WO2007129695A1 - Film de polysulfure d'arylène à orientation biaxiale - Google Patents

Film de polysulfure d'arylène à orientation biaxiale Download PDF

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Publication number
WO2007129695A1
WO2007129695A1 PCT/JP2007/059481 JP2007059481W WO2007129695A1 WO 2007129695 A1 WO2007129695 A1 WO 2007129695A1 JP 2007059481 W JP2007059481 W JP 2007059481W WO 2007129695 A1 WO2007129695 A1 WO 2007129695A1
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WO
WIPO (PCT)
Prior art keywords
film
polyarylene sulfide
biaxially oriented
capacitor
thermoplastic resin
Prior art date
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PCT/JP2007/059481
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English (en)
Japanese (ja)
Inventor
Masatoshi Ohkura
Yasuyuki Imanishi
Tetsuya Machida
Ryo Miyamoto
Mitsugu Shimizu
Original Assignee
Toray Industries, Inc.
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.)
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Publication date
Application filed by Toray Industries, Inc. filed Critical Toray Industries, Inc.
Priority to JP2008514491A priority Critical patent/JP5239855B2/ja
Publication of WO2007129695A1 publication Critical patent/WO2007129695A1/fr

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    • 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
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical properties and planar properties, a biaxially oriented polyarylene sulfide film for capacitors, and a metallized biaxial
  • the present invention relates to an oriented polyarylene sulfide film and a capacitor using them. Furthermore, the present invention forms a high-quality biaxially oriented polyarylene sulfide film with little variation in physical properties within the film surface, or fine fine protrusions on the surface, and is excellent in heat resistance and electrical characteristics, and is used in a capacitor.
  • the present invention relates to a biaxially oriented polyarylene sulfide film suitable for miniaturization and large capacity without impairing processing suitability, a metallized polyarylene sulfide film using the same, and a capacitor using the same.
  • the present invention relates to a polyarylene sulfide film, a metallized film, and a capacitor using the same.
  • a film capacitor is generally formed by a method of winding a film such as a biaxially oriented polyethylene terephthalate film or a biaxially oriented polypropylene film and a metal foil film such as an aluminum foil, or on the surface of the film. It is manufactured by a method of winding or laminating after forming a deposited film of aluminum, zinc or the like.
  • capacitors have also been miniaturized and surface-mounted, and heat resistance and thinning have been demanded. For this reason, capacitors using polyphenylene sulfide (PPS) film with excellent heat resistance and dielectric properties are manufactured, and polyester film and polypropylene film are used. Is used in high-performance circuits that have a high guaranteed operating temperature.
  • PPS Finolem is susceptible to tearing, causing film breakage during processing and shortage of self-healing properties at the time of dielectric breakdown due to low withstand voltage, and its use as a capacitor film is limited. The current situation is that you can build a place.
  • Patent Document 1 A biaxially oriented polyester film (hereinafter sometimes abbreviated as a PPS film) is disclosed in Patent Document 1 and the like.
  • Patent Document 2 proposes that a capacitor having excellent heat resistance, frequency characteristics, temperature characteristics, and the like can be provided by using a PPS film as a capacitor dielectric.
  • the range of manufacturing conditions is narrow in the manufacturing process, that is, the process of winding, cutting, molding, etc. If these controls are insufficient, defective products due to low voltage breakdown increase. There is a drawback.
  • the above capacitors often suffer from short-circuiting without self-healing (self-healing) when low-voltage breakdown occurs, which further increases the defect rate and has low reliability during use. To.
  • Patent Documents 3 to 5 propose using a PPS laminated film in which a polyester resin or a polyolefin resin is laminated on at least one side of a PPS film as a capacitor.
  • these conventional PPS laminated films do not have sufficient adhesion between the polyester and polyolefin resin layers and the PPS layer, and are often easily peeled off during the capacitor manufacturing process. Things were hard to get.
  • films laminated with resins other than PPS, such as polyester and polyolefin could not be substantially self-collected, and trimming edges and non-product films could not be used again as film raw materials.
  • Patent Document 6 proposes a PPS laminated film obtained by laminating an amorphous polyester resin composition in order to improve SH properties.
  • an amorphous polyester resin layer is formed on the PPS layer in-line and off-line, but the glass transition temperature Tg is at most 90 ° C, especially when used at high temperatures of 100 ° C or higher.
  • Tg glass transition temperature
  • Patent Document 7 in order to improve the SH property, the entire part in the thickness direction of the film is substantially A PPS film composed of PPS and having a surface layer that is more amorphous than the inner layer has been proposed.
  • the surface of the PPS film is melted and amorphousized by frame treatment, etc., or an amorphous PPS resin is laminated, but in any case, the surface becomes flat when the film becomes thin, for example, 3 ⁇ m or less.
  • productivity deteriorates
  • SH property is also insufficient.
  • Patent Document 8 a force is proposed for a PPS film in which a ceramic layer is provided on at least one side of a PPS film.
  • a ceramic layer is provided on at least one side of a PPS film.
  • sufficient self-recovery characteristics (SH property) are required unless the deposited layer is as thick as lOOnm. Since it could not be obtained, there were cases in which poor productivity and surface roughness due to the loss of heat of vapor deposition of the film caused problems.
  • Patent Documents 9 and 10 have been proposed in order to improve the characteristics of an insulator, particularly a capacitor, as a dielectric.
  • Patent Document 9 describes a PPS that has a melt specific resistance of 1 ⁇ 10 9 ⁇ 'cm or more by washing with pressurized ion exchanged water at 100 ° C or higher after polymerization and further acid cleaning, and biaxial stretching. By doing so, the film can be used to prevent the breakdown voltage from increasing and the capacitor usage rate from decreasing.
  • Patent Document 10 discloses a film having a high volume resistivity at a high temperature by stretching a PPS produced without using a polymerization aid. However, even with these methods, the SH performance was not improved, and the reliability of the capacitor was sometimes insufficient. In addition, there were cases where film forming stability and film flatness were inferior due to a narrow range of conditions for film formation.
  • Patent Documents 11 to 13 propose a blend of PPS and polyetherimide
  • Patent Document 13 proposes a blend of PPS and polyarylate.
  • the force to improve the tear resistance of the film by simply blending PPS and polyetherimide with a twin-screw extruder Simply disperse the two types of polymers and disperse the polyetherimide The long diameter is controlled to be 30 ⁇ m or less, and no mention is made of improvements in electrical characteristics and capacitor characteristics.
  • Patent Document 13 aims to improve the slipperiness of the film by a simple blend of PPS and polyarylate, and does not mention dispersion diameter control but mentions improvement of electrical characteristics and capacitor characteristics.
  • PPS there is no mention of the SH characteristics that have been proposed to improve the withstand voltage by increasing the glass transition temperature of the PPS film to 95 ° C or higher by compatibilizing monoterimide. Even if the performance of such small low-voltage capacitors can be improved by increasing the glass transition temperature and improving the heat-resistant temperature, for example, high-capacity capacitors that are used under high temperature and high voltage, such as inverter capacitors for hybrid cars. In some cases, the performance was insufficient when used in a wound condenser.
  • Patent Document 1 Japanese Patent Laid-Open No. 54-142275
  • Patent Document 2 Japanese Patent Laid-Open No. 57-187327
  • Patent Document 3 Japanese Patent Application No. 2 _ 168861
  • Patent Document 4 JP-A-4 219236
  • Patent Document 5 JP-A-5-318665
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2000-218738
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2002-20508
  • Patent Document 8 Japanese Unexamined Patent Publication No. 63-189458
  • Patent Document 9 Japanese Patent Application Laid-Open No. 62-158312
  • Patent Document 10 JP-A-7-312325
  • Patent Document 11 Japanese Patent Laid-Open No. 62-158312
  • Patent Document 12 Japanese Patent Laid-Open No. 2001-261959
  • Patent Document 13 JP-A-11266266
  • an object of the present invention is to provide a biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical characteristics, and planarity. Especially when used as a capacitor, it has high electrical characteristics and excellent self-healing (SH), so it forms a highly reliable capacitor even when used at high temperature and high voltage. It is to provide a polyarylene sulfide film, a metallized film, and a capacitor using the same. More specifically, such as capacitors for inverters in high-speed railways and hybrid cars that require high reliability at high temperature and high voltage as well as small capacitor applications such as chip capacitors where PPS films have been used in the past. The object is to provide a capacitor film that can also be used as a large-capacity winding capacitor used under high temperature and high voltage, this metallized film, and a capacitor using the same.
  • the present invention provides a film made of a thermoplastic resin including polyarylene sulfide and another thermoplastic resin A different from the polyarylene sulfide, wherein the thermoplastic resin A is dispersed.
  • the average phase diameter of the dispersed phase is 50 to 500 nm
  • the glass transition temperature of the film is observed to be 85 ° C or higher and lower than 95 ° C, and 95 ° C or higher and 130 ° C or lower.
  • a biaxially oriented polymer characterized in that the elongation at break in the longitudinal and width directions of the film is not more than 80% and the dielectric breakdown voltage at 150 ° C is not less than 300 V // 1 m. It is an Allensulfide Film.
  • biaxially oriented polyarylene sulfide film of the present invention is
  • thermoplastic resin A When the sum of the contents of polyarylene sulfide and thermoplastic resin A is 100 parts by weight, the content of polyarylene sulfide is 70 to 99.5 parts by weight, and the content of thermoplastic resin A Is 0.5 to 30 parts by weight,
  • the polyarylene sulfide is a polyphenylene sulfide
  • Thermoplastic resin A is an amorphous resin, and its glass transition temperature is 150 ° C or higher and lower than the melting point of the porous lens sulfide,
  • thermoplastic resin A is at least one polymer selected from the group consisting of polyarylate, polyphenylene ether, polyetherimide, polyethersulfone and polysulfone,
  • thermoplastic resin A force containing a silicon atom composed of a siloxane bond at the interface of the dispersed phase.
  • Polyarylene sulfide and thermoplastic resin A and epoxy group, amino group, isocyanate Melt-forming a resin composition obtained by kneading a raw material containing 0.05 to 3 parts by weight of a compatibilizer having at least one group selected from the group consisting of nate groups;
  • the volume resistivity at 150 ° C and DC 500V is 1.0 x 1014 ⁇ 'cm or more.
  • the melting specific resistance of the resin composition constituting the film at 310 ° C is 1.0 ⁇ 10 9 ⁇ ⁇ ⁇ m to l. 0 ⁇ 10 ⁇ ⁇ 'cm,
  • the average value of breakdown voltage measured at 30 locations in an atmosphere of 23 ° C and 65% RH is 350 V / ⁇ m or more, and the standard deviation of the breakdown voltage is 30V / ⁇ m or less.
  • the center line average roughness Ra is 30 nm or more and lOOnm or less, the maximum height Rmax is 700 nm or less, and the number of protrusions having a protrusion height of 50 nm or more in the region of 50 / im x 50 / im is 250 or more.
  • the friction coefficient is 0.2 or more and 0.6 or less
  • the heat setting temperature of the first stage is (previous stretching temperature + 5 ° C) to 240 ° C and the maximum heat setting temperature of the second stage is (Temperature + 20 ° C) or higher (melting point of the polyarylene sulfide constituting the film _ 5 ° C) or lower,
  • a biaxially oriented film for capacitors that is a biaxially oriented film as described above,
  • a capacitor comprising the above metallized film wound or laminated
  • Each of them is preferred and includes a mode.
  • a biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical characteristics, and planarity can be obtained, and particularly when used as a capacitor.
  • High electrical properties and excellent self-healing (SH) characteristics make it possible to form a large and small capacitor with high reliability even when used at high temperatures and voltages, and to use this. You can get the capacitor you had.
  • the biaxially oriented polyarylene sulfide film of the present invention the biaxially oriented polyarylene sulfide film for capacitors, the metallized biaxially oriented polyarylene sulfide film, and the capacitor using these are described. To do.
  • the biaxially oriented polyarylene film of the present invention has excellent heat resistance, dimensional stability, electrical properties, and planarity, and particularly has high electrical properties and excellent self-healing properties (SH property) when used for capacitors. By doing so, a highly reliable capacitor can be formed even when used at high temperature and high voltage.
  • SH property self-healing properties
  • the present invention includes a polyarylene sulfide and another thermoplastic resin A different from the polyarylene sulfide, and the thermoplastic resin A forms a dispersed phase,
  • the average dispersed diameter of the dispersed phase is 50 to 500 nm, and the glass transition temperature of the film is observed at 85 ° C or higher and lower than 95 ° C, while not observed at 95 ° C or higher and 130 ° C or lower; and
  • the breaking elongation in the longitudinal direction and the width direction of the film is preferably 80% or less, and the dielectric breakdown voltage at 150 ° C. is preferably 300 V // im or more.
  • polyarylene sulfide forms a continuous phase (sea phase or matrix), and other thermoplastic resin A forms a dispersed phase (island phase or domain), and the average dispersed diameter of the dispersed phase is determined.
  • the average value should be 50-500 nm.
  • the preferred range of the average value of the dispersion diameter is 60 to 300 nm, and more preferably 70 to 200 nm.
  • Heat resistance of polyarylene sulfide by forming a continuous phase It is possible to largely reflect the excellent chemical resistance and mechanical properties on the film.
  • by setting the average dispersion diameter in the above range it is excellent in flatness, and it is possible to impart SH properties to the film when used as a capacitor dielectric.
  • the average value of the average dispersed diameter of the dispersed phase is less than 50 nm, the effect of improving SH property when used as a dielectric of the capacitor of the present invention is insufficient.
  • the average value of the average dispersion diameter is larger than 500 nm, the heat resistance and flatness of the film are deteriorated, and the film is easily broken during stretching.
  • the average dispersion diameter of the dispersed phase is: (a) a direction parallel to the longitudinal direction and perpendicular to the film surface, (i) a direction parallel to the width direction and perpendicular to the film surface, (u) This is the number average of dispersed particle diameters observed on a plane cut in a direction parallel to the film plane.
  • Phase shape index 1 (number average value of lb + number average value of le) / 2
  • shape finger U (number average value of Id + number average value of lf) / 2
  • shape index K (la Number average value + lc number average value) / 2
  • the average dispersed diameter of the dispersed phase is (I + J + K) / 3.
  • a sample was prepared by an ultrathin section method, and observed using a transmission electron microscope under the condition of an applied voltage lOOkV, and a photograph was taken at 20,000 times.
  • the average dispersion diameter of any 100 dispersed particles is calculated by importing it into an image analyzer as an image and performing image processing as necessary.
  • the shape of the dispersed phase of the thermoplastic resin A is preferably a spherical or elongated island shape, an oval shape, or a fiber shape.
  • the aspect ratio of the dispersed phase is preferably in the range of 1-20.
  • a more preferable range of the aspect ratio of the dispersed phase is 1 to 10 and a more preferable range is:! To 5.
  • the aspect ratio means the ratio of the average major axis / average minor axis of the dispersed phase.
  • the aspect ratio can be measured using a technique such as a transmission electron microscope or a scanning electron microscope.
  • a sample is prepared by an ultrathin section method, and using a transmission electron microscope,
  • the aspect ratio can be calculated by observing under a pressure of lOOkV, taking a picture at 20,000 times, capturing the obtained picture as an image into an image analyzer, and performing image processing. (Details of the measurement method will be described later).
  • the glass transition temperature (Tg) of the biaxially oriented polyarylene film is observed at 85 ° C or more and less than 95 ° C, but not at 95 ° C or more and 130 ° C or less. Preferred. When Tg is less than 85 ° C, the heat resistance of the film may be lowered. If Tg is observed to be 95 ° C or higher and 130 ° C or lower, the SH property may be insufficient when the film is used as a capacitor dielectric.
  • the biaxially oriented polyarylene sulfide film of the present invention needs to have a breaking elongation of 80% or less in both the longitudinal direction and the width direction. 30% or more and 80% or less is preferable, 35% or more and less than 65%, more preferably 40% or more and less than 55%.
  • the breaking elongation of the film is 30. If it is less than / o, it will break easily when the film is slit, or it will be broken during processing such as bending, and if it is used especially for capacitors, it will break easily when manufacturing a wound capacitor. It becomes difficult.
  • the biaxially oriented polyarylene sulfide film of the present invention has a breaking strength in the longitudinal direction and the width direction of 230 MPa or more and 500 MPa or less, more preferably 250 MPa or more and 450 MPa or less, and further preferably 270 MPa or more and 400 MPa or less. If the breaking strength of the film is less than 230 MPa, warping may occur easily during processing such as bending, and the withstand voltage at high temperatures may be low.
  • a wound capacitor is manufactured. In this case, it is easy to break, making it difficult to process, or causing low voltage breakdown. On the other hand, in order to obtain a film exceeding 500 MPa, it is necessary to make the draw ratio at the time of film formation extremely high, which is not preferable because the film is easily broken during the film forming process.
  • the biaxially oriented polyarylene sulfide film of the present invention preferably has a hang ratio in the longitudinal direction and in the width direction of 3 GPa or more and less than 7 GPa, more preferably 3.2 GPa. a or more and less than 6 GPa, more preferably 3.5 GPa or more and less than 5 GPa. If any of the Young's modulus in the longitudinal and width directions of the film is less than 3 GPa, the withstand voltage at high temperatures may be low. This is preferable because it may be insufficient and the capacitor may be inferior in reliability.
  • the biaxially oriented polyarylene sulfide film of the present invention has an elongation of 2% and an elongation at break of 5% in the elongation-stress curve at 23 ° C in the longitudinal and width directions of the film.
  • Is preferably always 0 or more in any direction.
  • the differential coefficient in the direction of force is more preferably 0.1 (MPaZ%) or more, more preferably 0.5 (MPa / Q /.) Or more.
  • the differential coefficient When the differential coefficient is negative, the heat resistance, dimensional stability, electrical characteristics, planar characteristics, etc., as well as the decrease in film strength, or the difference in dielectric breakdown voltage between 150 ° C and 23 ° C It may be unfavorable because it becomes large or the SH property becomes poor. The cause of this is not necessarily clear, but the degree of relaxation of the amorphous molecular chains that make up the film is large. Especially at the glass transition point of polyarylene sulfide, the mobility of the polyarylene sulfide molecular chains increases. I think that is due to this. Also, if the derivative always exceeds 10 (MPa /%), the elongation of the film will be less than 30%, which may be undesirable.
  • the dielectric breakdown voltage force at 150 ° C. of the biaxially oriented polyarylene sulfide film is preferably 3 ⁇ 400 V // im or more, more preferably 400 V / ⁇ or more. 1
  • the dielectric breakdown resistance at 50 ° C is less than 300VZ ⁇ m
  • the resistance of the capacitor element at high temperature above the glass transition temperature of the film for example, at 95 ° C or higher.
  • the voltage may be low.
  • the upper limit of the withstand voltage of the biaxially oriented polyarylene sulfide film is not particularly set, but when it is 1000 V / zm or more, the SH property does not function when the capacitor is used, which may lead to penetration failure. is there.
  • the dielectric breakdown voltage at 23 ° C V (23) (V / zm) in order to reduce the fluctuation of withstand voltage due to temperature and increase the self-healing property (SH property) ) And 15 Dielectric breakdown voltage V (150) (V // im) at 0 ° C is
  • V (150) / V (23) ⁇ 0.9, and even more preferably V (150) / V (23) ⁇ 0.95.
  • the biaxially oriented polyarylene sulfide film of the present invention preferably has V (23) of 350 V / Zm or more and a standard deviation of 30 VZ ⁇ m or less.
  • V (23) 350 V / Zm or more
  • a standard deviation of 30 VZ ⁇ m or less When the standard deviation exceeds 30V / zm, the physical property variation in the film increases, and when a single capacitor is used, low voltage breakdown occurs, and continuous concentrated breakdown is likely to occur immediately at the breakdown location, and the SH property is improved. Does not function and impairs reliability.
  • the standard deviation of the preferable dielectric breakdown voltage is 25 V / ⁇ m or less, more preferably 20 VZ ⁇ m or less.
  • the molecular chain orientation in the film is controlled by highly orienting the polyarylene sulfide molecular chains in the stretching process during film formation, and further controlling the temperature of the subsequent heat setting process. It is considered that the structure can be fixed while keeping the chain tension high and the above-mentioned preferable characteristics are exhibited.
  • the stretching temperature is changed in both the longitudinal direction and the width direction (Tg (polyarylene). Rufido glass transition temperature)) to (Tg + 40), preferably (Tg + 5 ° C) to (Tg + 20 ° C), the draw ratio is 3 times or more in both the longitudinal direction and the width direction, preferably 3.
  • the area magnification is 11 times or more, preferably 13 times or more, more preferably 14 times or more
  • the heat setting temperature after stretching is 170 to (Tm (melting point of polyarylene sulfide) —5 ° C ) ° C, preferably 200-250 ° C
  • one-stage heat setting more preferably, heat setting after stretching is performed in two or more steps with different temperatures
  • the heat setting temperature of the first stage is (Previous stretching temperature + 5 ° C) to 240 ° C, preferably (Previous stretching temperature + 30 ° C) to 220 ° C.
  • the maximum value is (the first stage heat setting temperature + 20V) to (Tm_5 ° C), and after heat setting, the maximum value of the heat setting temperature in the latter stage is 8% or less, preferably 2 to 5% in the width direction. It can be made within the scope of the present invention by appropriately adjusting below.
  • the volume resistivity of the biaxially oriented polyarylene film at 150 ° C and DC 500V is preferably 1. OX 10 14 Q'cm or more, more preferably 1.0 X 1 0 5 Q 'cm or more. If the volume resistivity at 150 ° C and DC 500V is less than 1.0 X 10 4 ⁇ 'cm, when manufacturing a capacitor using this film, it is above the glass transition temperature of the film, that is, above 95 ° C. Capacitor leakage current at high temperatures may increase and stability at high temperatures may be poor.
  • volume resistivity of the biaxially oriented polyarylene sulfide film there is no specific upper limit for the volume resistivity of the biaxially oriented polyarylene sulfide film, but if it exceeds 1.0 X 10 16 Q'cm, the casting process using the electrostatic application method becomes difficult during melt film formation. There is a case.
  • the biaxially oriented polyarylene sulfide film of the present invention has a center line average roughness Ra of 30 nm or more and lOOnm or less, a maximum height Rmax of 700 nm or less, and a protrusion in 50 ⁇ mD (50 ⁇ m x 50 ⁇ m region)
  • the number of protrusions having a height of 50 nm or more is preferably 250 or more. If Ra is less than 30 nm, sufficient slipperiness cannot be imparted to the film, and wrinkles may occur during film formation, or wrinkles may occur during the manufacture of wound capacitors, making processing difficult. Become.
  • Ra is lOOnm or more
  • a deposited film such as aluminum or zinc is formed on the surface of the film having a large surface roughness, unevenness in the deposited film thickness occurs, or when a winding capacitor is used, it is between the films.
  • air is used, resulting in instability of electrical characteristics, lowering of withstand voltage, concentration of electric field during use, melting or burning of the film and metal thin film layer, and use as a film for capacitors In addition, it is difficult to improve the performance of capacitors.
  • the biaxially oriented polyarylene sulfide film of the present invention has a vapor deposited film such as aluminum or zinc deposited on the surface of the film having a large surface roughness.
  • a vapor deposited film such as aluminum or zinc deposited on the surface of the film having a large surface roughness.
  • the lower limit of Rmax is not particularly limited, but is set to 300 nm from the viewpoint of imparting appropriate slipperiness.
  • the biaxially oriented polyarylene sulfide film of the present invention has a fineness of fine protrusions insufficient when the number of protrusions having a protrusion height of 50 nm or more in a 50 ⁇ m mouth is less than 250, making the winding capacitor one. At times, air intervenes between the films, resulting in instability of electrical characteristics and a decrease in withstand voltage, electric field concentration during use, and film or metal thin film layer melting or burning. When used as a capacitor film, it may be difficult to improve the performance of the capacitor.
  • the upper limit of the number of protrusions with a height of 50 nm or more in the 50 ⁇ port is not particularly limited, but is 600 from the viewpoint of obtaining a high-performance capacitor.
  • the biaxially oriented polyarylene sulfide film of the present invention preferably has a friction coefficient of 0.2 or more and 0.8 or less. More preferably, it is 0.25 or more and 0.6 or less, and further preferably 0.3 or more and less than 0.5. If the coefficient of friction is less than 0.2, sufficient slipperiness cannot be imparted to the film, so that wrinkles may occur when the film is formed, or wrinkles may occur when a wound capacitor is manufactured. Processing becomes difficult. On the other hand, when the coefficient of friction exceeds 0.8, when a deposited film such as aluminum or zinc is formed on the surface of the film having a large surface roughness, the thickness of the deposited film may be uneven or the winding capacitor may be the same. Sometimes air intervenes between the films, resulting in unstable electrical characteristics and lowering of withstand voltage, electric field concentration during use, and film and metal thin film layer melting or burning. When used as a capacitor, it is difficult to improve the performance of the capacitor.
  • the biaxially oriented polyarylene sulfide film of the present invention achieves the above-mentioned friction coefficient range and surface roughness of the film in order to impart slipperiness to the film and improve processability.
  • Particles can be included.
  • the particles include inert particles such as inorganic particles such as titanium oxide, calcium carbonate, silica, and alumina zirconia, and organic particles such as silicon particles, crosslinked attalinole particles and crosslinked polystyrene particles, and acetic acid during polymerization of the polymer. It is also possible to deposit particles during the polymer polymerization process using calcium or lithium acetate.
  • the average particle size of the particles is more preferably 1/3 or less, more preferably 2/3 or less of the preferred film thickness.
  • coarse particles having a particle diameter of 2 zm or more or a film thickness or more are not included.
  • film formation may be inferior in stability, or particles may fall out of the film during use of the capacitor, resulting in an insulation defect and impairing the reliability of the capacitor.
  • inert particles such as inorganic particles and organic particles are made into a slurry in the solvent during PPS polymerization and dispersed with a medium stirring type dispersion device such as a sand grinder or an ultrasonic dispersion device, and then classified with a wet classification device.
  • the present invention may form a fine protrusion structure on the surface depending on the dispersion state of the thermoplastic resin A.
  • the above friction coefficient range is achieved without substantially adding particles.
  • the protrusion height tends to decrease. Therefore, when the average dispersion diameter is less than 200 nm, the inorganic or organic particles described above are added in order to impart the necessary processability. May need to be added
  • the content of sulfide is 70 to 99.5 parts by weight and the content of thermoplastic resin A is 0.5 to 30 parts by weight.
  • the content of polyarylene sulfide is 80 to 98 parts by weight. More preferably, the content of thermoplastic resin A is 2 to 20 parts by weight, the content of polyarylene sulfide is 90 to 97 parts by weight, and the content of thermoplastic resin A is 3 to 10 parts by weight. More preferably.
  • thermoplastic resin A which is different from polyarylene sulfide, exceeds 30 parts by weight, the heat resistance, mechanical properties, and electrical properties of the biaxially oriented polyarylene sulfide may be impaired. May be inferior in film forming property.
  • the content of the thermoplastic resin A is less than 0.5 parts by weight, it becomes difficult to provide excellent planar characteristics and SH properties when used as a dielectric of a capacitor.
  • the polyarylene sulfide referred to in the present invention is a homopolymer or copolymer having one (Ar-S)-repeating unit.
  • Ar includes structural units represented by the following formulas (A) to (K).
  • Rl and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.
  • the structural formula represented by the above formula (A) is preferable, and typical examples thereof include polyphenylenesulfide, polyphenylenesulfonesulfone, polyphenol. Examples thereof include dirensulfide ketones, random copolymers thereof, block copolymers, and mixtures thereof.
  • polyphenylene sulfide is preferably exemplified from the viewpoint of film properties and economy, and p represented by the following structural formula as the main structural unit of the polymer Phenylene and preferably Rensurufuido units 80 mole 0/0 or more, more preferably 90 mol 0/0 than on, more preferably a resin containing more than 95 mol%. If the p-phenylene sulfide component is less than 80 mol%, the crystallinity and thermal transition temperature of the polymer are low, which may impair the heat resistance, dimensional stability, mechanical properties, and dielectric properties of PPS. .
  • the PPS resin less than 20 mole 0/0 of the repeating unit, preferably is less than 10 mole 0/0, contains units containing other sulfides bond copolymerizable with Les, be There is no problem.
  • the repeating unit of less than 20 mol%, preferably less than 10 mol% of the repeating unit include, for example, a trifunctional unit, an ether unit, a sulfone unit, a ketone unit, a meta bond unit, an aryl unit having a substituent such as an alkyl group, Examples include biphenyl units, terfylene units, vinylene units, carbonate units, and the like, and specific examples include the following structural units. One or more of these can coexist.
  • the structural unit may be either a random type or a block type copolymerization method.
  • Cost as substantially p- phenylene Rensurufuido PPS consists only or trifunctional component 1 mole 0/0 following the added PPS films feedstock consisting of 99 mol% or more p- phenylene Rensurufuido, film From the viewpoints of film properties, particularly film performance at high temperatures. In this case, the melting point of the obtained PPS resin is 280 to 290. C, glass transition temperature 90-95. Observed in C.
  • the melt viscosity of the PPS resin and the PPS resin composition is not particularly limited as long as melt kneading is possible.
  • the melt viscosity is 100 at a temperature of 315 ° C and a shear rate of 1, OOO (lZsec). It is preferably in the range of ⁇ 2000 Pa ⁇ s, more preferably in the range of 200 to 1, OOOPa ′ s.
  • PPS as used in the present invention can be obtained by various methods, for example, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in JP-A-61-7332.
  • the obtained PPS resin is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, an organic solvent, hot water, an acid aqueous solution, and the like. It can also be used after various treatments such as washing, activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates and functional disulfide compounds.
  • a method for producing a PPS resin is exemplified, but the present invention is not particularly limited thereto.
  • sodium sulfide and ⁇ -dichlorobenzene are reacted in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) at high temperature and high pressure.
  • NMP N-methyl-2-pyrrolidone
  • a copolymer component such as trihalobenzene may be included.
  • a polymerization reaction is carried out at 230 to 280 ° C with addition of caustic potash or alkali metal carbonate as a polymerization degree adjusting agent.
  • the polymer After polymerization, the polymer is cooled, and the polymer is filtered through a filter as a water slurry to obtain a granular polymer. This is stirred in an aqueous solution such as acetic acid or acetate for 30 to 100 ° C for 10 to 60 minutes, washed with ion exchanged water at 30 to 80 ° C several times, and dried to obtain PPS powder.
  • This powder polymer is washed with NMP at an oxygen partial pressure of 10 torr or less, preferably 5 torr or less, then washed several times with ion exchange water at 30 to 80 ° C., and dried under a reduced pressure of 5 torr or less.
  • the resulting polymer is a substantially linear PPS polymer, enabling stable stretch film formation.
  • a specific method for crosslinking / high molecular weight by heating PPS resin is as follows: in an oxidizing gas atmosphere such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon Examples of the method include heating in a heating container at a predetermined temperature until a desired melt viscosity is obtained.
  • the heat treatment temperature is usually selected from 170 to 280 ° C, more preferably from 200 to 270 ° C
  • the heat treatment time is usually selected from 0.5 to 100 hours, more preferably.
  • a force of 2 to 50 hours By controlling both of these, a target viscosity level can be obtained.
  • the heat treatment apparatus may be a normal hot air drier, or a rotary type or a heating device with a stirring blade.
  • a heating device with a rotary type or a stirring blade is required. It is preferable to use it.
  • the heat treatment temperature is 150 to 280 under an inert gas atmosphere such as nitrogen or under reduced pressure.
  • C preferably 200 to 270 ° C.
  • calorie heat time is 0.5 to: 100 hours, preferably 2 to 50 hours.
  • the heat treatment apparatus may be a normal hot air dryer, or a rotary type or a heating apparatus with a stirring blade, but in order to treat the efficiency and force more uniformly, a heating apparatus with a rotary type or a stirring blade may be used. preferable.
  • the PPS resin used in the present invention preferably has a small amount of excess metal components or metal ions, or oligomers or impurities, and specific methods for that include acid aqueous solution washing treatment, hot water washing treatment, organic Examples of the solvent cleaning treatment and the entrainer treatment can be given. These treatments may be used in combination of two or more methods.
  • the alkaline earth metal salt treatment before and after the washing treatment can be exemplified as a specific method for introducing alkaline earth metal such as Ca into the PPS.
  • the organic solvent cleaning treatment of the PPS resin includes the following methods.
  • the organic solvent does not have the action of decomposing PPS resin.
  • N-methylpyrrolidone, dimethylformamide, nitrogen-containing polar solvents such as dimethylacetamide, sulfoxides such as dimethyl sulfoxide, dimethylsulfone, sulfone solvents, acetone, methylethyl Ketone solvents such as ketones, jetylketones, and acetophenones
  • ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, dichloroethane, tetrachloroethane, Halogen-based solvents such as benzene, methanol, ethanol, propanol, butanol, pentaanol, ethylene glycol, propylene glycol, phenol
  • Phenol-based solvents Do, benzene, and aromatic hydrocarbon solvents such as toluene and xylene.
  • aromatic hydrocarbon solvents such as toluene and xylene.
  • N-methylpyrrolidone, acetone, dimethylformamide and black mouth form are particularly preferably used.
  • These organic solvents are used alone or as a mixture of two or more.
  • a method of washing with an organic solvent there is a method of immersing a PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary.
  • Any temperature can be selected in the range of room temperature to 300 ° C, with no particular restriction on the washing temperature when washing PPS resin with organic solvent. The higher the cleaning temperature, the higher the cleaning efficiency tends to be. However, a sufficient effect is usually obtained at a temperature of room temperature to 150 ° C.
  • the PPS resin that has been subjected to organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.
  • the water used is preferably distilled water or deionized water in order to exhibit a preferable chemical modification effect of the PPS resin by hot water washing.
  • the operation of the hot water treatment is usually performed by adding a predetermined amount of PPS resin to a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel.
  • the ratio of PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected per liter of water.
  • the following method can be exemplified as a specific method for the acid aqueous solution cleaning treatment of the PPS resin. That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of the acid, and it is possible to appropriately stir or heat as necessary.
  • the acid used is PP s No particular limitation as long as it does not have the effect of decomposing the resin, aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halogen-substituted aliphatic saturated carboxylic acids such as black Acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, sulfuric acid, phosphorus Examples include inorganic acidic compounds such as acid, hydrochloric acid, carbonic acid and silicic acid.
  • acetic acid and hydrochloric acid are preferably used. It is preferable to wash the acid-treated PPS resin several times with water or warm water in order to remove residual acid or salt.
  • the water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effects of preferred chemical modification of the PPS resin by acid treatment.
  • the acid aqueous solution cleaning treatment is performed, the acid terminal component of the PPS resin increases, and when mixed with another thermoplastic resin A, the dispersibility increases and the average dispersed diameter of the dispersed phase is reduced. This is preferable because it is easily formed.
  • the acid aqueous solution washing treatment may be preferable because the amount of metal in the PPS is reduced, and electrical insulation at high temperature and high voltage can be improved.
  • PPS obtained by introducing an alkaline earth metal such as Ca into PPS may be used.
  • Introducing an alkaline earth metal may be preferable because it can improve the extrusion stability during film formation for a long period of time, such as suppressing the generation of gel-like substances.
  • a method for introducing a strong alkaline earth metal there are a method of adding an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with hot water or hot water.
  • Alkaline earth metals are preferably introduced into the PPS in the form of alkaline earth metal ions such as acetates, hydroxides and carbonates. It is preferable to remove excess alkaline earth metal salt by washing with warm water.
  • the alkaline earth metal ion concentration at the time of introduction of the above alkaline earth metal ions is preferably at least 0.001 mmol, more preferably at least 0 mmol, relative to PPSlg.
  • the temperature is preferably 50 ° C or higher, more preferably 75 ° C or higher, and particularly preferably 90 ° C or higher. Although there is no upper temperature limit, 280 ° C or less is usually preferred from the viewpoint of operability.
  • the bath ratio (the weight of the cleaning solution with respect to the dry PPS weight) is preferably 0.5 or more, more preferably 3 or more, and even more preferably 5 or more.
  • a specific method for the PPS resin entrainer treatment includes PPS resin or PPS.
  • a medium inert to the resin composition is fed to the extruder and sucked from the vent of the extruder after melt kneading.
  • impurities such as oligomers, metals and metal salt components contained in the resin together with the medium can be recovered, and oligomers and ionic metal components in the PPS resin or PPS resin composition can be reduced.
  • the medium inert to PPS include the organic solvent and supercritical carbon dioxide gas in the organic solvent washing process described above.
  • a medium inert to the resin composition a medium having no action such as decomposing the thermoplastic resin A can be appropriately selected.
  • the thermoplastic resin A is a polyetherimide
  • ethylene glycol is used.
  • propylene glycol is used as the extruder used in this treatment.
  • Thermoplastic resin A is preferably an amorphous resin with a glass transition temperature Tg of 150 ° C or higher and a melting point (Tm) of polyarylene sulfide of 170 ° C or higher (Tm-20) ° C or lower.
  • the amorphous resin is more preferably 180 ° C or more (Tm-50) ° C or less, and most preferably an amorphous resin. If the Tg of thermoplastic resin A is less than 150 ° C, it may be difficult to obtain the effect of improving heat resistance and electrical characteristics when this film is used as a capacitor dielectric. In addition, when Tg of thermoplastic resin A is higher than the melting point (Tm) of polyarylene sulfide, or when the thermoplastic resin shows crystallinity in the film, it may be inferior in SH property when used as a capacitor dielectric. .
  • the thermoplastic resin A is a polymer selected from the group consisting of polyarylate, polyphenylene ether, polyetherimide, polyethersulfone and polysulfone, or at least one from the viewpoint of the mixing of polyarylene sulfide and the manifestation of the effects of the present invention. It is preferred to have a blend containing seeds, especially in the case of polyetherimides. It is excellent in electrical properties when it is made into a biaxially oriented polyary 1 film because of its excellent dispersibility and the small amount of impurities and metal components.
  • the polyetherimide is not particularly limited, but, for example, as shown by the following general formula, it is possible to preferably enumerate a polymer which is a structural unit containing an ether bond as a polyimide constituent component.
  • R1 is a divalent organic group selected from the group consisting of a divalent aromatic or aliphatic group having 2 to 30 carbon atoms and an alicyclic group
  • R2 Is a divalent organic group similar to R.
  • Rl and R2 include aromatic groups represented by the following formula groups:
  • the most preferable polyarylene sulfide resin in the present invention is PPS composed of p_phenylene sulfide, or 1 mol% or less of a trifunctional component and 99 mol% or more of p-phenylene sulfide is added. It is a PPS resin that also has strength, and usually has a melting point of 280-290. C.
  • the glass transition temperature of the thermoplastic resin A is preferably not higher than the melting point (Tm) of the polyarylene sulfide, it is preferable to use a polyetherimide having a temperature of 280 ° C or lower, more preferably 260 ° C or lower.
  • Phenoxy) phenyl propane dianhydride and m-phenylene diamine Mines or condensates with p-phenylenediamine are preferred.
  • a polyetherimide having this structural unit is available from GI Plastics under the trade name "Ultem” (registered trademark).
  • Ultem 100 0” and “Ultem 1010” can be mentioned as poly-terimide having a structural unit (former formula) including a unit derived from m-phenylenediamine.
  • “Unoretem CRS5000” can be mentioned as a polyetherimide having a structural unit containing the unit derived from p-phenylenediamine (the latter formula).
  • thermoplastic resin A contained in the biaxially oriented polyarylene sulfide film of the present invention include polysulfone having a sulfonic group in the molecular skeleton and polyetherolsulfone.
  • Polysulfone and polyethersulfone can be used by using various known ones.
  • the terminal group of polyether sulfone includes a chlorine atom, an alkoxy group or a phenolic hydroxyl group.
  • preferred examples of the thermoplastic resin A include polyphenylene ether and polyarylate whose molecular structure is similar to that of polyarylene sulfide.
  • the timing of mixing the polyarylene sulfide and the other thermoplastic resin A is not particularly limited, but before the melt extrusion, a mixture of the polyarylene sulfide and the other thermoplastic resin A is added.
  • a method of pre-melting and kneading (pelletizing) to form a master chip and a method of mixing and melt-kneading during melt extrusion.
  • a twin screw extruder Preferred examples include a method of pre-kneading into a master chip using a high shear mixer with shearing stress.
  • the mixed master chip raw material is put into a normal single-screw extruder to form a melt film, and sheeting is directly performed without forming a master chip in a state where high shear is applied. May be.
  • a method of pre-melting and kneading (pelletizing) a mixture of the respective resins before melt extrusion to form a master chip is preferable, in which case the weight fraction of polyarylene sulfide and thermoplastic resin A is It is preferable to prepare a blend raw material of 99Zl to 70/30.
  • the melting point (Tm) of the PPS resin is preferred in the kneading section where a three-screw or two-screw type screw is preferred from the viewpoint of reducing poor dispersion.
  • a resin temperature range of +5 to Tm + 120 (° C) is preferred.
  • the preferred temperature range is 13 ⁇ 41 + 10 to 13 ⁇ 41 + 90 (°, and the preferred temperature range is 13 ⁇ 41 + 10 to 13 ⁇ 41 + 70 (°.
  • the temperature range of the kneading part should be in the preferred range.
  • the effect of increasing the shear stress and immediately reducing the defective dispersion can be increased, and the dispersion diameter of the dispersed phase can be controlled within the preferred range of the present invention, with a residence time of 0.5 to 5 minutes.
  • the dispersion diameter of the dispersed phase that is easily subjected to high shear stress can be controlled within the preferred range of the present invention, and the ratio of (screw shaft length / screw shaft diameter) of the twin screw extruder is 20-60. Is preferably in the range of 30-50.
  • a kneading part such as a needing paddle in order to increase the kneading force in the twin screw, and preferably two or more, more preferably three or more kneading parts are provided.
  • a kneading part such as a needing paddle in order to increase the kneading force in the twin screw, and preferably two or more, more preferably three or more kneading parts are provided.
  • the compatibilizer in order to control the dispersion diameter of the thermoplastic resin A domain, has one or more groups selected from an epoxy group, an amino group, and an isocyanate group. The compound is preferably added in an amount of 0.:!
  • force and such compatibilizers include bisphenol 8-resorcinol, hydride quinone, pyrotechnicol, bisphenol, saligenin, 1, 3, 5-trihydroxybenzene.
  • Bisphenol 3 trihydroxydidiphenyldimethylmethane, 4,4'-dihydroxybiphenylenolate, 1,5 dihydroxynaphthalene, cashew phenol, 2. 2. 5.
  • Glycidyl ethers of bisphenols such as xanthine, those using halogenated bisphenol instead of bisphenol, glycidyl ether compounds such as diglycidyl ether of butanediol, glycidyl ester compounds such as glycidyl phthalate, N Glycidylamine compounds such as glycidyl dilin etc.
  • Jill epoxy resin epoxidized polyolefin, linear epoxy compounds such Epokishii spoon soybean, hexene-dioxide to Bierushikuro, such as a non glycidioxypropyl Honoré epoxy resin of a cyclic system such as dicyclopenta diene-dioxide and the like.
  • Other examples include novolac type epoxy resins.
  • the novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting novolak type phenol resin with epichlorohydrin.
  • a novolac type phenol resin is obtained by a condensation reaction of phenols with formaldehyde.
  • the most preferred compatibilizer for use in the biaxially oriented polyarylene sulfide film of the present invention include alkoxysilanes having one or more functional groups selected from an epoxy group, an amino group, and an isocyanate group.
  • alkoxysilanes having one or more functional groups selected from an epoxy group, an amino group, and an isocyanate group.
  • powerful compounds include epoxy group-containing alkoxysilane compounds such as ⁇ - (3,4_epoxycyclohexyleno) ethinoretrimethoxysilane, ⁇ -ureidopropyltriethoxysilane, and ⁇ -ureidopropinoretrimethoxy.
  • Silane ureido group-containing alkoxysilane compounds such as ⁇ _ (2-ureidoethyl) aminopropyltrimethoxysilane, ⁇ -isocyanate propyltriethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanine
  • ⁇ _ (2-ureidoethyl) aminopropyltrimethoxysilane
  • ⁇ -isocyanate propyltriethoxysilane ⁇ -isocyanatopropyltrimethoxysilane
  • ⁇ -isocyanine Such as topropylmethyldimethoxysilane, ⁇ -isocyanate propylmethyl methoxysilane, ⁇ -isocyanate propylethyldimethoxysilane, ⁇ -isocyanate propylethyl methoxysilane, —isocyanane propyltrichlorosi
  • Amino group containing alkoxysilane compounds ⁇ _ (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ aminopropyltrimethoxysilane, etc.
  • Examples include alkoxysilane compounds.
  • ⁇ -isocyanatopropyltriethoxysilane ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane, ⁇ -isocyanatepropylmethyljetoxysilane, ⁇ -isocyanate
  • an alkoxysilane compound containing an isocyanate group such as propylethyldimethoxysilane, ⁇ -isocyanatepropylethyloxysilane, or ⁇ isocyanatepropyltrichlorosilane is used, a biaxially oriented polyarylene sulfide film is formed. It becomes easy to control the average dispersed diameter of the dispersed phase within the preferable range of the present invention.
  • an alkoxysilane-derived alcohol may be generated during kneading or extrusion.
  • a twin-screw extruder having at least two kneading parts, once with polyphenylene sulfide and thermoplastic resin ⁇
  • a preferred method is to melt and knead the compatibilizer and then melt and knead it once or more.
  • 0.02 part or more of water is added to 100 parts by weight of the total of the polyurethane sulfide and the thermoplastic resin A. More preferably, it may be preferable to add 0.1 to 5 parts.
  • hydrolysis of the alkoxysilane compound is promoted, and the amount of alcohol generated from the resulting resin composition can be reduced. It is possible to remove as much as possible the impure substances and oligomers in the polyarylene sulfide, thermoplastic resin A, alcohol generated from the reaction of the compatibilizing agent, etc., as much as possible.
  • the method of adding water is not particularly limited, but a method of side-feeding water using a liquid feed device such as a gear pump or plunger pump from the middle of the extruder, or once melt-kneading and then melt-kneading once more. In this case, a method of blending water or side feeding from the middle of the extruder is a preferable method.
  • the resin composition constituting the film has a melt specific resistance at 310 ° C of 1.0 X 10 9 Q 'cm to l. 0 X 10 ". ⁇ 'cm Power is preferable from the viewpoint of obtaining a film excellent in electrical insulation particularly at high temperature and high voltage.
  • the PPS resin used in the present invention is deionized or deoxidized. Specific examples of methods that are preferably treated with metal components include acid aqueous solution washing treatment, hot water washing treatment, organic solvent washing treatment, and entrainer treatment.
  • the treatment may be a combination of two or more methods, but it is more preferable to use PPS that has at least an acid aqueous solution cleaning treatment to reduce the amount of metal.
  • mass -It is also preferable to perform an entrainer treatment at the time of chip formation, and the above range can be achieved by combining these methods, and it is melted from the viewpoint of the electrical characteristics of the film, particularly the high temperature characteristics when a single capacitor is used.
  • a higher specific resistance is preferable, while a melting specific resistance is preferred.
  • the resistance is not particularly limited, but is preferably 1. ⁇ ⁇ ⁇ ⁇ ⁇ 'cm or less from the viewpoint of electrostatic castability during film formation.
  • a plasticizer In the film of the present invention, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a lubricant, an antistatic agent, an increase agent are used as long as the effects of the present invention are not impaired.
  • Whitening agents, coloring agents, conductive agents and fungicides may be added.
  • the biaxially oriented polyarylene sulfide film of the present invention preferably has a thickness of 00 x m or less depending on the application. In the case of a condenser, it is 0.5 to 20 111, more preferably 1 to 10 zm. In the case of a film for electrical insulation, the viewpoint power such as workability, etc., is more preferably in the range of 10 to 300 ⁇ , and still more preferably in the range of 20 to 200 ⁇ .
  • the biaxially oriented polyarylene sulfide film of the present invention includes a polyarylene sulfide film and other polymer layers, for example, a layer made of polyester, polyolefin, polyamide, polyimide, polyvinylidene chloride, or an acrylic polymer. These may be used by further laminating directly or via a layer such as an adhesive.
  • the biaxially oriented polyarylene sulfide film of the present invention is subjected to any processing such as heat treatment, molding, surface treatment, lamination, coating, printing, embossing and etching, as necessary. Motole.
  • the biaxially oriented polyarylene sulfide film of the present invention is a process such as a dielectric for capacitors, motors, transformers, and other electrical insulating materials and molding materials, circuit board materials, circuit / optical members, etc. Used for films, protective films, lithium-ion battery materials, fuel cell materials, diaphragms, etc. In particular, since it has excellent electrical insulation performance at high temperatures, it can be preferably used for capacitors, electrical insulation materials, circuit boards and the like. Furthermore, when used as a capacitor dielectric, it has excellent SH characteristics, so it can be used as a capacitor with high safety and heat resistance.
  • the polyarylene sulfide film is made of poly (rho) _phenylene sulfide and thermoplastic resin ⁇ made by GI Plastics Co., Ltd.
  • thermoplastic resin ⁇ made by GI Plastics Co., Ltd.
  • An example of the production of a biaxially oriented polyphenylenediamine film composed of the polyetherimide “Ultem 1010” will be described.
  • the present invention It is not limited to the description.
  • the PPS and PEI into a twin-screw kneading extruder to prepare a blend raw material having a weight fraction of PPS and PEI of 99Zl to 70Z30.
  • the mixing and kneading method of the resin composition of the blend raw material is not particularly limited, and various mixing and kneading means can be used.
  • each may be separately fed to a melt extruder and mixed, or only the powder raw material may be dry premixed using a mixer such as a Henschel mixer, ball mixer, blender or tumbler, Then, melt kneading with a melt kneader.
  • the blended raw material is put into an extruder together with PPS and these recovered raw materials, and the desired composition is used as the raw material from the viewpoint of film quality and film formability.
  • the desired composition is used as the raw material from the viewpoint of film quality and film formability.
  • various filters for example, filters made of materials such as sintered metal, porous ceramic, sand and wire mesh.
  • a gear pump may be provided as necessary to improve the quantitative supply.
  • PPS pellets or granules and PEI pellets are mixed at a constant ratio, supplied to a vent type twin-screw kneading extruder, and melt-kneaded to obtain a blended chip. It is preferable to use a high-shear mixer with high shear stress, such as a twin-screw extruder, and from the viewpoint of reducing poorly dispersed products, equipped with a three- or two-screw type screw
  • the residence time is preferably in the range of 1 to 5 minutes. Further, in the kneading part, it is preferable that the resin temperature range is 290 to 405 ° C, and a more preferable temperature range is 295 to 355 ° C.
  • the resin temperature range of the kneading part By setting the resin temperature range of the kneading part to a preferable range, the effect of increasing the shear stress and immediately reducing the defective dispersion is enhanced, and the dispersion diameter of the dispersed phase is reduced.
  • the preferred range of the invention can be controlled. Further, it is preferable to set the screw rotation speed to 100 to 500 rotations / minute, and more preferably 200 to 400 rotations / minute. By setting the screw rotation speed within a preferred range, a high shear stress is easily applied, and the dispersion diameter of the dispersed phase can be controlled within the preferred range of the present invention. Further, the ratio of (screw shaft length Z screw shaft diameter) of the twin screw extruder is preferably in the range of 20-60, more preferably in the range of 30-50.
  • a twin screw it is preferable to provide a kneading part with a needing paddle to increase the kneading force.
  • Two or more kneading parts are provided, and a normal feed screw is provided between each kneading part. It is more preferable to use a screw shape.
  • blend chips made of PPS and PEI obtained by the above pelletizing operation, and optionally mixed PPS, raw materials mixed with the collected raw materials after film formation and particles are mixed appropriately at a certain ratio.
  • it After drying at 180 ° C for 3 hours or more under reduced pressure of lOmmHg or less, it is put into an extruder heated to a temperature of 300 to 350 ° C, preferably 320 to 340 ° C. Thereafter, the molten polymer that has passed through the extruder is passed through a filter, and then the molten polymer is discharged into a sheet form using a die of a T die.
  • This sheet-like material is closely attached to a cooling drum having a surface temperature of 20 to 70 ° C. to be cooled and solidified to obtain a substantially non-oriented unstretched polyphenylene sulfide phenol.
  • the unstretched polyphenylene sulfide film is biaxially stretched to be biaxially oriented.
  • Stretching methods include sequential biaxial stretching (stretching that combines stretching in each direction, such as stretching in the longitudinal direction after stretching in the longitudinal direction), and simultaneous biaxial stretching (longitudinal and width directions). Can be used at the same time), or a combination thereof.
  • the unstretched polyphenylene sulfide film is heated with a heating roll group, and the stretching ratio is 3 to 5 times in the longitudinal direction (MD direction), preferably 3.3 to 4.7 from the viewpoint of improving the electrical characteristics. Double, more preferably 3.5 to 4.5 times, stretching in one or more stages (MD stretching) .
  • the stretching temperature is Tg (PPS glass transition temperature) to (Tg + 50) ° C, preferably (Tg + 5) to (Tg + 50) ° C, more preferably (Tg + 5) to (Tg + 40). ) ° C range. Then, it is cooled with a cooling roll group at 20 to 50 ° C.
  • a stretching method in the width direction (TD direction) following MD stretching for example, a method using a tenter is common.
  • the film is gripped at both ends with a clip, guided to a tenter, and stretched in the width direction (TD stretching).
  • the stretching temperature is properly preferred to Ding ⁇ ⁇ ⁇ + 60) in the preferred instrument (Tg + 5) ⁇ (Tg + 50).
  • C more preferably (Tg + 10) to (Tg + 40).
  • the draw ratio is 3 to 5 times, preferably 3.3 to 4.7 times, and more preferably 3.5 to 4.5 times from the viewpoint of improving electrical characteristics.
  • the stretched film is heat-set under tension.
  • the preferred heat fixation temperature is 170 to 275 ° C, preferably 200 to 250 ° C
  • the heat fixation time is 1 second to 1000 seconds, preferably 1 second to 60 seconds, more preferably. 1 to 30 seconds.
  • the heat setting after stretching is carried out in two or more steps with different temperatures, and the heat setting temperature of the first step is (previous stretching temperature + 5 ° C) to 240 ° C.
  • the maximum value of the heat setting temperature of the latter stage is 200 ° C or higher or (the heat setting temperature of the first stage + 5 ° C) or higher and (the melting point of the polyarylene sulfide constituting the film is 5 ° C or lower). More preferably, the heat setting temperature of the first stage is (the previous stretching temperature + 5 ° C) to 220 ° C, and the maximum value of the heat setting temperature of the second stage is 230 ° C or higher (or the heat of the first stage). (Fixing temperature + 30 ° C.) or higher and (the melting point of polyarylene sulfide constituting the film is 5 ° C.) or lower.
  • heat fixation at the first stage is 1 second to 1000 seconds, preferably 1 second to 60 seconds, more preferably 1 second to 30 seconds, and heat fixation at the highest temperature of the subsequent stage is 1 second to
  • the time is 1000 seconds, preferably 1 second to 60 seconds, more preferably 1 second to 10 seconds, and the entire heat setting time is 2000 seconds, preferably 120 seconds, more preferably 30 seconds.
  • the film is relaxed in the width direction at a temperature zone of 40 to the melting point of polyarylene sulfide, more preferably the stretching temperature or more and the heat setting temperature or less (in the case of multistage heat setting, the highest heat setting temperature or less).
  • the relaxation rate is preferably 0.1 to 8%, more preferably 1.5 to 6%, and even more preferably 2 to 5%.
  • the relaxation treatment is carried out in the above temperature range for 1 second to 100 seconds, preferably 1 second to 60 seconds, more preferably 1 second to 10 seconds.
  • the metallized film of the present invention has a metal layer formed on at least one side of a strong biaxially oriented film, and uses a metal thin film formed by a method such as vacuum evaporation or sputtering. can do.
  • metals include, but are not limited to, aluminum, zinc, tin, titanium, nickel oleore, or alloys thereof.
  • the film capacitor 1 of the present invention can be manufactured with a known method such as a winding method or a lamination method. As a conductor of such a capacitor, it is possible to use the above metallized film.
  • the metal foil and the laminated film of the present invention are alternately stacked by rolling the foil or inserting a tab in the middle of winding.
  • a capacitor element or a capacitor mother element is obtained by winding the dielectric body and the electrode alternately so that the electrode can be drawn to the outside.
  • the metallization method is preferably a vapor deposition method.
  • the metal to be deposited is preferably a metal containing aluminum as a main component.
  • the adhesion between the metal thin film and the film can be improved by a treatment such as corona discharge treatment or plasma treatment on the surface of the film to be metallized beforehand.
  • a non-metalized part so-called margin
  • a non-metallized band can also be provided using a laser beam or the like.
  • the metallized film is slit into a narrow tape shape with a margin at one end, and two sheets are stacked, or double-sided metallized film and non-metallized film are stacked. It is a common practice to move individual elements individually. There is also a method of winding a single composite film in which a second dielectric is provided on a double-sided metallized film by a coating method or the like.
  • the capacitor is wound around a large-diameter drum or flat plate. Get the mother element.
  • the film can be heated to a temperature of 100 ° C. or higher and below the melting point of the film.
  • the external electrode mounting process by metal spraying, conductive resin, etc.
  • resin or oil impregnation process when using a lead type capacitor, lead wire mounting process, exterior process, Obtainable.
  • the capacitor In the case of multilayer capacitors, pressure is applied in the thickness direction of the film, such as heat treatment of a large-diameter drum or mother element wound on a flat plate, tightening with a ring, or pressing with a parallel plate. Mold. In this case, the temperature range is from room temperature to the melting point of the film. Thereafter, the capacitor can be obtained through an external electrode attaching step (metal spraying, using a conductive resin), individual element cutting step, and if necessary, a resin or oil impregnation step.
  • an external electrode attaching step metal spraying, using a conductive resin
  • individual element cutting step if necessary, a resin or oil impregnation step.
  • the shape of the capacitor of the present invention may be any of the above.
  • the capacitor of the present invention can be developed for both AC and DC applications.
  • the characteristic value measuring method and the effect evaluating method of the present invention are as follows.
  • thermoplastic resin A is polyamide, dyeing with phosphotungstic acid is used.
  • the thermoplastic resin A is polyetherimide, dyeing is unnecessary.
  • the cut surface was observed with a transmission electron microscope (H-7100FA model, manufactured by Hitachi) under the condition of an applied voltage of lOOkV, and a photograph was taken at 20,000 times.
  • the obtained photographs were loaded into an image analyzer as images, 100 arbitrary dispersed phases were selected, and image processing was performed.
  • the size of each dispersed phase was determined as follows.
  • (u) The maximum length (le) in the film longitudinal direction and the maximum length (If) in the width direction were determined.
  • the shape index of the dispersed phase 1 (average value of lb + average value of le) / 2
  • shape index 3 ⁇ 4J (average value of Id + average value of lf) / 2
  • shape index K (average of la Value + lc average value) / 2
  • the average dispersion diameter of the dispersed phase was (I + J + K) Z3.
  • the average major axis L and the minimum minor axis D were determined from I, J, and K, and the aspect ratio of the dispersed phase was L / D.
  • the glass transition temperature of the raw material chips of polyarylene sulfide and thermoplastic resin A was measured in accordance with JIS K7121-1987.
  • the melting temperature using a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments Inc. and a disk station (SSC / 5200) manufactured by Seiko Instruments Inc. as a data analyzer, a 5 mg sample was obtained from room temperature on an aluminum tray. The temperature was raised to 20 ° C at a rate of 20 ° C / min, melted and held at 340 ° C for 5 minutes, rapidly solidified, held for 5 minutes, and then heated from room temperature at a rate of 20 ° C / min. . At that time, the peak temperature of the endothermic peak of melting observed was defined as the melting temperature (Tm).
  • Tm melting temperature
  • the measurement was performed under the conditions of an environmental temperature of 150 ° C according to the circular plate electrode method specified in JIS C2151—1990. After applying 500 V DC voltage at 150 ° C using a superinsulator (SM-5E type, manufactured by Toa Denpa Co., Ltd.), the sample was formed by vacuum-depositing aluminum on both sides of the film and forming electrodes 1 It calculated
  • SM-5E type manufactured by Toa Denpa Co., Ltd.
  • Dielectric breakdown voltage (withstand voltage) of film According to the method specified in JIS C2151-1990, the measurement was performed under the conditions of ambient temperature 23 ° C and 150 ° C. The measurement was performed using a 100 cm thick, 10 cm square aluminum foil electrode on the cathode, and a brass electrode with a diameter of 25 mm and a weight of 500 g on the anode, and a high voltage DC power supply (Kasuga Electric) The pressure was increased at a rate of 100 VZ seconds using TFV4—LC), and the dielectric breakdown was considered when 10 mA or more flowed. This measurement was repeated 30 times, and the average of the values divided by the film thickness was taken as the dielectric breakdown voltage of the film. The breakdown voltage at 23 ° C and 150 ° C was V (23) and V ( 150). For V (23), the standard deviation in the value measured 30 times was obtained.
  • the film was cut in a direction parallel to the longitudinal direction and perpendicular to the film surface, and a sample was prepared by an ultrathin section method.
  • it may be dyed with osmic acid, ruthenic acid, phosphotungstic acid or the like.
  • the thermoplastic resin A is polyamide, dyeing with phosphotungstic acid is preferably used.
  • the melt specific resistance (P) was determined according to the following formula.
  • V Applied voltage (V)
  • Aluminum was evaporated on one side of the film so that the surface resistance was 10 ⁇ .
  • vapor deposition was performed in a stripe shape having a margin portion running in the longitudinal direction (repetition of a vapor deposition portion width of 80 mm and a margin portion width of 10 mm).
  • a slit was put in the center of each vapor deposition part and the margin part of this vapor deposition film, and it was scraped off in the form of a tape having a total width of 45 mm having a 5 mm margin part on the left or right.
  • the obtained tape was overlapped and wound for each of the left margin and the right margin to obtain a wound body having a capacitance of 5 ⁇ F.
  • the two films were shifted and wound so that the vapor deposition part protruded 5 mm from the margin part in the width direction.
  • the core material was removed from these wound bodies and pressed as it was for 5 minutes at a temperature and pressure of 200 ° C, 25 kg / cm 2 .
  • metallicon was sprayed on both end surfaces to form external electrodes, and lead wires were welded to the metallicon to obtain capacitor elements.
  • the obtained element was heat-treated at 220 ° C. for 2 hours, and then packaged with a powder epoxy resin (average package thickness: 0.5 mm) to prepare a capacitor.
  • a capacitor element was prepared in the same manner as (a) above, and the shape of the element was confirmed visually.
  • Capacitor element film is slightly displaced or deformed, but there is no problem in the subsequent process.
  • Place 30 capacitors in a 150 ° C oven equip each capacitor with a switch that stops the charging voltage when broken, connect it in parallel with the DC power generator, and continue to apply m voltage for 1000 hours,
  • the destroyed capacitor element was regarded as a defective withstand voltage element, and the defect rate (%) was judged according to the following criteria. ⁇ and ⁇ are acceptable.
  • the base length was 10 mm
  • the base diameter was 1. Omm
  • the preheating time was set to 5 minutes
  • the measurement was performed at 310 ° C.
  • Peak Thresh ref (Threshold threshold): ZERO
  • the measurement conditions of the microscopic Raman by the laser Raman scattering method are as follows.
  • Microprobe Objective lens ⁇
  • Nd_YAG (wavelength 1064nm, output: 1W)
  • Diffraction grating Spectrograph 300g / mm Suritsu: 100 / im
  • the film used for measurement was sampled and embedded in an epoxy resin, and then the film cross section was taken out with a microtome.
  • the film cross section was adjusted to be parallel to the film longitudinal direction or width direction, and the average value was obtained by measuring 5 samples for each of the longitudinal direction and width direction with the central point of each sample as the measurement point. .
  • the orientation parameter of the lens was determined.
  • Measurement was performed using an Instron type tensile tester according to the method prescribed in ASTM-D882-97. The measurement was performed under the following conditions, and was performed with 10 samples in each of the longitudinal direction and the width direction. Breaking elongation, breaking strength, and Young's modulus are the average of elongation in the tensile test in the lower direction, higher in the higher direction, and removing the highest and lowest 2 measurements each for the remaining 6 measurements. Value. Also, for each of the data sampling points (excluding the sampling points at both ends), the differential coefficient is obtained for each of the longitudinal and width directions, and the two measurements at the center of the permutation of elongation. The average value of the minimum values of each measurement in the section of elongation 2% and (elongation at break (%)-5%) was taken, and the smaller value was compared with both, and the value of the lower one was the minimum derivative ⁇ min .
  • Measuring device Orientec Co., Ltd. film strong elongation automatic measuring device "Tensilon AMFZ RTA-100"
  • ⁇ (N) ⁇ S (N + 1)-S (N) ⁇ / ⁇ E (N + 1) — E (N) ⁇
  • the amount of water remaining in the system per mole of the alkali metal sulfide charged was 1.06 mol including the water consumed for the hydrolysis of NMP.
  • the amount of hydrogen sulfide scattered was 0.02 mol per mol of the alkali metal sulfide charged.
  • a PPS resin was prepared in the same manner as in Reference Example 1 except that the cleaning process in Reference Example 1 was as follows.
  • the content was taken out, diluted with 26,300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed 4 times with 31,900 g of NMP and filtered. This was washed 5 times with 56, OOOg of ion-exchanged water and filtered, then washed twice with 0.05% by weight acetic acid aqueous solution 70, OOOg and filtered. After washing with 70,000 g of ion-exchanged water 5 times and filtering, the obtained hydrous PPS particles were dried with hot air at 80 ° C and dried under reduced pressure at 120 ° C.
  • the obtained PP S had a melt viscosity of 200 Pa's (310 ° C, shear rate of 1,000 / s), a glass transition temperature force of S93 ° C, and a melting point of 285 ° C.
  • a PPS resin was prepared in the same manner as in Reference Example 1 except that a calcium acetate aqueous solution was used instead of the acetic acid aqueous solution in the cleaning process of the reference example.
  • the obtained PPS resin had a melt viscosity of 210 Pa's (310 ° C, shear rate of 1,000 / s), a glass transition temperature of 93 ° C, and a melting point of 285 ° C.
  • silica spherical fine particles with an average particle size of 0.55 ⁇ (“Chihoster KEP-50” manufactured by Nippon Shokubai Co., Ltd.) were added and the same with a vent.
  • NMP N methyl _ 2_pyrrolidone
  • dewatering 89 8 mol% of over-dichlorobenzene finished into the system as the main component monomer, 10 mol 0/0 as a secondary component monomers m- dichlorobenzene, and 0. 2 Monore 0/0 1, 2, 4 - the trichloroacetic port benzene was added with 5 liters of NMP, after nitrogen 3 kg / cm 2 Caro pressure sealed at 170 ° C, the temperature was raised, and polymerized for 4 hours at 260 ° C. After completion of the polymerization, the mixture was cooled, the polymer was precipitated in distilled water, and a small polymer was collected with a wire mesh having a 150 mesh opening.
  • This polymer was washed 5 times with distilled water at 90 ° C and then dried at 120 ° C under reduced pressure to obtain a copolymerized PPS composition in the form of white particles having a melting point of 50 ° C.
  • PPS-1 resin prepared in Reference Example 1 was dried at 180 ° C for 3 hours under a reduced pressure of ImmHg.
  • Polyetherimide as thermoplastic resin A (“Ultem 10 10" manufactured by GE Plastics) (PEI) Were dried separately under reduced pressure of ImmHg at 120 ° C for 3 hours.
  • the polymer melted by the extruder was filtered through a filter set at a temperature of 320 ° C, melt-extruded from a die of a T die set at a temperature of 320 ° C, and then cast at a surface temperature of 25 ° C. While applying an electrostatic charge to the film, it was closely cooled and solidified to produce an unstretched polyresin film film.
  • This unstretched polyphenylene sulfide film is composed of a plurality of heated roll groups. Using a longitudinal stretching machine, the film was stretched at a magnification of 3.8 times in the longitudinal direction of the film at a film temperature of 103 ° C and a stretching speed of 3000 0% / min. Then, grip both ends of this film with clips and guide it to a tenter, and stretch it in the width direction of the film at a stretching temperature of 105 ° C, a stretching speed of 1 100% / min, and a stretching ratio of 3.8 times.
  • Table 1 shows the measurement, evaluation results, and capacitor characteristics of the resulting biaxially oriented polyphenylene sulfide film, and the characteristics of the biaxially oriented polyphenylene sulfide film.
  • the insulation characteristics and withstand voltage were excellent, and the capacitor was in good condition.
  • the raw material prepared by dry blending 90 parts by weight of PPS-1 resin and 10 parts by weight of particle master chip prepared in Reference Example 1 was dried at 180 ° C for 7 hours under a reduced pressure of ImmHg, and then the melting part was adjusted to 320 ° C. It was fed to a heated full flight single screw extruder.
  • the measurement, evaluation results, and capacitor characteristics of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1.
  • This biaxially oriented polyphenylene sulfide film is an example. Compared to 1, the volume resistivity was almost the same, but it was inferior to the dielectric breakdown voltage at high temperature. Furthermore, in terms of capacitor characteristics, the SH property was low and the high-temperature heat resistance was low and insufficient.
  • thermoplastic resin A As shown in Table 1.
  • Both the biaxially oriented polyphenylene sulfide films of Examples 2 and 4 were excellent in capacitor performance with high dielectric breakdown voltage at high temperatures.
  • thermoplastic resin A The amount of PEI and compatibilizer added to thermoplastic resin A was changed as shown in Table 1, and the longitudinal stretch was stretched 3.4 times at a film temperature of 105 ° C and the transverse stretch was 3.6 times at 106 ° C.
  • a biaxially oriented polyphenylene sulfide film having a thickness of 3.8 zm and a capacitor using the same were prepared in the same manner as in Example 1 except that the drawing was performed. Compared with Example 1, the film formation stability was slightly inferior, and tearing occurred during film formation.
  • the biaxially oriented polysulfide film of this example has a slightly lower withstand voltage and a slightly lower withstand voltage in terms of capacitor characteristics, but it is sufficiently high compared to Comparative Example 1 and is problematic in practical use. There was no level. (Example 5)
  • the capacitor used was created.
  • the biaxially oriented polyimide film of this example had excellent withstand voltage and good capacitor characteristics.
  • Biaxially oriented polyphenylene sulfide film having a thickness of 3.5 zm and the same as in Example 1 except that polyphenylene ether (YPX-100A manufactured by Mitsubishi Gas Chemical Co., Ltd.) (PPE) is used as thermoplastic resin A.
  • PPE polyphenylene ether
  • a capacitor was made using Second of this example The axially oriented polyphenylene sulfide film had excellent withstand voltage and good capacitor characteristics.
  • Biaxially oriented polyphenylene sulfide film having a thickness of 3.7 xm as in Example 1 except that polyethersulfone ("RADEL" A_200A) (P ES) manufactured by Amoco is used as thermoplastic resin A And the capacitor which used it was made.
  • the biaxially oriented polyphenylene sulfide film of this example had excellent withstand voltage and good capacitor characteristics.
  • ⁇ -isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “ ⁇ 9007”) is bisphenol type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., described as “Epicord 1004, C2”), and longitudinal stretching is performed at the film temperature.
  • a biaxially oriented polyethylene sulfide film with a thickness of 3.8 ⁇ and a 3.8 ⁇ -thick biaxially oriented film are the same as in Example 1 except that the film is stretched 3.5 times at 103 ° C and stretched 3.6 times at 105 ° C.
  • Capacitors used were prepared.Slightly inferior in film formation stability compared to Example 1 and tearing occurred during film formation.
  • the biaxially oriented polyphenylene sulfide film of this example had a little withstand voltage. The power is slightly lower and the withstand voltage is slightly inferior even in the capacitor characteristics. This is a sufficiently high level compared to the comparative example, and there is no problem in practical use.
  • PPS-1 resin prepared in Reference Example 1 was dried at 180 ° C for 3 hours under a reduced pressure of ImmHg.
  • Polyetherimide as thermoplastic resin A ("Ultem 10 10" manufactured by GE Plastics) (PEI) Were dried separately under reduced pressure of ImmHg at 120 ° C for 3 hours.
  • PEI thermoplastic resin A
  • y-isocyanate propyltriethoxysilane (KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.
  • the resulting PPS / PEI (70/30 parts by weight) blend chip raw material 17 parts by weight, PPS-3 resin prepared in Reference Example 3 73 parts by weight and particle master chip 10 parts by weight were drive-lensed and used as raw materials
  • a biaxially oriented polyphenylene sulfide film having a thickness of 3 and a capacitor using the same were prepared in the same manner as in Example 1 except that the film was extruded as.
  • the stretched film-forming property is good, the melt specific resistance is somewhat low, and the volume resistivity is also low compared to Example 1, but the obtained biaxially oriented polyphenylene sulfide film of this example is excellent in withstand voltage, The capacitor characteristics were also good.
  • thermoplastic resin A Except that the amount of PEI added to thermoplastic resin A was changed as shown in Table 1, the force of film formation was the same as in Example 1. .
  • Example 1 In the same manner as in Example 1, except that the amount of the thermoplastic resin A— isocyanate propyltriethoxysilane added was changed to 0.05 parts by weight as shown in Table 1, a thickness of 3.7 zm was obtained. An axially oriented polyphenylene sulfide film and a capacitor using the same were prepared. The average dispersion diameter of PEI was as large as 650 nm, and this film had insufficient low SH characteristics and insufficient capacitor properties with low high-temperature withstand voltage. (Examples 12, 14, 15)
  • a biaxially oriented polyester film and a capacitor using the same were prepared in the same manner as in Example 11 except that the film forming conditions and the film thickness were changed as shown in Table 2.
  • the measurement, evaluation results, and capacitor characteristics of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 2, both of which have high dielectric breakdown due to high temperature and room temperature withstand voltage. Capacitor characteristics with very little variation in measured voltage values were also very good.
  • PPS-1 resin prepared in Reference Example 1 was dried at 180 ° C for 3 hours under a reduced pressure of ImmHg.
  • Polyetherimide as thermoplastic resin A (“Ultem 10 10" manufactured by GE Plastics) (PEI) Were dried separately under reduced pressure of ImmHg at 120 ° C for 3 hours.
  • PEI thermoplastic resin A
  • y-isocyanate propyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., "KBE9007
  • a biaxially oriented polyimide film having a thickness of 3.4 xm and a capacitor using the same were prepared in the same manner as in Example 11.
  • the stretched film-forming property was good, and even when the film was formed for a long time, it was stable with few generated gas and eyes.
  • the obtained biaxially oriented polyphenylene sulfide film has excellent withstand voltage and is a capacitor. One characteristic was also good.
  • a biaxially oriented polyethylene film and a capacitor using the same were prepared in the same manner as in Comparative Example 3 except that the film forming conditions and film thickness were changed as shown in Table 2.
  • the characteristics and capacitor characteristics of the obtained biaxially oriented polyester film are as shown in Table 2.
  • the SH characteristics of the capacitor characteristics were improved and there was no problem in practical use.
  • thermoplastic resin A was nylon 610 resin (nylon resin "Amilan CM2001” manufactured by Toray Industries, Inc.) (polyamide (PA)) and the film forming conditions were changed as shown in Table 2, Example 6 and Similarly, a biaxially oriented polyester film and a capacitor using the same were prepared.
  • the characteristics and capacitor characteristics of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 2. This biaxially oriented polyphenylene sulfide film has a slightly lower dielectric breakdown voltage, but the capacitor characteristics. In SH, the SH characteristics were improved and there was no problem in practical use.
  • the thickness of 3.5 / m was the same as in Example 11 except that 73 parts by weight of PPS-4 resin was used instead of PPS-3 resin and the film forming conditions were changed as shown in Table 2.
  • a biaxially oriented polyphenylene sulfide film and a capacitor using the same were prepared. This capacitor had good SH characteristics for its withstand voltage at high temperatures.
  • a biaxially oriented polyphenylene sulfide film having a thickness of 3.5 ⁇ m and a capacitor using the same were prepared in the same manner as in Example 11 except that the film forming conditions were changed as shown in Table 2.
  • the film of Comparative Example 6 and its capacitor had extremely low withstand voltage at high temperatures.
  • the film of Comparative Example 7 had a higher withstand voltage than Comparative Example 6, the film elongation exceeded 80%, and the SH property when using a single capacitor was insufficient.
  • the polymer melted by the extruder is filtered through a filter set at a temperature of 320 ° C, melt-extruded from a die of a T die set at a temperature of 320 ° C, and then cast at a surface temperature of 25 ° C. While applying an electrostatic charge to the film, it was closely cooled and solidified to produce an unstretched polyphenylene sulfide film.
  • This unstretched polyphenylene sulfide film was used in the longitudinal direction of the film at a temperature of 103 ° C using a longitudinal stretching machine composed of a plurality of heated roll groups and utilizing the peripheral speed difference of the rolls. 3. Stretched at a magnification of 8 times. After that, both ends of this film are gripped with clips and guided to a tenter, and stretched in the width direction of the film at a stretching temperature of 105 ° C and a stretching ratio of 3.8 times.
  • a biaxially oriented polyester film and a capacitor using the same were prepared in the same manner as in Example 18 except that the amount of PEI added to the thermoplastic resin (A) was changed as shown in Table 3. did.
  • the biaxially oriented polyphenylene sulfide film of Example 19 was excellent in voltage resistance and capacitor characteristics.
  • the biaxially oriented polyphenylene sulfide film of Example 20 was excellent in withstand voltage, and was slightly inferior in heat resistance in terms of capacitor characteristics, but at a level where there was no problem in practical use.
  • a biaxially oriented polyester film and a capacitor using the same were prepared in the same manner as in Example 18 except that the PPS resin (PPS-2) prepared in Reference Example 2 was used as the PPS resin.
  • the biaxially oriented polysulfide film of this example was excellent in withstand voltage, had poor capacitor characteristics, and was slightly inferior in heat resistance, but was problematic in practical use.
  • the biaxially oriented polyphenylene sulfide in this example had excellent withstand voltage and good capacitor characteristics.
  • a biaxially oriented polyurethane film and the same were used in the same manner as in Example 18 except that polyphenylene ether (YPX-100A manufactured by Mitsubishi Gas Chemical Company) (PPE) was used as the thermoplastic resin (A).
  • PPE polyphenylene ether
  • a capacitor was created.
  • the biaxially oriented polyester film of this example had excellent withstand voltage and good capacitor characteristics.
  • the polymer melted by the extruder is filtered through a filter set at a temperature of 320 ° C, and then melt-extruded from a die of a T die set at a temperature of 320 ° C, and then cast at a surface temperature of 25 ° C.
  • An electrostatic charge was applied to the drum, and it was closely cooled and solidified to produce an unstretched polyphenylene sulfide film.
  • a biaxially oriented polyphenylene sulfide film and a capacitor using the unstretched polyphenylene sulfide film were prepared.
  • the evaluation results and capacitor characteristics of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 3.
  • This biaxially oriented polyphenylene sulfide film has a surface protrusion height that is preferred in the present invention. It was out of range, and the withstand voltage and heat resistance when using a single capacitor was slightly low, but it was a problem.
  • the biaxially oriented polyarylene sulfide film of the present invention is to provide a biaxially oriented polyarylene sulfide film having excellent heat resistance, dimensional stability, electrical properties and planarity, particularly for capacitors. When used, it has high electrical characteristics and excellent self-healing property (SH property), so that it can be suitably used as a highly reliable film for a capacitor even when used at high temperature and high voltage. Furthermore, in the biaxially oriented polyarylene sulfide film of the present invention, a capacitor using a film can be suitably used as a small-sized and high-capacity high-performance capacitor.

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Abstract

L'invention concerne un film de polysulfure d'arylène à orientation biaxiale qui est excellent en termes de résistance à la chaleur, de stabilité des dimensions, de caractéristiques électriques et de planéité. En particulier, le film de polysulfure d'arylène a des caractéristiques électriques élevées et une excellente propriété d'autocicatrisation (SH) et il permet donc d'obtenir un condensateur présentant une fiabilité élevée au cours de l'utilisation à haute température et sous une tension élevée lorsque le film de polysulfure d'arylène est utilisé dans un condensateur. L'invention concerne également un film métallisé d'un tel film de polysulfure d'arylène et un condensateur utilisant le film métallisé. L'invention concerne précisément un film étiré de façon biaxiale caractérisé en ce qu'il contient un polysulfure d'arylène et une résine thermoplastique A autre que le polysulfure d'arylène et en ce qu'il a une phase en dispersion composée de la résine thermoplastique A et en ce qu'il a un diamètre moyen de la dispersion de 50-500 nm. Le film étiré de façon biaxiale est en outre caractérisé en ce qu'on observe une transition vitreuse du film sur la plage des températures étant égales ou supérieures à 85°C mais inférieures à 95°C mais en ce qu'on n'observe pas de transition vitreuse du film sur la plage des températures supérieures ou égales à 95°C et inférieures à 130°C.
PCT/JP2007/059481 2006-05-10 2007-05-08 Film de polysulfure d'arylène à orientation biaxiale WO2007129695A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009256608A (ja) * 2008-03-28 2009-11-05 Toray Ind Inc ポリフェニレンスルフィド樹脂組成物の製造方法およびポリフェニレンスルフィド樹脂組成物
WO2010004700A1 (fr) * 2008-07-08 2010-01-14 パナソニック株式会社 Condensateur à film métallisé
WO2016052303A1 (fr) * 2014-09-30 2016-04-07 日本ゼオン株式会社 Condensateur à film
WO2018142922A1 (fr) * 2017-02-03 2018-08-09 株式会社村田製作所 Condensateur à film, procédé de fabrication d'un condensateur à film, film de résine diélectrique et procédé de fabrication d'un film de résine diélectrique
EP3438165A4 (fr) * 2016-03-31 2019-11-20 Toray Industries, Inc. Film, feuille d'isolation électrique l'utilisant, bande adhésive, et machine rotative

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