WO2020138426A1 - Film de résine thermoplastique amorphe, film métallisé de condensateur, rouleau de film et condensateur - Google Patents

Film de résine thermoplastique amorphe, film métallisé de condensateur, rouleau de film et condensateur Download PDF

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Publication number
WO2020138426A1
WO2020138426A1 PCT/JP2019/051446 JP2019051446W WO2020138426A1 WO 2020138426 A1 WO2020138426 A1 WO 2020138426A1 JP 2019051446 W JP2019051446 W JP 2019051446W WO 2020138426 A1 WO2020138426 A1 WO 2020138426A1
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Prior art keywords
thermoplastic resin
film
amorphous thermoplastic
resin film
capacitor
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PCT/JP2019/051446
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English (en)
Japanese (ja)
Inventor
匠 末井
一雄 池田
明洋 筧
忠和 石渡
Original Assignee
王子ホールディングス株式会社
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Priority claimed from JP2019225009A external-priority patent/JP7419785B2/ja
Priority claimed from JP2019225008A external-priority patent/JP7467902B2/ja
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to EP19901661.9A priority Critical patent/EP3904048A4/fr
Priority to CN201980085957.1A priority patent/CN113272113B/zh
Publication of WO2020138426A1 publication Critical patent/WO2020138426A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • 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

Definitions

  • the present invention relates to an amorphous thermoplastic resin film, a metallized film for capacitors, and capacitors.
  • the resin film is used as a dielectric film for a capacitor, for example, (i) on the dielectric film, for example, vacuum deposition such as metal deposition or sputtering, or coating/drying of a metal-containing paste, A method of forming a so-called "metallized film" provided with a conductive layer such as a metal layer by a method such as pressure bonding of a metal foil or metal powder, (ii) a dielectric film not provided with a conductive layer such as a metal layer, and a metal A capacitor is formed by a method such as laminating another conductor such as a metallized film provided with a metal layer by a method similar to that of foil or (i) or the like.
  • the dielectric film for a capacitor is also used as a capacitor
  • capacitors used for automobiles are used in a high temperature environment, so dielectric films for capacitors are required to have high dielectric breakdown strength even at high temperatures. Further, in recent years, the required temperature for automobiles has been higher than before, and the required temperature may exceed 120°C and reach 140°C in some cases.
  • Patent Document 1 discloses a plastic film capacitor in which a film containing an aromatic polyether sulfone resin having high heat resistance as a main component is used as a dielectric thin film.
  • capacitors used in high temperature environments are required to have dielectric films for capacitors that have high dielectric breakdown strength at high temperatures.
  • the dielectric film for capacitors is usually continuously produced, stored and distributed as a long film roll. Further, when a metal layer is laminated on a dielectric film for a capacitor to produce a metallized film for a capacitor, or when it is used for a capacitor, the dielectric film for a capacitor may be unwound from a winding body while desired. The width is cut (slit processing), and the step of obtaining a small winding body is performed again. In the slit processing step of such a dielectric film for a capacitor, if the slip property of the dielectric film for a capacitor is low, a deviation or a wrinkle may be formed on the dielectric film for a capacitor during unwinding or winding. Occurs.
  • the present invention mainly has an object to provide an amorphous thermoplastic resin film having a high dielectric breakdown strength at high temperature, a thin thickness, and further excellent slit processing suitability.
  • an amorphous resin composed of a resin film containing an amorphous thermoplastic resin having a glass transition temperature (Tg) within a predetermined range and at least one kind of particles selected from the group consisting of silica and calcium carbonate
  • Tg glass transition temperature
  • the average particle size of the particles is set to a predetermined range
  • the content ratio of the particles to the entire film is set to a predetermined range, and when the thickness is reduced to 9.5 ⁇ m or less. It has been found below that an amorphous thermoplastic resin film having a high dielectric breakdown strength, a small thickness, and an excellent slit processing suitability can be obtained.
  • the amorphous thermoplastic resin film Since the amorphous thermoplastic resin film has a high dielectric breakdown strength at high temperatures, it can be suitably used for capacitors used in high temperature environments such as automobile capacitors. Further, since the amorphous thermoplastic resin film has a very small thickness of 9.5 ⁇ m or less, it has a large capacitance per unit volume. Furthermore, since the amorphous thermoplastic resin film has excellent slit processability, it has excellent productivity.
  • an amorphous thermoplastic resin having a glass transition temperature (Tg) within a predetermined range and containing a sulfonyl group (—SO 2 —) in the main chain, and at least one selected from the group consisting of silica and calcium carbonate.
  • An amorphous thermoplastic resin film composed of a resin film containing one kind of particles, wherein the average particle diameter of the particles is within a predetermined range, and the content rate of the particles in the entire film is within a predetermined range.
  • the thickness is set to 9.5 ⁇ m or less after setting, an amorphous thermoplastic resin film having a high dielectric breakdown strength at high temperature, a small thickness, and excellent slit workability can be obtained.
  • the amorphous thermoplastic resin film has a high dielectric breakdown strength at high temperatures, it can be suitably used for capacitors used in high temperature environments such as automobile capacitors. Further, since the amorphous thermoplastic resin film has a very small thickness of 9.5 ⁇ m or less, it has a large capacitance per unit volume. Furthermore, since the amorphous thermoplastic resin film has excellent slit processability, it has excellent productivity.
  • the present invention was completed by further studies based on these findings.
  • the present invention includes the following.
  • Item 1 Amorphous thermoplastic resin film containing an amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or more and less than 200° C., and at least one kind of particles selected from the group consisting of silica and calcium carbonate And The average particle diameter of the particles is 0.1 ⁇ m or more and 1.5 ⁇ m or less, The content of the particles is 0.1% by mass or more and 1.5% by mass or less, An amorphous thermoplastic resin film having a thickness of 9.5 ⁇ m or less.
  • Item 2. Item 2. The amorphous thermoplastic resin film according to Item 1, which has a dielectric breakdown strength of 300 VDC / ⁇ m or more in an environment of 125°C.
  • Item 3 The amorphous thermoplastic resin according to Item 1 or 2, wherein the amorphous thermoplastic resin has a repeating unit represented by the formula: -[Ph-C(CH 3 ) 2 -Ph]- in the main chain. the film.
  • Item 4. The amorphous thermoplastic resin film according to any one of Items 1 to 3, wherein the amorphous thermoplastic resin film is composed of an unstretched film.
  • Item 5. An amorphous thermoplastic resin having a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower and containing a sulfonyl group in the main chain, and at least one kind of particles selected from the group consisting of silica and calcium carbonate.
  • Tg glass transition temperature
  • An amorphous thermoplastic resin film containing, The average particle diameter of the particles is 0.1 ⁇ m or more and 1.5 ⁇ m or less, The content of the particles is 0.1% by mass or more and 1.5% by mass or less, An amorphous thermoplastic resin film having a thickness of 9.5 ⁇ m or less.
  • Item 6. The amorphous thermoplastic resin film according to item 5, which has a dielectric breakdown strength of 300 VDC / ⁇ m or more in a 140° C. environment.
  • Item 9. Item 9. The amorphous thermoplastic resin film according to any one of items 1 to 8, which is a dielectric film for capacitors.
  • Item 10. Item 10. A film roll obtained by winding the amorphous thermoplastic resin film according to any one of Items 1 to 9.
  • Item 11. Item 10.
  • Item 12. A capacitor comprising the amorphous thermoplastic resin film according to items 1 to 9.
  • an amorphous thermoplastic resin film having a high dielectric breakdown strength at high temperature, a small thickness, and an excellent slit processability. Further, according to the present invention, it is also possible to provide a film roll using the amorphous thermoplastic resin film, a metallized film for a capacitor which has a small thickness and a high capacity, and a capacitor.
  • the amorphous thermoplastic resin film according to the first embodiment of the present invention is selected from the group consisting of an amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or higher and lower than 200° C., and silica and calcium carbonate.
  • the content of the particles is 0.1% by mass or more and 1.5% by mass or less and the thickness is 9.5 ⁇ m or less when the mass% is set.
  • the amorphous thermoplastic resin film according to the first embodiment of the present invention has such a configuration, it has a high dielectric breakdown strength at high temperature, has a small thickness, and is suitable for slit processing. Demonstrate the characteristics of being excellent.
  • the amorphous thermoplastic resin film according to the first embodiment has a high dielectric breakdown strength at high temperature (for example, dielectric breakdown strength in a 125° C. environment is 300 V DC / ⁇ m or more), and therefore it is used for capacitors. It can be preferably used as a dielectric film, and can be particularly preferably used for a capacitor used in a high temperature environment.
  • the amorphous thermoplastic resin film according to the first embodiment has a very thin thickness of 9.5 ⁇ m or less, when the film capacitor is used as a dielectric film, the capacitance per unit volume is small. large. Furthermore, the amorphous thermoplastic resin film according to the first embodiment has excellent slit processing suitability, and thus has excellent productivity.
  • the amorphous thermoplastic resin film according to the first embodiment has a film thickness exceeding 9.5 ⁇ m (for example, 10 ⁇ m, 11 ⁇ m, 20 ⁇ m, etc.) in order to increase the capacitance per unit volume when used as a film capacitor. ) Is not assumed.
  • the amorphous thermoplastic resin film according to the second embodiment of the present invention has a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower, and an amorphous thermoplastic resin containing a sulfonyl group in the main chain.
  • the content of the amorphous thermoplastic resin film is 100% by mass, the content of the particles is 0.1% by mass or more and 1.5% by mass or less, and the thickness is 9.5 ⁇ m or less. ..
  • the amorphous thermoplastic resin film according to the second embodiment has such a configuration, it has high dielectric breakdown strength at high temperature, is thin, and is excellent in slit processing suitability. Demonstrate the characteristics.
  • the amorphous thermoplastic resin film according to the second embodiment has a high dielectric breakdown strength at high temperature (for example, dielectric breakdown strength in a 125° C. environment is 300 V DC / ⁇ m or more, and further insulation in a 140° C. environment). Since it has a breaking strength of 300 V DC / ⁇ m or more), it can be suitably used as a dielectric film for a capacitor, and particularly can be suitably used for a capacitor used in a high temperature environment.
  • the amorphous thermoplastic resin film according to the second embodiment has a very thin thickness of 9.5 ⁇ m or less, when the film capacitor is used as a dielectric film, the capacitance per unit volume is small. large. Furthermore, the amorphous thermoplastic resin film according to the second embodiment has excellent slit processing suitability, and thus has excellent productivity. Also in the amorphous thermoplastic resin film according to the second embodiment, the thickness of the film exceeds 9.5 ⁇ m (for example, 10 ⁇ m, 11 ⁇ m, 20 ⁇ m) in order to increase the capacitance per unit volume when the film capacitor is used. Etc.) are not assumed.
  • the amorphous thermoplastic resin film according to the first embodiment of the present invention and the amorphous thermoplastic resin film according to the second embodiment will be described in detail in order. Further, a metallized film for a capacitor and a capacitor using the amorphous thermoplastic resin film according to these embodiments will be described in detail.
  • the numerical range “to” means above and below. That is, the notation ⁇ to ⁇ means ⁇ or more and ⁇ or less, or ⁇ or more and ⁇ or less, and includes ⁇ and ⁇ as the range.
  • “mass %” indicating the content of each component indicates the ratio of the content when the amorphous thermoplastic resin film is 100 mass %, unless otherwise specified.
  • the amorphous thermoplastic resin film according to the first embodiment is at least one selected from the group consisting of an amorphous thermoplastic resin, silica and calcium carbonate. It is composed of a film containing particles.
  • the amorphous thermoplastic resin film according to the first embodiment is a resin film in which particles of at least one of silica and calcium carbonate are dispersed in an amorphous thermoplastic resin as a base resin.
  • Amorphous thermoplastic resin has a glass transition temperature (Tg) of 130°C or higher and lower than 200°C. Having high dielectric breakdown strength at high temperature, thin thickness, and further exhibiting the property of being excellent in slit processing suitability, while further enhancing the continuous film-forming property of the amorphous thermoplastic resin film (specifically, From the viewpoint of increasing the length at which the film can be formed without breaking, it is preferably 135 to 195°C, more preferably 140 to 190°C, further preferably 150 to 190°C, particularly preferably 160 to 190. °C is mentioned.
  • the glass transition temperature (Tg) is a value measured by using a differential scanning calorimeter (DSC), and specifically, it is measured by the method described in the examples.
  • DSC differential scanning calorimeter
  • the "amorphous thermoplastic resin” means a measurement using a differential scanning calorimeter (DSC) (specifically, the measurement is performed by the method described in Examples), It is a resin having a glass transition temperature (Tg) but no clear endothermic peak (melting point) associated with melting.
  • DSC differential scanning calorimeter
  • the amorphous thermoplastic resin include polycarbonate, polysulfone, polyether sulfone, polyphenyl sulfone, amorphous polystyrene, acrylic resin, ABS resin, polyphenylene ether, polyarylate, polyamideimide, polyetherimide, thermoplastic resin.
  • Amorphous polyimide, amorphous cycloolefin polymer, amorphous cycloolefin copolymer and the like can be mentioned.
  • the amorphous thermoplastic resin is not particularly limited as long as it has a glass transition temperature (Tg) of 130° C. or higher and lower than 200° C., but has a high dielectric breakdown strength at high temperature, a small thickness, and
  • An amorphous thermoplastic resin having a repeating unit represented by the formula: -[Ph-C(CH 3 ) 2 -Ph]- in the main chain is preferable from the viewpoint of suitably exhibiting the property of being excellent in slit processing suitability. ..
  • amorphous thermoplastic resin examples include polysulfone and polycarbonate having the above repeating unit.
  • the amorphous thermoplastic resin contained in the amorphous thermoplastic resin film may be one type or two or more types.
  • the polysulfone is not particularly limited, and known ones can be used, and commercially available products can also be used.
  • Examples of commercially available products of polysulfone include, for example, trade name Ultrazone (registered trademark) manufactured by BASF (for example, Ultrazone (registered trademark) S6010, Ultrazone (registered trademark) S3010, Ultrazone (registered trademark) S2010) and Solvey.
  • the trade name is Udel (registered trademark) (for example, Udel (registered trademark) P-1700) manufactured by the company.
  • the glass transition temperature (Tg) of polysulfone may be in the range of 130° C. or higher and lower than 200° C., preferably 160 to 195° C., more preferably 170 to 190° C., and further preferably 180 to 190° C. ..
  • the mass (weight) average molecular weight of the polysulfone is not particularly limited, but is, for example, about 10,000 to 100,000, preferably about 15,000 to 80,000.
  • the MVR (melt volume flow rate) of polysulfone is preferably 100 cm 3 /10 minutes or less, more preferably 50 cm 3 /10 minutes or less, and further preferably 35 cm 3 /10 minutes or less. ..
  • the lower limit of MVR is, for example, 20 cm 3 /10 minutes.
  • the mass (weight) average molecular weight of the resin can be measured using a gel permeation chromatograph (GPC) device.
  • GPC gel permeation chromatograph
  • the MVR of polysulfone is a value measured in accordance with ISO 1133 regulations under the conditions of a temperature of 360° C. and a load of 10 kg.
  • the polycarbonate is not particularly limited, and known ones can be used, and commercially available products can also be used.
  • Examples of commercially available products of polycarbonate include Panlite (registered trademark) manufactured by Teijin Limited (for example, Panlite (registered trademark) K-1300Y) and Upilon (registered trademark) manufactured by Mitsubishi Engineering-Plastics Corporation. (For example, Iupilon (registered trademark) E-2000), Novalex (registered trademark) (for example, Novalex (registered trademark) 7030R), and the like.
  • the glass transition temperature (Tg) of the polycarbonate may be in the range of 130° C. or higher and lower than 200° C., preferably 130 to 170° C., more preferably 140 to 165° C., further preferably 145 to 160° C. ..
  • the mass (weight) average molecular weight of the polycarbonate is not particularly limited, but is, for example, about 10,000 to 100,000, preferably about 15,000 to 80,000.
  • the content of the amorphous thermoplastic resin in the amorphous thermoplastic resin film according to the first embodiment is, for example, 55% by mass or more, preferably 60 to 99.9% by mass, more preferably 65 to 99.%. 5% by mass, and more preferably 70 to 99.0% by mass.
  • the amorphous thermoplastic resin film according to the first embodiment is different from the amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or higher and lower than 200° C., unless the effects of the present invention are impaired.
  • Other resins may be included. Examples of such other resin include an amorphous thermoplastic resin having a glass transition temperature (Tg) of less than 130° C., an amorphous thermoplastic resin having a glass transition temperature (Tg) of 200° C. or more, and a crystalline thermoplastic resin. Etc.
  • amorphous thermoplastic resin as another resin include polyether sulfone, polyphenyl sulfone, amorphous polystyrene, acrylic resin, ABS resin, polyphenylene ether, polyarylate, polyamide imide, polyether imide, and heat.
  • examples thereof include a plastic amorphous polyimide, an amorphous cycloolefin polymer, and an amorphous cycloolefin copolymer.
  • the crystalline thermoplastic resin as another resin include polyethylene, polypropylene, polyvinyl alcohol, polymethylpentene, syndiotactic polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyether ether.
  • examples thereof include ketones, polyacetals, liquid crystal polymers, crystalline cycloolefin polymers, crystalline cycloolefin copolymers and fluororesins.
  • the content thereof is 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably Is 15% by mass or less.
  • substantially only the amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or higher and lower than 200° C. for example, amorphous thermoplastic resin
  • the proportion of the amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or more and less than 200° C. in the resin contained in the plastic resin film may be 99% by mass or more).
  • the silica is not particularly limited as long as the average particle diameter is in the range of 0.1 to 1.5 ⁇ m, and known silica can be used, and commercially available products can also be used.
  • synthetic amorphous silica is preferable because it can easily obtain particles having a preferable particle size.
  • the shape of silica is not particularly limited and may be, for example, spherical silica composed of single particles, amorphous silica forming secondary particles or tertiary particles from a plurality of primary particles, and the like, but composed of single particles. Spherical silica is preferred.
  • the calcium carbonate is not particularly limited as long as it has an average particle size of 0.1 ⁇ m or more and 1.5 ⁇ m or less, and known ones can be used, and commercially available products can also be used.
  • As the calcium carbonate light calcium carbonate is preferable because it is easy to obtain one having a preferable particle size.
  • the amorphous thermoplastic resin film according to the first embodiment is selected from the group consisting of silica and calcium carbonate from the viewpoint of increasing the dielectric breakdown strength under high temperature and reducing the thickness while further enhancing the slit processing suitability.
  • the average particle size of at least one kind of particles is preferably 0.2 to 1.5 ⁇ m, more preferably 0.3 to 1.2 ⁇ m, and further preferably 0.5 to 1.0 ⁇ m.
  • the average particle size of at least one kind of particles selected from the group consisting of silica and calcium carbonate is a value measured by the following method.
  • the average particle size is 10 particles from one side (20 points in total on both sides) on the surface of the film using an ultra-high resolution field emission scanning electron microscope ((FE-SEM) Hitachi High Technologies S-5200). At a magnification of 20,000, an accelerating voltage of 8 kV, a beam current of 10 ⁇ A, and the detector is observed using a backscattered electron detector to obtain an observed image. From the observed image, the longest diameter is measured using image analysis software, and the average particle diameter obtained by averaging the measured values is obtained. In this method, particles at a position deeper than about 3 ⁇ m from the film surface will be blurred and cannot be measured. However, since particles at such deep positions do not function as a lubricant, they are not targets for measurement in the first embodiment.
  • the ratio of () is not particularly limited as long as it is in the range of 0.1 to 1.5 mass %. From the viewpoint of increasing the dielectric breakdown strength of the amorphous thermoplastic resin film according to the first embodiment at high temperature and reducing the thickness, further improving the slit processing suitability and further improving the continuous film-forming property, it is preferable. 0.12-1.5% by mass, more preferably 0.2-1.2% by mass, further preferably 0.2-1.0% by mass, particularly preferably 0.2-0.7% by mass. To be
  • the thickness of the amorphous thermoplastic resin film according to the first embodiment may be 9.5 ⁇ m or less, but preferably 9.0 ⁇ m from the viewpoint of reducing the volume of the capacitor and increasing the capacitance.
  • the thickness is more preferably 8.5 ⁇ m or less, still more preferably 6.0 ⁇ m or less.
  • the lower limit of the thickness of the amorphous thermoplastic resin film according to the first embodiment is, for example, 1. 5 ⁇ m, preferably 2.0 ⁇ m, more preferably 2.5 ⁇ m.
  • the dielectric constant ⁇ here is determined by the material used. Then, as long as the material is not changed, as can be seen from the above formula, the capacitance per unit volume (C/V) is inversely proportional to the square of the thickness of the resin film when the thickness of the resin film is reduced, It can be seen that (C/V) is improved.
  • the thickness of the dielectric film is as thin as possible within a range in which dielectric breakdown strength (V DC ), suitability for slit processing, and continuous film forming property are ensured.
  • the thickness of the amorphous thermoplastic resin film is a value measured according to JIS K 7130:1999 A method using an outside micrometer (high precision digimatic micrometer MDH-25MB manufactured by Mitutoyo Corporation). ..
  • the dielectric breakdown strength of at 125 ° C. environment amorphous thermoplastic resin film according to the first embodiment from the viewpoint of dielectric breakdown strength at high temperatures, preferably 300 V DC / [mu] m or more, more preferably 320 V DC / ⁇ m or more, further 350V DC / ⁇ m or more.
  • 300 V DC / [mu] m or more preferably 300 V DC / [mu] m or more, more preferably 320 V DC / ⁇ m or more, further 350V DC / ⁇ m or more.
  • 600 VDC / ⁇ m can be mentioned.
  • the dielectric breakdown strength in a 125° C. environment is a value measured by the following measuring method.
  • a measuring device according to JIS C2151:2006, 17.2.2 (flat plate electrode method) is prepared.
  • conductive rubber E12S10 manufactured by Seiwa Electric Co., Ltd.
  • the measurement environment is set in a forced circulation type oven at a set temperature of 125° C., and the electrodes and film are used after the temperature is controlled in the oven for 30 minutes.
  • the voltage increase starts from 0 V and is set to a speed of 100 V/sec, and the time when the current value exceeds 5 mA is the time of breakdown.
  • the dielectric breakdown voltage was measured 20 times, the dielectric breakdown voltage value V DC was divided by the film thickness ( ⁇ m), and the average value of 16 points excluding the upper 2 points and the lower 2 points in the calculation results of the 20 times was calculated. Is the dielectric breakdown strength (V DC / ⁇ m).
  • the amorphous thermoplastic breakdown strength at the 23 ° C. environment resin film according to the first embodiment preferably 300 V DC / [mu] m or more, more preferably 320 V DC / [mu] m or more, further 350 V DC / [mu] m
  • the upper limit of the dielectric breakdown strength of the amorphous thermoplastic resin film according to the first embodiment in the 23° C. environment is not limited, but, for example, 650 VDC / ⁇ m can be mentioned.
  • the dielectric breakdown strength in a 23° C. environment is calculated by performing the same measurement as in 125° C., not in a forced circulation oven at a set temperature of 125° C., but in an environment of 23° C. and a relative humidity of 50%.
  • the ratio of the dielectric breakdown strength in the 125°C environment to the dielectric breakdown strength in the 23°C environment is preferably 0. 8 or more, more preferably 0.9 or more, further preferably 0.95 or more, and particularly preferably 1.0 or more.
  • the upper limit of the ratio is preferably 1.1 or less.
  • the amorphous thermoplastic resin film according to the first embodiment may be an unstretched film or a stretched film. From the viewpoint of further improving the slit processability of the amorphous thermoplastic resin film according to the first embodiment and further improving the continuous film-forming property, an unstretched film is preferable. On the other hand, a stretched film is preferable from the viewpoint of increasing the dielectric strength at high temperature and reducing the thickness.
  • the amorphous thermoplastic resin film is a stretched film, it may be a uniaxially stretched film or a biaxially stretched film.
  • the amorphous thermoplastic resin film according to the first embodiment may be a single layer or multiple layers.
  • a single layer is preferable because the film thickness can be easily reduced.
  • a multi-layer structure is preferable because the effect is easily obtained with a small addition amount and the dielectric breakdown strength is also increased by adding silica and/or calcium carbonate only to the surface layer.
  • the amorphous thermoplastic resin film according to the first embodiment is a multilayer, it may have a configuration in which two or more layers of the same or different amorphous thermoplastic resin films are laminated.
  • the amorphous thermoplastic resin film according to the first embodiment may be in a state of being laminated on a metal foil such as an aluminum foil or a base material formed of another resin film, Preferably, it is not formed on the base material, and is manufactured as a single unit of the amorphous thermoplastic resin film according to the first embodiment (preferably, after film formation, it is independently wound on a winding core to obtain a winding body. ), and is preferably used for the production of a metallized film for capacitors and capacitors described later.
  • the amorphous thermoplastic resin film according to the first embodiment may contain an additive.
  • the additive is not particularly limited as long as it does not impair the effects of the present invention, and additives known in the known amorphous thermoplastic resin film can be used.
  • Additives include, for example, necessary stabilizers such as antioxidants, chlorine absorbers, etc., lubricants (different from the aforementioned silica and calcium carbonate), plasticizers, flame retardants, colorants, etc. ..
  • the amorphous thermoplastic resin film according to the first embodiment may include such an additive in an amount that does not adversely affect the amorphous thermoplastic resin film of the first embodiment.
  • the amorphous thermoplastic resin film according to the first embodiment preferably does not use spherical crosslinked polymer resin particles such as silicone resin.
  • the “antioxidant” is not particularly limited as long as the amorphous thermoplastic resin film of the first embodiment can be obtained.
  • Antioxidants are generally used for two purposes. One purpose is to suppress thermal deterioration and oxidative deterioration in the extruder, and another purpose is to contribute to suppression of deterioration in long-term use as a capacitor film and improvement of capacitor performance.
  • the “chlorine absorbent” is not particularly limited as long as it does not impair the effects of the present invention. If a chlorine absorbent is used, it is easy to enhance the performance of the capacitor by supplementing the chlorine contained in the resin in a trace amount due to the polymerization catalyst and the like, and suppressing the chlorination of the metal vapor deposition film described later.
  • Examples of the chlorine absorbent include metal soap such as calcium stearate and the like.
  • the “lubricant” is not particularly limited as long as the effect of the present invention is not impaired.
  • examples of lubricants include primary amides (stearic acid amides, etc.), secondary amides (N-stearyl stearic acid amides, etc.), ethylenebisamides (N,N′-ethylenebisstearic acid amides, etc.), polyethylene waxes, etc.
  • Various waxes can be exemplified.
  • silica and calcium carbonate also function as a lubricant, a lubricant different from silica and calcium carbonate is not substantially contained (for example, silica in the lubricant). And the proportion of calcium carbonate is 99% by mass or more).
  • the “plasticizer” is not particularly limited as long as it does not impair the effects of the present invention.
  • examples of the plasticizer include bis(2-ethylhexyl) phthalate and the like.
  • the “flame retardant” is not particularly limited as long as it does not impair the effects of the present invention.
  • Examples of the flame retardant include halogen compounds, aluminum hydroxide, magnesium hydroxide, phosphates, borates, antimony oxides and the like.
  • the “colorant” is not particularly limited as long as it does not impair the effects of the present invention.
  • the colorant include inorganic colorants such as titanium dioxide, carbon black, talc, chromium compounds and zinc sulfide, and organic colorants such as azo type, quinacridone type and phthalocyanine type colorants.
  • the amorphous thermoplastic resin film of the first embodiment has a thin thickness of 9.5 ⁇ m or less and has a high dielectric breakdown strength at high temperatures, so it is used in a high temperature environment, is small, and has a high capacity (for example, the capacitor of 5 ⁇ F or more, preferably 10 ⁇ F or more, more preferably 20 ⁇ F or more) can be very suitably used.
  • the amorphous thermoplastic resin film of the first embodiment includes an amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or higher and lower than 200° C., and an average particle diameter of 0.1 ⁇ m or more and 1.5 ⁇ m or less silica. And a resin composition containing at least one kind of particles selected from the group consisting of calcium carbonate in the range of 0.1 to 1.5% by mass, and molding the resin composition into a film having a thickness of 9.5 ⁇ m. You can
  • the details of the amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or more and less than 200° C. and the particles having an average particle size of 0.1 ⁇ m or more and 1.5 ⁇ m or less are as described above.
  • the method of molding the resin composition into a film having a thickness of 9.5 ⁇ m is not particularly limited, and a known film molding method can be adopted.
  • a method in which a resin composition supplied to an extruder is melted by heating, filtered through a filter, extruded into a film using a T-die, and solidified by contact with a roll set to a predetermined surface temperature for molding. are listed.
  • the amorphous thermoplastic resin film of the first embodiment can be made into a roll (film roll) by forming the film and then winding it around the core.
  • the composition of the resin composition can also be adjusted by mixing a plurality of resin compositions (resin mixing). For example, by mixing an amorphous thermoplastic resin containing at least one kind of particles selected from the group consisting of silica and calcium carbonate with an amorphous thermoplastic resin not containing the particles, The content ratio of the particles in the composition can be adjusted to 0.1 to 1.5% by mass, based on 100% by mass of the resin composition.
  • the method for mixing a plurality of resin compositions is not particularly limited, pellets of a plurality of resin compositions, a method of dry blending using a mixer or the like, pellets of a plurality of resin compositions, in a kneader
  • a method of supplying and melting and kneading to obtain a blended resin is not particularly limited, pellets of a plurality of resin compositions, a method of dry blending using a mixer or the like, pellets of a plurality of resin compositions, in a kneader
  • the mixer or kneading machine may be either a single screw type, a twin screw type or a multi-screw type more than that, and in the case of a screw type having two or more screws. It does not matter whether the kneading type is the same direction rotation or different direction rotation.
  • the kneading temperature is not particularly limited as long as good kneading can be obtained, but generally 230 to 400° C., preferably 280 to 350° C., more preferably 290 to 340. It is in the range of °C.
  • an inert gas such as nitrogen may be purged into the kneading machine.
  • the extrusion temperature when molding the resin composition into a film in the molten state and the surface temperature of the cooling roll are appropriately adjusted according to the glass transition temperature (Tg) of the amorphous thermoplastic resin.
  • Tg glass transition temperature
  • the extrusion temperature is, for example, 230 to 400° C., preferably 280 to 350° C., and more preferably 290 to 340° C.
  • the surface temperature of the cooling roll is, for example, 80 to 230°C, preferably 100 to 160°C, more preferably 110 to 150°C.
  • a known method such as an air knife, electrostatic pinning, an elastic roll nip, a metal roll nip, or an elastic metal roll nip can be used as a contact method when the molten resin composition is solidified by contact with a cooling roll.
  • the amorphous thermoplastic resin film of the first embodiment is used as a stretched film
  • the above resin composition is formed into a film and then the film is further stretched.
  • the stretching ratio is not particularly limited and may be about 1.1 to 4.0 times in the MD direction and about 1.1 to 4.0 times in the TD direction.
  • the stretched film may be a uniaxially stretched film or a biaxially stretched film.
  • the temperature during stretching is appropriately adjusted according to the glass transition temperature (Tg) of the amorphous thermoplastic resin.
  • the stretching temperature is, for example, about 100 to 270°C. From the viewpoint of improving the thickness accuracy after stretching, the range of Tg+2° C. to Tg+70° C. or Tg ⁇ 90° C. to Tg ⁇ 2° C. is preferable, and the range of Tg+5° C. to Tg+65° C. or Tg ⁇ 80° C. The range of Tg-5°C is more preferable. That is, the preferred temperature during stretching may be a temperature range higher than the glass transition temperature or a temperature range lower than the glass transition temperature.
  • the stretched film may be annealed for the purpose of relaxation of residual stress and adjustment of thermal shrinkage, and the temperature is preferably in the range of Tg-1°C to Tg-60°C, and Tg-3°C. The range of to Tg-50°C is more preferable.
  • a relaxation treatment for lowering the draw ratio may be performed.
  • the amorphous thermoplastic resin film according to the second embodiment is at least one selected from the group consisting of an amorphous thermoplastic resin, silica and calcium carbonate. It is composed of a film containing particles.
  • the amorphous thermoplastic resin film according to the second embodiment is a resin film in which particles of at least one of silica and calcium carbonate are dispersed in an amorphous thermoplastic resin as a base resin.
  • the amorphous thermoplastic resin has a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower, and contains a sulfonyl group (—SO 2 —) in the main chain.
  • Tg glass transition temperature
  • —SO 2 — sulfonyl group
  • the glass transition temperature (Tg) is a value measured by using a differential scanning calorimeter (DSC), and specifically, it is measured by the method described in the examples.
  • amorphous thermoplastic resin is the same as the description in "1st Embodiment.”
  • Specific examples of the amorphous thermoplastic resin containing a sulfonyl group (—SO 2 —) in the main chain include polysulfone, polyether sulfone, polyphenyl sulfone and the like.
  • the amorphous thermoplastic resin further has high dielectric breakdown strength at high temperature, has a thin thickness, and further has excellent suitability for slit processing.
  • An amorphous thermoplastic resin having a repeating unit represented by Ph-C(CH 3 ) 2 -Ph]- is preferable.
  • the amorphous thermoplastic resin contained in the amorphous thermoplastic resin film may be one kind or two or more kinds.
  • the polysulfone is not particularly limited, and known ones can be used, and commercially available products can also be used. Examples of commercially available products of polysulfone include the same as those exemplified in the "first embodiment".
  • the glass transition temperature (Tg) of polysulfone may be in the range of 170° C. to 230° C., preferably 160 to 195° C., more preferably 170 to 190° C., and further preferably 180 to 190° C. ..
  • the mass (weight) average molecular weight of the polysulfone is not particularly limited, but is, for example, about 10,000 to 100,000, preferably about 15,000 to 80,000.
  • the polysulfone has an MVR (melt volume flow rate) of preferably 50 cm 3 /10 minutes or less, more preferably 35 cm 3 /10 minutes or less. The lower limit of MVR is, for example, 20 cm 3 /10 minutes.
  • the mass (weight) average molecular weight of the resin is a value measured by the same method as that described in the "first embodiment".
  • the polyether sulfone is not particularly limited, and known ones can be used, and commercially available products can also be used.
  • Examples of commercially available products of polyethersulfone include trade names of Ultrazone (registered trademark) manufactured by BASF (for example, Ultrazone (registered trademark) E2010 and Ultrazone (registered trademark) E3010).
  • the glass transition temperature (Tg) of the polyether sulfone may be in the range of 170° C. or higher and 230° C. or lower, preferably 200 to 230° C., more preferably 210 to 230° C., further preferably 220 to 230° C. Can be mentioned.
  • the mass (weight) average molecular weight of the polyether sulfone is not particularly limited, but is, for example, about 10,000 to 100,000, preferably about 15,000 to 80,000.
  • the polyphenyl sulfone is not particularly limited, and known ones can be used, and commercially available products can also be used.
  • Examples of commercial products of polyphenylsulfone include, for example, trade name Ultrazone (registered trademark) manufactured by BASF (for example, Ultrazone (registered trademark) P3010), trade name Radel (registered trademark) manufactured by Solvey (for example, Radel). (Registered trademark) R-5100) and the like.
  • the glass transition temperature (Tg) of polyphenyl sulfone may be in the range of 170° C. or higher and 230° C. or lower, preferably 195 to 225° C., more preferably 205 to 225° C., and further preferably 215 to 225° C. Can be mentioned.
  • the mass (weight) average molecular weight of the polyphenyl sulfone is not particularly limited, but is, for example, about 10,000 to 100,000, preferably about 15,000 to 80,000.
  • the content of the amorphous thermoplastic resin in the amorphous thermoplastic resin film according to the second embodiment is, for example, 55% by mass or more, preferably 60 to 99.9% by mass, more preferably 65 to 99.%. 5% by mass, and more preferably 70 to 99.0% by mass.
  • the amorphous thermoplastic resin film according to the second embodiment has a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower, and a sulfonyl group in the main chain, unless the effects of the present invention are impaired.
  • Other resin different from the amorphous thermoplastic resin containing may be contained.
  • an amorphous thermoplastic resin having a glass transition temperature (Tg) of lower than 170° C. an amorphous thermoplastic resin having a glass transition temperature (Tg) of higher than 230° C., 170° C. or higher and 230° C.
  • examples thereof include an amorphous thermoplastic resin having no sulfonyl group in the main chain and a crystalline thermoplastic resin.
  • amorphous thermoplastic resin as another resin include polycarbonate, amorphous polystyrene, acrylic resin, ABS resin, polyphenylene ether, polyarylate, polyamide imide, polyether imide, thermoplastic amorphous polyimide, Examples thereof include an amorphous cycloolefin polymer and an amorphous cycloolefin copolymer.
  • thermoplastic resin as the other resin include the same as those exemplified in the “first embodiment”.
  • the other resin is contained in the amorphous thermoplastic resin film according to the second embodiment, its content is 40 mass% or less, preferably 30 mass% or less, more preferably 20 mass% or less, and further preferably Is 15% by mass or less.
  • the resin contained in the amorphous thermoplastic resin film according to the second embodiment has a glass transition temperature (Tg) of substantially 170° C. or higher and 230° C. or lower and is amorphous containing a sulfonyl group in the main chain. Only a thermoplastic resin (for example, an amorphous heat having a glass transition temperature (Tg) in the resin contained in the amorphous thermoplastic resin film of 170° C. to 230° C. and containing a sulfonyl group in the main chain) The proportion of the plastic resin is 99% by mass or more).
  • the silica is not particularly limited as long as the average particle diameter is in the range of 0.1 to 1.5 ⁇ m, and known silica can be used, and commercially available products can also be used. As the silica, synthetic amorphous silica is preferable because it can easily obtain particles having a preferable particle size.
  • the shape of silica is not particularly limited, and the same shapes as those exemplified in the "first embodiment" are exemplified.
  • the calcium carbonate is not particularly limited as long as it has an average particle size of 0.1 ⁇ m or more and 1.5 ⁇ m or less, and known ones can be used, and commercially available products can also be used.
  • As the calcium carbonate light calcium carbonate is preferable because it is easy to obtain one having a preferable particle size.
  • the amorphous thermoplastic resin film according to the second embodiment is selected from the group consisting of silica and calcium carbonate from the viewpoint of increasing the dielectric breakdown strength under high temperature and increasing the slit processing suitability while reducing the thickness.
  • the average particle size of at least one kind of particles is preferably 0.2 to 1.5 ⁇ m, more preferably 0.3 to 1.2 ⁇ m, and further preferably 0.5 to 1.0 ⁇ m.
  • the average particle size of at least one kind of particles selected from the group consisting of silica and calcium carbonate is a value measured by the method described in “First embodiment”.
  • the ratio is not particularly limited as long as it is in the range of 0.1 to 1.5% by mass, and the preferable range is the same as the range exemplified in the "first embodiment".
  • the thickness of the amorphous thermoplastic resin film according to the second embodiment may be 9.5 ⁇ m or less, and the preferable thickness is the same as that illustrated in the “first embodiment”. ..
  • the relationship among the thickness of the dielectric film, the volume of the capacitor, and the capacitance is as described in detail in the “first embodiment”.
  • the thickness of the amorphous thermoplastic resin film is a value measured by the method described in detail in the "first embodiment".
  • the dielectric breakdown strength of at 125 ° C. environment amorphous thermoplastic resin film according to the second embodiment from the viewpoint of dielectric breakdown strength at high temperatures, preferably 300 V DC / [mu] m or more, more preferably 320 V DC / ⁇ m or more, further 350V DC / ⁇ m or more, especially 400V DC / ⁇ m or more.
  • 300 V DC / [mu] m or more preferably 300 V DC / [mu] m or more, more preferably 320 V DC / ⁇ m or more, further 350V DC / ⁇ m or more, especially 400V DC / ⁇ m or more.
  • 600 VDC / ⁇ m can be mentioned.
  • the dielectric breakdown strength in a 125° C. environment is a value measured by the above-described measuring method described in “First Embodiment”.
  • the dielectric breakdown strength of the amorphous thermoplastic resin film according to the second embodiment in a 140° C. environment is preferably 300 V DC / ⁇ m or more, more preferably from the viewpoint of the dielectric breakdown strength at high temperature. 320 V DC / [mu] m or more, and a more further 350V DC / ⁇ m.
  • the dielectric breakdown strength in a 140° C. environment is calculated and calculated in the same manner as the dielectric breakdown strength in a 125° C. environment, except that the measurement environment is set in a forced circulation oven at a set temperature of 140° C.
  • the amorphous thermoplastic breakdown strength at the 23 ° C. environment resin film according to the second embodiment preferably 300 V DC / [mu] m or more, more preferably 320 V DC / [mu] m or more, further 350 V DC / [mu] m
  • the upper limit of the dielectric breakdown strength of the amorphous thermoplastic resin film according to the second embodiment in a 23° C. environment is not limited, but for example, 650 VDC / ⁇ m can be mentioned.
  • the dielectric breakdown strength in a 23° C. environment is calculated by performing the same measurement as in 125° C., not in a forced circulation oven at a set temperature of 125° C., but in an environment of 23° C. and a relative humidity of 50%.
  • the amorphous thermoplastic resin film according to the second embodiment may be an unstretched film or a stretched film. From the viewpoint of further enhancing the slit processing suitability of the amorphous thermoplastic resin film according to the second embodiment and further improving the continuous film-forming property, an unstretched film is preferable. On the other hand, a stretched film is preferable from the viewpoint of increasing the dielectric strength at high temperature and reducing the thickness.
  • the amorphous thermoplastic resin film is a stretched film, it may be a uniaxially stretched film or a biaxially stretched film.
  • the amorphous thermoplastic resin film according to the second embodiment may be a single layer or a multilayer.
  • a single layer is preferable because the film thickness can be easily reduced.
  • a multi-layer structure is preferable because the effect is easily obtained with a small addition amount and the dielectric breakdown strength is also increased by adding silica and/or calcium carbonate only to the surface layer.
  • the amorphous thermoplastic resin film according to the second embodiment is a multi-layer, it may have a structure in which two or more layers of the same or different amorphous thermoplastic resin films are laminated.
  • the amorphous thermoplastic resin film according to the second embodiment may be in a state of being laminated on a metal foil such as an aluminum foil or a base material formed of another resin film or the like, Preferably, it is not formed on a base material, and is manufactured as a single unit of the amorphous thermoplastic resin film according to the second embodiment (preferably, after film formation, the film is independently wound on a winding core to obtain a winding body. ), and is preferably used for the production of a metallized film for capacitors and capacitors described later.
  • the amorphous thermoplastic resin film according to the second embodiment may contain an additive.
  • the description of the additive is the same as in the “first embodiment”.
  • the amorphous thermoplastic resin film of the second embodiment has a thin thickness of 9.5 ⁇ m or less and has a high dielectric breakdown strength at high temperatures, so it is used in a high temperature environment, is small, and has a high capacity (for example, the capacitor of 5 ⁇ F or more, preferably 10 ⁇ F or more, more preferably 20 ⁇ F or more) can be very suitably used.
  • the amorphous thermoplastic resin film of the second embodiment has a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower, and an amorphous thermoplastic resin containing a sulfonyl group in the main chain, and an average particle diameter. Having a thickness of 9.5 ⁇ m and a resin composition containing 0.1 to 1.5% by mass of at least one kind of particles selected from the group consisting of silica and calcium carbonate of 0.1 ⁇ m to 1.5 ⁇ m. It can be manufactured by molding into a film.
  • Tg glass transition temperature
  • amorphous thermoplastic resin having a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower and containing a sulfonyl group in the main chain, and particles having an average particle diameter of 0.1 ⁇ m or more and 1.5 ⁇ m or less, Each is as described above.
  • the method of molding the resin composition into a film having a thickness of 9.5 ⁇ m is not particularly limited and is the same method as in the “first embodiment”.
  • the composition of the resin composition can also be adjusted by mixing a plurality of resin compositions (resin mixing). For example, by mixing an amorphous thermoplastic resin containing at least one kind of particles selected from the group consisting of silica and calcium carbonate with an amorphous thermoplastic resin not containing the particles, The content ratio of the particles in the composition can be adjusted to 0.1 to 1.5% by mass, based on 100% by mass of the resin composition.
  • the method for mixing a plurality of resin compositions is not particularly limited, and is the same method as the “first embodiment”.
  • the extrusion temperature when molding the resin composition into a film in the molten state and the surface temperature of the cooling roll are appropriately adjusted according to the glass transition temperature (Tg) of the amorphous thermoplastic resin.
  • Tg glass transition temperature
  • the extrusion temperature is, for example, 230 to 400°C, preferably 310 to 380°C, more preferably 320 to 370°C.
  • the surface temperature of the cooling roll is, for example, 80 to 230° C., preferably 120 to 190° C., and more preferably 130 to 180° C.
  • the contact method when the molten resin composition is solidified by contact with a cooling roll is the same as in the “first embodiment”.
  • the amorphous thermoplastic resin film of the second embodiment is used as a stretched film
  • the above resin composition is formed into a film and then the film is further stretched.
  • the stretching ratio is the same as that in the "first embodiment".
  • the stretched film may be a uniaxially stretched film or a biaxially stretched film.
  • the temperature during stretching is appropriately adjusted according to the glass transition temperature (Tg) of the amorphous thermoplastic resin.
  • the stretching temperature is, for example, about 100 to 270°C. From the viewpoint of improving the thickness accuracy after stretching, the range of Tg+2° C. to Tg+70° C. or Tg ⁇ 90° C. to Tg ⁇ 2° C. is preferable, and the range of Tg+5° C. to Tg+65° C. or Tg ⁇ 80° C. The range of Tg-5°C is more preferable. That is, the preferred temperature during stretching may be a temperature range higher than the glass transition temperature or a temperature range lower than the glass transition temperature.
  • the stretched film may be annealed for the purpose of relaxation of residual stress and adjustment of thermal shrinkage, and the temperature is preferably in the range of Tg-1°C to Tg-60°C, and Tg-3°C. The range of to Tg-50°C is more preferable.
  • a relaxation treatment for lowering the draw ratio may be performed.
  • the metallized film for capacitors according to the present embodiment has a metal film on one side or both sides of the amorphous thermoplastic resin film according to the first or second embodiment, respectively.
  • the amorphous thermoplastic resin film of the second embodiment can be provided with a metal film as an electrode on one side or both sides for processing as a capacitor, respectively.
  • a metal film as an electrode on one side or both sides for processing as a capacitor, respectively.
  • Such an electrode is not particularly limited as long as the capacitor intended by the present invention can be obtained, and an electrode usually used for manufacturing a capacitor can be used.
  • capacitors are required to be smaller and lighter, it is necessary to directly form (metallize) electrodes (metallize) on one side or both sides of the resin film of the first or second embodiment to form a metallized film. Is preferred.
  • vacuum plating such as vacuum deposition or sputtering, coating/drying of a metal-containing paste, or pressure bonding of a metal foil or metal powder.
  • a metal layer is provided by such a method.
  • the vacuum deposition method and the sputtering method are preferable, and the vacuum deposition method is preferable from the viewpoints of productivity and economical efficiency, in order to meet the further demands for reducing the size and weight of the capacitor.
  • the vacuum vapor deposition method a crucible method, a wire method, etc. can be generally exemplified, but the method is not particularly limited as long as the capacitor intended by the present invention can be obtained, and an optimum method is appropriately selected. be able to.
  • the metal used for the electrode for example, a simple metal such as zinc, lead, silver, chromium, aluminum, copper, and nickel, a mixture of a plurality of kinds thereof, and an alloy thereof can be used.
  • Zinc and aluminum are preferable in consideration of economical efficiency and capacitor performance.
  • the film resistance of the metal vapor deposition film is preferably about 1 to 100 ⁇ / ⁇ from the viewpoint of electric characteristics of the capacitor. Even within this range, a higher value is desirable from the viewpoint of self-healing (self-healing) characteristics, and the film resistance is more preferably 5 ⁇ / ⁇ or more, further preferably 10 ⁇ / ⁇ or more. Further, from the viewpoint of safety as a capacitor, the film resistance is more preferably 50 ⁇ / ⁇ or less, further preferably 30 ⁇ / ⁇ or less.
  • the film resistance can be measured during metal vapor deposition by, for example, a four-terminal method known to those skilled in the art.
  • the film resistance of the metal vapor deposition film can be adjusted, for example, by adjusting the output of the evaporation source to adjust the evaporation amount.
  • a metal vapor deposition film is formed on one surface of the amorphous thermoplastic resin film of the first embodiment or the second embodiment, a certain width is provided from one end of the film so that a capacitor is formed when the film is wound.
  • An insulating margin is formed without vapor deposition.
  • the heavy edge film resistance is usually 1 to 8 ⁇ / ⁇ . And is preferably about 1 to 5 ⁇ / ⁇ .
  • the thickness of the heavy edge metal film is not particularly limited, but is preferably 1 to 200 nm.
  • the vapor deposition pattern (margin pattern) of the metal vapor deposition film to be formed there is no particular limitation on the vapor deposition pattern (margin pattern) of the metal vapor deposition film to be formed, but from the viewpoint of improving the characteristics such as the security of the capacitor, a pattern including a so-called special margin such as a fishnet pattern or a T margin pattern is used. It is preferable to form a fuse.
  • the metal vapor deposition film is formed on at least one surface of the amorphous thermoplastic resin film of the first or second embodiment with the vapor deposition pattern including the special margin, the security of the obtained capacitor is improved, and the capacitor is destroyed or short-circuited. It is also effective and preferable in terms of suppressing
  • known methods such as a tape method in which masking is performed with a tape during vapor deposition and an oil method in which masking is performed by applying oil can be used without any limitation.
  • a protective layer may be provided on the metallized film of the present embodiment for the purpose of physical protection of the metal vapor deposition film, prevention of moisture absorption, prevention of oxidation, and the like.
  • silicone oil, fluorine oil or the like can be preferably used.
  • the metallized film of this embodiment can be processed into a capacitor of this embodiment described later.
  • Capacitor The capacitor according to the present embodiment includes the amorphous thermoplastic resin film of the first embodiment or the second embodiment, and/or the metallized film.
  • the film of the present invention is used as a dielectric film for a capacitor, for example, (i) a method of using the metallized film described above, (ii) the film of the present invention without electrodes, and other conductive films.
  • a capacitor can be formed by a method of laminating bodies (for example, metal foil, the film of the present invention having one or both sides metallized, paper having one or both sides metallized, and other plastic films).
  • Film winding process is performed in the process of making capacitors.
  • the metal film in the metallized film of the present embodiment and the amorphous thermoplastic resin film of the first embodiment or the second embodiment are alternately laminated, and further, the insulating margin portion has the opposite side.
  • a pair of two metallized films of this embodiment are superposed and wound so that At this time, it is preferable to stack a pair of two metallized films of this embodiment with a shift of 1 to 2 mm.
  • the non-metallized amorphous thermoplastic resin film may be laminated with another conductor such as a metal foil or another metallized film.
  • the winding machine used is not particularly limited, and for example, an automatic winding machine 3KAW-N2 type manufactured by Minato Manufacturing Co., Ltd. can be used.
  • the film winding process is not limited to the above method, and other methods, for example, a film of the present embodiment that is vapor-deposited on both sides (in that case, the heavy edge is arranged on the opposite ends on the front surface and the back surface)
  • the film of the present embodiment which has not been vapor-deposited (the width of the film is narrower by 2 to 3 mm than the film of the present embodiment which is vapor-deposited on both sides) may be alternately laminated and wound.
  • the applied pressure has an optimum value that varies depending on the thickness of the amorphous thermoplastic resin film of the first embodiment or the second embodiment, but is, for example, 2 to 20 kg/cm. Is 2 .
  • a capacitor is produced by spraying metal on both end faces of the wound material and providing metallikon electrodes.
  • ⁇ Capacitor is further subjected to prescribed heat treatment. That is, in the present embodiment, a step of subjecting the capacitor to heat treatment under atmospheric or vacuum conditions at a temperature of 80 to 190° C. for 1 hour or more within a range not exceeding the Tg of the amorphous thermoplastic resin (hereinafter, Sometimes referred to as "heat aging").
  • the temperature of the heat treatment is preferably in the range of 10°C to 100°C lower than the Tg of the amorphous thermoplastic resin, more preferably in the range of 15°C to 80°C lower.
  • the heat aging effect can be obtained by performing the heat treatment at the above temperature. Specifically, the voids between the films constituting the metallized film-based capacitor of the present embodiment are reduced, and corona discharge is suppressed. Alternatively, the strain (internal stress) of the amorphous thermoplastic resin film is eliminated. As a result, the withstand voltage is considered to be improved.
  • the heat treatment temperature is lower than the predetermined temperature, the above effect due to thermal aging cannot be sufficiently obtained.
  • the amorphous thermoplastic resin film may undergo thermal decomposition or oxidative deterioration.
  • the heat treatment method for the capacitor may be appropriately selected from known methods including, for example, a method using a constant temperature bath and a method using high frequency induction heating in a vacuum atmosphere. Specifically, it is preferable to employ a method using a constant temperature bath.
  • the heat treatment time is preferably 1 hour or longer, more preferably 10 hours or longer, from the viewpoint of obtaining mechanical and thermal stability, but it prevents molding defects such as heat wrinkles and molding. In this respect, it is more preferable that the time is 72 hours or less.
  • Lead wires are usually joined to the metallikon electrodes of heat aged capacitors.
  • the joining method is not particularly limited, but for example, welding, ultrasonic welding, or soldering can be used. Further, in order to impart weather resistance and prevent especially humidity deterioration, it is preferable to encapsulate the capacitor in a case and pot it with an epoxy resin.
  • the amorphous thermoplastic resin film of the first embodiment or the second embodiment has a thin thickness of 9.5 ⁇ m or less, respectively, and has a high dielectric breakdown strength at high temperature, and therefore, in the high temperature environment. It can be used very suitably for a small capacitor, and further for a high capacity (for example, 5 ⁇ F or more, preferably 10 ⁇ F or more, more preferably 20 ⁇ F or more) capacitor. That is, the capacitor of the present embodiment, which uses the amorphous thermoplastic resin film of the first embodiment or the second embodiment, is preferably used in a high temperature environment, and has a small size and a high capacity.
  • the capacitor of the present embodiment can be used as a high-voltage capacitor, a switching capacitor for various switching power supplies, a filter capacitor for converters and inverters, a smoothing capacitor, and the like used in electronic devices, electric devices, and the like.
  • the capacitor of the present embodiment can be suitably used as a capacitor for an inverter power supply device that controls a drive motor of electric vehicles, hybrid vehicles, and the like, for which demand is increasing in recent years.
  • Glass transition temperature It was calculated by the following procedure using an input compensation type DSC and a DiamondDSC manufactured by Perkin-Elmer. 5 mg of each resin was weighed, packed in an aluminum sample holder, and set in a DSC apparatus. Under nitrogen flow, the temperature was raised from 30°C to 300°C at a rate of 20°C/min, held at 300°C for 5 minutes, cooled to 30°C at 20°C/min, and held at 30°C for 5 minutes. Then, the glass transition temperature was determined from the DSC curve when the temperature was raised again to 300° C. at 20° C./min. The midpoint glass transition temperature defined in JIS K7121:1987, 9.3(1) was taken as the glass transition temperature.
  • Dielectric breakdown strength (dielectric breakdown strength in 125°C environment)
  • a measuring device according to JIS C2151:2006, 17.2.2 (flat plate electrode method) is prepared.
  • conductive rubber (E12S10 manufactured by Seiwa Electric Co., Ltd.) is used as an electrode instead of the elastic body described in 17.2.2 of JIS C2151:2006, and the aluminum foil is not wound.
  • the measurement environment is set in a forced circulation type oven at a set temperature of 125° C., and the electrodes and film are used after the temperature is controlled in the oven for 30 minutes.
  • the voltage increase starts from 0 V and is set to a speed of 100 V/sec, and the time when the current value exceeds 5 mA is the time of breakdown.
  • the dielectric breakdown voltage was measured 20 times, the dielectric breakdown voltage value V DC was divided by the film thickness ( ⁇ m), and the average value of 16 points excluding the upper 2 points and the lower 2 points in the calculation results of the 20 times was calculated. Is the dielectric breakdown strength (V DC / ⁇ m).
  • Continuous film-forming property A continuous film-forming property was evaluated according to the following criteria based on the film-forming length capable of forming a film under the conditions described in each Example and forming a film without breakage.
  • ⁇ The film-forming length is 1000 m or more and the continuous film-forming property is very high.
  • the film-forming length is 500 m or more and less than 1000 m and the continuous film-forming property is high.
  • ⁇ The film-forming length is 250 m or more and less than 500 m.
  • the continuous film forming property is slightly low.
  • the film forming length is less than 250 m, and the continuous film forming property is low.
  • Roll Diameter A cylindrical winding core (diameter of circular cross section is 12 mm) is laminated with two films obtained in each of Examples and Comparative Examples and wound for a length of 30 m (two layers are laminated). Therefore, a total length of 60 m was used) to form a roll. The diameter (the longest diameter if not a perfect circle) of both sides of the roll was measured, and the average of the measured values was defined as the roll diameter. The smaller the roll diameter, the smaller the capacitance of a film capacitor when using a dielectric film having a similar relative dielectric constant (that is, the capacitance per unit volume is smaller). A (large) capacitor can be manufactured, which is preferable. Roll diameter less than 30 mm: Suitable for small capacitors. Roll diameter 30 mm or more: unsuitable for small capacitors.
  • the average particle size is 10 particles from one side (20 points in total on both sides) on the surface of the film using an ultra-high resolution field emission scanning electron microscope ((FE-SEM) Hitachi High Technologies S-5200). At a magnification of 20,000, an accelerating voltage of 8 kV, a beam current of 10 ⁇ A, and the detector is observed using a backscattered electron detector to obtain an observed image. From the observed image, the longest diameter is measured using image analysis software, and the average particle diameter obtained by averaging the measured values is obtained. In this method, particles at a position deeper than about 3 ⁇ m from the film surface will be blurred and cannot be measured. However, since particles at such deep positions do not function as a lubricant, they are not targets for measurement in the first and second embodiments.
  • Example 1A [Preparation of masterbatch]
  • PSU polysulfone
  • Example 2A In the preparation of the masterbatch of Example 1A, instead of silica spherical fine particles having an average particle diameter of 1.0 ⁇ m, silica spherical fine particles having an average particle diameter of 0.5 ⁇ m [manufactured by Nippon Shokubai Co., Ltd.: trade name Seahoster (registered trademark) KE] An amorphous thermoplastic resin film was obtained in the same manner as in Example 1A except that -P50] was used.
  • Example 3A In the production of the unstretched film of Example 1A, the same procedure as in Example 1A was carried out except that the content of the spherical silica fine particles in the dry blend of polysulfone and the masterbatch was 0.25% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 4A In the production of the unstretched film of Example 1A, the same procedure as in Example 1A was performed except that the content of the spherical silica fine particles in the dry blended product of polysulfone and the masterbatch was 0.12% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 5A In the production of the unstretched film of Example 1A, the same procedure as in Example 1A was carried out except that the content of the spherical silica fine particles in the dry blend of polysulfone and the masterbatch was 1.40% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 6A In the production of the masterbatch of Example 1A, instead of the silica spherical fine particles having an average particle diameter of 1.0 ⁇ m, silica spherical fine particles having an average particle diameter of 0.1 ⁇ m (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name Shin-Etsu Silicone (registered trademark) ):OSG-100] was used to obtain an amorphous thermoplastic resin film in the same manner as in Example 1A.
  • Silica spherical fine particles having an average particle diameter of 1.0 ⁇ m silica spherical fine particles having an average particle diameter of 0.1 ⁇ m (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name Shin-Etsu Silicone (registered trademark) ):OSG-100] was used to obtain an amorphous thermoplastic resin film in the same manner as in Example 1A.
  • Example 7A In the preparation of the masterbatch of Example 1A, instead of the silica spherical fine particles having an average particle diameter of 1.0 ⁇ m, calcium carbonate fine particles having an average particle diameter of 0.2 ⁇ m [manufactured by Shiraishi Industry Co., Ltd.: BRILLIANT (registered trademark): 1500] An amorphous thermoplastic resin film was obtained in the same manner as in Example 1A except that was used.
  • Example 8A In the production of the masterbatch and the unstretched film of Example 1A, polysulfone was a low-viscosity polysulfone instead of [BASF Japan Ltd.: trade name Ultrazone (registered trademark) S6010], respectively. Co., Ltd.: trade name Ultrazone (registered trademark) S2010, glass transition temperature 187° C.] was used, and in the production of an unstretched film, the extrusion amount and the take-up speed were adjusted so that the thickness was 9.5 ⁇ m. An amorphous thermoplastic resin film was obtained in the same manner as in Example 1A except for the above.
  • MVR Melt volume of low-viscosity polysulfone (manufactured by BASF Japan Ltd.: trade name Ultrazone (registered trademark) S2010) was measured under the conditions of ISO 1133, temperature 360° C. and load 10 kg. -Flow rate) was 90 cm 3 /10 min.
  • Example 9A [Production of uniaxially stretched film] An unstretched film produced in the same manner as in Example 1A was introduced into a longitudinal stretching machine, stretched 1.5 times in the MD direction, and a uniaxially stretched film having a thickness of 5.3 ⁇ m was wound to obtain an amorphous thermoplastic resin film. It was The film temperature during stretching was 200°C.
  • Example 10A Preparation of biaxially stretched film
  • the uniaxially stretched film produced in the same manner as in Example 9A was introduced into a tenter, and stretched 1.5 times in the TD direction in an oven at a temperature of 245° C. to wind a biaxially stretched film having a thickness of 3.6 ⁇ m, A crystalline thermoplastic resin film was obtained.
  • Example 11A In the preparation of the masterbatch and the unstretched film of Example 1A, polycarbonate (PC) was used instead of polysulfone (trade name: Panlite (registered trademark) K-1300Y, manufactured by Teijin Limited, glass transition temperature 150° C.). Was used, and in the preparation of the masterbatch and the unstretched film, melting was performed at a resin temperature of 300° C., and the surface temperature of the mirror-finished metal roll was maintained at 120° C., in the same manner as in Example 1A, An amorphous thermoplastic resin film was obtained.
  • PC polycarbonate
  • Psulfone trade name: Panlite (registered trademark) K-1300Y, manufactured by Teijin Limited, glass transition temperature 150° C.
  • Example 12A [Production of uniaxially stretched film] A uniaxially stretched film having a thickness of 5.3 ⁇ m was wound up to obtain an amorphous thermoplastic resin film in the same manner as in Example 9A except that the film temperature during stretching was 120° C.
  • Example 13A Preparation of biaxially stretched film
  • the uniaxially stretched film produced in the same manner as in Example 12A was introduced into a tenter, and stretched 1.5 times in the TD direction in an oven at a temperature of 245° C. to wind a biaxially stretched film having a thickness of 3.6 ⁇ m, A crystalline thermoplastic resin film was obtained.
  • Example 14A In the production of the masterbatch and the unstretched film of Example 13A, polysulfone having a medium viscosity was used instead of [BASF Japan KK: Ultrazone (registered trademark) S6010] as polysulfone [BASF Japan ( Co., Ltd.: trade name Ultrazone (registered trademark) S3010, glass transition temperature 187° C.] was used, and an amorphous thermoplastic resin film was obtained in the same manner as in Example 13A.
  • MVR Melt volume
  • Example 1A In the preparation of the masterbatch of Example 1A, the spherical silica fine particles were not blended (that is, the content of the spherical silica fine particles in the amorphous thermoplastic resin film was 0.00% by mass), and In the same manner, an amorphous thermoplastic resin film was obtained.
  • Example 2A In the production of the unstretched film of Example 1A, the same procedure as in Example 1A was performed except that the content of the spherical silica fine particles in the dry blend of polysulfone and the masterbatch was adjusted to 2.00% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 3A In the production of the unstretched film of Example 1A, the same procedure as in Example 1A was carried out except that the content of the spherical silica fine particles in the dry blended product of polysulfone and the masterbatch was 3.00% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 4A In the production of the unstretched film of Example 1A, an amorphous thermoplastic resin film was obtained in the same manner as in Example 1A except that the extrusion rate and the take-up speed were adjusted so that the thickness was 15.0 ⁇ m. ..
  • Example 5A In the preparation of the masterbatch of Example 1A, instead of silica spherical fine particles having an average particle diameter of 1.0 ⁇ m, calcined kaolin fine particles having an average particle diameter of 0.5 ⁇ m (manufactured by Imerys Minerals Japan Co., Ltd.: trade name Alphatex ( Amorphous thermoplastic resin film was obtained in the same manner as in Example 1A, except that (registered trademark)] was used.
  • Example 6A In the preparation of the masterbatch of Example 1, talc fine particles having an average particle diameter of 0.6 ⁇ m (manufactured by Nippon Talc Co., Ltd.: trade name Nano Ace (registered trademark) D- 600] was used, and an amorphous thermoplastic resin film was obtained in the same manner as in Example 1A.
  • Example 7A In the preparation of the masterbatch of Example 1A, instead of the silica spherical fine particles having an average particle diameter of 1.0 ⁇ m, silica spherical fine particles having an average particle diameter of 2.0 ⁇ m (manufactured by Mizusawa Chemical Industry Co., Ltd.: trade name Shilton (registered trademark)) JC-20] was used and an amorphous thermoplastic resin film was obtained in the same manner as in Example 1A.
  • silica spherical fine particles having an average particle diameter of 2.0 ⁇ m manufactured by Mizusawa Chemical Industry Co., Ltd.: trade name Shilton (registered trademark)
  • Example 8A In the production of the masterbatch and the unstretched film of Example 1A, polyethylene naphthalate (PEN) [manufactured by Teijin Limited: trade name Teonex (registered trademark) TN8065S, glass transition temperature 120° C.] was used instead of polysulfone.
  • PEN polyethylene naphthalate
  • Teijin Limited trade name Teonex (registered trademark) TN8065S, glass transition temperature 120° C.
  • An unstretched film was obtained in the same manner as in Example 1A, except that the resin was melted at a resin temperature of 300° C. in the production of the masterbatch and the unstretched film. The obtained unstretched film was introduced into a longitudinal stretching machine and stretched 3.0 times in the MD direction to obtain a uniaxially stretched film. The film temperature during stretching was 130°C.
  • the uniaxially stretched film was introduced into a tenter, and stretched 3.2 times in the TD direction in an oven at a temperature of 130° C., and then heat-treated in an oven at a temperature of 220° C. to give a biaxially stretched film having a thickness of 3.6 ⁇ m.
  • a crystalline thermoplastic resin film was taken up to obtain a crystalline thermoplastic resin film.
  • Example 9A In the production of the masterbatch and unstretched film of Example 1A, instead of polysulfone, cyclic olefin copolymer (COC) [manufactured by Polyplastics Co., Ltd.: trade name TOPAS (registered trademark) 8007F-04, glass transition temperature] 78° C.] was used, in the production of the masterbatch and the unstretched film, melting was performed at a resin temperature of 200° C., and the surface temperature of the mirror-finished metal roll was maintained at 60° C., as in Example 1A. Then, an amorphous thermoplastic resin film was obtained.
  • COC cyclic olefin copolymer
  • the films of Examples 1A to 14A and Comparative Examples 1A to 11A are each composed of a single layer.
  • the resin (also referred to as a base resin) forming the films of Examples 1A to 10A, 12A to 14A and Comparative Examples 1A to 7A is PSU, and the resin forming the film of Example 11A is PC.
  • the resin forming the film of 8A is PEN
  • the resin forming the film of Comparative Example 9A is COC
  • the resin forming the film of Comparative Example 10A is PPS
  • the resin forming the film of Comparative Example 11A is It is PI.
  • the amorphous thermoplastic resin films of Examples 1A to 14A are at least selected from the group consisting of an amorphous thermoplastic resin having a glass transition temperature (Tg) of 130° C. or higher and lower than 200° C., and silica and calcium carbonate. It contains one kind of particles, the average particle size of the particles is 0.1 ⁇ m or more and 1.5 ⁇ m or less, the content rate of the particles is 0.1% by mass or more and 1.5% by mass or less, and the thickness is It is 9.5 ⁇ m or less.
  • Tg glass transition temperature
  • the amorphous thermoplastic resin films of Examples 1A to 14A have a high dielectric breakdown strength at high temperature, have a small roll diameter at the time of winding due to their thin thickness, and are excellent in slit processing suitability. ..
  • Example 1B Preparation of masterbatch
  • PSU polysulfone
  • Example 2B In the preparation of the masterbatch of Example 1B, instead of the silica spherical fine particles having an average particle diameter of 1.0 ⁇ m, the silica spherical fine particles having an average particle diameter of 0.5 ⁇ m [manufactured by Nippon Shokubai Co., Ltd.: trade name Seahoster (registered trademark) KE] An amorphous thermoplastic resin film was obtained in the same manner as in Example 1B except that -P50] was used.
  • Example 3B In the production of the unstretched film of Example 1B, the same procedure as in Example 1B was carried out except that the content of the spherical silica fine particles in the dry blend of polysulfone and the masterbatch was 0.25% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 4B In preparation of the unstretched film of Example 1B, the same procedure as in Example 1B was carried out except that the content of the spherical silica fine particles in the dry blended product of polysulfone and the masterbatch was set to 0.12% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 5B In the preparation of the unstretched film of Example 1B, the same procedure as in Example 1B was carried out except that the content of the spherical silica fine particles in the dry blend of polysulfone and the masterbatch was 1.40% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 6B [Production of uniaxially stretched film]
  • the unstretched film produced in the same manner as in Example 1B was introduced into a longitudinal stretching machine and stretched 1.5 times in the MD direction. Then, the film was held by a clip and heat-treated in a 220° C. oven for 10 seconds. A uniaxially stretched film having a thickness of 5.3 ⁇ m was wound up. The film temperature during stretching was 200°C.
  • Example 7B Preparation of biaxially stretched film
  • the uniaxially stretched film produced in the same manner as in Example 6B was introduced into a tenter, and stretched 1.5 times in the TD direction in an oven at a temperature of 245°C. Then, while holding the film with a clip, heat treatment was performed in a 220° C. oven for 10 seconds. A biaxially stretched film having a thickness of 3.6 ⁇ m was wound up.
  • Example 8B In the production of the masterbatch and the unstretched film of Example 1B, polyether sulfone (PES) [manufactured by BASF Japan Ltd.: trade name Ultrazone (registered trademark) E2010, glass transition temperature 225°C instead of polysulfone, respectively.
  • PES polyether sulfone
  • silica spherical fine particles having an average particle diameter of 1.0 ⁇ m silica spherical fine particles having an average particle diameter of 0.1 ⁇ m [manufactured by Shin-Etsu Chemical Co., Ltd.: trade name Shin-Etsu Silicone ( (Registered trademark): OSG-100], and melted at a resin temperature of 360° C. in the production of the masterbatch and the unstretched film, and the surface temperature of the mirror-finished metal roll was 170° C. in the production of the unstretched film An amorphous thermoplastic resin film was obtained in the same manner as in Example 1B except that it was held.
  • Example 9B In the production of the masterbatch and the unstretched film of Example 1B, polyphenylsulfone (PPSU) [manufactured by BASF Japan Ltd.: trade name Ultrazone (registered trademark) P3010, glass transition temperature 220° C., instead of polysulfone, respectively.
  • PPSU polyphenylsulfone
  • silica spherical fine particles having an average particle diameter of 1.0 ⁇ m silica spherical fine particles having an average particle diameter of 0.1 ⁇ m [manufactured by Shin-Etsu Chemical Co., Ltd.: trade name Shin-Etsu Silicone ( (Registered trademark): OSG-100], melted at a resin temperature of 360° C. in the production of the masterbatch and the unstretched film, and made the surface temperature of the mirror-finished metal roll 160° C. in the production of the unstretched film. An amorphous thermoplastic resin film was obtained in the same manner as in Example 1B except that it was held.
  • Example 10B [Production of uniaxially stretched film] A uniaxially stretched film having a thickness of 5.3 ⁇ m was wound up in the same manner as in Example 6B except that the film temperature at the time of stretching was 120° C. to obtain an amorphous thermoplastic resin film.
  • Example 11B Preparation of biaxially stretched film
  • the uniaxially stretched film produced in the same manner as in Example 10B was introduced into a tenter, and stretched 1.5 times in the TD direction in an oven at a temperature of 245°C. Then, while holding the film with a clip, heat treatment was performed in a 220° C. oven for 10 seconds. A biaxially stretched film having a thickness of 3.6 ⁇ m was wound up.
  • Example 12B In the production of the masterbatch and the unstretched film of Example 11B, instead of [BASF Japan Co., Ltd.: trade name Ultrazone (registered trademark) S6010] as polysulfone, polysulfone having a medium viscosity [BASF Japan ( Amorphous thermoplastic resin film was obtained in the same manner as in Example 11B, except that the product name was Ultrazone (registered trademark) S3010, glass transition temperature 187° C.].
  • MVR Melt volume
  • Example 1B In the preparation of the masterbatch of Example 1B, the spherical silica fine particles were not blended (that is, the content of the spherical silica fine particles of the amorphous thermoplastic resin film was 0.00% by mass), and In the same manner, an amorphous thermoplastic resin film was obtained.
  • Example 2B In the production of the unstretched film of Example 1B, the same procedure as in Example 1B was carried out except that the content of the spherical silica fine particles in the dry blend of polysulfone and the masterbatch was adjusted to 2.00% by mass. , An amorphous thermoplastic resin film was obtained.
  • Example 3B In the production of the unstretched film of Example 8B, the content of the spherical silica fine particles in the dry blend of polyether sulfone and the masterbatch was set to 30.00% by mass, and in the production of the unstretched film An amorphous thermoplastic resin film was obtained in the same manner as in Example 8B except that the extrusion rate and the take-up speed were adjusted so that the thickness was 5.0 ⁇ m.
  • Example 4B In the production of the unstretched film of Example 9B, the content of the spherical silica fine particles in the dry blended product of polyphenyl sulfone and the masterbatch was 1.00% by mass, and in the production of the unstretched film.
  • An amorphous thermoplastic resin film was obtained in the same manner as in Example 9B except that the extrusion rate and the take-up speed were adjusted so that the thickness was 55.0 ⁇ m.
  • Example 5B In the preparation of the masterbatch of Example 9B, instead of the silica spherical fine particles having an average particle diameter of 0.1 ⁇ m, the silica spherical fine particles having an average particle diameter of 2.0 ⁇ m [manufactured by Mizusawa Chemical Industry Co., Ltd.: trade name Shilton (registered trademark)] JC-20] was used, and an amorphous thermoplastic resin film was obtained in the same manner as in Example 9B.
  • Shilton registered trademark
  • Example 6B In the preparation of the masterbatch and unstretched film of Example 1B, polyphenylene sulfide (PPS) [manufactured by DIC Corporation: trade name PPSMA520, glass transition temperature 88° C.] was used instead of polysulfone, respectively. And, in the production of the unstretched film, an unstretched film was obtained in the same manner as in Example 1B except that the resin was melted at a temperature of 310°C. The obtained unstretched film was introduced into a longitudinal stretching machine and stretched 3.0 times in the MD direction to obtain a uniaxially stretched film. The film temperature during stretching was 100°C.
  • PPS polyphenylene sulfide
  • the uniaxially stretched film was introduced into a tenter, and stretched 3.2 times in the TD direction in an oven at a temperature of 100° C., and then heat treated in an oven at a temperature of 220° C. to give a biaxially stretched film having a thickness of 3.6 ⁇ m.
  • a crystalline thermoplastic resin film was taken up to obtain a crystalline thermoplastic resin film.
  • the films of Examples 1B to 8B and Comparative Examples 1B to 8B are each composed of a single layer. Further, the resin (also referred to as a base resin) forming the films of Examples 1B to 7B and Comparative Examples 1B to 2B was PSU, and the resin forming the films of Examples 8B and Comparative Example 3B was PES.
  • the resin constituting the films of 9B and Comparative Examples 4B to 5B is PPSU
  • the resin constituting the film of Comparative Example 6B is PPS
  • the resin constituting the film of Comparative Example 7B is PI
  • the resin of Comparative Example 8B The resin forming the film is PEI.
  • the amorphous thermoplastic resin films of Examples 1B to 12B have a glass transition temperature (Tg) of 170° C. or higher and 230° C. or lower, an amorphous thermoplastic resin containing a sulfonyl group in the main chain, silica and calcium carbonate. Containing at least one kind of particles selected from the group consisting of, the average particle size of the particles is 0.1 ⁇ m or more and 1.5 ⁇ m or less, and the content rate of the particles is 0.1% by mass or more and 1.5% or more. The content is not more than mass% and the thickness is not more than 9.5 ⁇ m. It can be seen that the amorphous thermoplastic resin films of Examples 1B to 12B have a high dielectric breakdown strength at high temperature, have a small roll diameter during winding because of their thin thickness, and are excellent in slit processing suitability. ..

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Abstract

L'invention concerne un film de résine thermoplastique amorphe ayant une résistance à la rupture diélectrique élevée à une température élevée, ayant une faible épaisseur, et ayant une excellente aptitude au traitement de fente. Le présent film de résine thermoplastique amorphe a une épaisseur de 9,5 µm ou moins, et comprend une résine thermoplastique amorphe ayant un point de transition vitreuse (Tg) d'au moins 130 °C, mais inférieur à 200 °C, et un type de particule choisi parmi le groupe constitué par la silice et le carbonate de calcium. Le diamètre de particule moyen des particules est de 0,1 à 1,5 µm, le rapport de teneur des particules est de 0,1 à 1,5 % en masse.
PCT/JP2019/051446 2018-12-27 2019-12-27 Film de résine thermoplastique amorphe, film métallisé de condensateur, rouleau de film et condensateur WO2020138426A1 (fr)

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JPS5714849A (en) * 1980-06-30 1982-01-26 Fuji Photo Film Co Ltd Transfer film for electrophotographic copier
JPS6068505A (ja) 1983-09-26 1985-04-19 三井東圧化学株式会社 プラスチツクフイルムコンデンサ
JPS63270760A (ja) * 1987-04-30 1988-11-08 Idemitsu Petrochem Co Ltd 液晶性フイルム
JPH06258522A (ja) * 1993-03-03 1994-09-16 Fuji Photo Film Co Ltd 複屈折フイルム、複屈折フイルムの製造方法及び液晶表示装置
WO2001014462A1 (fr) * 1999-08-25 2001-03-01 Toray Industries, Inc. Film a orientation biaxiale et support d'enregistrement magnetique
JP2001261959A (ja) * 2000-03-21 2001-09-26 Toray Ind Inc 二軸配向フィルム、金属化フィルムおよびフィルムコンデンサー
JP2001323146A (ja) * 2000-03-09 2001-11-20 Toray Ind Inc ２軸配向ポリエステルフィルム
JP2013055270A (ja) * 2011-09-06 2013-03-21 Toray Ind Inc 積層シートおよびそれを用いた太陽電池
JP2019065119A (ja) * 2017-09-29 2019-04-25 帝人フィルムソリューション株式会社 配向フィルム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5714849A (en) * 1980-06-30 1982-01-26 Fuji Photo Film Co Ltd Transfer film for electrophotographic copier
JPS6068505A (ja) 1983-09-26 1985-04-19 三井東圧化学株式会社 プラスチツクフイルムコンデンサ
JPS63270760A (ja) * 1987-04-30 1988-11-08 Idemitsu Petrochem Co Ltd 液晶性フイルム
JPH06258522A (ja) * 1993-03-03 1994-09-16 Fuji Photo Film Co Ltd 複屈折フイルム、複屈折フイルムの製造方法及び液晶表示装置
WO2001014462A1 (fr) * 1999-08-25 2001-03-01 Toray Industries, Inc. Film a orientation biaxiale et support d'enregistrement magnetique
JP2001323146A (ja) * 2000-03-09 2001-11-20 Toray Ind Inc ２軸配向ポリエステルフィルム
JP2001261959A (ja) * 2000-03-21 2001-09-26 Toray Ind Inc 二軸配向フィルム、金属化フィルムおよびフィルムコンデンサー
JP2013055270A (ja) * 2011-09-06 2013-03-21 Toray Ind Inc 積層シートおよびそれを用いた太陽電池
JP2019065119A (ja) * 2017-09-29 2019-04-25 帝人フィルムソリューション株式会社 配向フィルム

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