surface of a copper plate having a thickness of 0.3 mm and a thickness of 30 mm ⁇ 20 mm so that the film thickness after heating becomes 10 ⁇ m. A product was produced. The film thickness was measured by filling a copper plate on which an insulating film was formed with a resin, taking out a cross section, and observing with a laser microscope. Next, the electrodeposition product was heated at 250 ° C. for 3 minutes in an air atmosphere to produce an insulating film having a thickness of 10 ⁇ m on the copper plate surface. Note that the electrodeposition solutions prepared in Comparative Examples 1-3 and 1-5 could not produce a uniform insulating film. In Table 2, “A” indicates that the insulating film could be manufactured, and “B” indicates that the insulating film could not be manufactured.
  • the insulating film was peeled off from the copper plate, cut into a predetermined size, and used as a sample. Using this sample, the content (mass%) of the ceramic particles of the insulating film was measured by thermogravimetric analysis (TG). And the value of content of the ceramic particle was converted into volume% using the density of the ceramic particle and polyamideimide shown below.
  • the withstand voltage per film thickness was measured using a multifunctional safety tester 7440 of Measurement Technology Laboratory Co., Ltd.
  • An electrode plate was placed on the surface of the insulating film opposite to the copper plate (substrate) side.
  • the copper plate (substrate) and the electrode plate were each connected to a power source, and the voltage was increased to 6000 V in 30 seconds.
  • the voltage when the value of the current flowing between the copper plate and the electrode plate reached 5000 ⁇ A was divided by the film thickness of the insulating film, and this value was taken as the withstand voltage per film thickness.
  • Thermal conductivity thermal conductivity in the thickness direction of the insulating film
  • LFA477 Nanoflash manufactured by NETZSCH-Geratebau GmbH.
  • a two-layer model that does not consider the interfacial thermal resistance was used for the measurement.
  • the thickness of the copper plate was 0.3 mm
  • the thermal diffusivity of the copper plate was 117.2 mm 2 / sec.
  • the surface roughness Ra was measured by performing a 1 mm scan using a Dektak 150 manufactured by Bruker Nano. The load was 5.00 mg and the scan speed was 1 mm / 30 s.
  • the insulation (flexibility) at the time of bending was evaluated by performing a pinhole test in JIS C 3216-5 before and after the substrate was bent.
  • a laminated body was produced by laminating a copper plate (sample) on which an insulating film was produced and a copper substrate prepared by stacking two copper plates having a thickness of 0.3 mm so that the sample copper plate and the copper substrate were in contact with each other. .
  • the produced laminated body was bent along the thickness of the laminated body, and then returned to the original state.
  • the laminated plate and a separately prepared stainless steel plate are immersed in a sodium chloride aqueous solution (concentration: 0.2%) in which a phenolphthalein solution is dropped, and the laminated copper substrate is used as a negative electrode and the stainless steel plate is used as a positive electrode.
  • a sodium chloride aqueous solution concentration: 0.2%) in which a phenolphthalein solution is dropped
  • the laminated copper substrate is used as a negative electrode
  • the stainless steel plate is used as a positive electrode.
  • the performance value of the insulating film of Comparative Example 1-1 was as low as 1.19 times. This is presumed to be because the specific surface area of the ceramic particles was less than 10 m 2 / g and the withstand voltage was lowered.
  • the performance values of the insulating films of Comparative Examples 1-2 and 1-4 were also about 1.17 times and 1.16 times. This is because the thermal conductivity is as low as that of a polyamideimide film not containing a filler. The low thermal conductivity is presumed to be because the content of ceramic particles is less than 5% by volume.
  • the electrodeposition solutions prepared in Comparative Examples 1-3 and 1-5 failed to produce an insulating film. This is presumably because the content of the ceramic particles exceeds 60% by volume.
  • the performance of the insulating films of Examples 1-1 to 1-18 increased greatly from 1.29 times to 4.13 times, and the performance was significantly improved. It was. This is because the withstand voltage is almost the same or improved as compared with the polyamideimide film containing no filler, and is excellent in both the thermal conductivity and the withstand voltage.
  • the surface roughness Ra was slightly high. This is presumably because the specific surface area of the ceramic particles is slightly large.
  • the surface roughness Ra was slightly high, and the insulation at the time of bending was “B”. This is presumably because the content of ceramic particles is slightly high.
  • Ceramic particles described in Table 3 below were prepared. 1.0 g of the prepared ceramic particles were added to 10 g of NMP and subjected to ultrasonic treatment for 30 minutes to prepare a ceramic particle dispersion. Subsequently, the polyamic acid solution, the ceramic particle dispersion, and NMP were mixed so that the polyamic acid concentration in the solution was finally 5% by mass and the ceramic particle concentration was a value described in Table 4 below. Subsequently, the obtained mixture was subjected to a dispersion treatment by repeating a high-pressure injection treatment at a pressure of 50 MPa 10 times using a Starburst manufactured by Sugino Machine Co., to prepare a ceramic particle-dispersed resin solution.
  • ⁇ Preparation of insulating film by coating method The prepared ceramic particle-dispersed resin solution was applied to the surface of a copper plate having a thickness of 0.3 mm and a size of 30 mm ⁇ 20 mm so that the film thickness after heating was 10 ⁇ m to form a coating film.
  • the coating film is placed on a hot plate and heated from room temperature to 60 ° C. at 3 ° C./minute, then heated to 60 ° C. for 100 minutes, further raised to 120 ° C. at 1 ° C./minute, and then at 120 ° C. for 100 minutes. Heated and dried to form a dry film. Thereafter, the dried film was heated at 250 ° C. for 1 minute and at 400 ° C. for 1 minute to produce an insulating film having a thickness of 10 ⁇ m on the copper plate surface.
  • the ceramic particle-dispersed resin solutions prepared in Comparative Examples 2-3, 2-5, 2-7, 2-9, and 2-16 could not produce an insulating film.
  • the insulating films of Comparative Examples 2-1 and 2-13 to 15 had a low withstand voltage per film thickness. This is presumed to be because the specific surface area of the ceramic particles is less than 10 m 2 / g.
  • the insulating films of Comparative Examples 2-2, 2-4, 2-6, and 2-8 were equivalent in thermal conductivity to polyimide films that did not contain filler. This is presumably because the content of ceramic particles is less than 5% by volume.
  • Insulating films of Comparative Examples 2-10 to 12 have the same or slightly lower withstand voltage per film thickness than the polyimide film containing no filler, and the thermal conductivity is equivalent to the polyimide film containing no filler. The effect of adding particles was not obtained.
  • the withstand voltage per film thickness was slightly lower than that of the polyimide film containing no filler.
  • the conductivity was remarkably improved as compared with the polyimide film containing no filler, and as a result, the performance value increased to 1.3 times or more.
  • the surface roughness Ra was slightly high. This is presumably because the specific surface area of the ceramic particles is slightly large.
  • the surface roughness Ra was slightly high, and the insulation at the time of bending was “B”. This is presumably because the content of ceramic particles is slightly high.
  • Examples 3-1 to 3-22 A 20 mm ⁇ 20 mm copper plate having a thickness of 1 mm was prepared. As shown in Table 5 below, an insulating film was formed on the prepared copper plate using the same ceramic particle-dispersed resin solution and method as in Examples 1-1 to 1-6. Table 5 shows the thickness of the obtained insulating film.
  • the resin material shown in Table 5 below and NMP N-methyl-2-pyrrolidone were mixed in such a ratio that the amount of NMP relative to 1 part by mass of the resin material would be the amount shown in Table 5.
  • a resin solution was prepared by dissolving. The surface on the insulating film side of the copper plate with an insulating film was immersed in this resin solution, and the resin solution was applied to the surface of the insulating film. Thereafter, the coating layer was heat-dried at 250 ° C. for 30 minutes to form a resin layer on the surface of the insulating film, and a laminated body in which the copper plate, the insulating film, and the resin layer were laminated in this order was obtained. Table 5 shows the thickness of the obtained resin layer. In Examples 3-21 to 3-22, no resin layer was formed.
  • thermo resistance (one laminate) of the laminates produced in the above Examples 3-1 to 3-22 was measured by the following method. Further, with respect to the laminates produced in Examples 3-1 to 3-20, the thermal resistance and peel strength were measured by the following methods in a state where two laminates were laminated via the resin layer. The results are shown in Table 5.
  • Thermal resistance 1 laminate
  • grease (not shown) is applied on the resin layer 13 of the laminate 10 in which the copper plate 11, the insulating film 12, and the resin layer 13 are laminated in this order, and heat is generated on the grease.
  • the body 20 was placed.
  • TO-3P was used as the heating element 20.
  • the thermal resistance from the heat generating body 20 to the copper plate 11 of a laminated body was measured using T3Ster, pressing in the lamination direction from the upper part of a heat generating body with the screw of torque 40Ncm.
  • the copper plate 11 was cooled by natural convection.
  • the thermal resistance of Examples 3-21 to 3-22 in which the resin layer was not formed is as follows. Grease was applied to the insulating film of the laminated body in which the insulating film was laminated on the copper plate, and the heating element was mounted on the grease. The measurement was performed in the same manner as in Examples 3-1 to 3-20 except that the placed sample was used. The thermal resistance was a relative value where the value of Example 3-21 was 1.
  • a laminated body 10a in which a copper plate 11a, an insulating film 12a, and a resin layer 13a are laminated in this order, and a laminated body 10b in which a copper plate 11b, an insulating film 12b, and a resin layer 13b are laminated in this order Were prepared so that the resin layers 13a and 13b of the laminates 10a and 10b were in contact with each other. While applying a pressure of 5 MPa using a carbon jig, the stacked laminates 10 a and 10 b are heated in a vacuum at a temperature of 215 ° C. for 20 minutes to be thermocompression-bonded to produce a sample of two stacked laminates.
  • the thermal resistance of Examples 3-21 to 3-22 in which no resin layer was formed was prepared by stacking two laminated bodies in which an insulating film was laminated on a copper plate so that the insulating films of the laminated body were in contact with each other. The measurement was performed in the same manner as in Examples 3-1 to 3-20 except that the sample was used. The thermal resistance was a relative value where the value of Example 3-21 was 1.
  • the laminates obtained in Examples 3-1 to 3-22 each exhibited a low thermal resistance.
  • the laminates obtained in Examples 3-1 to 3-20 provided with the resin layer exhibit low thermal resistance as one laminate, and at the same time, low thermal resistance even when two laminates are stacked. In addition, high peel strength was exhibited.
  • the laminate exhibits both low thermal resistance and high peel strength.
  • Example 4-1 to 4-22 Except that an insulating film was formed on a copper plate using the same ceramic particle-dispersed resin solution and method as in Examples 2-1 to 2-6 as shown in Table 6 below, the above Example 3- In the same manner as in 1 to 3-22, an insulating film was formed on the copper plate. Table 6 shows the thickness of the obtained insulating film.
  • the thermal resistance (one laminate) of the laminates produced in the above Examples 4-1 to 4-22 was measured by the above method. Further, with respect to the laminates produced in Examples 4-1 to 4-20, the thermal resistance and peel strength were measured by the above methods in a state where two laminates were stacked with the resin layer interposed therebetween. With respect to the laminates manufactured in Examples 4-21 to 4-22, the thermal resistance and peel strength were measured in a state where the two laminates were overlapped so that the insulating films of the respective laminates were in contact with each other. The results are shown in Table 6.
  • the laminates obtained in Examples 4-1 to 4-22 each exhibited a low thermal resistance.
  • the laminates obtained in Examples 4-1 to 4-20 provided with the resin layer exhibit low thermal resistance as one laminate, and at the same time, low thermal resistance even when two laminates are stacked. In addition, high peel strength was exhibited.
  • the laminate exhibits both low thermal resistance and high peel strength.
  • the insulating film of the present invention has both high thermal conductivity and high voltage resistance, and is excellent in heat resistance and mechanical properties. Therefore, the insulating film of the present invention is used in a coating film for a metal wire used for a coil or a motor, a protective film for protecting the surface of an electronic component such as a semiconductor chip or an LED element or a circuit board, or a metal base circuit board. Suitable for insulating material between layer and substrate.

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Abstract

This insulating film includes: a resin comprising a polyimide, a polyamide imide, or a mixture thereof; and ceramic particles having a specific surface area of 10 m2/g or more, the ceramic particles forming an agglomerated particle, and the content of the ceramic particles being in the range of 5-60 vol%.

Description

絶縁膜Insulation film
　本発明は、絶縁膜に関する。
　本願は、２０１６年８月１日に、日本に出願された特願２０１６－１５１２２２号、及び２０１７年３月２３日に、日本に出願された特願２０１７－０５７８１６号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an insulating film.
This application claims priority based on Japanese Patent Application No. 2016-151222 filed in Japan on August 1, 2016 and Japanese Patent Application No. 2017-057816 filed on March 23, 2017 in Japan. , The contents of which are incorporated herein.
　絶縁膜は、例えば、コイルやモータに利用される金属線の被覆膜、半導体チップやＬＥＤ素子などの電子部品や回路基板の表面を保護する保護膜、金属ベース回路基板などにおいて回路層と基板との間の絶縁材として用いられている。
　絶縁膜としては、樹脂と無機フィラーとを含む樹脂組成物から形成された膜が使用されている。樹脂としては、ポリイミドやポリアミドイミドのような耐熱性、化学的耐性、機械的強度が高い樹脂が利用されている。 Insulating films are, for example, coating layers for metal wires used in coils and motors, protective films that protect the surface of electronic components such as semiconductor chips and LED elements and circuit boards, and circuit layers and substrates in metal-based circuit boards. It is used as an insulating material.
As the insulating film, a film formed from a resin composition containing a resin and an inorganic filler is used. As the resin, a resin having high heat resistance, chemical resistance, and mechanical strength such as polyimide and polyamideimide is used.
　近年の電子部品の作動電圧の高電圧化や高集積化に伴って、電子部品の発熱量は増加する傾向にあり、熱抵抗が低く、放熱性が高い絶縁膜が求められている（コイル、放熱基板、熱伝導材料（ＴＩＭ）など）。絶縁膜の熱抵抗を低減させる方法としては、熱伝導性が高い無機フィラーを添加する方法がある。しかしながら、絶縁膜に粒子径が大きな無機フィラーを添加すると、耐電圧（絶縁破壊電圧）が低下するという問題がある（非特許文献１）。 With the recent increase in operating voltage and integration of electronic components, the amount of heat generated by electronic components tends to increase, and there is a demand for insulating films with low thermal resistance and high heat dissipation (coils, Heat dissipation substrate, heat conduction material (TIM), etc.). As a method of reducing the thermal resistance of the insulating film, there is a method of adding an inorganic filler having high thermal conductivity. However, when an inorganic filler having a large particle size is added to the insulating film, there is a problem that the withstand voltage (dielectric breakdown voltage) decreases (Non-patent Document 1).
　ここで、絶縁膜の耐電圧ＶＲは、絶縁膜の膜厚をｈ、膜厚当たりの耐電圧をＶＦとすると、下記の式（１）で表される。
　　ＶＲ＝ＶＦ×ｈ　・・・（１）
　一方、絶縁膜の熱抵抗Ｒは、絶縁膜の膜厚をｈ、絶縁膜の熱伝導度をλとすると下記の式（２）で表される。
　　Ｒ∝ｈ／λ　・・・（２）
　式（１）と式（２）から、絶縁膜の熱抵抗Ｒは、下記の式（３）で表すことができる。
　　Ｒ∝ＶＲ／（λ×ＶＦ）・・・（３）
　上記の式（３）から、絶縁膜の熱抵抗Ｒは、絶縁層の膜厚当たりの耐電圧ＶＦ×熱伝導度λの逆数に比例することがわかる。従って、絶縁膜の熱抵抗Ｒを低減させるためには、絶縁層の膜厚当たりの耐電圧ＶＦ×熱伝導度λの値（以下、「性能値」ともいう）を大きくすることが重要となる。 Here, the withstand voltage V R of the insulating film, h the thickness of the insulating film, when the withstand voltage per thickness and V F, represented by the following formula (1).
V R = V F × h (1)
On the other hand, the thermal resistance R of the insulating film is expressed by the following equation (2), where h is the thickness of the insulating film and λ is the thermal conductivity of the insulating film.
R∝h / λ (2)
From the expressions (1) and (2), the thermal resistance R of the insulating film can be expressed by the following expression (3).
R∝V R / (λ × V F ) (3)
From the above equation (3), it can be seen that the thermal resistance R of the insulating film is proportional to the inverse voltage V F × thermal conductivity λ per film thickness of the insulating layer. Therefore, in order to reduce the thermal resistance R of the insulating film, it is important to increase the value of the withstand voltage V F per unit thickness of the insulating layer × the thermal conductivity λ (hereinafter also referred to as “performance value”). Become.
　特許文献１、２には、絶縁膜の耐電圧を向上させるために、無機フィラーとしてナノ粒子を用いることが記載されている。
　特許文献１には、無機フィラーとして、平均最大径が５００ｎｍ以下のナノ粒子を用いた絶縁膜が開示されている。この特許文献１の実施例には、ナノ粒子を２．５質量％、または、５質量％添加した絶縁膜が記載されている。
　特許文献２では、ポリアミドイミド樹脂と、平均一次粒子径が２００ｎｍ以下である絶縁性微粒子とを含む絶縁膜が開示されている。この特許文献２の実施例には、絶縁性微粒子を５質量％添加した絶縁膜が記載されている。しかしながら、一般的に、絶縁膜にナノ粒子を添加しても、熱伝導度はあまり向上しないとされている。 Patent Documents 1 and 2 describe using nanoparticles as an inorganic filler in order to improve the withstand voltage of an insulating film.
Patent Document 1 discloses an insulating film using nanoparticles having an average maximum diameter of 500 nm or less as an inorganic filler. In the example of Patent Document 1, an insulating film added with 2.5% by mass or 5% by mass of nanoparticles is described.
Patent Document 2 discloses an insulating film including a polyamideimide resin and insulating fine particles having an average primary particle diameter of 200 nm or less. In the example of Patent Document 2, an insulating film to which 5% by mass of insulating fine particles are added is described. However, it is generally said that even when nanoparticles are added to the insulating film, the thermal conductivity is not improved so much.
　特許文献３、４には、熱伝導度をより向上させるために、無機フィラーとしてナノ粒子とマイクロ粒子の両者を併用した絶縁膜が記載されている。
　特許文献３には、無機フィラーとして、マイクロ粒子サイズの第１の無機フィラーと、所定の材料からなるナノ粒子サイズの第２の無機フィラーとを含有する電気絶縁材料用の樹脂組成物が開示されている。
　特許文献４には、無機フィラーとして、マイクロ粒子サイズの熱伝導性無機球状マイクロフィラーと、板状、棒状、繊維状、或いは鱗片状形状のマイクロフィラーと、ナノ粒子サイズの熱伝導性無機ナノフィラーとを充填した樹脂組成物が開示されている。
　しかしながら、上記の非特許文献１に記載されているように、マイクロ粒子を添加した絶縁膜は耐電圧が低下するという問題がある。 Patent Documents 3 and 4 describe an insulating film using both nanoparticles and microparticles as inorganic fillers in order to further improve the thermal conductivity.
Patent Document 3 discloses a resin composition for an electrically insulating material, which contains a microparticle-sized first inorganic filler and a nanoparticle-sized second inorganic filler made of a predetermined material as the inorganic filler. ing.
Patent Document 4 discloses, as inorganic fillers, microparticle-sized thermally conductive inorganic spherical microfillers, plate-like, rod-like, fiber-like, or scale-like microfillers, and nanoparticle-sized thermally conductive inorganic nanofillers. A resin composition filled with is disclosed.
However, as described in Non-Patent Document 1 described above, the insulating film to which microparticles are added has a problem that the withstand voltage decreases.
米国特許出願公開第２００７／０１１６９７６号明細書US Patent Application Publication No. 2007/0116976 特開２０１３－６０５７５号公報JP 2013-60575 A 特開２００９－１３２２７号公報JP 2009-13227 A 特開２０１３－１５９７４８号公報JP 2013-159748 A
　本発明は、上記事情に鑑みてなされたものであって、熱伝導度と耐電圧性の両者が高く、さらに耐熱性、化学的耐性、及び機械特性に優れた絶縁膜を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an insulating film having both high thermal conductivity and high voltage resistance, and excellent in heat resistance, chemical resistance, and mechanical properties. And
　前述の課題を解決するために、本発明の一態様である絶縁膜は、ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなる樹脂と、比表面積が１０ｍ２／ｇ以上であるセラミック粒子と、を有し、前記セラミック粒子が凝集粒子を形成し、かつ前記セラミック粒子の含有量が５体積％以上６０体積％以下の範囲にあることを特徴としている。 In order to solve the above-described problems, an insulating film which is one embodiment of the present invention includes a resin including polyimide, polyamideimide, or a mixture thereof, and ceramic particles having a specific surface area of 10 m 2 / g or more. And the ceramic particles form aggregated particles, and the content of the ceramic particles is in the range of 5% by volume to 60% by volume.
　この構成の絶縁膜によれば、樹脂がポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなるので、耐熱性、化学的耐性、及び機械特性が向上する。 According to the insulating film having this configuration, since the resin is made of polyimide, polyamideimide, or a mixture thereof, heat resistance, chemical resistance, and mechanical properties are improved.
　また、比表面積が１０ｍ２／ｇ以上である微細なセラミック粒子を含むので、耐電圧が向上し、また、セラミック粒子を大量に添加しても耐電圧が低下しにくい。
　さらに、微細なセラミック粒子が凝集粒子を形成しているので、セラミック粒子の一次粒子間を熱が伝導しやすくなり、熱の伝導ネットワーク構造を作りやすい。そのため、絶縁膜の熱伝導度が向上する。
　そして、セラミック粒子の含有量が５体積％以上６０体積％以下の範囲とされているので、ポリイミドやポリアミドイミドが有する優れた耐熱性、化学的耐性、及び機械特性を損なうことなく、耐電圧と熱伝導度とをさらに向上させることが可能となる。 In addition, since fine ceramic particles having a specific surface area of 10 m 2 / g or more are included, the withstand voltage is improved, and the withstand voltage is not easily lowered even when a large amount of ceramic particles are added.
Furthermore, since the fine ceramic particles form aggregated particles, heat is easily conducted between the primary particles of the ceramic particles, and a heat conduction network structure can be easily formed. Therefore, the thermal conductivity of the insulating film is improved.
And since the content of the ceramic particles is in the range of 5 vol% or more and 60 vol% or less, withstand voltage and without impairing the excellent heat resistance, chemical resistance, and mechanical properties of polyimide and polyamideimide It becomes possible to further improve the thermal conductivity.
　ここで、本発明の一態様である絶縁膜においては、前記絶縁膜の少なくとも一方の表面に、ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなる樹脂層が備えられていることが好ましい。
　この場合、例えば、絶縁膜と被固定物とを固定するときは、樹脂層を介在させることができるので、絶縁膜と被固定物とを強く密着させると共に、絶縁膜と被固定物との間の熱抵抗を低くすることができる。また、絶縁膜をコイルやモータ用の金属線（エナメル線）の被覆膜として使用するときは、コイル状に巻かれたエナメル線間に、２枚重ねの絶縁膜が形成されるが、その２枚重ねの絶縁膜の間に樹脂層を介在させることができるので、２枚重ねの絶縁膜同士を強く密着させることができると共に、２枚重ねの絶縁膜間の熱抵抗を低くすることができる。これより、コイル状に巻かれたエナメル線間の層界面熱抵抗を小さくすることができる。 Here, in the insulating film which is one embodiment of the present invention, it is preferable that a resin layer made of polyimide, polyamideimide, or a mixture thereof is provided on at least one surface of the insulating film.
In this case, for example, when the insulating film and the object to be fixed are fixed, the resin layer can be interposed, so that the insulating film and the object to be fixed are closely adhered and the insulating film and the object to be fixed are interposed. The thermal resistance can be lowered. When an insulating film is used as a coating film for a coil or motor metal wire (enameled wire), a double-layered insulating film is formed between enameled wires wound in a coil shape. Since the resin layer can be interposed between the two stacked insulating films, the two stacked insulating films can be strongly adhered to each other and the thermal resistance between the two stacked insulating films can be lowered. it can. Thus, the layer interface thermal resistance between enameled wires wound in a coil shape can be reduced.
　本発明によれば、熱伝導度と耐電圧性の両者が高く、かつ耐熱性と化学的耐性と機械特性とに優れた絶縁膜を提供することが可能となる。 According to the present invention, it is possible to provide an insulating film having both high thermal conductivity and voltage resistance, and excellent heat resistance, chemical resistance, and mechanical properties.
実施例で作製した積層体に、発熱体を配置した状態を説明する模式図である。It is a schematic diagram explaining the state which has arrange | positioned the heat generating body to the laminated body produced in the Example. 実施例で作製した積層体を２枚重ねたものに、発熱体を配置した状態を説明する模式図である。It is a schematic diagram explaining the state which has arrange | positioned the heat generating body to what laminated | stacked the two laminated bodies produced in the Example.
　以下に、本発明の一実施形態である絶縁膜について説明する。
　本実施形態である絶縁膜は、例えば、エナメル線のエナメル膜のように、コイルやモータに利用される金属線の絶縁被膜として用いることができる。また、電子部品や回路基板の表面を保護する保護膜として用いることができる。さらに、金属ベース回路基板などにおいて、回路層と基板の間に配置する絶縁膜として用いることができる。また、単独のシートまたはフィルムとして、例えば、フレキシブルプリント基板などの回路基板用の絶縁材として用いることができる。 The insulating film which is one embodiment of the present invention will be described below.
The insulating film which is this embodiment can be used as an insulating film of a metal wire used for a coil or a motor like an enamel film of an enameled wire, for example. Further, it can be used as a protective film for protecting the surface of an electronic component or a circuit board. Further, in a metal base circuit board or the like, it can be used as an insulating film disposed between the circuit layer and the board. Moreover, it can use as an insulating material for circuit boards, such as a flexible printed circuit board, as a single sheet | seat or film, for example.
　本実施形態である絶縁膜は、ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなる樹脂と、比表面積が１０ｍ２／ｇ以上であるセラミック粒子とを含む。セラミック粒子は、凝集粒子を形成している。また、セラミック粒子の含有量は５体積％以上６０体積％以下の範囲とされている。以下に、本実施形態である絶縁膜の組成を上述のように規定した理由について説明する。 The insulating film according to the present embodiment includes a resin made of polyimide, polyamideimide, or a mixture thereof, and ceramic particles having a specific surface area of 10 m 2 / g or more. The ceramic particles form aggregated particles. The content of the ceramic particles is in the range of 5% by volume to 60% by volume. The reason why the composition of the insulating film according to this embodiment is defined as described above will be described below.
（樹脂）
　本実施形態の絶縁膜において用いる樹脂は、絶縁膜の基材となる。ポリイミドおよびポリアミドイミドは、イミド結合を持つので、優れた耐熱性や機械特性を有する。
　このため、本実施形態では、樹脂としてポリイミド、またはポリアミドイミド、もしくはこれらの混合物を用いる。 (resin)
The resin used in the insulating film of this embodiment is a base material for the insulating film. Since polyimide and polyamideimide have an imide bond, they have excellent heat resistance and mechanical properties.
For this reason, in this embodiment, polyimide, polyamideimide, or a mixture thereof is used as the resin.
　なお、ポリアミドイミドおよびポリイミドは、質量平均分子量が１０万以上であることが好ましく、１０万以上５０万以下の範囲にあることがより好ましい。質量平均分子量が上記の範囲内にあるポリアミドイミドまたはポリイミドを含む絶縁膜は、耐熱性と機械特性がより向上する。 In addition, the polyamide-imide and the polyimide preferably have a mass average molecular weight of 100,000 or more, and more preferably in the range of 100,000 to 500,000. An insulating film containing polyamide-imide or polyimide having a mass average molecular weight within the above range is further improved in heat resistance and mechanical properties.
（セラミック粒子）
　本実施形態の絶縁膜において用いるセラミック粒子は、絶縁膜の性能値を効率的に向上させる作用がある。
　ここで、セラミック粒子の比表面積が小さくなりすぎる、即ちセラミック粒子の一次粒子の粒子径が大きくなりすぎると、絶縁膜の耐電圧性が低下するおそれがある。
　このため、本実施形態では、セラミック粒子の比表面積を１０ｍ２／ｇ以上と設定している。絶縁膜の熱伝導性を確実に向上させるためには、セラミック粒子の比表面積は、５０ｍ２／ｇ以上であることが好ましい。 (Ceramic particles)
The ceramic particles used in the insulating film of this embodiment have an effect of efficiently improving the performance value of the insulating film.
Here, if the specific surface area of the ceramic particles becomes too small, that is, if the particle size of the primary particles of the ceramic particles becomes too large, the voltage resistance of the insulating film may be lowered.
For this reason, in this embodiment, the specific surface area of the ceramic particles is set to 10 m 2 / g or more. In order to reliably improve the thermal conductivity of the insulating film, the specific surface area of the ceramic particles is preferably 50 m 2 / g or more.
　なお、セラミック粒子の比表面積が大きくなりすぎる、即ちセラミック粒子の一次粒子の粒子径が小さくなりすぎると、セラミック粒子が過剰に大きな凝集粒子を形成しやすくなり、絶縁膜の表面粗さＲａが大きくなるおそれがある。絶縁膜の表面粗さＲａが過度に大きくなると、電子部品や回路基板などの表面との接触面積が狭くなって、絶縁膜が電子部品や回路基板などから剥がれやすくなる、また電子部品や回路基板にて発生した熱を、絶縁膜を介して外部に放熱しにくくなるなどの問題が生じるおそれがある。このため、絶縁膜の表面粗さＲａは小さい方が好ましい。絶縁膜の表面粗さＲａを過度に大きくしないためには、セラミック粒子の比表面積は、３００ｍ２／ｇ以下であることが好ましい。 If the specific surface area of the ceramic particles becomes too large, that is, if the particle size of the primary particles of the ceramic particles becomes too small, the ceramic particles tend to form excessively large aggregated particles, and the surface roughness Ra of the insulating film becomes large. There is a risk. If the surface roughness Ra of the insulating film becomes excessively large, the contact area with the surface of the electronic component or circuit board becomes narrow, and the insulating film is easily peeled off from the electronic component or circuit board. There is a possibility that problems such as difficulty in dissipating the heat generated by the heat to the outside through the insulating film may occur. For this reason, the surface roughness Ra of the insulating film is preferably small. In order not to excessively increase the surface roughness Ra of the insulating film, the specific surface area of the ceramic particles is preferably 300 m 2 / g or less.
　セラミック粒子の比表面積は、ＢＥＴ法で測定されたＢＥＴ比表面積である。絶縁膜中のセラミック粒子の比表面積は、絶縁膜を加熱して、樹脂成分を熱分解して除去し、残部のセラミック粒子を回収することによって測定することができる。 The specific surface area of the ceramic particles is the BET specific surface area measured by the BET method. The specific surface area of the ceramic particles in the insulating film can be measured by heating the insulating film, pyrolyzing and removing the resin component, and collecting the remaining ceramic particles.
　セラミック粒子は、ＢＥＴ比表面積と密度から下記の式を用いて算出されるＢＥＴ径が、１ｎｍ以上２００ｎｍ以下の範囲であることが好ましい。ＢＥＴ径が上記の範囲にあるセラミック粒子を含む絶縁膜は、耐電圧性がより向上する。
　ＢＥＴ径＝６／（密度×ＢＥＴ比表面積） The ceramic particles preferably have a BET diameter calculated from the BET specific surface area and density using the following formula within a range of 1 nm to 200 nm. An insulating film containing ceramic particles having a BET diameter in the above range is further improved in voltage resistance.
BET diameter = 6 / (density × BET specific surface area)
　セラミック粒子は凝集粒子を形成している。凝集粒子は、一次粒子が比較的弱く連結しているアグロメレートであってもよいし、一次粒子が比較的強く連結しているアグリゲートであってもよい。また、凝集粒子同士がさらに集合した粒子集合体を形成していてもよい。セラミック粒子の一次粒子が凝集粒子を形成して絶縁膜中に分散していることによって、セラミック粒子間の相互接触によるネットワークが形成されて、セラミック粒子の一次粒子間を熱が伝導しやすくなり、絶縁膜の熱伝導度が向上する。 Ceramic particles form agglomerated particles. Aggregated particles may be agglomerates in which primary particles are relatively weakly connected, or may be aggregates in which primary particles are relatively strongly connected. Moreover, you may form the particle assembly which aggregated particles further aggregated. When the primary particles of the ceramic particles form aggregated particles and are dispersed in the insulating film, a network due to mutual contact between the ceramic particles is formed, and heat is easily conducted between the primary particles of the ceramic particles, The thermal conductivity of the insulating film is improved.
　セラミック粒子の凝集粒子は、一次粒子同士が点接触して連結した異方性を持つ形状であることが好ましい。この場合、セラミック粒子の一次粒子同士は、化学的に強く結合していることが好ましい。
　また、凝集粒子の平均粒径は、上記のＢＥＴ径に対して、５倍以上であることが好ましく、５倍以上１００倍以下の範囲にあることが好ましい。また、凝集粒子の平均粒子径は、２０ｎｍ以上５００ｎｍ以下の範囲にあることが好ましい。凝集粒子の平均粒子径が上記の範囲にあると、絶縁膜の熱伝導度を確実に向上させることができる。
　なお、凝集粒子の平均粒子径は、セラミック粒子を分散剤とともにＮＭＰ溶媒中にて超音波分散にかけ、レーザー回折式粒度分布測定装置で測定したＤｖ５０の値である。絶縁膜中の凝集粒子（セラミック粒子）は、絶縁膜を加熱して、樹脂成分を熱分解して除去することによって回収することができる。 The agglomerated particles of the ceramic particles preferably have a shape having anisotropy in which the primary particles are connected by point contact. In this case, it is preferable that the primary particles of the ceramic particles are chemically strongly bonded.
The average particle size of the aggregated particles is preferably 5 times or more, and preferably in the range of 5 times to 100 times the BET diameter. Moreover, it is preferable that the average particle diameter of aggregated particles exists in the range of 20 nm or more and 500 nm or less. When the average particle diameter of the aggregated particles is in the above range, the thermal conductivity of the insulating film can be reliably improved.
The average particle size of the agglomerated particles is a value of Dv50 measured with a laser diffraction particle size distribution analyzer after subjecting ceramic particles to ultrasonic dispersion in a NMP solvent together with a dispersant. Aggregated particles (ceramic particles) in the insulating film can be recovered by heating the insulating film to thermally decompose and remove the resin component.
　絶縁膜中のセラミック粒子の含有量は、５体積％以上６０体積％以下とされている。セラミック粒子の含有量が少なくなりすぎると、絶縁膜の熱伝導性が十分に向上しないおそれがある。一方、セラミック粒子の含有量が多くなりすぎると、すなわち樹脂の含有量が相対的に減少して、絶縁膜の形状を安定に維持できなくなるおそれがある。また、セラミック粒子が過剰に大きな凝集粒子を形成しやすくなり、絶縁膜の表面粗さＲａが大きくなるおそれがある。
　絶縁膜の熱伝導性を確実に向上させるためには、セラミック粒子の含有量は１０体積％以上であることが好ましい。また、絶縁膜の形状の安定性を確実に向上させ、表面粗さＲａを低くするためには、セラミック粒子の含有量は５０体積％以下であることが好ましい。 The content of the ceramic particles in the insulating film is 5% by volume or more and 60% by volume or less. If the ceramic particle content is too low, the thermal conductivity of the insulating film may not be sufficiently improved. On the other hand, if the content of ceramic particles is too large, that is, the resin content is relatively reduced, the shape of the insulating film may not be stably maintained. In addition, ceramic particles tend to form excessively large agglomerated particles, which may increase the surface roughness Ra of the insulating film.
In order to reliably improve the thermal conductivity of the insulating film, the content of the ceramic particles is preferably 10% by volume or more. In order to reliably improve the stability of the shape of the insulating film and to reduce the surface roughness Ra, the content of the ceramic particles is preferably 50% by volume or less.
　セラミック粒子の例としては、シリカ（二酸化ケイ素）粒子、アルミナ（酸化アルミニウム）粒子、窒化ホウ素粒子、酸化チタン粒子、アルミナドープシリカ粒子、及びアルミナ水和物粒子が挙げられる。セラミック粒子は、一種を単独で使用してもよいし、二種以上を組合せて使用してもよい。これらのセラミック粒子の中では、アルミナ粒子が熱伝導性が高い点で好ましい。 Examples of ceramic particles include silica (silicon dioxide) particles, alumina (aluminum oxide) particles, boron nitride particles, titanium oxide particles, alumina-doped silica particles, and alumina hydrate particles. A ceramic particle may be used individually by 1 type, and may be used in combination of 2 or more type. Among these ceramic particles, alumina particles are preferable because of their high thermal conductivity.
　セラミック粒子は、市販品を使用してもよい。市販品としては、ＡＥ５０、ＡＥ１３０、ＡＥ２００、ＡＥ３００、ＡＥ３８０、ＡＥ９０Ｅ（いずれも、日本アエロジル株式会社製）、Ｔ４００（ワッカー社製）、ＳＦＰ－２０Ｍ（デンカ株式会社）などのシリカ粒子、Ａｌｕ６５（日本アエロジル株式会社製）などのアルミナ粒子、ＡＰ－１７０Ｓ（Ｍａｒｕｋａ社製）などの窒化ホウ素粒子、ＡＥＲＯＸＩＤＥ（Ｒ）ＴｉＯ２　Ｐ９０（日本アエロジル株式会社製）などの酸化チタン粒子、ＭＯＸ１７０（日本アエロジル株式会社製）などのアルミナドープシリカ粒子、Ｓａｓｏｌ社製のアルミナ水和物粒子を用いることができる。 As the ceramic particles, commercially available products may be used. Commercially available products include silica particles such as AE50, AE130, AE200, AE300, AE380, AE90E (all manufactured by Nippon Aerosil Co., Ltd.), T400 (manufactured by Wacker), SFP-20M (Denka Corporation), Alu65 (Japan) Alumina particles such as Aerosil Co., Ltd., boron nitride particles such as AP-170S (Maruka Corp.), titanium oxide particles such as AEROXIDE (R) TiO 2 P90 (Nippon Aerosil Co., Ltd.), MOX170 (Nippon Aerosil Co., Ltd.) Alumina-doped silica particles such as those manufactured by Sasol, and alumina hydrate particles manufactured by Sasol can be used.
（樹脂層）
　本実施形態である絶縁膜は、少なくとも一方の表面に、樹脂層が備えられていてもよい。樹脂層は、ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなることが好ましい。
　樹脂層は、絶縁膜の基材となる樹脂と親和性が高く、層中にセラミック粒子を含有しないので、絶縁膜と比較して変形しやすい。このため、例えば、絶縁膜と被固定物（例えば、電子部品や回路基板などの発熱体、回路用銅箔の金属箔などの導電体）とを固定するときは、樹脂層を介在させることができるので、絶縁膜と被固定物とを強く密着させることができる。これによって、絶縁膜と被固定物のピール強度が向上する。また、絶縁膜と被固定物との間の熱抵抗を低くすることができる。
　また、絶縁膜を、コイルやモータに利用される金属線の被覆膜として用いる場合、コイル状に巻かれた金属線（エナメル線）間に、２枚重ねの絶縁膜が形成されるが、その２枚重ねの絶縁膜の間に樹脂層を介在させることができるので、２枚重ねの絶縁膜同士を強く密着させることができる。これによって、２枚重ね絶縁膜のピール強度が向上する。また、２枚重ね絶縁膜間の熱抵抗を低くすることができるので、コイル状に巻かれたエナメル線間の層界面熱抵抗を小さくすることができる。 (Resin layer)
The insulating film according to this embodiment may be provided with a resin layer on at least one surface. The resin layer is preferably made of polyimide, polyamideimide, or a mixture thereof.
The resin layer has a high affinity with the resin that is the base material of the insulating film, and does not contain ceramic particles in the layer, and thus is easily deformed as compared with the insulating film. For this reason, for example, when fixing an insulating film and an object to be fixed (for example, a heating element such as an electronic component or a circuit board, or a conductor such as a metal foil of a copper foil for a circuit), a resin layer may be interposed. As a result, the insulating film and the object to be fixed can be strongly adhered. This improves the peel strength between the insulating film and the object to be fixed. In addition, the thermal resistance between the insulating film and the object to be fixed can be reduced.
In addition, when an insulating film is used as a coating film for a metal wire used in a coil or a motor, a two-layered insulating film is formed between metal wires wound in a coil shape (enameled wire). Since the resin layer can be interposed between the two stacked insulating films, the two stacked insulating films can be strongly adhered to each other. This improves the peel strength of the two-layered insulating film. Further, since the thermal resistance between the two stacked insulating films can be lowered, the layer interface thermal resistance between enameled wires wound in a coil shape can be reduced.
　樹脂層の厚さは、０．１μｍ以上２μｍ以下の範囲にあることが好ましい。樹脂層の厚さが上記の範囲にあると、絶縁膜と被固定物および２枚重ねの絶縁膜同士の密着性を確実に高くすることができ、絶縁膜と被固形物との間および２枚重ねの絶縁膜間の熱抵抗を確実に低くすることができる。樹脂層の厚さが薄くなりすぎると、絶縁膜と被固定物および２枚重ねの絶縁膜同士の密着性が低下するおそれがある。一方、樹脂層の厚さが厚くなりすぎると、熱抵抗が高くなるおそれがある。 The thickness of the resin layer is preferably in the range of 0.1 μm to 2 μm. When the thickness of the resin layer is in the above range, the adhesion between the insulating film and the object to be fixed and the two stacked insulating films can be surely increased, and between the insulating film and the solid object and 2 The thermal resistance between the stacked insulating films can be reliably lowered. If the thickness of the resin layer becomes too thin, the adhesion between the insulating film, the object to be fixed, and the two stacked insulating films may be reduced. On the other hand, if the resin layer is too thick, the thermal resistance may be increased.
（絶縁膜の作製方法）
　本実施態である絶縁膜は、例えば、溶媒中に、ポリイミドあるいはポリアミドイミドもしくはこれらの前駆体が溶解し、比表面積が１０ｍ２／ｇ以上であって、凝集粒子を形成しているセラミック粒子が分散しているセラミック粒子分散樹脂溶液を調製し、次いでこのセラミック粒子分散樹脂溶液を用いて膜状に成形することによって作製することができる。溶媒の例としては、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジグライム、トリグライム、γ－ブチロラクトン、ジメチルスルホキシド（ＤＭＳＯ）などの非プロトン性の極性溶媒およびこれらの混合液を挙げることができる。 (Insulating film manufacturing method)
The insulating film according to the present embodiment includes, for example, ceramic particles in which polyimide, polyamideimide, or a precursor thereof is dissolved in a solvent, a specific surface area is 10 m 2 / g or more, and aggregated particles are formed. It can be produced by preparing a dispersed ceramic particle-dispersed resin solution and then forming the ceramic particle-dispersed resin solution into a film using the ceramic particle-dispersed resin solution. Examples of the solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP), diglyme, triglyme, γ-butyrolactone, dimethyl sulfoxide (DMSO), and mixtures thereof.
　セラミック粒子分散樹脂溶液は、溶媒中にポリイミドあるいはポリアミドイミドもしくはこれらの前駆体が溶解している樹脂溶液と、セラミック粒子とを混合し、樹脂溶液中にセラミック粒子を分散させる方法によって調製することができる。また、セラミック粒子分散樹脂溶液は、溶媒中にセラミック粒子が分散しているセラミック粒子分散液と、ポリイミドあるいはポリアミドイミドもしくはこれらの前駆体とを混合して、セラミック粒子分散液中にポリイミドあるいはポリアミドイミドもしくはこれらの前駆体を溶解させる方法によって調製することができる。さらに、セラミック粒子分散樹脂溶液は、溶媒中にポリイミドあるいはポリアミドイミドもしくはこれらの前駆体が溶解している樹脂溶液と、溶媒中にセラミック粒子が分散しているセラミック粒子分散液とを混合することによっても調製することができる。 The ceramic particle-dispersed resin solution may be prepared by a method in which a ceramic solution is mixed with a resin solution in which polyimide or polyamideimide or a precursor thereof is dissolved in a solvent, and the ceramic particles are dispersed in the resin solution. it can. The ceramic particle-dispersed resin solution is prepared by mixing a ceramic particle dispersion in which ceramic particles are dispersed in a solvent and polyimide or polyamideimide or a precursor thereof, and mixing the polyimide or polyamideimide in the ceramic particle dispersion. Or it can prepare by the method of dissolving these precursors. Further, the ceramic particle dispersion resin solution is obtained by mixing a resin solution in which polyimide or polyamideimide or a precursor thereof is dissolved in a solvent and a ceramic particle dispersion in which ceramic particles are dispersed in the solvent. Can also be prepared.
　基板の上に絶縁膜を作製する方法としては、例えば、電着法、及び塗布法を用いることができる。
　電着法は、セラミック粒子分散樹脂溶液に水を加えて調製した電着液を用いて、電着塗布法により、基板の上に電着生成物を生成させ、次いで、電着生成物を加熱して乾燥、硬化させることによって、絶縁膜を作製する方法である。
　また、塗布法は、セラミック粒子分散樹脂溶液を基板の上に塗布して塗布膜を形成し、次いで、塗布膜を乾燥して乾燥膜とした後、加熱して硬化させることによって、絶縁膜を作製する方法である。 As a method for forming the insulating film on the substrate, for example, an electrodeposition method and a coating method can be used.
The electrodeposition method uses an electrodeposition solution prepared by adding water to a ceramic particle-dispersed resin solution to generate an electrodeposition product on a substrate by an electrodeposition coating method, and then heats the electrodeposition product. Then, the insulating film is produced by drying and curing.
In addition, the coating method is to apply a ceramic particle-dispersed resin solution on a substrate to form a coating film, then dry the coating film to form a dry film, and then heat and cure to form an insulating film. It is a manufacturing method.
　フィルムもしくはシート状の絶縁膜は、例えば、セラミック粒子分散樹脂溶液を離型フィルムの上に塗布して塗布膜を形成し、次いで、塗布膜を乾燥した後、乾燥膜を離型フィルムから剥離した後、乾燥膜を加熱処理して硬化させることによって得ることができる。 A film or sheet-like insulating film is formed by, for example, applying a ceramic particle-dispersed resin solution on a release film to form a coating film, and then drying the coating film and then peeling the dry film from the release film. Thereafter, the dried film can be obtained by heat treatment and curing.
　樹脂層を備えた絶縁膜は、例えば、次のようにして製造することができる。
　樹脂層を形成する樹脂材料と溶剤とを混合し、樹脂材料を溶解させて、樹脂溶液を調製する。次いで、この樹脂溶液を絶縁膜に塗布して、塗布層を形成する。そして、塗布層を加熱乾燥する。
　樹脂材料を溶解させるための溶剤の例としては、溶媒の例としては、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、ジグライム、トリグライム、γ-ブチロラクトン、ジメチルスルホキシド（ＤＭＳＯ）などの非プロトン性の極性溶媒およびこれらの混合液を挙げることができる。樹脂溶液を絶縁膜に塗布する方法としては、浸漬法、スピンコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法などの用いることができる。 The insulating film provided with the resin layer can be manufactured as follows, for example.
A resin material for forming the resin layer and a solvent are mixed, and the resin material is dissolved to prepare a resin solution. Next, this resin solution is applied to the insulating film to form a coating layer. Then, the coating layer is heated and dried.
Examples of solvents for dissolving the resin material include aprotic polarities such as N-methyl-2-pyrrolidone (NMP), diglyme, triglyme, γ-butyrolactone, dimethyl sulfoxide (DMSO), etc. Mention may be made of solvents and mixtures thereof. As a method for applying the resin solution to the insulating film, a dipping method, a spin coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
　以上のような構成とされた本実施形態である絶縁膜によれば、樹脂がポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなるので、耐熱性と機械特性が向上する。また、比表面積が１０ｍ２／ｇ以上である微細なセラミック粒子を含むので、耐電圧性が向上する。さらに、微細なセラミック粒子が凝集粒子を形成しているので、セラミック粒子の一次粒子間を熱が伝導しやすくなり、絶縁膜の熱伝導度が向上する。
　そして、セラミック粒子の含有量が５体積％以上６０体積％以下の範囲とされているので、ポリイミドやポリアミドイミドが有する優れた耐熱性と機械特性とを損なうことなく、耐電圧性と熱伝導性とをさらに向上させることが可能となる。 According to the insulating film of the present embodiment configured as described above, since the resin is made of polyimide, polyamideimide, or a mixture thereof, heat resistance and mechanical properties are improved. Moreover, since it contains the fine ceramic particle | grains whose specific surface area is 10 m < 2 > / g or more, withstand voltage property improves. Further, since the fine ceramic particles form aggregated particles, heat is easily conducted between the primary particles of the ceramic particles, and the thermal conductivity of the insulating film is improved.
And, since the content of the ceramic particles is in the range of 5 vol% or more and 60 vol% or less, withstand voltage and thermal conductivity without impairing the excellent heat resistance and mechanical properties of polyimide and polyamideimide. Can be further improved.
　また、本実施形態の絶縁膜においては、少なくとも一方の表面に、ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなる樹脂層を備える構成とすることができる。これによって、例えば、絶縁膜と被固定物とを固定するときは、樹脂層を介在させることができるので、絶縁膜と被固定物とを強く密着させると共に、絶縁膜と被固定物との間の熱抵抗を低くすることができる。また、絶縁膜をコイルやモータ用の金属線（エナメル線）の被覆膜として使用するときは、コイル状に巻かれたエナメル線間に、２枚重ねの絶縁膜が形成されるが、その２枚重ねの絶縁膜の間に樹脂層を介在させることができるので、２枚重ねの絶縁膜同士を強く密着させることができると共に、２枚重ねの絶縁膜間の熱抵抗を低くすることができる。これにより、コイル状に巻かれたエナメル線間の層界面熱抵抗を小さくすることができる。 In addition, the insulating film of this embodiment can be configured to include a resin layer made of polyimide, polyamideimide, or a mixture thereof on at least one surface. Thus, for example, when the insulating film and the object to be fixed are fixed, the resin layer can be interposed, so that the insulating film and the object to be fixed are closely adhered, and the insulating film and the object to be fixed are interposed. The thermal resistance can be lowered. When an insulating film is used as a coating film for a coil or motor metal wire (enameled wire), a double-layered insulating film is formed between enameled wires wound in a coil shape. Since the resin layer can be interposed between the two stacked insulating films, the two stacked insulating films can be strongly adhered to each other and the thermal resistance between the two stacked insulating films can be lowered. it can. Thereby, the layer interface thermal resistance between the enamel wires wound in a coil shape can be reduced.
　以上、この発明の実施形態について詳述してきたが、具体的な構成はこの実施形態に限られるものではなく、この発明の要旨を逸脱しない範囲の設計等も含まれる。 The embodiment of the present invention has been described in detail above, but the specific configuration is not limited to this embodiment, and includes a design and the like within the scope not departing from the gist of the present invention.
　以下、本発明の効果を実施例及び比較例を用いて詳細に説明するが、本発明は下記の実施例に限定されるものではない。 Hereinafter, the effects of the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the following examples.
［実施例１－１～１－１８、比較例１－１～１－５］
＜セラミック粒子分散樹脂溶液の調製＞
　下記の表１に記載されている、セラミック粒子を用意した。なお、表１に記載されている比表面積は、ＢＥＴ法により測定したＢＥＴ比表面積である。凝集粒子の平均粒子径は、分散剤とともにＮＭＰ（Ｎ－メチル－２－ピロリドン）溶媒中にて超音波分散にかけ、レーザー回折式粒度分布測定装置で測定したＤｖ５０の値である。
　用意したセラミック粒子を、ＮＭＰを６２．５ｇ、１Ｍ２Ｐ（１－メトキシ－２－プロパノール）を１０ｇ、ＡＥ（アミノエーテル）を０．２２ｇの質量で含む混合溶媒に対して１ｇ投入し、３０分間超音波処理して、セラミック粒子分散液を調製した。
　次いで、ポリアミドイミド溶液３．３ｇに、セラミック粒子分散液をセラミック粒子濃度が下記の表２に記載されている値となるように加えて、セラミック粒子分散樹脂溶液を調製した。なお、セラミック粒子濃度は、ポリアミドイミドとセラミック粒子の合計体積量に対するセラミック粒子の体積含有量である。 [Examples 1-1 to 1-18, Comparative Examples 1-1 to 1-5]
<Preparation of ceramic particle-dispersed resin solution>
Ceramic particles described in Table 1 below were prepared. In addition, the specific surface area described in Table 1 is a BET specific surface area measured by the BET method. The average particle size of the agglomerated particles is a value of Dv50 measured by a laser diffraction particle size distribution analyzer after ultrasonic dispersion in an NMP (N-methyl-2-pyrrolidone) solvent together with a dispersant.
1 g of the prepared ceramic particles is added to a mixed solvent containing 62.5 g of NMP, 10 g of 1M2P (1-methoxy-2-propanol) and 0.22 g of AE (amino ether), and the mixture is over 30 minutes. A ceramic particle dispersion was prepared by sonication.
Next, a ceramic particle dispersion resin solution was prepared by adding the ceramic particle dispersion to 3.3 g of the polyamideimide solution so that the ceramic particle concentration becomes a value described in Table 2 below. The ceramic particle concentration is the volume content of ceramic particles relative to the total volume of polyamideimide and ceramic particles.
＜電着液の調製＞
　調製したセラミック粒子分散樹脂溶液を、５０００ｒｐｍの回転速度で撹拌しながら、そのセラミック粒子分散樹脂溶液に水を２１ｇ滴下して、電着液を調製した。 <Preparation of electrodeposition solution>
While stirring the prepared ceramic particle-dispersed resin solution at a rotational speed of 5000 rpm, 21 g of water was added dropwise to the ceramic particle-dispersed resin solution to prepare an electrodeposition solution.
＜電着法による絶縁膜の作製＞
　調製した電着液を用いて、電着法により１００Ｖの直流電圧を印加して、厚さ０．３ｍｍで３０ｍｍ×２０ｍｍの銅板の表面に、加熱後の膜厚が１０μｍとなるように電着生成物を生成させた。なお、膜厚は、絶縁膜を作製した銅板を樹脂埋めした後、断面を出し、レーザー顕微鏡で観察することによって測定した。次いで電着生成物を大気雰囲気下、２５０℃で３分間加熱して、銅板表面に厚さ１０μｍの絶縁膜を作製した。なお、比較例１－３、１－５で調製した電着液は、均一な絶縁膜を作製できなかった。表２では、絶縁膜を作製できたものを「Ａ」とし、絶縁膜を作製できなかったものを「Ｂ」とした。 <Preparation of insulating film by electrodeposition method>
Using the prepared electrodeposition solution, a DC voltage of 100 V is applied by the electrodeposition method, and electrodeposition is performed on the surface of a copper plate having a thickness of 0.3 mm and a thickness of 30 mm × 20 mm so that the film thickness after heating becomes 10 μm. A product was produced. The film thickness was measured by filling a copper plate on which an insulating film was formed with a resin, taking out a cross section, and observing with a laser microscope. Next, the electrodeposition product was heated at 250 ° C. for 3 minutes in an air atmosphere to produce an insulating film having a thickness of 10 μm on the copper plate surface. Note that the electrodeposition solutions prepared in Comparative Examples 1-3 and 1-5 could not produce a uniform insulating film. In Table 2, “A” indicates that the insulating film could be manufactured, and “B” indicates that the insulating film could not be manufactured.
＜評価＞
　上記の実施例および比較例で作製した絶縁膜について、セラミック粒子の含有量、膜厚当たりの耐電圧、熱伝導度（絶縁膜の厚さ方向の熱伝導度）、表面粗さＲａ、折り曲げ時の絶縁性をそれぞれ下記の方法により測定した。また膜厚当たりの耐電圧と熱伝導度より、性能値（膜厚当たりの耐電圧ＶＦ×熱伝導度λ）を計算した。その結果を、表２に示す。なお、膜厚当たりの耐電圧、熱伝導度および性能値は、セラミック粒子を添加しなかったこと以外は、実施例１－１と同様にして作製した膜厚１０μｍのポリアミドイミド膜の値を１とした相対値とした。 <Evaluation>
For the insulating films produced in the above examples and comparative examples, the content of ceramic particles, withstand voltage per film thickness, thermal conductivity (thermal conductivity in the thickness direction of the insulating film), surface roughness Ra, and bending The insulating properties were measured by the following methods. Moreover, the performance value (withstand voltage V F per film thickness × heat conductivity λ) was calculated from the withstand voltage and heat conductivity per film thickness. The results are shown in Table 2. The withstand voltage per film thickness, the thermal conductivity, and the performance value are 1 for the polyamideimide film having a thickness of 10 μm that was produced in the same manner as in Example 1-1 except that the ceramic particles were not added. Relative value.
（セラミック粒子の含有量）
　銅板から絶縁膜を剥がし取り、所定サイズに切り出して試料とした。この試料を用いて、熱重量分析（ＴＧ）により、絶縁膜のセラミック粒子の含有量（質量％）を測定した。
　そして、そのセラミック粒子の含有量の値を、下記に示すセラミック粒子、ポリアミドイミドの密度を用いて体積％に換算した。 (Content of ceramic particles)
The insulating film was peeled off from the copper plate, cut into a predetermined size, and used as a sample. Using this sample, the content (mass%) of the ceramic particles of the insulating film was measured by thermogravimetric analysis (TG).
And the value of content of the ceramic particle was converted into volume% using the density of the ceramic particle and polyamideimide shown below.
（膜厚当たりの耐電圧）
　膜厚当たりの耐電圧は、株式会社計測技術研究所の多機能安全試験器７４４０を用いて測定した。絶縁膜の銅板（基板）側とは反対側の表面に電極板を配置した。銅板（基板）と電極板をそれぞれ電源に接続し、６０００Ｖまで３０秒で昇圧した。銅板と電極板との間に流れる電流値が５０００μＡになった時点の電圧を絶縁膜の膜厚で除算し、この値を膜厚当たりの耐電圧とした。 (Withstand voltage per film thickness)
The withstand voltage per film thickness was measured using a multifunctional safety tester 7440 of Measurement Technology Laboratory Co., Ltd. An electrode plate was placed on the surface of the insulating film opposite to the copper plate (substrate) side. The copper plate (substrate) and the electrode plate were each connected to a power source, and the voltage was increased to 6000 V in 30 seconds. The voltage when the value of the current flowing between the copper plate and the electrode plate reached 5000 μA was divided by the film thickness of the insulating film, and this value was taken as the withstand voltage per film thickness.
（熱伝導度）
　熱伝導度（絶縁膜の厚さ方向の熱伝導度）は、ＮＥＴＺＳＣＨ－ＧｅｒａｔｅｂａｕＧｍｂＨ製のＬＦＡ４７７　Ｎａｎｏｆｌａｓｈを用いて、レーザーフラッシュ法により測定した。測定には界面熱抵抗を考慮しない２層モデルを用いた。なお、銅板の厚さは既述したように０．３ｍｍ、銅板の熱拡散率は１１７．２ｍｍ２／秒とした。絶縁膜の熱伝導度の計算には、シリカ粒子の密度２．２ｇ／ｃｍ３、シリカ粒子の比熱０．７６Ｊ／ｇＫ、アルミナ粒子の密度３．８９ｇ／ｃｍ３、アルミナ粒子の比熱０．７８Ｊ／ｇＫ、窒化ホウ素の密度２．１ｇ／ｃｍ３、窒化ホウ素の比熱０．８Ｊ／ｇＫ、酸化チタンの密度３．９８ｇ／ｃｍ３、酸化チタンの比熱０．６８９Ｊ／ｇＫ、アルミナ１％ドープシリカの密度２．２ｇ／ｃｍ３、アルミナ１％ドープシリカの比熱０．７６Ｊ／ｇＫ、アルミナ水和物の密度３．０７ｇ／ｃｍ３、アルミナ水和物の比熱１．０２、ポリイミドの密度１．４ｇ／ｃｍ３、ポリイミドの比熱１．１３Ｊ／ｇＫ、ポリアミドイミド樹脂の密度１．４１ｇ／ｃｍ３、ポリアミドイミド樹脂の比熱１．０９Ｊ／ｇＫを用いた。 (Thermal conductivity)
Thermal conductivity (thermal conductivity in the thickness direction of the insulating film) was measured by a laser flash method using an LFA477 Nanoflash manufactured by NETZSCH-Geratebau GmbH. A two-layer model that does not consider the interfacial thermal resistance was used for the measurement. As described above, the thickness of the copper plate was 0.3 mm, and the thermal diffusivity of the copper plate was 117.2 mm 2 / sec. The calculation of the thermal conductivity of the insulating film, density 2.2 g / cm 3 silica particles, the silica particles specific heat 0.76J / gK, the density of the alumina particles 3.89 g / cm 3, the alumina particles specific heat 0.78J / gK, density 2.1 g / cm 3 of boron nitride, boron nitride specific heat 0.8 J / gK, titanium oxide density 3.98 g / cm 3, the specific heat 0.689J / gK of titanium oxide, alumina 1% doped silica of density 2.2 g / cm 3, an alumina 1% doped silica of specific heat 0.76J / gK, the density of the alumina hydrate 3.07 g / cm 3, the specific heat 1.02 of the alumina hydrate, the density of the polyimide 1.4 g / cm 3 , specific heat of polyimide 1.13 J / gK, density of polyamideimide resin 1.41 g / cm 3 and specific heat of polyamideimide resin 1.09 J / gK were used.
（表面粗さＲａ）
　表面粗さＲａはＢｒｕｋｅｒ　Ｎａｎｏ社製Ｄｅｋｔａｋ１５０を用いて１ｍｍスキャンを行い、計測した。なお荷重は、５．００ｍｇ、スキャンスピードは１ｍｍ／３０ｓを用いた。 (Surface roughness Ra)
The surface roughness Ra was measured by performing a 1 mm scan using a Dektak 150 manufactured by Bruker Nano. The load was 5.00 mg and the scan speed was 1 mm / 30 s.
（折り曲げ時の絶縁性）
　折り曲げ時の絶縁性（可撓性）を、基板折り曲げ前後においてＪＩＳ　Ｃ　３２１６－５におけるピンホール試験を実施することによって評価した。絶縁膜を作製した銅板（試料）と、厚さ０．３ｍｍの銅板を２枚重ねて作成した銅基板とを、試料の銅板と銅基板とが接するように積層して、積層体を作製した。作製した積層体を、積層体の厚みに沿って折り曲げて、次いで、元の状態に戻した。その後、積層板と、別に用意したステンレス板とを、フェノールフタレイン溶液を滴下した塩化ナトリウム水溶液（濃度０．２％）に浸漬させ、積層体の銅基板を負極、ステンレス板を正極として、１２Ｖの直流電圧を１分間印加して、絶縁膜内に発生したピンホール、つまり絶縁膜表面から銅板まで貫通する欠陥の有無を確認した（ＪＩＳ　Ｃ３２１６－５）。絶縁膜表面に、フェノールフタレインによる赤紫色の筋（小さな気泡の集まり）が１個でも確認された場合は、ピンホールが有ったものとして、折り曲げ後の絶縁性が確保できていない（可撓性無し）と判断し、「Ｂ」とした。絶縁膜表面に赤紫色の筋が確認されなかった場合は、ピンホールが無かったものとして、折り曲げ後の絶縁性が確保できている（可撓性有り）と判断し、「Ａ」とした。 (Insulation when bent)
The insulation (flexibility) at the time of bending was evaluated by performing a pinhole test in JIS C 3216-5 before and after the substrate was bent. A laminated body was produced by laminating a copper plate (sample) on which an insulating film was produced and a copper substrate prepared by stacking two copper plates having a thickness of 0.3 mm so that the sample copper plate and the copper substrate were in contact with each other. . The produced laminated body was bent along the thickness of the laminated body, and then returned to the original state. Thereafter, the laminated plate and a separately prepared stainless steel plate are immersed in a sodium chloride aqueous solution (concentration: 0.2%) in which a phenolphthalein solution is dropped, and the laminated copper substrate is used as a negative electrode and the stainless steel plate is used as a positive electrode. Was applied for 1 minute to confirm the presence or absence of a pinhole generated in the insulating film, that is, a defect penetrating from the surface of the insulating film to the copper plate (JIS C3216-5). If even one red-purple streak (gathering of small bubbles) due to phenolphthalein is confirmed on the surface of the insulating film, it is assumed that there is a pinhole and insulation after bending cannot be secured (possible It was determined that there was no flexibility, and the result was “B”. When no reddish purple streaks were found on the surface of the insulating film, it was determined that there was no pinhole, and that insulation after bending was ensured (flexible), and “A” was assigned.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　比較例１－１の絶縁膜は、性能値が１．１９倍と低かった。これは、セラミック粒子の比表面積が１０ｍ２／ｇ未満で、耐電圧が低下したためであると推察される。
　比較例１－２、１－４の絶縁膜も性能値が１．１７倍、１．１６倍程度であった。これは、熱伝導度がフィラーを含まないポリアミドイミド膜と同等に低いためである。熱伝導度が低いのは、セラミック粒子の含有量が５体積％よりも少ないためであると推察される。
　比較例１－３、１－５で調製した電着液は、絶縁膜を作製できなかった。これは、セラミック粒子の含有量が６０体積％を超えているためであると推察される。 The performance value of the insulating film of Comparative Example 1-1 was as low as 1.19 times. This is presumed to be because the specific surface area of the ceramic particles was less than 10 m 2 / g and the withstand voltage was lowered.
The performance values of the insulating films of Comparative Examples 1-2 and 1-4 were also about 1.17 times and 1.16 times. This is because the thermal conductivity is as low as that of a polyamideimide film not containing a filler. The low thermal conductivity is presumed to be because the content of ceramic particles is less than 5% by volume.
The electrodeposition solutions prepared in Comparative Examples 1-3 and 1-5 failed to produce an insulating film. This is presumably because the content of the ceramic particles exceeds 60% by volume.
　これに対して、実施例１－１～１－１８の絶縁膜は、性能値が１．２９倍から高いものでは４．１３倍になっており、性能が大幅に向上していることがわかった。これは耐電圧が、熱伝導度がフィラーを含まないポリアミドイミド膜と比較してほぼ同等もしくは向上し、かつ熱伝導度と耐電圧性の両者に優れているためである。なお、実施例１－８は、表面粗さＲａがやや高くなった。これは、セラミック粒子の比表面積がやや大きいためであると推察される。また、実施例１－１３、１－１８は、表面粗さＲａがやや高く、折り曲げ時の絶縁性が「Ｂ」であった。これは、セラミック粒子の含有量がやや多いためであると推察される。 In contrast, the performance of the insulating films of Examples 1-1 to 1-18 increased greatly from 1.29 times to 4.13 times, and the performance was significantly improved. It was. This is because the withstand voltage is almost the same or improved as compared with the polyamideimide film containing no filler, and is excellent in both the thermal conductivity and the withstand voltage. In Example 1-8, the surface roughness Ra was slightly high. This is presumably because the specific surface area of the ceramic particles is slightly large. In Examples 1-13 and 1-18, the surface roughness Ra was slightly high, and the insulation at the time of bending was “B”. This is presumably because the content of ceramic particles is slightly high.
［実施例２－１～２－３１、比較例２－１～２－１６］
（ポリアミック酸の合成）
　容量３００ｍＬのセパラブルフラスコに、４，４’－ジアミノジフェニルエーテル、およびＮＭＰを仕込んだ。ＮＭＰ量は、得られるポリアミック酸の濃度が４０ｗｔ％になるように調整した。常温で撹拌して、４，４’－ジアミノジフェニルエーテルを完全に溶解させた後、内温が３０℃を超えないよう、所定量のテトラカルボン酸２無水物を少量ずつ添加した。その後、窒素雰囲気下で１６時間の撹拌を続け、ポリアミック酸溶液として得た。 [Examples 2-1 to 2-31 and Comparative Examples 2-1 to 2-16]
(Synthesis of polyamic acid)
4,4′-Diaminodiphenyl ether and NMP were charged into a separable flask having a volume of 300 mL. The amount of NMP was adjusted so that the concentration of the polyamic acid obtained was 40 wt%. After stirring at room temperature to completely dissolve 4,4′-diaminodiphenyl ether, a predetermined amount of tetracarboxylic dianhydride was added little by little so that the internal temperature did not exceed 30 ° C. Thereafter, stirring was continued for 16 hours under a nitrogen atmosphere to obtain a polyamic acid solution.
（セラミック粒子分散樹脂溶液の調製）
　下記の表３に記載されている、セラミック粒子を用意した。用意したセラミック粒子を、ＮＭＰ１０ｇに対して１．０ｇ投入し、３０分間超音波処理して、セラミック粒子分散液を調製した。
　次いで、ポリアミック酸溶液とセラミック粒子分散液とＮＭＰを、最終的に溶液中のポリアミック酸濃度が５質量％で、セラミック粒子濃度が下記の表４に記載されている値となるように混合した。続いて得られた混合物を、スギノマシン社製スターバーストを用い、圧力５０ＭＰａの高圧噴射処理を１０回繰り返すことにより分散処理を行って、セラミック粒子分散樹脂溶液を調製した。 (Preparation of ceramic particle-dispersed resin solution)
Ceramic particles described in Table 3 below were prepared. 1.0 g of the prepared ceramic particles were added to 10 g of NMP and subjected to ultrasonic treatment for 30 minutes to prepare a ceramic particle dispersion.
Subsequently, the polyamic acid solution, the ceramic particle dispersion, and NMP were mixed so that the polyamic acid concentration in the solution was finally 5% by mass and the ceramic particle concentration was a value described in Table 4 below. Subsequently, the obtained mixture was subjected to a dispersion treatment by repeating a high-pressure injection treatment at a pressure of 50 MPa 10 times using a Starburst manufactured by Sugino Machine Co., to prepare a ceramic particle-dispersed resin solution.
＜塗布法による絶縁膜の作製＞
　調製したセラミック粒子分散樹脂溶液を、厚さ０．３ｍｍで３０ｍｍ×２０ｍｍの銅板の表面に、加熱後の膜厚が１０μｍとなるように塗布して塗布膜を形成した。次いで塗布膜をホットプレート上に配置して、室温から３℃／分で６０℃まで昇温し、６０℃で１００分間、さらに１℃／分で１２０℃まで昇温し、１２０℃で１００分間加熱して、乾燥して乾燥膜とした。その後、乾燥膜を２５０℃で１分間、４００℃で１分間加熱して、銅板表面に厚さ１０μｍの絶縁膜を作製した。なお、比較例２－３、２－５、２－７、２－９、２－１６で調製したセラミック粒子分散樹脂溶液は、絶縁膜を作製できなかった。 <Preparation of insulating film by coating method>
The prepared ceramic particle-dispersed resin solution was applied to the surface of a copper plate having a thickness of 0.3 mm and a size of 30 mm × 20 mm so that the film thickness after heating was 10 μm to form a coating film. Next, the coating film is placed on a hot plate and heated from room temperature to 60 ° C. at 3 ° C./minute, then heated to 60 ° C. for 100 minutes, further raised to 120 ° C. at 1 ° C./minute, and then at 120 ° C. for 100 minutes. Heated and dried to form a dry film. Thereafter, the dried film was heated at 250 ° C. for 1 minute and at 400 ° C. for 1 minute to produce an insulating film having a thickness of 10 μm on the copper plate surface. The ceramic particle-dispersed resin solutions prepared in Comparative Examples 2-3, 2-5, 2-7, 2-9, and 2-16 could not produce an insulating film.
＜評価＞
　上記の実施例および比較例で作製した絶縁膜について、セラミック粒子の含有量、膜厚当たりの耐電圧、熱伝導度（絶縁膜の厚さ方向の熱伝導度）、性能値、表面粗さＲａ、折り曲げ時の絶縁性をそれぞれ上記の方法により測定した。その結果を、表４に示す。なお、膜厚当たりの耐電圧、熱伝導度および性能値は、セラミック粒子を添加しなかったこと以外は、実施例２－１と同様にして作製した膜厚１０μｍのポリイミド膜の値を１とした相対値とした。 <Evaluation>
For the insulating films prepared in the above examples and comparative examples, the content of ceramic particles, the withstand voltage per film thickness, the thermal conductivity (thermal conductivity in the thickness direction of the insulating film), the performance value, the surface roughness Ra The insulation at the time of bending was measured by the above method. The results are shown in Table 4. The withstand voltage per film thickness, thermal conductivity, and performance values were set to 1 for a 10 μm thick polyimide film produced in the same manner as in Example 2-1, except that ceramic particles were not added. Relative value.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　比較例２－１、２－１３～１５の絶縁膜は、膜厚当たりの耐電圧が低くなった。これは、セラミック粒子の比表面積が１０ｍ２／ｇ未満であるためであると推察される。
　比較例２－２、２－４、２－６、２－８の絶縁膜は、熱伝導度がフィラーを含まないポリイミド膜と同等であった。これは、セラミック粒子の含有量が５体積％よりも少ないためであると推察される。
　比較例２－１０～１２の絶縁膜は、膜厚当たりの耐電圧がフィラーを含まないポリイミド膜と同等、もしくはわずかに低下し、熱伝導度がフィラーを含まないポリイミド膜と同等であり、セラミック粒子の添加による効果が得られなかった。これは、セラミック粒子の比表面積が１０ｍ２／ｇ未満であり、またその含有量も少ないためであると推察される。
　比較例２－３、２－５、２－７、２－９、２－１６で調製したセラミック粒子分散樹脂溶液は、絶縁膜を作製できなかった。これは、セラミック粒子の含有量が６０体積％を超えているためであると推察される。 The insulating films of Comparative Examples 2-1 and 2-13 to 15 had a low withstand voltage per film thickness. This is presumed to be because the specific surface area of the ceramic particles is less than 10 m 2 / g.
The insulating films of Comparative Examples 2-2, 2-4, 2-6, and 2-8 were equivalent in thermal conductivity to polyimide films that did not contain filler. This is presumably because the content of ceramic particles is less than 5% by volume.
Insulating films of Comparative Examples 2-10 to 12 have the same or slightly lower withstand voltage per film thickness than the polyimide film containing no filler, and the thermal conductivity is equivalent to the polyimide film containing no filler. The effect of adding particles was not obtained. This is presumably because the specific surface area of the ceramic particles is less than 10 m 2 / g and the content thereof is also small.
The ceramic particle-dispersed resin solutions prepared in Comparative Examples 2-3, 2-5, 2-7, 2-9, and 2-16 could not produce an insulating film. This is presumably because the content of the ceramic particles exceeds 60% by volume.
　これに対して、実施例２－１～２－３１の絶縁膜は、膜厚当たりの耐電圧が、フィラーを含まないポリイミド膜と比較してわずかに低下しているものもあったが、熱伝導度がフィラーを含まないポリイミド膜と比較して顕著に向上しており、その結果、性能値が１．３倍以上と大きくなった。なお、実施例２－８、２－２７～３０は、表面粗さＲａがやや高くなった。これは、セラミック粒子の比表面積がやや大きいためであると推察される。また、実施例２－１３、２－１８、２－２３、２―３１は、表面粗さＲａがやや高く、折り曲げ時の絶縁性が「Ｂ」であった。これは、セラミック粒子の含有量がやや多いためであると推察される。 In contrast, in the insulating films of Examples 2-1 to 2-31, the withstand voltage per film thickness was slightly lower than that of the polyimide film containing no filler. The conductivity was remarkably improved as compared with the polyimide film containing no filler, and as a result, the performance value increased to 1.3 times or more. In Examples 2-8 and 2-27 to 30, the surface roughness Ra was slightly high. This is presumably because the specific surface area of the ceramic particles is slightly large. In Examples 2-13, 2-18, 2-23, and 2-31, the surface roughness Ra was slightly high, and the insulation at the time of bending was “B”. This is presumably because the content of ceramic particles is slightly high.
［実施例３－１～３－２２］
　厚さ１ｍｍで２０ｍｍ×２０ｍｍの銅板を用意した。用意した銅板の上に、下記の表５に示すように、実施例１－１～１－６と同様のセラミック粒子分散樹脂溶液及び方法を用いて絶縁膜を形成した。得られた絶縁膜の厚さを表５に示す。 [Examples 3-1 to 3-22]
A 20 mm × 20 mm copper plate having a thickness of 1 mm was prepared. As shown in Table 5 below, an insulating film was formed on the prepared copper plate using the same ceramic particle-dispersed resin solution and method as in Examples 1-1 to 1-6. Table 5 shows the thickness of the obtained insulating film.
　次いで、下記の表５に示す樹脂材料とＮＭＰ（Ｎ－メチル－２－ピロリドン）とを、樹脂材料１質量部に対するＮＭＰの量が、表５に示す量となる割合で混合し、樹脂材料を溶解させて樹脂溶液を調製した。この樹脂溶液に上記絶縁膜付銅板の絶縁膜側の面を浸漬して、樹脂溶液を絶縁膜の表面に塗布した。その後、塗布層を、２５０℃で３０分間加熱乾燥して、絶縁膜の表面に樹脂層を形成して、銅板、絶縁膜、樹脂層がこの順で積層した積層体を得た。得られた樹脂層の厚さを表５に示す。
　なお、実施例３－２１～３－２２では、樹脂層を形成しなかった。 Next, the resin material shown in Table 5 below and NMP (N-methyl-2-pyrrolidone) were mixed in such a ratio that the amount of NMP relative to 1 part by mass of the resin material would be the amount shown in Table 5. A resin solution was prepared by dissolving. The surface on the insulating film side of the copper plate with an insulating film was immersed in this resin solution, and the resin solution was applied to the surface of the insulating film. Thereafter, the coating layer was heat-dried at 250 ° C. for 30 minutes to form a resin layer on the surface of the insulating film, and a laminated body in which the copper plate, the insulating film, and the resin layer were laminated in this order was obtained. Table 5 shows the thickness of the obtained resin layer.
In Examples 3-21 to 3-22, no resin layer was formed.
＜評価＞
　上記の実施例３－１～３－２２で作製した積層体の熱抵抗（積層体１枚）を、下記の方法により測定した。さらに、上記の実施例３－１～３－２０で作製した積層体については、樹脂層を介して２枚重ねた状態で、熱抵抗とピール強度とを下記の方法により測定した。その結果を表５に示す。 <Evaluation>
The thermal resistance (one laminate) of the laminates produced in the above Examples 3-1 to 3-22 was measured by the following method. Further, with respect to the laminates produced in Examples 3-1 to 3-20, the thermal resistance and peel strength were measured by the following methods in a state where two laminates were laminated via the resin layer. The results are shown in Table 5.
（熱抵抗：積層体１枚）
　図１に示すように、銅板１１、絶縁膜１２、樹脂層１３がこの順で積層された積層体１０の樹脂層１３の上にグリース（図示せず）を塗布し、そのグリースの上に発熱体２０を載置した。発熱体２０としては、ＴＯ－３Ｐを用いた。そして、発熱体の上部からトルク４０Ｎｃｍのねじによって積層方向に加圧しながら、発熱体２０から積層体の銅板１１までの熱抵抗を、Ｔ３Ｓｔｅｒを用いて測定した。熱抵抗の測定条件は、発熱：１Ａ、３０ｓｅｃ（素子温度：ΔＴ＝２．６℃）、測定：０．０１Ａ、測定時間：４５秒とした。なお、銅板１１は自然対流によって冷却した。樹脂層を形成しなかった実施例３－２１～３－２２の熱抵抗は、銅板上に絶縁膜が積層された積層体の絶縁膜上にグリースを塗布し、そのグリース上に発熱体を載置した試料を用いたこと以外は、実施例３－１～３－２０と同様の方法で測定した。熱抵抗は、実施例３－２１の値を１とした相対値とした。 (Thermal resistance: 1 laminate)
As shown in FIG. 1, grease (not shown) is applied on the resin layer 13 of the laminate 10 in which the copper plate 11, the insulating film 12, and the resin layer 13 are laminated in this order, and heat is generated on the grease. The body 20 was placed. As the heating element 20, TO-3P was used. And the thermal resistance from the heat generating body 20 to the copper plate 11 of a laminated body was measured using T3Ster, pressing in the lamination direction from the upper part of a heat generating body with the screw of torque 40Ncm. The measurement conditions for the thermal resistance were heat generation: 1 A, 30 sec (element temperature: ΔT = 2.6 ° C.), measurement: 0.01 A, and measurement time: 45 seconds. The copper plate 11 was cooled by natural convection. The thermal resistance of Examples 3-21 to 3-22 in which the resin layer was not formed is as follows. Grease was applied to the insulating film of the laminated body in which the insulating film was laminated on the copper plate, and the heating element was mounted on the grease. The measurement was performed in the same manner as in Examples 3-1 to 3-20 except that the placed sample was used. The thermal resistance was a relative value where the value of Example 3-21 was 1.
（熱抵抗：積層体２枚重ね）
　図２に示すように、銅板１１ａ、絶縁膜１２ａ、樹脂層１３ａがこの順で積層された積層体１０ａと、銅板１１ｂ、絶縁膜１２ｂ、樹脂層１３ｂがこの順で積層された積層体１０ｂとを用意し、積層体１０ａ、１０ｂの樹脂層１３ａ、１３ｂが互いに接するように重ねた。重ねた積層体１０ａ、１０ｂをカーボン治具を用いて５ＭＰａの圧力を付与しながら、真空中にて２１５℃の温度で２０分間加熱して熱圧着させて、積層体２枚重ねの試料を作製した。次いで、図２に示すように、試料の上側の銅板１１ａの上にグリース（図示せず）を塗布し、そのグリースの上に発熱体２０を載置した。発熱体２０としては、ＴＯ－３Ｐを用いた。そして、発熱体２０の上部からトルク４０Ｎｃｍのねじによって積層方向に加圧しながら、発熱体２０から試料の下側の銅板１１ｂまでの熱抵抗を、Ｔ３Ｓｔｅｒを用いて測定した。熱抵抗の測定条件は、発熱：１Ａ、３０ｓｅｃ（素子温度：ΔＴ＝２．６℃）、測定：０．０１Ａ、測定時間：４５秒とした。樹脂層を形成しなかった実施例３－２１～３－２２の熱抵抗は、銅板上に絶縁膜が積層された積層体を２つ用意し、積層体の絶縁膜が互いに接するように重ねた試料を用いたこと以外は、実施例３－１～３－２０と同様の方法で測定した。熱抵抗は、実施例３－２１の値を１とした相対値とした。 (Thermal resistance: 2 stacked layers)
As shown in FIG. 2, a laminated body 10a in which a copper plate 11a, an insulating film 12a, and a resin layer 13a are laminated in this order, and a laminated body 10b in which a copper plate 11b, an insulating film 12b, and a resin layer 13b are laminated in this order Were prepared so that the resin layers 13a and 13b of the laminates 10a and 10b were in contact with each other. While applying a pressure of 5 MPa using a carbon jig, the stacked laminates 10 a and 10 b are heated in a vacuum at a temperature of 215 ° C. for 20 minutes to be thermocompression-bonded to produce a sample of two stacked laminates. did. Next, as shown in FIG. 2, grease (not shown) was applied on the upper copper plate 11a of the sample, and the heating element 20 was placed on the grease. As the heating element 20, TO-3P was used. The thermal resistance from the heating element 20 to the lower copper plate 11b of the sample was measured using T3Ster while pressing from the upper part of the heating element 20 with a screw having a torque of 40 Ncm in the stacking direction. The measurement conditions for the thermal resistance were heat generation: 1 A, 30 sec (element temperature: ΔT = 2.6 ° C.), measurement: 0.01 A, and measurement time: 45 seconds. The thermal resistance of Examples 3-21 to 3-22 in which no resin layer was formed was prepared by stacking two laminated bodies in which an insulating film was laminated on a copper plate so that the insulating films of the laminated body were in contact with each other. The measurement was performed in the same manner as in Examples 3-1 to 3-20 except that the sample was used. The thermal resistance was a relative value where the value of Example 3-21 was 1.
（ピール強度）
　積層体の樹脂層と、厚み１８μｍで幅１ｃｍの銅箔（ＣＦ－Ｔ４Ｘ－ＳＶ－１８：福田金属箔粉工業株式会社製）とを、カーボン治具を用いて５ＭＰａの圧力を付与しながら、真空中にて２１５℃の温度で２０分間加熱して熱圧着させた。次いで、ＪＩＳ　Ｃ　６４８１に準拠して、銅箔を積層体の樹脂層から１８０度の角度で、剥離速度５０ｍｍ／分で引き剥がしたときのピール強度を測定した。ピール強度の測定装置は、テンシロン万能材料試験機（株式会社エー・アンド・デイ製）を用いた。 (Peel strength)
While applying a pressure of 5 MPa using a carbon jig, a resin layer of the laminate and a copper foil having a thickness of 18 μm and a width of 1 cm (CF-T4X-SV-18: manufactured by Fukuda Metal Foil Powder Co., Ltd.) Thermocompression bonding was performed by heating at a temperature of 215 ° C. for 20 minutes in a vacuum. Next, in accordance with JIS C 6481, the peel strength was measured when the copper foil was peeled off from the resin layer of the laminate at an angle of 180 ° at a peeling rate of 50 mm / min. As a measuring device for peel strength, a Tensilon universal material testing machine (manufactured by A & D Co., Ltd.) was used.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例３－１～３－２２で得られた積層体は、１枚でそれぞれ低い熱抵抗を示した。樹脂層が備えられている実施例３－１～３－２０で得られた積層体は、積層体１枚として低い熱抵抗を示すと同時に、積層体２枚を重ねた場合でも低い熱抵抗を示す上、高いピール強度を示した。特に樹脂層の厚さが０．１μｍ以上２μｍ以下の範囲にある実施例３－２～３－５、３－７、３－９～３－１２、３－１４～３－２０で得られた積層体は低い熱抵抗と高いピール強度を両立して示す。 The laminates obtained in Examples 3-1 to 3-22 each exhibited a low thermal resistance. The laminates obtained in Examples 3-1 to 3-20 provided with the resin layer exhibit low thermal resistance as one laminate, and at the same time, low thermal resistance even when two laminates are stacked. In addition, high peel strength was exhibited. Particularly obtained in Examples 3-2 to 3-5, 3-7, 3-9 to 3-12, and 3-14 to 3-20 in which the thickness of the resin layer is in the range of 0.1 μm to 2 μm. The laminate exhibits both low thermal resistance and high peel strength.
［実施例４－１～４－２２］
　銅板の上に、下記の表６に示すように、実施例２－１～２－６と同様のセラミック粒子分散樹脂溶液及び方法を用いて絶縁膜を形成したこと以外は、上記実施例３－１～３－２２と同様にして、銅板の上に絶縁膜を形成した。得られた絶縁膜の厚さを表６に示す。 [Examples 4-1 to 4-22]
Except that an insulating film was formed on a copper plate using the same ceramic particle-dispersed resin solution and method as in Examples 2-1 to 2-6 as shown in Table 6 below, the above Example 3- In the same manner as in 1 to 3-22, an insulating film was formed on the copper plate. Table 6 shows the thickness of the obtained insulating film.
　次いで、下記の表６に示す樹脂材料とＮＭＰ（Ｎ－メチル－２－ピロリドン）とを、樹脂材料１質量部に対するＮＭＰの量が、表６に示す量となる割合で混合し、樹脂材料を溶解させて樹脂溶液を用いたこと以外は、上記実施例３－１～３－２０と同様にして、絶縁膜の表面に樹脂層を形成して、銅板、絶縁膜、樹脂層がこの順で積層した積層体を得た。
　得られた樹脂層の厚さを表６に示す。
　なお、実施例４－２１～４－２２では、樹脂層を形成しなかった。実施例４－２１～４－２２では、銅板上に絶縁膜を形成した積層体を得た。 Next, the resin material shown in Table 6 below and NMP (N-methyl-2-pyrrolidone) were mixed in such a ratio that the amount of NMP relative to 1 part by mass of the resin material would be the amount shown in Table 6. A resin layer was formed on the surface of the insulating film in the same manner as in Examples 3-1 to 3-20 except that the resin solution was dissolved and the copper plate, the insulating film, and the resin layer were in this order. A laminated body was obtained.
Table 6 shows the thickness of the obtained resin layer.
In Examples 4-21 to 4-22, no resin layer was formed. In Examples 4-21 to 4-22, a laminated body in which an insulating film was formed on a copper plate was obtained.
＜評価＞
　上記の実施例４－１～４－２２で作製した積層体の熱抵抗（積層体１枚）を、上記の方法により測定した。さらに、上記の実施例４－１～４－２０で作製した積層体については、樹脂層を介して２枚重ねた状態で、熱抵抗とピール強度とを上記の方法により測定した。上記の実施例４－２１～４－２２で作製した積層体については、２つの積層体をそれぞれの積層体の絶縁膜が接するように重ねた状態で、熱抵抗とピール強度とを測定した。その結果を表６に示す。 <Evaluation>
The thermal resistance (one laminate) of the laminates produced in the above Examples 4-1 to 4-22 was measured by the above method. Further, with respect to the laminates produced in Examples 4-1 to 4-20, the thermal resistance and peel strength were measured by the above methods in a state where two laminates were stacked with the resin layer interposed therebetween. With respect to the laminates manufactured in Examples 4-21 to 4-22, the thermal resistance and peel strength were measured in a state where the two laminates were overlapped so that the insulating films of the respective laminates were in contact with each other. The results are shown in Table 6.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　実施例４－１～４－２２で得られた積層体は、１枚でそれぞれ低い熱抵抗を示した。樹脂層が備えられている実施例４－１～４－２０で得られた積層体は、積層体１枚として低い熱抵抗を示すと同時に、積層体２枚を重ねた場合でも低い熱抵抗を示す上、高いピール強度を示した。特に樹脂層の厚さが０．１μｍ以上２μｍ以下の範囲にある実施例４－２～４－５、４－７、４－９～４－１２、４－１４～４－２０で得られた積層体は低い熱抵抗と高いピール強度を両立して示す。 The laminates obtained in Examples 4-1 to 4-22 each exhibited a low thermal resistance. The laminates obtained in Examples 4-1 to 4-20 provided with the resin layer exhibit low thermal resistance as one laminate, and at the same time, low thermal resistance even when two laminates are stacked. In addition, high peel strength was exhibited. Particularly obtained in Examples 4-2 to 4-5, 4-7, 4-9 to 4-12, and 4-14 to 4-20 in which the thickness of the resin layer is in the range of 0.1 μm to 2 μm. The laminate exhibits both low thermal resistance and high peel strength.
　本発明の絶縁膜は、熱伝導度と耐電圧性の両者が高く、かつ耐熱性と機械特性とに優れている。そのため、本発明の絶縁膜は、コイルやモータに利用される金属線の被覆膜、半導体チップやＬＥＤ素子などの電子部品や回路基板の表面を保護する保護膜、金属ベース回路基板などにおいて回路層と基板との間の絶縁材に好適である。 The insulating film of the present invention has both high thermal conductivity and high voltage resistance, and is excellent in heat resistance and mechanical properties. Therefore, the insulating film of the present invention is used in a coating film for a metal wire used for a coil or a motor, a protective film for protecting the surface of an electronic component such as a semiconductor chip or an LED element or a circuit board, or a metal base circuit board. Suitable for insulating material between layer and substrate.
　１０、１０ａ、１０ｂ　　積層体
　１１、１１ａ、１１ｂ　　銅板
　１２、１２ａ、１２ｂ　　絶縁膜
　１３、１３ａ、１３ｂ　　樹脂層
　２０　　発熱体 10, 10a, 10b Laminate 11, 11a, 11b Copper plate 12, 12a, 12b Insulating film 13, 13a, 13b Resin layer 20 Heating element

Claims (2)

  1. 　ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなる樹脂と、比表面積が１０ｍ２／ｇ以上であるセラミック粒子と、を含み、前記セラミック粒子が凝集粒子を形成し、かつ前記セラミック粒子の含有量が５体積％以上６０体積％以下の範囲にあることを特徴とする絶縁膜。 A resin comprising polyimide, polyamideimide, or a mixture thereof; and ceramic particles having a specific surface area of 10 m 2 / g or more, wherein the ceramic particles form aggregated particles, and the content of the ceramic particles is An insulating film in a range of 5% by volume to 60% by volume.
  2. 　前記絶縁膜の少なくとも一方の表面に、ポリイミド、またはポリアミドイミド、もしくはこれらの混合物からなる樹脂層が備えられていることを特徴とする請求項１に記載の絶縁膜。 The insulating film according to claim 1, wherein a resin layer made of polyimide, polyamideimide, or a mixture thereof is provided on at least one surface of the insulating film.
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