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WO2018186424A1 - Film de polypropylène, film de polypropylène avec couche métallique intégrée, et condensateur à film - Google Patents

Film de polypropylène, film de polypropylène avec couche métallique intégrée, et condensateur à film Download PDF

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Publication number
WO2018186424A1
WO2018186424A1 PCT/JP2018/014342 JP2018014342W WO2018186424A1 WO 2018186424 A1 WO2018186424 A1 WO 2018186424A1 JP 2018014342 W JP2018014342 W JP 2018014342W WO 2018186424 A1 WO2018186424 A1 WO 2018186424A1
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WO
WIPO (PCT)
Prior art keywords
polypropylene film
polypropylene
resin
less
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/014342
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English (en)
Japanese (ja)
Inventor
立治 石田
剛史 冨永
中田　将裕
忠和 石渡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oji Holdings Corp
Original Assignee
Oji Holdings Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oji Holdings Corp filed Critical Oji Holdings Corp
Priority to EP18781449.6A priority Critical patent/EP3608353B1/fr
Priority to KR1020227040040A priority patent/KR102494812B1/ko
Priority to CN201880020055.5A priority patent/CN110461914A/zh
Priority to KR1020197026700A priority patent/KR102468929B1/ko
Priority claimed from JP2018071964A external-priority patent/JP6973249B2/ja
Publication of WO2018186424A1 publication Critical patent/WO2018186424A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/32—Wound capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present disclosure relates to a polypropylene film, a metal layer integrated polypropylene film, and a film capacitor.
  • Polypropylene film can be used for capacitor derivatives.
  • it can be used as a capacitor derivative in an inverter constituting a power control unit of a hybrid vehicle / electric vehicle.
  • Capacitors that use polypropylene film as a capacitor derivative are small, light, and high in capacity from the viewpoint of the above-mentioned usage environment (for example, the environment in which the temperature rises in the engine room and the self-heating of the capacitor). It is desirable that the dielectric breakdown strength (dielectric breakdown strength) when a DC voltage is applied at a high temperature of about 120 ° C. and the dielectric breakdown strength when an AC voltage is applied are excellent. That is, it is desirable that the polypropylene film is as thin as less than 20 ⁇ m and has excellent dielectric breakdown strength.
  • the polypropylene film described in Patent Document 1 uses a low stereoregular resin, and when such a film is used as a capacitor element, excellent dielectric breakdown strength is obtained at a high temperature (for example, 120 ° C.). There is a problem that there may not be.
  • the present disclosure has been made in view of the above-described problems, and an object of the present disclosure is to provide a polypropylene film having excellent dielectric strength at high temperatures, and having good voltage resistance as a result. That is. More specifically, the purpose is to have a dielectric breakdown strength measured by applying a DC voltage with a DC power source in an environment of 120 ° C. (hereinafter referred to as a dielectric breakdown strength at a DC voltage at 120 ° C., or V DC 120 ° C.). The dielectric breakdown strength measured by applying an AC voltage with an AC power source in an environment of 120 ° C. (hereinafter also referred to as the AC breakdown voltage at 120 ° C. or VAC 120 ° C.). Is to provide an excellent polypropylene film.
  • Another object of the present disclosure is to provide a metal layer integrated polypropylene film having a polypropylene film and a film capacitor having a metal layer integrated polypropylene film.
  • the inventors of the present invention have intensively studied a polypropylene film.
  • the present inventors have found that the smaller the crystallite size of the polypropylene film, the higher the dielectric breakdown strength at a DC voltage at 120 ° C. and the dielectric breakdown strength at an AC voltage at 120 ° C.
  • the higher the melting enthalpy of the polypropylene film the higher the dielectric breakdown strength at a DC voltage at 120 ° C. and the higher the dielectric breakdown strength at an AC voltage at 120 ° C. were found.
  • the present inventors have also intensively studied the relationship between the crystallite size of the polypropylene film and the melting enthalpy.
  • ⁇ y is the yield stress (yield strength) of the polycrystal
  • a is the yield stress (or frictional stress against dislocation motion) in the case of a single crystal
  • ⁇ O is a constant expressed as ⁇ O
  • b is the grain boundary Is a constant indicating the resistance to slippage and also expressed as k
  • d is an average crystal grain size.
  • the main cause of deformation of metallic materials is the slip deformation caused by the movement of lattice defects called dislocations existing in the crystal. It is said to produce great resistance when passing through.
  • the present inventors consider the dielectric breakdown of the polypropylene film when a DC voltage or an AC voltage is applied to the polypropylene film capacitor as deformation of the metal material, and the difference in the yield stress value represented by ⁇ y ⁇ a is determined as the polypropylene film.
  • the relationship between b and d was examined as an index of the dielectric breakdown strength at 120 ° C.
  • the polypropylene film of the present disclosure satisfies Formula I and has a thickness of 1.0 ⁇ m to 19 ⁇ m. 31.5 ⁇ enthalpy of melting / ⁇ crystallite size ⁇ 33.0 (I)
  • the unit of melting enthalpy is J / g and the unit of crystallite size is nm.
  • the crystallite size is determined by using the Scherrer equation from the half width of the reflection peak of the ⁇ crystal (040) plane measured by the wide-angle X-ray diffraction method.
  • the metal layer-integrated polypropylene film of the present disclosure has the polypropylene film of the present disclosure and a metal layer laminated on one side or both sides of the polypropylene film.
  • the film capacitor of the present disclosure has the metal layer integrated polypropylene film of the present disclosure.
  • the polypropylene film of the present disclosure is excellent in electrical insulation resistance at 120 ° C. More specifically, according to the present disclosure, an excellent breakdown strength at a DC voltage at a high temperature can be obtained, and an excellent breakdown strength at an AC voltage at a high temperature can be obtained. As a result, a polypropylene film having good voltage resistance at high temperatures can be provided. Moreover, the polypropylene film of the present disclosure is thin. Therefore, the polypropylene film of the present disclosure is suitable for use as a film capacitor.
  • the polypropylene film of the embodiment in the present disclosure satisfies Formula I and has a thickness of 1.0 ⁇ m to 19 ⁇ m. 31.5 ⁇ enthalpy of melting / ⁇ crystallite size ⁇ 33.0 (I)
  • the unit of melting enthalpy is J / g and the unit of crystallite size is nm.
  • the crystallite size is determined by using the Scherrer equation from the half width of the reflection peak of the ⁇ crystal (040) plane measured by the wide-angle X-ray diffraction method.
  • the melting enthalpy / ⁇ crystallite size is also referred to as H m / ⁇ S c hereinafter.
  • H m is the melting enthalpy (unit: J / g) of the polypropylene film is
  • S c is the crystallite size of the polypropylene film (unit: nm).
  • the polypropylene film of the embodiment in the present disclosure has a melting enthalpy / ⁇ crystallite size of 31.5 or more and 33.0 or less, the polypropylene film has excellent dielectric breakdown strength at a DC voltage at 120 ° C., and Excellent dielectric breakdown strength at AC voltage at 120 ° C. (in other words, excellent electrical insulation resistance at 120 ° C.).
  • the reason for the excellent electrical insulation resistance at 120 ° C. is that the quality (amount) and quantity of crystallites having an effective inhibitory effect on the propagation of leakage current in the polypropylene film, and the crystallite size appropriately As a result of the control, it is presumed that the structural destruction caused by Joule heat generation is suppressed.
  • the dielectric breakdown strength at a DC voltage at 120 ° C. and / or the dielectric breakdown strength at an AC voltage at 120 ° C. is inferior.
  • the reason for this is that the crystallite size in the polypropylene film is not miniaturized, the crystallite is small, and / or the crystallite is not strong, so that leakage current is likely to propagate, resulting in Joule heat generation. It is presumed that the structural breakdown that occurs in When the enthalpy of fusion / ⁇ crystallite size is significantly larger than 33.0, the dielectric breakdown strength at a DC voltage at 120 ° C.
  • the thickness of the polypropylene film according to the embodiment of the present disclosure is 1.0 ⁇ m to 19 ⁇ m, when the polypropylene film is used as a film capacitor, the capacitor can be reduced in size, weight, and capacity. Therefore, it is suitably used for a film capacitor application required for an electric vehicle / hybrid vehicle application used in a high temperature environment. If it exceeds 19 ⁇ m, it is difficult to reduce the size and to increase the capacity. If it is significantly less than 1.0 ⁇ m, the variation in capacitance as a film capacitor tends to increase.
  • the present inventors have found that the electrical insulation resistance at 120 ° C. tends to become stronger as the melting point becomes higher, and has found this discovery and a theoretical formula for obtaining the equilibrium melting point T m ° of the polymer crystal. And formula II. That is, even when the polypropylene film satisfies the formula II, it has been found that the dielectric breakdown strength at a DC voltage at 120 ° C. and the dielectric breakdown strength at an AC voltage at 120 ° C. are excellent. T m ° is the melting point when the thickness of the lamella is infinite.
  • T m T m ° ⁇ (T m ° ⁇ k) / l
  • T m a melting point (more specifically, by performing DSC measurement on a polypropylene film).
  • k a constant
  • l the thickness of the lamella.
  • the polypropylene film of the embodiment in the present disclosure preferably satisfies Formula II. 176 ⁇ melting point + 50 / crystallite size (II)
  • the unit of melting point is ° C.
  • the unit of crystallite size is nm.
  • the melting point + 50 / crystallite size is 176 or more, the crystallite size is difficult to propagate current and / or has high lamellar integrity, and therefore has excellent electrical insulation resistance at 120 ° C. Presumed to be.
  • the polypropylene film of the embodiment in the present disclosure is preferably for a capacitor.
  • the polypropylene film of the embodiment in the present disclosure contains the first polypropylene resin as a main component, the number average molecular weight Mn of the first polypropylene resin is 30000 to 54000, and the weight average molecular weight Mw of the first polypropylene resin is It is preferably 250,000 or more and less than 350,000, and the ratio of Mw to Mn in the first polypropylene resin is preferably 5.0 or more and 10.0 or less.
  • the first polypropylene resin has a heptane insoluble content of 97.0% or more and 98.5% or less, and the first polypropylene resin has a melt flow rate of 4.0 g / 10 min or more and 10.0 g / 10 min or less. Preferably there is.
  • the metal layer-integrated polypropylene film according to the embodiment of the present disclosure has a polypropylene film and a metal layer laminated on one side or both sides of the polypropylene film.
  • the film capacitor according to the embodiment of the present disclosure includes a wound metal layer-integrated polypropylene film.
  • the film capacitor may have a configuration in which a plurality of metal layer integrated polypropylene films are laminated.
  • polypropylene may be abbreviated as PP
  • polypropylene resin may be abbreviated as PP resin
  • the expressions “containing” and “including” include the concepts of “containing”, “including”, “consisting essentially of”, and “consisting only of”.
  • the expression “capacitor” includes the concept of “capacitor”, “capacitor element”, and “film capacitor”. Since the polypropylene film of this embodiment is not a microporous film, it does not have a large number of pores.
  • the polypropylene film of the embodiment in the present disclosure may be composed of two or more layers, but is preferably composed of a single layer.
  • the longitudinal direction of the polypropylene film may be referred to as the longitudinal direction.
  • the vertical direction is the same direction as Machine Direction (hereinafter referred to as “MD direction”).
  • MD direction may be referred to as the flow direction.
  • the present invention is not limited to the form in which the vertical direction indicates the same direction as the MD direction.
  • the horizontal direction of a polypropylene film may be called a width direction.
  • the horizontal direction is the same direction as Transverse Direction (hereinafter referred to as “TD direction”).
  • TD direction Transverse Direction
  • the present invention is not limited to the form in which the horizontal direction indicates the same direction as the TD direction.
  • Embodiment 1 From here, the present disclosure will be described in the first embodiment.
  • Both sides of the polypropylene film in Embodiment 1 can be defined by a first surface and a second surface.
  • the first surface can be a rough surface. When the first surface is a rough surface, wrinkles are unlikely to occur due to element winding in capacitor fabrication.
  • the second surface can also be a rough surface.
  • the center line average roughness Ra of the first surface of the polypropylene film is, for example, 0.03 ⁇ m or more and 0.08 ⁇ m or less.
  • the maximum height Rz of the first surface in the polypropylene film is, for example, not less than 0.3 ⁇ m and not more than 0.8 ⁇ m. Both Ra and Rz are obtained in accordance with the method described in JIS-B0601: 2001, using a three-dimensional surface roughness meter, SURFCOM 1400D-3DF-12, manufactured by Tokyo Seimitsu Co., Ltd.
  • Ra of the 2nd surface in a polypropylene film is 0.03 micrometer or more and 0.08 micrometer or less, for example.
  • Rz of the 2nd surface in a polypropylene film is 0.3 micrometer or more and 0.8 micrometers or less, for example.
  • the thickness of the polypropylene film in Embodiment 1 is 1.0 ⁇ m to 19 ⁇ m. Since the thickness is 1.0 ⁇ m to 19 ⁇ m, when the polypropylene film is used for a film capacitor, the capacitor can be reduced in size, weight, and capacity. Therefore, it is suitably used for a film capacitor application required for an electric vehicle / hybrid vehicle application used in a high temperature environment.
  • the thickness of the polypropylene film is 19 ⁇ m or less, preferably 18 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 6.0 ⁇ m or less, still more preferably 4.0 ⁇ m or less, and particularly preferably 3.0 ⁇ m or less. .
  • the thickness of the polypropylene film in Embodiment 1 is 1.0 ⁇ m or more, preferably 1.5 ⁇ m or more, more preferably 1.8 ⁇ m or more, and further preferably 2.0 ⁇ m or more. If it is significantly less than 1.0 ⁇ m, the variation in capacitance as a film capacitor tends to increase.
  • the thickness is measured according to JIS-C2330 using a micrometer (JIS-B7502).
  • the polypropylene film of Embodiment 1 satisfies Formula I. 31.5 ⁇ enthalpy of melting / ⁇ crystallite size ⁇ 33.0 (I)
  • the unit of melting enthalpy is J / g and the unit of crystallite size is nm.
  • the polypropylene film of Embodiment 1 is excellent in dielectric breakdown strength at a DC voltage at 120 ° C. and excellent in dielectric breakdown strength at an AC voltage at 120 ° C. by satisfying the formula I. Therefore, the polypropylene film of Embodiment 1 can produce a film capacitor having excellent dielectric breakdown strength at a DC voltage at 120 ° C. and excellent dielectric breakdown strength at an AC voltage at 120 ° C.
  • the polypropylene film of Embodiment 1 is not only excellent in dielectric breakdown strength at a DC voltage at 120 ° C. and also excellent in dielectric breakdown strength at an AC voltage at 120 ° C., but also at 100 ° C. in an AC voltage. Excellent strength.
  • Formula I is 31.5 ⁇ H m ⁇ (S c ) 0.5 ⁇ 33.0 (I ′) (H m is the melting enthalpy (unit of polypropylene films: a J / g), S c is the crystallite size (in the polypropylene film:. Nm) is) and can also be represented.
  • the melting enthalpy / ⁇ crystallite size is also referred to as H m / ⁇ S c hereinafter.
  • H m is the melting enthalpy (unit: J / g) of the polypropylene film is
  • S c is the crystallite size of the polypropylene film (unit: nm).
  • the value of H m / ⁇ S c is preferably 31.6 or greater, more preferably 31.7 or greater, and even more preferably 31.8 or greater.
  • the value of H m / ⁇ S c is preferably 32.8 or less, more preferably 32.5 or less, further preferably 32.3 or less, and particularly preferably 32.1 or less.
  • the melting enthalpy (H m ) of the polypropylene film is, for example, 105 J / g or more, preferably 108 J / g or more. 105 J / g or more is preferable because the crystallite is strong.
  • the upper limit of the melting enthalpy is, for example, 125 J / g, preferably 122 J / g.
  • the melting enthalpy is not only influenced by the raw material, but also the conditions during stretching (for example, the temperature during longitudinal stretching, the stretching speed during longitudinal stretching, the stretching ratio during longitudinal stretching, and the transverse stretching.
  • the melting enthalpy tends to increase as the temperature during longitudinal stretching and lateral stretching increases.
  • the degree of the influence of the stretching speed on the melting enthalpy varies depending on the stretching temperature, the melting enthalpy tends to increase as the speed during the longitudinal stretching and the lateral stretching decreases. There exists a tendency for melting enthalpy to become high, so that the ratio of longitudinal stretch and lateral stretch is low.
  • Relaxation rate (%) ⁇ 1 ⁇ (lateral stretching ratio after relaxation / maximum lateral stretching ratio) ⁇ ⁇ 100
  • the melting enthalpy of the polypropylene film is a value obtained by a first run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
  • the crystallite size (S c ) of the polypropylene film is preferably 14.5 nm or less, more preferably 14.2 nm or less, still more preferably 13.0 nm or less, and particularly preferably 12 from the viewpoint of dielectric breakdown strength. .5 nm or less.
  • the crystallite size is 14.5 nm or less, the polypropylene film includes a crystallite interface having a large area, and the leakage current tends to hardly propagate.
  • the crystallite size is preferably 10.0 nm or more, more preferably 10.5 nm or more, further preferably 11.0 nm or more, and particularly preferably 11.5 nm or more.
  • the thickness is preferably 10.0 nm or more is that it is desirable to ensure voltage resistance without passing through the crystallite.
  • the crystallite size is not only influenced by the blending amount and molecular weight of the polypropylene resin, but also the conditions during stretching (for example, the temperature during longitudinal stretching, the speed during longitudinal stretching, It is influenced by the preheating temperature before stretching, the temperature during transverse stretching, and the speed during transverse stretching.
  • the crystallite size tends to decrease as the temperature during longitudinal stretching decreases.
  • the crystallite size tends to increase as the speed during longitudinal stretching decreases.
  • the preheating temperature before transverse stretching is higher, the crystallite size tends to increase.
  • the crystallite size tends to decrease as the temperature during transverse stretching decreases.
  • the crystallite size tends to increase as the speed during transverse stretching decreases.
  • the crystallite size is calculated by using the Scherrer equation from the half width of the reflection peak of the ⁇ crystal (040) plane measured by the wide angle X-ray diffraction method (XRD method).
  • the Scherrer equation is expressed as equation (1) below.
  • D is the crystallite size (nm)
  • K is a constant (shape factor)
  • ⁇ the X-ray wavelength used (nm)
  • ⁇ is the half width
  • ⁇ is the diffraction Bragg angle.
  • 0.94 is used as K.
  • 0.15418 nm is used as ⁇ .
  • the polypropylene film of Embodiment 1 preferably satisfies Formula II. 176 ⁇ melting point + 50 / crystallite size (II)
  • the unit of melting point is ° C.
  • the unit of crystallite size is nm.
  • Formula II is 176 ⁇ T m + 50 ⁇ S c (II ′) (T m is the melting point (unit of polypropylene films: A ° C.), S c is the crystallite size (in the polypropylene film:. Nm) is) and can also be represented.
  • T m is the melting point (unit of polypropylene films: A ° C.)
  • S c is the crystallite size (in the polypropylene film:. Nm) is) and can also be represented.
  • Examples of the lower limit of the melting point + 50 / crystallite size include 176.05 and 176.1.
  • Examples of the upper limit of the melting point + 50 / crystallite size include 180, 179, 178.4.
  • the melting point of the polypropylene film is, for example, 170 ° C. or higher, preferably 171 ° C. or higher. When the melting point is 170 ° C. or higher, the lamellar integrity is high and current tends to hardly propagate.
  • the upper limit of the melting point is, for example, 176 ° C., preferably 175 ° C.
  • the melting point is not only affected by the raw materials, but also the conditions during stretching (for example, the temperature during longitudinal stretching, the speed during longitudinal stretching, the ratio of longitudinal stretching, preheating before lateral stretching. Temperature, temperature during transverse stretching, speed during transverse stretching, magnification of transverse stretching) and relaxation conditions after stretching.
  • the lamella is less likely to be refined and the melting point tends to increase.
  • the degree of influence of the stretching speed on the melting point varies depending on the stretching temperature, the melting point tends to increase as the speed during longitudinal stretching and lateral stretching decreases.
  • the melting point tends to be higher as the ratio of longitudinal stretching and lateral stretching is lower.
  • the melting point of the polypropylene film is a value obtained by a first run of differential scanning calorimetry, and specifically, a value measured by the method described in the examples.
  • the dielectric breakdown strength (V DC 120 ° C. ) of the polypropylene film in Embodiment 1 at a direct current voltage at 120 ° C. is preferably 510 V / ⁇ m or more, more preferably 515 V / ⁇ m or more, and further preferably 530 V / ⁇ m or more. It is.
  • the upper limit of the dielectric breakdown strength at a DC voltage at 120 ° C. is preferably as high as possible, but is, for example, 600 V / ⁇ m, 580 V / ⁇ m, or the like.
  • the dielectric breakdown strength ( VAC 120 ° C. ) of the polypropylene film in Embodiment 1 at an AC voltage of 120 ° C. is preferably 230 V / ⁇ m or more, more preferably 232 V / ⁇ m or more, and further preferably 233 V / ⁇ m or more.
  • the upper limit of the dielectric breakdown strength at an AC voltage at 120 ° C. is preferably as high as possible, but is, for example, 300 V / ⁇ m, 270 V / ⁇ m, or the like.
  • the total value ( VAC 120 ° C. + V DC 120 ° C. ) of the VAC 120 ° C. and the V DC 120 ° C. of the polypropylene film in Embodiment 1 is preferably 750 V / ⁇ m or more, more preferably 760 V / ⁇ m or more, and further preferably. Is 770 V / ⁇ m or more.
  • the upper limit of the total value of the VAC 120 ° C. and the V DC 120 ° C. is preferably as high as possible, but is, for example, 1000 V / ⁇ m, 900 V / ⁇ m, 850 V / ⁇ m, or the like.
  • the polypropylene film of Embodiment 1 Since the polypropylene film of Embodiment 1 has a melting enthalpy / ⁇ crystallite size of 31.5 or more and 33.0 or less, it is excellent not only in electrical insulation resistance at 120 ° C. but also in dielectric breakdown strength at AC 100 ° C. . Therefore, the polypropylene film of Embodiment 1 can increase the capacitor rated voltage for rectifying the current including the AC component, and can save energy.
  • the alternating current 100 ° C. dielectric breakdown strength ( VAC 100 ° C. ) of the polypropylene film in the first embodiment is preferably 243 V / ⁇ m or more.
  • the upper limit of the AC 100 ° C. dielectric breakdown strength is preferably as high as possible, but is, for example, 300 V / ⁇ m.
  • the polypropylene film of Embodiment 1 includes a polypropylene resin.
  • the content of the polypropylene resin is preferably 90% by weight or more, more preferably 95% by weight or more with respect to the entire polypropylene film (when the entire polypropylene film is 100% by weight).
  • the upper limit of the content of the polypropylene resin is, for example, 100% by weight or 98% by weight with respect to the entire polypropylene film.
  • the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, still more preferably 30 ppm or less, based on the polypropylene resin.
  • the lower limit of the total ash content is, for example, 2 ppm, 5 ppm, and the like.
  • the polypropylene resin may contain one kind of polypropylene resin alone or may contain two or more kinds of polypropylene resins.
  • the polypropylene resin with the highest content is positioned as the main component in this specification, and is referred to as “main component polypropylene resin” in this specification.
  • the polypropylene resin contained in the said polypropylene film is 1 type, the said polypropylene resin is also positioned as a main component in this specification, and is called "the main component polypropylene resin" in this specification.
  • the polypropylene film of Embodiment 1 can contain, for example, only the following first polypropylene resin, or can contain the following second polypropylene resin together with the first polypropylene resin.
  • the polypropylene resin can include a first polypropylene resin.
  • the content of the first polypropylene resin is preferably 50% by weight or more, more preferably 55% by weight or more, and further preferably 60% by weight with respect to 100% by weight of the polypropylene resin. That's it.
  • the upper limit of the content of the first polypropylene resin for example, 100% by weight or less, 99% by weight or less, 98% by weight or less, 95% by weight or less can be mentioned with respect to 100% by weight of the polypropylene resin.
  • it is 90 weight% or less with respect to weight%, More preferably, it is 85 weight% or less, More preferably, it is 80 weight% or less.
  • the polypropylene film of Embodiment 1 can contain the first polypropylene resin as a main component.
  • the first polypropylene resin include isotactic polypropylene.
  • the weight average molecular weight Mw of the first polypropylene resin is preferably 250,000 or more and less than 350,000, more preferably 250,000 or more and 345,000 or less, and further preferably 270,000 or more and 340000 or less.
  • Mw is 250,000 or more and less than 350,000, it is easy to obtain a polypropylene film having a value of H m / ⁇ S c of 31.5 or more and 33.0 or less.
  • Mw is 250,000 or more and less than 350,000, it is easy to control the thickness of the cast original fabric sheet, and thickness unevenness hardly occurs.
  • the number average molecular weight Mn of the first polypropylene resin is preferably 30000 or more and 54000 or less, more preferably 33000 or more and 52000 or less, and further preferably 33000 or more and 50000 or less.
  • the number average molecular weight Mn of the first polypropylene resin is 30000 or more and 54000 or less, it is easy to obtain a polypropylene film having a value of the H m / ⁇ S c of 31.5 or more and 33.0 or less.
  • the z-average molecular weight Mz of the first polypropylene resin is preferably 700,000 or more and 1550,000 or less, more preferably 750000 or more and 1500,000 or less.
  • the z average molecular weight Mz of the first polypropylene resin is 700,000 or more and 1550,000 or less, it is easy to obtain a polypropylene film having a value of the H m / ⁇ S c of 31.5 or more and 33.0 or less.
  • the molecular weight distribution (Mw / Mn) of the first polypropylene resin is preferably 5.0 or more, more preferably 5.5 or more.
  • the Mw / Mn of the first polypropylene resin is preferably 10.0 or less, and more preferably 9.5 or less.
  • the molecular weight distribution Mw / Mn is a ratio of the weight average molecular weight Mw to the number average molecular weight Mn.
  • the molecular weight distribution (Mz / Mn) of the first polypropylene resin is preferably 10 or more and 70 or less, more preferably 15 or more and 60 or less, and further preferably 15 or more and 50 or less.
  • the molecular weight distribution Mz / Mn is a ratio of the z average molecular weight Mz to the number average molecular weight Mn.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), z average molecular weight (Mz), and molecular weight distribution (Mw / Mn and Mz / Mn) of the polypropylene resin are gel permeation. It is the value measured using the chromatograph (GPC) apparatus. More specifically, it is a value measured using an HLC-8121 GPC-HT (trade name), a high-temperature GPC measuring machine with a built-in differential refractometer (RI) manufactured by Tosoh Corporation. As GPC columns, three TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation are connected and used.
  • GPC chromatograph
  • the column temperature is set to 140 ° C., and trichlorobenzene is allowed to flow as an eluent at a flow rate of 1.0 ml / 10 minutes to obtain measured values of Mw and Mn.
  • a calibration curve related to the molecular weight M is prepared using standard polystyrene manufactured by Tosoh Corporation, and the measured values are converted into polystyrene values to obtain Mw, Mn and Mz.
  • the melt flow rate (MFR) at 230 ° C. of the first polypropylene resin is preferably 10.0 g / 10 min or less, more preferably 7.0 g / 10 min or less, and even more preferably 6.0 g / 10 min or less. .
  • the melt flow rate at 230 ° C. is preferably 4.0 g / 10 min or more.
  • the melt flow rate at 230 ° C. is measured at 230 ° C. under a load of 2.16 kg in accordance with JIS K 7210-1999.
  • the unit g / 10 minutes of the melt flow rate is also referred to as dg / min.
  • the heptane-insoluble content of the first polypropylene resin is preferably 97.0% or more.
  • the heptane-insoluble content is preferably 98.5% or less.
  • the stereoregularity of the resin increases.
  • the heptane-insoluble content (HI) is 97.0% or more and 98.5% or less, the crystallinity of the polypropylene resin in the polypropylene film is moderately improved due to a reasonably high stereoregularity, and at a high temperature. Withstand voltage is improved. Furthermore, the rate of solidification (crystallization) at the time of forming the cast original fabric sheet becomes moderate, and it has appropriate stretchability.
  • the method for measuring heptane-insoluble matter (HI) is according to the method described in the examples.
  • the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 30 ppm or less, based on the first polypropylene resin.
  • the lower limit of the total ash content is, for example, 2 ppm, 5 ppm, and the like.
  • the polypropylene resin can further include a second polypropylene resin. It is preferable that the polypropylene film of this embodiment contains 2nd polypropylene resin in addition to 1st polypropylene resin, and it is still more preferable that resin which comprises a polypropylene film is 1st polypropylene resin and 2nd polypropylene resin.
  • the content of the second polypropylene resin is preferably 50% by weight or less, more preferably 49% by weight or less, and further 45% by weight or less with respect to 100% by weight of the polypropylene resin. 40% by weight or less is particularly preferable.
  • the content of the second polypropylene resin is, for example, 1% by weight or more, 2% by weight or more, 5% by weight or more with respect to 100% by weight of the polypropylene resin.
  • the amount is preferably 10% by weight or more, more preferably 15% by weight or more, and still more preferably 20% by weight or more with respect to 100% by weight of the polypropylene resin.
  • the second polypropylene resin is isotactic polypropylene.
  • the second polypropylene resin has at least Mw of 350,000 to 550,000, Mw / Mn of 3.0 to 11.0, and a melt flow rate at 230 ° C. of less than 4.0 g / 10 minutes. It is preferable.
  • the Mw of the second polypropylene resin is preferably 350,000 or more.
  • Mw in the second polypropylene resin is preferably 550,000 or less, more preferably 450,000 or less, and even more preferably 380,000 or less.
  • the Mn of the second polypropylene resin is preferably 40000 or more and 54000 or less, more preferably 42000 or more and 50000 or less, and further preferably 44000 or more and 48000 or less.
  • the Mz of the second polypropylene resin is preferably more than 150,000 and less than or equal to 2,000,000, more preferably not less than 1580000 and not more than 170,000.
  • the ratio of Mw to Mn is preferably 3.0 or more, more preferably 4.5 or more, further preferably 5.0 or more, more preferably 5.5 or more, Preferably it is 7.0 or more, Most preferably, it is 7.5 or more.
  • the upper limit of Mw / Mn in the second polypropylene resin is 11.0, 10.0, 9.0, 8.5, for example. It is possible to easily reduce the crystallite size by using the second polypropylene resin in which Mw / Mn and Mw satisfy the above ranges together with the first polypropylene resin.
  • the ratio of Mz to Mn (Mz / Mn) in the second polypropylene resin is preferably 30 or more and 40 or less, more preferably 33 or more and 36 or less.
  • the melt flow rate at 230 ° C. in the second polypropylene resin is preferably less than 4.0 g / 10 minutes, more preferably 3.9 g / 10 minutes or less, and even more preferably 3.8 g / 10 minutes or less. Further, the melt flow rate at 230 ° C. is preferably 1.0 g / 10 minutes or more, more preferably 1.5 g / 10 minutes or more, and further preferably 2.0 g / 10 minutes or more.
  • the heptane-insoluble content of the second polypropylene resin is preferably 97.5% or more, more preferably 98.0% or more, further preferably more than 98.5%, and particularly preferably 98.6% or more. Further, the heptane-insoluble content is preferably 99.5% or less, more preferably 99.0% or less.
  • the total ash content of the second polypropylene resin is preferably as small as possible because of electrical characteristics.
  • the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, and even more preferably 30 ppm or less, based on the second polypropylene resin.
  • the lower limit of the total ash content is, for example, 2 ppm, 5 ppm, and the like.
  • the total amount of the first polypropylene resin and the second polypropylene resin can be, for example, 90% by weight or more, or 95% by weight or more, and 100% by weight when the entire polypropylene resin is 100% by weight. It can also be.
  • the polypropylene film of Embodiment 1 may further contain a resin other than polypropylene resin.
  • resins include polyethylene, poly (1-butene), polyisobutene, poly (1-pentene), poly (1-methylpentene), ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-butene.
  • examples thereof include a copolymer, a styrene-butadiene random copolymer, and a styrene-butadiene-styrene copolymer block copolymer.
  • the polypropylene film of Embodiment 1 can further contain an additive.
  • the additive include an antioxidant, a chlorine absorbent, an ultraviolet absorbent, a lubricant, a plasticizer, a flame retardant, an antistatic agent, and a colorant.
  • the polypropylene film of Embodiment 1 may be a biaxially stretched film, a uniaxially stretched film, or an unstretched film, but is preferably a biaxially stretched film.
  • the polypropylene film of Embodiment 1 can be produced, for example, by a procedure of producing a cast original fabric sheet and biaxially stretching the cast original fabric sheet.
  • the cast original fabric sheet can be produced, for example, by a procedure in which a resin and, if necessary, an additive are supplied to an extruder, melt-extruded from a T die, and solidified.
  • the biaxial stretching of the cast original fabric sheet is preferably sequential biaxial stretching. In sequential biaxial stretching, for example, a cast raw sheet is guided between rolls having a difference in speed, stretched in the flow direction (hereinafter sometimes referred to as “longitudinal stretching”), cooled as necessary, and a tenter.
  • the film is stretched in the width direction (hereinafter, sometimes referred to as “lateral stretching”), relaxed, heat-set, and wound up.
  • This is subjected to an aging treatment in an atmosphere of about 20 ° C. to 45 ° C. as necessary, and cut into a desired product width.
  • a corona discharge treatment is performed on one side or both sides of the polypropylene film thus obtained as necessary.
  • Extrusion for forming the cast raw sheet is preferably performed at an extrusion temperature of 220 ° C. to 270 ° C.
  • the casting temperature that is, the surface temperature of the metal drum is preferably 40 ° C. to 100 ° C., more preferably 45 ° C. to 95 ° C.
  • the H m / ⁇ S c is less than 31.5, and as a result, the electrical insulation resistance at 120 ° C. may be inferior.
  • the melting enthalpy / ⁇ crystallite size that is, the value of H m / ⁇ S c tends to increase. Further, the lower the casting temperature, the smaller the value of H m / ⁇ S c tends to be.
  • the thickness of the cast original sheet can be, for example, 0.05 mm or more, and can also be 0.1 mm or more. Examples of the upper limit of the thickness of the cast original fabric sheet include 2 mm and 1 mm.
  • preheating temperature before longitudinal stretching may be referred to as preheating temperature before longitudinal stretching.
  • the temperature during longitudinal stretching is preferably 125 ° C. to 165 ° C.
  • the H m / ⁇ S c is less than 31.5, and as a result, the electrical insulation resistance at 120 ° C. may be inferior.
  • the higher the longitudinal stretching temperature the smaller the value of H m / ⁇ S c tends to be.
  • the lower the longitudinal stretching temperature the larger the value of H m / ⁇ S c tends to be.
  • the stretching speed during longitudinal stretching is preferably 400% / second or more, and more preferably 500% / second to 60000% / second.
  • the draw ratio of the longitudinal stretch is preferably from 3.5 times to 5.5 times, more preferably from 4.0 times to 5.4 times, and even more preferably from 4.0 times to 5.0 times. If it exceeds 5.5 times significantly, the value of H m / ⁇ S c exceeds 33, and the electrical insulation resistance at 120 ° C. may be inferior. As the longitudinal stretch ratio is increased, the value of H m / ⁇ S c tends to increase. Further, the value of H m / ⁇ S c tends to decrease as the longitudinal stretching ratio decreases.
  • the film after longitudinal stretching is preferably preheated to 155 ° C. to 172 ° C. before transverse stretching. If the temperature is significantly higher than 172 ° C., the value of H m / ⁇ S c is less than 31.5, and as a result, the electrical insulation resistance at 120 ° C. may be inferior.
  • Preheating temperature performed before the transverse stretching higher the (hereinafter sometimes referred to as "lateral stretching before preheating temperature”.), The value of the H m / ⁇ S c tends to decrease. As the preheating temperature before transverse stretching is lowered, the value of H m / ⁇ S c tends to increase.
  • the preheated film before transverse stretching is preferably transversely stretched at 150 ° C. to 165 ° C.
  • the temperature during the transverse stretching (hereinafter sometimes referred to as “lateral stretching temperature”) is preferably 155 ° C. to 165 ° C., more preferably 160 ° C. to 165 ° C. However, if it significantly exceeds 165 ° C., the value of H m / ⁇ S c is less than 31.5, and the electrical insulation resistance at 120 ° C. may be inferior.
  • the higher the transverse stretching temperature the smaller the value of the H m / ⁇ S c tends to be. As the transverse stretching temperature is lowered, the value of H m / ⁇ S c tends to increase.
  • the stretching speed during transverse stretching is preferably 280% / second to 350% / second.
  • the value of H m / ⁇ S c is less than 31.5, and the electrical insulation resistance at 120 ° C. may be inferior.
  • the value of H m / ⁇ S c may exceed 33 or the film may be broken during transverse stretching.
  • the lower the lateral stretching speed the smaller the H m / ⁇ S c tends to be. Also, the higher the transverse stretching speed, the H m / ⁇ S c tends to be large.
  • the draw ratio of the transverse stretching is preferably 9 to 11 times, and more preferably 9.2 to 10.7 times. If it is significantly lower than 9 times, the value of H m / ⁇ S c is less than 31.5, and as a result, the electrical insulation resistance at 120 ° C. may be inferior. On the other hand, if it is significantly higher than 11 times, the value of H m / ⁇ S c may exceed 33.0, or the film may break during transverse stretching.
  • the film after transverse stretching is preferably relaxed at 157 ° C to 170 ° C.
  • the temperature at the time of relaxation may be referred to as the relaxation temperature.
  • the time for relaxation that is, the time for heat fixation is preferably within 10 seconds, and more preferably from 1 second to 9 seconds.
  • the relaxation rate [ ⁇ 1- (lateral stretching ratio after relaxation / maximum lateral stretching ratio) ⁇ ⁇ 100] is preferably relaxed by 1% to 15%.
  • the melting enthalpy and the crystallite size are affected by the conditions during stretching. For example, when the transverse stretching speed is changed, both the melting enthalpy and the crystallite size are changed. Therefore, it is difficult to change the other after fixing either the melting enthalpy or the crystallite size.
  • H m / ⁇ S c considering both the melting enthalpy and the crystallite size satisfies a certain range, that is, 31.5 or more and 33.0 or less. That is, the melting enthalpy and the crystallite size are not controlled individually, but H m / ⁇ S c taking into account both is controlled.
  • the polypropylene film of Embodiment 1 obtained in this way can be used as a capacitor dielectric.
  • it can be used for a derivative of a capacitor constituting an inverter in a hybrid vehicle / electric vehicle.
  • a metal layer may be laminated on one or both sides of the polypropylene film in Embodiment 1 to form a metal layer integrated polypropylene film.
  • the metal layer functions as an electrode.
  • a simple metal such as zinc, lead, silver, chromium, aluminum, copper, nickel, a mixture of plural kinds thereof, an alloy thereof or the like can be used. In view of economy and capacitor performance, zinc and aluminum are preferable.
  • Examples of a method for laminating a metal layer on one or both surfaces of a polypropylene film include a vacuum deposition method and a sputtering method. From the viewpoint of productivity and economy, the vacuum deposition method is preferable. Examples of the vacuum deposition method generally include a crucible method and a wire method, but are not particularly limited, and an optimum one can be selected as appropriate.
  • the margin pattern when the metal layer is laminated by vapor deposition is not particularly limited, but a pattern including a so-called special margin such as a fishnet pattern or a T margin pattern is used in order to improve the characteristics such as the safety of the capacitor. It is preferable to apply on one side of the polypropylene film. It is effective from the viewpoint of improving the safety and preventing the destruction of the capacitor and the short circuit.
  • a generally known method such as a tape method or an oil method can be used without any limitation.
  • the metal layer integrated polypropylene film of Embodiment 1 can be laminated by a conventionally known method or wound to form a film capacitor.
  • the film capacitor of Embodiment 1 may have a configuration in which a plurality of metal layer integrated polypropylene films are stacked, or may have a wound metal layer integrated polypropylene film.
  • Such a film capacitor can be suitably used as a capacitor for an inverter power supply device that controls a drive motor of an electric vehicle or a hybrid vehicle.
  • it can also be suitably used for railway vehicles, wind power generation, solar power generation, general household appliances, and the like.
  • Table 1 shows the physical properties of the polypropylene resin used to produce the biaxially stretched polypropylene film.
  • the polypropylene resin B shown in Table 1 is HPT-1 manufactured by Korea Oil Chemical Co., Ltd.
  • the polypropylene resin C is S802M manufactured by Korea Oil Chemical Co., Ltd.
  • Polypropylene resin D is HC300-BF manufactured by Borealis
  • polypropylene resin G is HB311-BF manufactured by Borealis
  • polypropylene resin J is HC318-BF manufactured by Borealis.
  • Polypropylene resin A, polypropylene resin E, polypropylene resin F, and polypropylene resin H are products manufactured by Prime Polymer Co., Ltd.
  • Measuring instrument differential refractometer (RI) built-in high-temperature GPC device manufactured by Tosoh Corporation, HLC-8121GPC-HT type Column: TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation is connected Column temperature: 140 ° C Eluent: Trichlorobenzene Flow rate: 1.0 mL / min
  • melt flow rate The melt flow rate (MFR) was measured at 230 ° C. under a load of 2.16 kg according to JIS K 7210-1999.
  • a dry blend resin composition was obtained by mixing at (weight ratio). Next, the dry blend resin composition was supplied to an extruder, melted at 230 ° C., extruded with a T-die, and wound around a metal drum having a surface temperature (cast temperature) maintained at 45 ° C. to be solidified. As a result, a cast original fabric sheet having a thickness of 900 ⁇ m was obtained. Next, the cast original sheet is preheated at 165 ° C.
  • Example 5 Production of Biaxially Stretched Polypropylene Film in Example 5
  • operation was performed at 160 ° C. for the temperature of any of the preheating before longitudinal stretching, longitudinal stretching, preheating before transverse stretching, transverse stretching, and relaxation.
  • Example 1 Example 1, and obtained the biaxially stretched polypropylene film.
  • Example 6 Production of Biaxially Stretched Polypropylene Film in Example 6
  • the crystallite size of the biaxially stretched polypropylene film was measured with an XRD (wide angle X-ray diffraction) apparatus as follows.
  • Measuring device Rigaku's desktop X-ray diffractometer "MiniFlex300"
  • X-ray generation output 30 kV
  • Irradiation X-ray Monochromator monochromated CuK ⁇ ray (wavelength 0.15418 nm)
  • Detector Scintillation counter
  • Goniometer scan 2 ⁇ / ⁇ interlocking scan From the obtained data, diffraction reflection of ⁇ crystal (040) plane using analysis computer and integrated powder X-ray analysis software PDXL The half width of the peak was calculated.
  • Equation (1) D is the crystallite size (nm)
  • K is a constant (shape factor)
  • ⁇ is the X-ray wavelength used (nm)
  • ⁇ is the half width obtained
  • ⁇ is the diffraction Bragg angle. 0.94 was used as K.
  • dielectric breakdown strength According to JIS C2330 (2001) 7.4.11.2 B method (plate electrode method), the dielectric breakdown voltage was measured 12 times, and these dielectric breakdown voltages were measured for the thickness of the biaxially stretched polypropylene film ( The average value of 8 times excluding the upper 2 times and the lower 2 times was obtained, and this was taken as the dielectric breakdown strength.
  • the dielectric breakdown voltage was measured at an ambient temperature of 100 ° C. and 120 ° C.
  • the dielectric breakdown voltage was measured at an ambient temperature of 120 ° C.
  • the “melting point + 50 / crystallite size” of the biaxially stretched polypropylene film is 177.2 in Example 1, 178.4 in Example 2, 177.5 in Example 3, 178.4 in Example 4, and Example. 177.4 in Example 6, 178.3 in Example 6, 178.5 in Example 7, 175.9 in Comparative Example 1, 174.1 in Comparative Example 2, 178.0 in Comparative Example 3, 178.0 in Comparative Example 4 174.8, Comparative Example 5 was 178.7, and Comparative Example 6 was 178.5.
  • the biaxially stretched polypropylene films of Examples 1 to 7 were excellent in the dielectric breakdown strength at a direct current of 120 ° C., and were excellent in the dielectric breakdown strength at an alternating current of 120 ° C. Also, the biaxially stretched polypropylene films of Examples 1 to 7 was also excellent in dielectric breakdown strength at an alternating current of 100 ° C. In the dielectric breakdown strength test with an AC power supply, heat generation and deterioration (decomposition etc.) of the film due to the occurrence of corona discharge, leakage current due to alternating polarity, and Joule heat generation due to the leakage current It differs from the dielectric breakdown strength test with a DC power source in that it occurs. As described above, the biaxially stretched polypropylene films of Examples 1 to 7 were excellent in dielectric breakdown strength even when both DC voltage and AC voltage were applied at 120 ° C.
  • a dry blend resin composition was obtained by mixing at (weight ratio). Next, the dry blend resin composition was supplied to an extruder, melted at 250 ° C., extruded with a T die, and wound around a metal drum maintained at a surface temperature (cast temperature) of 95 ° C. to be solidified. Thereby, an unstretched cast original fabric sheet having a thickness of 100 ⁇ m was obtained. The obtained unstretched cast raw sheet is preheated to 130 ° C.
  • the film was stretched 4.0 times and immediately cooled to room temperature. Subsequently, the uniaxially stretched film was guided to a tenter, preheated at 171 ° C. before stretching in the transverse direction, and then stretched 10.0 times in the transverse direction at a stretching speed of 300% / second at a transverse stretching temperature of 160 ° C. Thereafter, the biaxially stretched film was relaxed 9 times in the transverse direction, heat-set, wound up, and subjected to an aging treatment in an atmosphere of about 30 ° C.
  • the relaxation (heat setting) temperature was 160 ° C., and the relaxation time was 4 seconds.
  • the melting point, melting enthalpy, crystallite size, and dielectric breakdown strength of the biaxially stretched polypropylene film were measured by the methods described above.
  • the “melting point + 50 / crystallite size” of the biaxially stretched polypropylene film is 176.1 in Example 8, 177.8 in Example 9, 176.8 in Example 10, 176.7 in Example 11, and Comparative Example 8 was 177.2, and Comparative Example 9 was 177.3.
  • the biaxially stretched polypropylene films of Examples 8 to 11 were excellent in the dielectric breakdown strength at a direct current of 120 ° C. and excellent in the dielectric breakdown strength at an alternating current of 120 ° C. In addition, the biaxially stretched polypropylene films of Examples 8 to 11 were further excellent in dielectric breakdown strength at an alternating current of 100 ° C.

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Abstract

La présente invention aborde le problème de la fourniture d'un film de polypropylène qui présente une résistance à la rupture diélectrique à 120 °C en présence d'un courant continu et une résistance à la rupture diélectrique à 120 °C en présence d'un courant alternatif supérieures. Le film de polypropylène selon la présente invention est conforme à la formule I et présente une épaisseur de 1,0 à 19 µm. 31,5 ≤ enthalpie de fusion/√taille des cristallites ≤ 33,0 (I) Dans la formule I, l'unité d'enthalpie de fusion est le J/g, et l'unité de taille des cristallites est le nm. La taille des cristallites est calculée à l'aide de l'équation de Scherrer à partir de la largeur totale à mi-hauteur d'un pic de réflexion dans le plan du cristal α (040) comme mesuré par diffraction des rayons X aux grands angles.
PCT/JP2018/014342 2017-04-03 2018-04-03 Film de polypropylène, film de polypropylène avec couche métallique intégrée, et condensateur à film Ceased WO2018186424A1 (fr)

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EP18781449.6A EP3608353B1 (fr) 2017-04-03 2018-04-03 Film de polypropylène, film de polypropylène avec couche métallique intégrée, et condensateur à film
KR1020227040040A KR102494812B1 (ko) 2017-04-03 2018-04-03 폴리프로필렌 필름, 금속층 일체형 폴리프로필렌 필름 및 필름 콘덴서
CN201880020055.5A CN110461914A (zh) 2017-04-03 2018-04-03 聚丙烯薄膜、金属层一体型聚丙烯薄膜及薄膜电容器
KR1020197026700A KR102468929B1 (ko) 2017-04-03 2018-04-03 폴리프로필렌 필름, 금속층 일체형 폴리프로필렌 필름 및 필름 콘덴서

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022220248A1 (fr) * 2021-04-12 2022-10-20 王子ホールディングス株式会社 Film de polypropylène métallisé
JP2022162462A (ja) * 2021-04-12 2022-10-24 王子ホールディングス株式会社 金属層一体型ポリプロピレンフィルム
JP2022171319A (ja) * 2021-04-30 2022-11-11 王子ホールディングス株式会社 金属化ポリプロピレンフィルム
US20230416479A1 (en) * 2020-11-17 2023-12-28 Oji Holdings Corporation Polypropylene film, polypropylene film integrated with metal layer, and film capacitor

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59211908A (ja) * 1983-05-17 1984-11-30 株式会社東芝 油入フイルムコンデンサ
JPS6238403B2 (fr) 1980-12-16 1987-08-18 Ishikawajima Harima Heavy Ind
JPH09148176A (ja) * 1995-11-29 1997-06-06 Toray Ind Inc 耐熱性コンデンサ用ポリプロピレンフィルム
JP3689009B2 (ja) 2001-02-27 2005-08-31 株式会社日立製作所 高耐食性高強度オーステナイト系ステンレス鋼とその製法
JP2010280795A (ja) 2009-06-04 2010-12-16 Oji Paper Co Ltd コンデンサー用二軸延伸ポリプロピレンフィルム、その金属蒸着フィルム及びキャスト原反シート
WO2013105552A1 (fr) * 2012-01-11 2013-07-18 王子ホールディングス株式会社 Film de polypropylène à orientation biaxiale pour condensateurs
JP2014051657A (ja) * 2012-08-09 2014-03-20 Toyobo Co Ltd ポリプロピレンフィルム
JP2016012705A (ja) * 2014-06-30 2016-01-21 王子ホールディングス株式会社 コンデンサ用二軸延伸ポリプロピレンフィルム
WO2016017752A1 (fr) * 2014-07-31 2016-02-04 三井化学株式会社 Composition homopolymère de propylène pour condensateur à film, son procédé de production, et condensateur à film
JP2016033211A (ja) * 2014-07-30 2016-03-10 東レ株式会社 ポリプロピレンフィルム
WO2016051496A1 (fr) * 2014-09-30 2016-04-07 王子ホールディングス株式会社 Film de polypropylène étiré bi-axialement pour condensateur
WO2016167328A1 (fr) * 2015-04-15 2016-10-20 王子ホールディングス株式会社 Film de polypropylène étiré de manière biaxiale pour condensateur
JP6089186B2 (ja) 2012-11-12 2017-03-08 国立大学法人弘前大学 超微細粉末、高強度鋼焼結体及びそれらの製造方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6238403B2 (fr) 1980-12-16 1987-08-18 Ishikawajima Harima Heavy Ind
JPS59211908A (ja) * 1983-05-17 1984-11-30 株式会社東芝 油入フイルムコンデンサ
JPH09148176A (ja) * 1995-11-29 1997-06-06 Toray Ind Inc 耐熱性コンデンサ用ポリプロピレンフィルム
JP3689009B2 (ja) 2001-02-27 2005-08-31 株式会社日立製作所 高耐食性高強度オーステナイト系ステンレス鋼とその製法
JP2010280795A (ja) 2009-06-04 2010-12-16 Oji Paper Co Ltd コンデンサー用二軸延伸ポリプロピレンフィルム、その金属蒸着フィルム及びキャスト原反シート
WO2013105552A1 (fr) * 2012-01-11 2013-07-18 王子ホールディングス株式会社 Film de polypropylène à orientation biaxiale pour condensateurs
JP2014051657A (ja) * 2012-08-09 2014-03-20 Toyobo Co Ltd ポリプロピレンフィルム
JP6089186B2 (ja) 2012-11-12 2017-03-08 国立大学法人弘前大学 超微細粉末、高強度鋼焼結体及びそれらの製造方法
JP2016012705A (ja) * 2014-06-30 2016-01-21 王子ホールディングス株式会社 コンデンサ用二軸延伸ポリプロピレンフィルム
JP2016033211A (ja) * 2014-07-30 2016-03-10 東レ株式会社 ポリプロピレンフィルム
WO2016017752A1 (fr) * 2014-07-31 2016-02-04 三井化学株式会社 Composition homopolymère de propylène pour condensateur à film, son procédé de production, et condensateur à film
WO2016051496A1 (fr) * 2014-09-30 2016-04-07 王子ホールディングス株式会社 Film de polypropylène étiré bi-axialement pour condensateur
WO2016167328A1 (fr) * 2015-04-15 2016-10-20 王子ホールディングス株式会社 Film de polypropylène étiré de manière biaxiale pour condensateur

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUMIYUKIHAMADA: "High Polymers", vol. 16, 1967, KOBUNSHI, pages: 694 - 706

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230416479A1 (en) * 2020-11-17 2023-12-28 Oji Holdings Corporation Polypropylene film, polypropylene film integrated with metal layer, and film capacitor
WO2022220248A1 (fr) * 2021-04-12 2022-10-20 王子ホールディングス株式会社 Film de polypropylène métallisé
JP2022162462A (ja) * 2021-04-12 2022-10-24 王子ホールディングス株式会社 金属層一体型ポリプロピレンフィルム
JP2022171319A (ja) * 2021-04-30 2022-11-11 王子ホールディングス株式会社 金属化ポリプロピレンフィルム

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