WO2016080356A1 - Alignment film - Google Patents
Alignment film Download PDFInfo
- Publication number
- WO2016080356A1 WO2016080356A1 PCT/JP2015/082141 JP2015082141W WO2016080356A1 WO 2016080356 A1 WO2016080356 A1 WO 2016080356A1 JP 2015082141 W JP2015082141 W JP 2015082141W WO 2016080356 A1 WO2016080356 A1 WO 2016080356A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- heat
- less
- oriented film
- temperature
- Prior art date
Links
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- the present invention relates to an oriented film made of a styrene polymer having a syndiotactic structure. More specifically, the present invention relates to an oriented film made of a styrene-based polymer having a syndiotactic structure in which generation of heat loss due to wrinkles during heat treatment at a high temperature such as an evaporation process is suppressed.
- a film capacitor is manufactured by a method in which a film such as a biaxially oriented polyethylene terephthalate film or a biaxially oriented polypropylene film and a metal thin film such as an aluminum foil are overlapped and wound or laminated.
- film capacitors have also been miniaturized and mounted, and further heat resistance has been demanded in addition to electrical characteristics.
- the range of use extends not only in the cab, but also in the engine room.
- film capacitors that are suitable for environments with higher temperatures and higher humidity are required. Yes.
- Patent Document 1 Japanese Patent Laid-Open No. 2-143851
- Patent Document 2 Japanese Patent Laid-Open No. 3-124750
- Patent Document 3 Japanese Patent Laid-Open No. 5-200788
- Patent Document 4 International JP 2008/156210 pamphlet proposes a method using an ultrathin syndiotactic polystyrene film excellent in heat resistance and electrical properties.
- JP 2011-1111592 A discloses a thermoplastic amorphous resin having a glass transition temperature of 130 ° C. or higher in order to improve the heat resistance of the syndiotactic polystyrene film and further improve the film forming property. It has been proposed to be used in combination.
- Japanese Patent Laid-Open No. 2-143851 Japanese Patent Laid-Open No. 3-124750 Japanese Patent Laid-Open No. 5-200858 International Publication No. 2008/156210 Pamphlet JP 2011-1111592 A
- the present invention has been made in view of the above-described background art, and an object thereof is to provide an alignment film of a syndiotactic polystyrene resin that is excellent in suppressing generation of heat loss due to wrinkles during high-temperature heat treatment.
- the inventors of the present invention conducted intensive research to achieve the above-mentioned object, and conventionally, the heat yield at 200 ° C. was preferably less than 6% due to the occurrence of wrinkles and flatness.
- the film-forming conditions are shifted to a higher temperature side in accordance with the improvement in heat resistance. It was found that the breaking strength is lowered when the properties are improved.
- the inventors have found that by increasing the heat shrinkage rate at 200 ° C., the occurrence of heat loss due to shrinkage can be suppressed and the breaking strength can be improved, and the present invention has been achieved.
- a resin composition containing a thermoplastic amorphous resin having a syndiotactic styrene polymer as a main resin component and having a glass transition temperature of 130 ° C. or higher, and at 130 ° C. for 30 minutes.
- a thermoplastic amorphous resin having a syndiotactic styrene polymer as a main resin component and having a glass transition temperature of 130 ° C. or higher, and at 130 ° C. for 30 minutes.
- an oriented film having a heat shrinkage rate in the in-plane direction of 5.0% or less when treated and a heat shrinkage rate in at least one direction in the in-plane direction of 6.5% or more when heat-treated at 200 ° C. for 10 minutes. Is done.
- the peak temperature of the loss elastic modulus (E ′′) at a vibration frequency of 10 Hz is 125 ° C. or higher and the breaking strength is 90 MPa or higher.
- the average value of the heat shrinkage rate in the film forming direction and the width direction when the heat treatment is performed is 6.5% or more and 15.0% or less, and the heat shrinkage rate in the in-plane direction when heat treatment is performed at 130 ° C. for 30 minutes. It is at least one of 0.0% or more and 5.0% or less, that the thermoplastic amorphous resin is polyphenylene ether, that the film thickness is 0.3 to 30 ⁇ m, or that it is used for vapor deposition processing. An oriented film comprising one is also provided.
- the oriented film of the present invention suppresses generation of heat loss due to wrinkles during heat treatment at a high temperature such as a vapor deposition process, while using a polystyrene polymer having a syndiotactic structure excellent in electrical characteristics and heat resistance. Can do.
- the dielectric breakdown voltage is high, flatness can be secured even after high-temperature heat treatment such as a vapor deposition process, and it can be suitably used as a base film for a film capacitor that is extremely thin and difficult to handle.
- the oriented film of the present invention comprises a resin composition in which a thermoplastic amorphous resin having a glass transition temperature of 130 ° C. or higher is contained in a syndiotactic styrene polymer.
- the polystyrene resin having a syndiotactic structure in the present invention (hereinafter sometimes referred to as “syndiotactic polystyrene resin” or “SPS”) is used as a main chain formed of carbon-carbon bonds.
- the side chain has a three-dimensional structure in which phenyl groups and substituted phenyl groups are alternately positioned in opposite directions.
- tacticity is quantified by nuclear magnetic resonance ( 13 C-NMR) with isotope carbon, and abundance ratio of a plurality of consecutive structural units, for example, dyad in the case of two, triad in the case of three, In the case of five, it can be indicated by a pentad or the like.
- the polystyrene-based resin having a syndiotactic structure is polystyrene, poly (alkyl) having a syndiotacticity of 75% or more, preferably 85% or more, or 30% or more, preferably 50% or more, of pentad.
- Styrene poly (halogenated styrene), poly (alkoxystyrene), poly (vinyl benzoate), polymers in which a part of these benzene rings are hydrogenated, mixtures thereof, or structural units thereof.
- the copolymer containing is designated.
- poly (alkyl styrene) includes poly (methyl styrene), poly (ethyl styrene), poly (propyl styrene), poly (butyl styrene), poly (phenyl styrene), and the like. ) Include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like.
- poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
- polystyrene resins include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiarybutylstyrene), poly (p-chlorostyrene), and poly (m- Chlorostyrene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.
- polystyrene is preferable.
- polystyrene resin in the present invention is used as a copolymer containing a copolymer component, as its comonomer, in addition to the above-mentioned polystyrene resin monomer, ethylene, propylene, butene, hexene, octene.
- Olefin monomers such as diene monomers such as butadiene and isoprene, cyclic diene monomers, polar vinyl monomers such as methyl methacrylate, maleic anhydride, and acrylonitrile.
- the weight average molecular weight of this syndiotactic polystyrene resin is preferably 1.0 ⁇ 10 4 to 3.0 ⁇ 10 6 , more preferably 5.0 ⁇ 10 4 to 1.5 ⁇ 10 6. 6 , particularly preferably 1.1 ⁇ 10 5 to 8.0 ⁇ 10 5 .
- the weight average molecular weight is preferably 1.0 ⁇ 10 4 or more, preferably 5.0 ⁇ 10 4 or more, and particularly preferably 1.1 ⁇ 10 5 or more, the strength and elongation characteristics are excellent and the heat resistance is further improved.
- a molded product such as a film can be obtained.
- the stretching tension is in a suitable range, and at the time of film formation, etc. Breakage and the like are less likely to occur.
- the thermal contraction rate in the in-plane direction when the oriented film of the present invention is heat-treated at 130 ° C. for 30 minutes is 5.0% or less, preferably 3.0% or less. If the shrinkage rate exceeds the upper limit, the film after the high temperature heat treatment cannot maintain flatness, which is not preferable.
- the lower limit is not particularly limited, but wrinkles due to elongation of the film tend to occur when the negative heat shrinkage rate is reached, so that it is preferably ⁇ 1.0% or more, and more preferably 0.0% or more.
- the heat shrinkage rate in the in-plane direction of the film means the average value of the heat shrinkage rates in both directions when the film forming direction of the film and the direction perpendicular thereto are measured.
- the heat shrinkage rate in at least one direction in the in-plane direction when treated at 200 ° C. for 10 minutes is 6.5% or more, preferably 7.5% or more, and more preferably 8.5% or more. If the shrinkage rate is less than the lower limit, generation of heat loss due to wrinkles during high-temperature heat treatment cannot be suppressed, and the breaking strength is also reduced.
- the upper limit of the heat shrinkage rate is not particularly limited, but if it becomes excessively high, it becomes difficult to maintain the flatness of the film after the heat treatment, so it is 20% or less, further 18% or less, especially 15%. The following is preferable.
- any one of the film forming direction and the direction perpendicular to the film (width direction) has the above heat shrinkage characteristics. It means that it only needs to have a direction. Furthermore, it is preferable that the average value of the film forming direction of a film and the width direction exists in the said range, and it is preferable that each value of the film forming direction of a film and the width direction exists in the said range especially.
- the heat shrinkage rate in at least one direction in the in-plane direction when treated at 150 ° C. for 30 minutes is 3.0% or more, preferably 4.0% or more, which suppresses generation of heat loss due to wrinkles during high-temperature heat treatment. This is preferable because it is easy to increase the breaking strength.
- the upper limit of the heat shrinkage rate is not particularly limited, but if it becomes excessively high, it is difficult to maintain the flatness of the film after the heat treatment, so that it is 12% or less, and further 10% or less. preferable.
- either the film forming direction or the direction perpendicular to the film (width direction) has the above heat shrinkage characteristics. It means that it only needs to have a direction.
- the direction which comprises the said heat shrinkage rate is a direction with the largest heat shrinkage rate.
- the thermal shrinkage rate in at least one direction in the in-plane direction when treated at 180 ° C. for 10 minutes is 4.5% or more, preferably 5.5% or more. If the shrinkage rate is less than the lower limit, generation of heat loss due to wrinkles during high-temperature heat treatment cannot be suppressed, and the breaking strength is also reduced. On the other hand, the upper limit of the heat shrinkage rate is not particularly limited, but if it becomes too high, it tends to be difficult to maintain the flatness of the film after heat treatment, so that it is 15% or less, and further 13% or less. preferable.
- either the film forming direction or the direction perpendicular to the film (width direction) has the above heat shrinkage characteristics. It means that it only needs to have a direction.
- the direction which comprises the said heat shrinkage rate is a direction with the largest heat shrinkage rate.
- the heat shrinkage rate as described above can be achieved by a combination with a thermoplastic amorphous resin, which will be described later, and a film forming condition, particularly control of a heat setting temperature.
- the oriented film of the present invention preferably has a peak temperature of loss elastic modulus (E ′′) measured at a vibration frequency of 10 Hz by dynamic viscoelasticity measurement of 120 ° C. or more and 150 ° C. or less.
- a high peak temperature of the loss modulus (E ′′) means that the temperature at which molecular motion becomes active is high and the heat resistance is excellent.
- the peak temperature of the loss elastic modulus (E ′′) is more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher.
- the peak temperature of the loss modulus (E ′′) is too high, it also has the effect that the molecular motion is less likely to be active. Is more likely to occur.
- the peak temperature of the loss elastic modulus (E ′′) is more preferably 145 ° C. or less, and further preferably 140 ° C. or less.
- a thermoplastic amorphous resin may be employed and the content thereof may be adjusted as appropriate.
- the breaking strength decreases.
- the oriented film of the present invention preferably has a breaking strength of 90 MPa or more, and 100 MPa or more. Further preferred.
- Such a breaking strength can be achieved by a combination with a thermoplastic amorphous resin, which will be described later, and a film forming condition, particularly control of a heat setting temperature.
- the resin composition in the present invention contains a thermoplastic amorphous resin.
- the thermoplastic amorphous resin here is a thermoplastic amorphous resin having a glass transition temperature Tg determined by DSC (differential scanning calorimeter) of 130 ° C. or higher, which is higher than SPS.
- Tg glass transition temperature
- the substantial upper limit is preferably 350 ° C., more preferably 300 ° C.
- thermoplastic amorphous resins include aromatic polyethers such as polyphenylene ether and polyetherimide, polycarbonate, polyarylate, polysulfone, polyethersulfone, and polyimide.
- aromatic polyethers such as polyphenylene ether and polyetherimide
- polycarbonate such as polyethylene glycol
- polyarylate such as polysulfone
- polyethersulfone such as polyethylene glycol
- polyimide such as poly(ethylene glycol)
- polycarbonate such as polycarbonate, polyarylate, polysulfone, polyethersulfone, and polyimide.
- polyphenylene ether resin used here include conventionally known resins such as poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether) and poly (2-methyl-6-chloromethyl-1).
- 4-phenylene ether poly (2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene ether), poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1) , 4-phenylene ether), poly (2- (4′-methylphenyl) -1,4-phenylene ether), poly (2-bromo-6-phenyl-1,4-phenylene ether), poly 2-methyl-6-phenyl-1,4-phenylene ether), poly (2-phenyl-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2 -Methyl-1,4-phenylene ether), poly (2-chloro-6-ethyl-1,4-phenylene ether), poly (2-chloro
- those modified with a modifying agent such as maleic anhydride or fumaric acid are also preferably used.
- a copolymer obtained by graft copolymerization or block copolymerization of a vinyl aromatic compound such as styrene with the polyphenylene ether is also used.
- poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferred.
- the intrinsic viscosity (measured in chloroform at 30 ° C.) of the thermoplastic amorphous resin is preferably in the range of 0.2 to 0.8 dl / g, more preferably in the range of 0.3 to 0.6 dl / g.
- the intrinsic viscosity is less than 0.2 dl / g, the mechanical strength of the resulting resin composition may be lowered.
- it exceeds 0.8 dl / g the fluidity of the resulting resin composition is lowered, and the processing during melt molding into a film or the like tends to be difficult.
- Two or more kinds of thermoplastic amorphous resins may be used in combination, and in this case, those having different intrinsic viscosities may be mixed to obtain a desired intrinsic viscosity.
- the oriented film of the present invention preferably contains 5% by mass or more and 48% by mass or less of the above thermoplastic amorphous resin with respect to the mass of the oriented film.
- the thermoplastic amorphous resin By blending the thermoplastic amorphous resin in an amount within the above range, the heat resistance is excellent and the effect of improving the dielectric breakdown voltage can be increased, that is, the dielectric breakdown voltage at a high temperature can be increased.
- the content of the thermoplastic amorphous resin is more preferably 8% by mass or more, further preferably 11% by mass or more, and particularly preferably 20% by mass or more.
- the content of the thermoplastic amorphous resin is more preferably 45% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less.
- the oriented film of the present invention may be used in combination with other resins in addition to the SPS and the thermoplastic amorphous resin as long as the object of the present invention is not impaired.
- the oriented film of the present invention preferably contains an antioxidant.
- the antioxidant may be either a primary antioxidant that captures the generated radicals to prevent oxidation, or a secondary antioxidant that decomposes the generated peroxides to prevent oxidation.
- Examples of the primary antioxidant include phenol-based antioxidants and amine-based antioxidants, and examples of the secondary antioxidant include phosphorus-based antioxidants and sulfur-based antioxidants. Of these, primary antioxidants are preferred, and phenolic antioxidants are particularly preferred.
- the antioxidant has a thermal decomposition temperature of 250 ° C. or higher.
- the thermal decomposition temperature of the antioxidant is more preferably 280 ° C. or higher, further preferably 300 ° C. or higher, and particularly preferably 320 ° C. or higher.
- the antioxidant in the present invention is preferably less susceptible to thermal decomposition and preferably has a higher thermal decomposition temperature, but in reality, the upper limit is about 500 ° C. or less.
- the melting point of the antioxidant is preferably 90 ° C. or higher. If the melting point is too low, the antioxidant melts faster than the polymer during melt extrusion, and the polymer tends to slip at the screw supply portion of the extruder. As a result, the supply of the polymer becomes unstable, and problems such as the uneven thickness of the film occur. From such a viewpoint, the melting point of the antioxidant is more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 200 ° C. or higher. On the other hand, when the melting point of the antioxidant is too high, the antioxidant becomes difficult to melt during melt extrusion, and the dispersion in the polymer tends to be poor. Thereby, problems such as the effect of adding the antioxidant appear only locally. From such a viewpoint, the melting point of the antioxidant is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, further preferably 220 ° C. or lower, and particularly preferably 170 ° C. or lower.
- antioxidants commercially available products can be used as they are.
- Commercially available products include, for example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals: trade name IRGANOX 1010), N, N′— Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine (manufactured by Ciba Specialty Chemicals: trade name IRGANOX1024), N, N′-hexane-1,6-diylbis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide] (manufactured by Ciba Specialty Chemicals: trade name IRGANOX 1098) is preferred.
- the content of the antioxidant is preferably 0.1% by mass or more and 5% by mass or less based on the mass of the oriented film.
- the content of the antioxidant is more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 0.7% by mass or more.
- the content of the antioxidant is more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less.
- antioxidants may be used alone or in combination of two or more.
- the oriented film of the present invention may contain other resin components different from the thermoplastic amorphous resin, for example, in order to further improve the moldability, mechanical properties, surface properties, etc., within the range not impairing the object of the present invention.
- Additives such as antistatic agents, colorants, weathering agents, lubricants and the like can be added.
- the oriented film of the present invention becomes a capacitor by, for example, laminating a metal layer on at least one side.
- the material of the metal layer is not particularly limited, and examples thereof include aluminum, zinc, nickel, chromium, tin, copper, and alloys thereof. Further, these metal layers may be slightly oxidized. Moreover, since a metal layer can be formed easily, it is preferable that a metal layer is a vapor deposition type metal layer formed by the vapor deposition method.
- the oriented film of the present invention preferably has a plane orientation coefficient by refractive index of ⁇ 0.030 or less.
- the more negative the plane orientation coefficient the more the molecular chains are oriented in the film plane direction, and the plane orientation coefficient is kept below the upper limit, which will be described later. It is possible to improve the dynamic viscoelasticity E ′′.
- the upper limit of the plane orientation coefficient is preferably ⁇ 0.030 or less, more preferably ⁇ 0.032 or less, and particularly preferably ⁇ 0.033 or less.
- the lower limit of the plane orientation coefficient is not particularly limited, but the frequency of film breakage in the film production process, particularly in the stretching process tends to increase, and the productivity of the film tends to decrease. From such a viewpoint, the lower limit of the plane orientation coefficient is preferably ⁇ 0.050 or more, more preferably ⁇ 0.045 or more, and particularly preferably ⁇ 0.040 or more.
- the thickness of the oriented film of the present invention is not particularly limited, it is 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, particularly 1.0 ⁇ m or more, and most preferably 1.5 ⁇ m or more from the viewpoint of easily preventing breakage as a film.
- the oriented film of the present invention preferably has a dielectric breakdown voltage (BDV) at room temperature of 500 kV / mm or more.
- the breakdown voltage is more preferably 520 kV / mm or more, and further preferably 550 kV / mm or more.
- the oriented film of the present invention preferably has an arithmetic average roughness (Ra) of 20 nm to 150 nm, more preferably 25 nm to 120 nm, still more preferably 30 nm to 100 nm. If Ra exceeds the upper limit, it becomes difficult to maintain flatness even after high-temperature heat treatment. On the other hand, when Ra is lower than the lower limit, the winding property deteriorates, which is not preferable. In order to make Ra within the above range, particles that form irregularities on the surface of the oriented film may be added as a lubricant. The material and shape of the lubricant can be known per se.
- the oriented film of the present invention preferably has a Young's modulus of 3.0 GPa to 6.0 GPa, more preferably 3.3 GPa to 5.7 GPa, and still more preferably 3.5 GPa to 5.5 GPa.
- Young's modulus is within the above range, stable film formation is possible under appropriate film formation conditions.
- the oriented film of the present invention can basically be obtained by a method conventionally known or accumulated in the art.
- the production method for obtaining the oriented film of the present invention will be described in detail.
- the oriented film of the present invention may be a uniaxially oriented film or a biaxially oriented film, but is preferably a biaxially oriented film from the viewpoint of the balance between productivity and physical properties.
- a biaxially oriented film will be described as an example.
- a resin composition containing SPS and a thermoplastic amorphous resin is heated and melted to prepare an unstretched sheet.
- the resin composition is heated and melted at a temperature not lower than the melting point (Tm, unit: ° C.) and not higher than (Tm + 50 ° C.), extruded into a sheet, cooled and solidified to obtain an unstretched sheet.
- Tm melting point
- this unstretched sheet is stretched biaxially. Stretching may be performed simultaneously in the machine direction (machine axis direction) and the transverse direction (direction perpendicular to the machine axis direction and the thickness direction) or sequentially in any order.
- a uniaxial direction glass transition temperature (Tg, unit: ° C.) ⁇ 10 ° C.) to (Tg + 70 ° C.) or less at a temperature of 3.2 to 5.8 times
- the film is stretched at a magnification of 3.3 times to 5.4 times, more preferably 3.4 times to 5.0 times, and then a temperature of Tg or more (Tg + 80 ° C.) in a direction perpendicular to the uniaxial direction.
- the coating layer is formed by applying a coating solution for forming a coating layer on an unstretched sheet or a uniaxially stretched film obtained by uniaxially stretching the unstretched sheet in the longitudinal direction. It may be formed.
- heat setting is performed at a temperature of 160 to 230 ° C.
- the heat setting temperature is 165 ° C. or higher and 225 ° C. or lower, preferably 170 ° C. or higher and 220 ° C. or lower, and more preferably 195 ° C. or higher and 215 ° C. or lower.
- the above-described heat shrinkage rate can be set to a desired range.
- relaxation treatment or tension treatment may be performed at a temperature lower by 20 ° C. to 90 ° C. than the heat setting temperature, and the above-described heat shrinkage rate may be adjusted.
- each characteristic value is measured with the following method, and the film forming direction of a film is called a longitudinal direction, a longitudinal direction, or MD direction, and the direction orthogonal to it is called the width direction, a horizontal direction, or a TD direction.
- polyphenylene ether The contents of polyphenylene ether and antioxidant were measured by the methods described later.
- Polyphenylene ether The components of the thermoplastic amorphous resin and the amount of each component were identified by 1H-NMR measurement and 13C-NMR measurement.
- Antioxidant Components of the antioxidant and the amount of each component were specified by 1H-NMR measurement and 13C-NMR measurement.
- N N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (registered trademark Irg1098), tert-butyl-4-
- the peak intensity due to hydrogen due to the hydrocarbon chain between the hydroxyphenyl and the amide bond was measured.
- Film-forming stretchability was performed under the film-forming conditions of each example and comparative example, and evaluated according to the following criteria.
- the dielectric loss tangent (tan ⁇ ) and the dielectric constant ( ⁇ ) were obtained by measurement using a Ando Electric dielectric loss measuring machine (TR-10C) under conditions of a temperature of 120 ° C. and a vibration frequency of 1 kHz.
- TR-10C Ando Electric dielectric loss measuring machine
- the sample was prepared by aluminum vapor deposition according to JIS C 2151. In addition, it measured about each of the vertical direction and the horizontal direction of a film, and calculated
- the strength at break is an Instron type with a film width of 10 mm and a length of 150 mm, a chuck spacing of 100 mm, a tensile speed of 100 mm / min, and a chart speed of 500 mm / min.
- the tensile strength was calculated using the universal tensile test apparatus, and the elongation at break was regarded as the elongation at break, and the stress calculated from the load at the break was calculated as the breaking strength.
- the cross-sectional area at the time of calculating the breaking strength was the cross-sectional area at break (cross-sectional area of the measurement sample / (1 + breaking elongation (%) / 100)).
- the film is cut into a sample width of 10 mm and a length of 150 mm, the chuck is set to 100 mm, and the film is pulled with an Instron type universal tensile tester under the conditions of a tensile speed of 10 mm / min and a chart speed of 500 mm / min.
- the Young's modulus is calculated from the tangent of the rising portion of the obtained load-elongation curve.
- Thermal contraction rate The film has a thermal contraction rate in the tensionless state at 130 ° C. for 30 minutes, at 150 ° C. for 30 minutes, at 180 ° C. for 10 minutes, and at 200 ° C. for 10 minutes (longitudinal). Direction and lateral direction) (unit:%).
- thermomechanical analyzer manufactured by SII Technology, TMA6000
- TMA6000 thermomechanical analyzer
- the dimensional change rate of ⁇ 160 ° C. was calculated.
- the sample length was 30 mm in the measurement direction ⁇ 4 mm in the width direction (20 mm between chucks). Only the width direction of the film was measured.
- the elongation of TMA is 30000 ppm or more.
- the elongation of TMA is 10,000ppm to less than 30000ppm ⁇ ⁇ ⁇ ⁇
- the elongation of TMA is 3000ppm to less than 10,000ppm.
- the elongation of TMA is less than 3000 ppm ...
- the obtained resin composition was dried at 120 ° C. for 7 hours, then fed to an extruder, melted at 300 ° C., extruded from a die slit, solidified by cooling on a casting drum cooled to 50 ° C., and unstretched Created a sheet.
- This unstretched sheet was stretched 3.0 times in the longitudinal direction (machine axis direction) at 140 ° C., and subsequently led to a tenter, and then 4.0 in the lateral direction (direction perpendicular to the machine axis direction and the thickness direction).
- the film was stretched twice. At that time, the stretched portion was divided into four equal zones, and the stretching speed in the transverse direction was set to 5000% / min. Further, the stretching temperature in the transverse direction was also divided into four equal stages, and the first stage temperature was 118 ° C. and the final stage temperature was 137 ° C. Thereafter, the film was heat-fixed at 200 ° C.
- Examples 2 to 11, Comparative Examples 1 to 4 As shown in Table 1, the same operation as in Example 1 was repeated except that the film composition, film forming conditions, and final film thickness were changed. The evaluation results of the obtained oriented film are shown in Table 1 for Examples and Comparative Examples.
- thermoplastic amorphous resin (PA) used in Example 9 was polyarylate (U polymer manufactured by Unitika, trade name: U-100).
- the intrinsic viscosity of this resin measured in 1,1,2,2-tetrachloroethane was 0.64 dl / g, and the glass transition temperature was 193 ° C.
- PPE means polyphenylene ether
- PA means polyarylate
- the oriented film of the present invention suppresses generation of heat loss due to wrinkles during heat treatment at a high temperature such as a vapor deposition process, while using a polystyrene polymer having a syndiotactic structure excellent in electrical characteristics and heat resistance. Therefore, it can be suitably used as a base film for a film capacitor. In addition, it can be suitably used for applications such as electrodes for power storage elements such as lithium ion secondary batteries and electric double layer capacitors.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明の配向フィルムは、酸化防止剤を含有することが好ましい。酸化防止剤としては、生成したラジカルを捕捉して酸化を防止する一次酸化防止剤、あるいは生成したパーオキサイドを分解して酸化を防止する二次酸化防止剤のいずれであってもよい。一次酸化防止剤としてはフェノール系酸化防止剤、アミン系酸化防止剤が挙げられ、二次酸化防止剤としてはリン系酸化防止剤、硫黄系酸化防止剤が挙げられる。これらの中でも一次酸化防止剤が好ましく、特にフェノール系酸化防止剤が好ましい。 <Antioxidant>
The oriented film of the present invention preferably contains an antioxidant. The antioxidant may be either a primary antioxidant that captures the generated radicals to prevent oxidation, or a secondary antioxidant that decomposes the generated peroxides to prevent oxidation. Examples of the primary antioxidant include phenol-based antioxidants and amine-based antioxidants, and examples of the secondary antioxidant include phosphorus-based antioxidants and sulfur-based antioxidants. Of these, primary antioxidants are preferred, and phenolic antioxidants are particularly preferred.
本発明の配向フィルムは、本発明の目的を阻害しない範囲で、例えばさらに成形性、力学物性、表面性等を改良するために、熱可塑性非晶樹脂とは異なる他の樹脂成分を含有させたり、帯電防止剤、着色剤、耐候剤、滑剤等の添加剤を加えることができる。 <Other additives>
The oriented film of the present invention may contain other resin components different from the thermoplastic amorphous resin, for example, in order to further improve the moldability, mechanical properties, surface properties, etc., within the range not impairing the object of the present invention. Additives such as antistatic agents, colorants, weathering agents, lubricants and the like can be added.
本発明の配向フィルムは、例えば少なくとも片面に金属層を積層することでコンデンサーとなる。金属層の材質については、特に制限はないが、例えばアルミニウム、亜鉛、ニッケル、クロム、錫、銅およびこれらの合金が挙げられる。さらにこれらの金属層は若干量酸化されていてもよい。また、金属層を簡便に形成できるため、金属層は蒸着法により形成された蒸着型金属層であることが好ましい。 <Metal layer>
The oriented film of the present invention becomes a capacitor by, for example, laminating a metal layer on at least one side. The material of the metal layer is not particularly limited, and examples thereof include aluminum, zinc, nickel, chromium, tin, copper, and alloys thereof. Further, these metal layers may be slightly oxidized. Moreover, since a metal layer can be formed easily, it is preferable that a metal layer is a vapor deposition type metal layer formed by the vapor deposition method.
(厚み方向の屈折率)
本発明の配向フィルムは、屈折率による面配向係数が-0.030以下であることが好ましい。なお、本発明の配向フィルムでは、面配向係数が負の値になればなるほど、フィルム面方向に分子鎖が配向されていることを意味し、面配向係数を上限以下にしていくことで、後述の動的粘弾性E’’を向上させることができる。このような観点から、面配向係数の上限は、-0.030以下が好ましく、-0.032以下がより好ましく、-0.033以下が特に好ましい。 <Film characteristics>
(Refractive index in the thickness direction)
The oriented film of the present invention preferably has a plane orientation coefficient by refractive index of −0.030 or less. In the oriented film of the present invention, the more negative the plane orientation coefficient, the more the molecular chains are oriented in the film plane direction, and the plane orientation coefficient is kept below the upper limit, which will be described later. It is possible to improve the dynamic viscoelasticity E ″. From such a viewpoint, the upper limit of the plane orientation coefficient is preferably −0.030 or less, more preferably −0.032 or less, and particularly preferably −0.033 or less.
本発明の配向フィルムは、その厚みは特に制限されないが、フィルムとしての破断を抑制しやすい点から、0.3μm以上、さらに0.5μm以上、特に1.0μm以上、最も好ましくは1.5μm以上であり、他方薄くなるほど本発明の効果が出やすいことから、30.0μm以下、さらに20.0μm以下、特に好ましくは10.0μm以下、最も好ましくは5μm以下である。 (Film thickness)
Although the thickness of the oriented film of the present invention is not particularly limited, it is 0.3 μm or more, more preferably 0.5 μm or more, particularly 1.0 μm or more, and most preferably 1.5 μm or more from the viewpoint of easily preventing breakage as a film. On the other hand, the thinner the film is, the more easily the effect of the present invention can be obtained.
本発明の配向フィルムは、室温における絶縁破壊電圧(BDV)が500kV/mm以上であることが好ましい。かかる絶縁破壊電圧はより好ましくは520kV/mm以上、さらに好ましくは550kV/mm以上である。 (Dielectric breakdown voltage (BDV))
The oriented film of the present invention preferably has a dielectric breakdown voltage (BDV) at room temperature of 500 kV / mm or more. The breakdown voltage is more preferably 520 kV / mm or more, and further preferably 550 kV / mm or more.
本発明の配向フィルムは、算術平均粗さ(Ra)が20nm~150nmであることが好ましく、より好ましくは25nm~120nm、さらに好ましくは30nm~100nmである。Raが上限を超えると、高温熱処理後も平面性を維持するのが難しくなる。また、Raが下限以下となると、巻取性が悪化するため好ましくない。Raを上記範囲内とするために滑剤として、配向フィルム表面に凹凸を形成する粒子などを添加してもよい。滑剤の材質、形状はそれ自体公知のものを採用できる。 (Surface roughness)
The oriented film of the present invention preferably has an arithmetic average roughness (Ra) of 20 nm to 150 nm, more preferably 25 nm to 120 nm, still more preferably 30 nm to 100 nm. If Ra exceeds the upper limit, it becomes difficult to maintain flatness even after high-temperature heat treatment. On the other hand, when Ra is lower than the lower limit, the winding property deteriorates, which is not preferable. In order to make Ra within the above range, particles that form irregularities on the surface of the oriented film may be added as a lubricant. The material and shape of the lubricant can be known per se.
本発明の配向フィルムは、ヤング率が3.0GPa~6.0GPaであることが好ましく、より好ましくは3.3GPa~5.7GPa、さらに好ましくは3.5GPa~5.5GPaである。ヤング率が上記範囲内にあると適正な製膜条件で安定製膜が可能である。ところで、本発明の特徴は、従来通りヤング率で見ても差がないものの、加工性に大きな差が生じることを新たに見出したものと言える。 (Young's modulus)
The oriented film of the present invention preferably has a Young's modulus of 3.0 GPa to 6.0 GPa, more preferably 3.3 GPa to 5.7 GPa, and still more preferably 3.5 GPa to 5.5 GPa. When the Young's modulus is within the above range, stable film formation is possible under appropriate film formation conditions. By the way, it can be said that the feature of the present invention is a new finding that a large difference occurs in workability although there is no difference in Young's modulus as usual.
本発明の配向フィルムは、基本的には従来から知られている、あるいは当業界に蓄積されている方法で得ることができる。以下、本発明の配向フィルムを得るための製造方法について詳記する。なお、本発明の配向フィルムは、一軸配向フィルムであっても二軸配向フィルムであっても良いが、生産性や物性のバランスの点から二軸配向フィルムであることが好ましい。以下、二軸配向フィルムを例にとって、説明する。 <Film production method>
The oriented film of the present invention can basically be obtained by a method conventionally known or accumulated in the art. Hereinafter, the production method for obtaining the oriented film of the present invention will be described in detail. The oriented film of the present invention may be a uniaxially oriented film or a biaxially oriented film, but is preferably a biaxially oriented film from the viewpoint of the balance between productivity and physical properties. Hereinafter, a biaxially oriented film will be described as an example.
電子マイクロメータ(アンリツ(株)製の商品名「K-312A型」)を用いて針圧30gにてフィルム厚みを測定した。 (1) Film thickness Using an electronic micrometer (trade name “K-312A type” manufactured by Anritsu Corporation), the film thickness was measured at a needle pressure of 30 g.
サンプル10mgを測定用のアルミニウム製パンに封入して示差走査熱量計(DSC)(TA Instruments社製:商品名DSCQ100に装着し、室温(25℃)から20℃/分の速度で320℃まで昇温させ、その後サンプルを急冷してから再度20℃/分の速度で昇温してガラス転移温度(単位:℃)を測定した。 (2) Glass transition temperature 10 mg of sample was sealed in an aluminum pan for measurement and mounted on a differential scanning calorimeter (DSC) (manufactured by TA Instruments: trade name DSCQ100, from room temperature (25 ° C.) to 20 ° C./min. The temperature was raised to 320 ° C. at a rate, and then the sample was quenched, and then the temperature was raised again at a rate of 20 ° C./min to measure the glass transition temperature (unit: ° C.).
ポリフェニレンエーテル:1H-NMR測定、13C-NMR測定により、熱可塑性非晶樹脂の成分および各成分量を特定した。
酸化防止剤:1H-NMR測定、13C-NMR測定により、酸化防止剤の成分および各成分量を特定した。なお、N,N’-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオンアミド](登録商標Irg1098)の場合はtert-ブチル-4-ヒドロキシフェニルとアミド結合との間の炭化水素鎖に起因する水素に起因するピーク強度を測定した。かかるNMR測定結果をもとに、安定剤が樹脂と反応している場合はもとの安定剤に換算した含有量を求めた。また、ポリマーと未反応な安定剤と、ポリマーと反応した安定剤とが混在し、同じ炭化水素鎖に着目しても複数のピーク位置が検出される場合は、それらの合計値より含有量を求めた。 (3) The contents of polyphenylene ether and antioxidant were measured by the methods described later.
Polyphenylene ether: The components of the thermoplastic amorphous resin and the amount of each component were identified by 1H-NMR measurement and 13C-NMR measurement.
Antioxidant: Components of the antioxidant and the amount of each component were specified by 1H-NMR measurement and 13C-NMR measurement. In the case of N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (registered trademark Irg1098), tert-butyl-4- The peak intensity due to hydrogen due to the hydrocarbon chain between the hydroxyphenyl and the amide bond was measured. Based on the NMR measurement results, when the stabilizer reacted with the resin, the content converted to the original stabilizer was determined. In addition, if a polymer and an unreacted stabilizer are mixed with a stabilizer that has reacted with a polymer and a plurality of peak positions are detected even when focusing on the same hydrocarbon chain, the content is calculated from the total value of them. Asked.
各実施例・比較例の製膜条件にて製膜を行い、下記の基準で評価した。
製膜延伸性◎ :5万mの製膜当り、破断が1回未満
製膜延伸性○ :5万mの製膜当り、破断が1回~2回未満
製膜延伸性△ :5万mの製膜当り、破断が2回~4回未満
製膜延伸性× :5万mの製膜当り、破断が4回~8回未満
製膜延伸性××:5万mの製膜当り、破断が8回以上 (4) Film-forming stretchability Film-forming was performed under the film-forming conditions of each example and comparative example, and evaluated according to the following criteria.
Film-forming stretchability ◎: Less than 1 break per 50,000 m film-forming film forming property ○: Film-forming stretchability △: 50,000 m per 50,000-m film forming Per film formation, film breakability ×: less than 50,000 m film formation, breakage less than 4 to less than 8 times film formation stretchability ×: per film formation of 50,000 m 8 or more breaks
動的粘弾性測定装置(Perkin Elmer社製、DMA8000)を用い、20℃から230℃まで2℃/分の速度で昇温しながら振動周波数10Hzの条件で、フィルムサンプルの損失弾性率(E’’)(単位:MPa)を測定した。このとき、サンプル長は、測定方向2cm×幅方向5mm(チャック間1cm)とした。上記測定結果から、損失弾性率(E’’)のピーク温度(単位:℃)を求めた。なお、フィルムの縦方向および横方向のそれぞれについて測定を実施し、それらの平均値を算出して求めた。また、ピークが2つある場合には、低温側のピーク温度を採用した。 (5) Loss elastic modulus (E ″), dielectric loss tangent (tan δ), dielectric constant (ε)
Using a dynamic viscoelasticity measuring device (Perkin Elmer, DMA8000), the loss elastic modulus (E ′) of the film sample was measured at a vibration frequency of 10 Hz while being heated from 20 ° C. to 230 ° C. at a rate of 2 ° C./min. ') (Unit: MPa) was measured. At this time, the sample length was 2 cm in the measurement direction × 5 mm in the width direction (1 cm between the chucks). From the measurement results, the peak temperature (unit: ° C.) of the loss elastic modulus (E ″) was determined. In addition, it measured about each of the vertical direction and the horizontal direction of a film, and calculated | required and calculated | required those average values. Moreover, when there were two peaks, the peak temperature on the low temperature side was adopted.
ナトリウムD線(589nm)を光源としたアッベ屈折計を用いて23℃65%RHにて、縦方向(Nx)、横方向(Ny)、厚み方向の屈折率(Nz)を測定し、面配向係数(ΔP)を算出した。面配向係数の算出方法は以下の通り。
ΔP=(Nx+Ny)/2-Nz (6) Refractive index The refractive index (Nz) in the longitudinal direction (Nx), transverse direction (Ny), and thickness direction at 23 ° C. and 65% RH using an Abbe refractometer using sodium D-line (589 nm) as a light source. Measurements were made to calculate the plane orientation coefficient (ΔP). The calculation method of the plane orientation coefficient is as follows.
ΔP = (Nx + Ny) / 2−Nz
破断強伸度はフィルムを試料幅10mm、長さ150mmに切り、チャック間100mmにして、引張速度100mm/min、チャート速度500mm/minの条件でインストロンタイプの万能引張試験装置にて引っ張り、破断点の伸度を破断伸度とし、破断点の荷重から計算した応力を破断強度として算出した。なお、破断強度を算出する際の断面積は、破断時の断面積(測定サンプルの断面積/(1+破断伸度(%)/100)で割った値)を用いた。 (7) Tensile strength at break and Young's modulus The strength at break is an Instron type with a film width of 10 mm and a length of 150 mm, a chuck spacing of 100 mm, a tensile speed of 100 mm / min, and a chart speed of 500 mm / min. The tensile strength was calculated using the universal tensile test apparatus, and the elongation at break was regarded as the elongation at break, and the stress calculated from the load at the break was calculated as the breaking strength. The cross-sectional area at the time of calculating the breaking strength was the cross-sectional area at break (cross-sectional area of the measurement sample / (1 + breaking elongation (%) / 100)).
無張力の状態で130℃の雰囲気中30分、150℃の雰囲気中30分、180℃の雰囲気中10分、200℃の雰囲気中10分におけるフィルムの熱収縮率(縦方向および横方向)(単位:%)を求めた。 (8) Thermal contraction rate The film has a thermal contraction rate in the tensionless state at 130 ° C. for 30 minutes, at 150 ° C. for 30 minutes, at 180 ° C. for 10 minutes, and at 200 ° C. for 10 minutes (longitudinal). Direction and lateral direction) (unit:%).
非接触式三次元粗さ計(小坂研究所製、ET-30HK)を用いて波長780nmの半導体レーザー、ビーム径1.6μmの光触針で測定長(Lx)1mm、サンプリングピッチ2μm、カットオフ0.25mm、厚み方向拡大倍率1万倍、横方向拡大倍率200倍、走査線数100本(従って、Y方向の測定長Ly=0.2mm)の条件にてフィルム表面の突起プロファイルを測定した。なおフィルムの巻内面、巻外面それぞれの表面について測定を実施した。その粗さ曲面をZ=f(x,y)で表わしたとき、次の式で得られる値をフィルムの中心線平均表面粗さ(Ra、単位:nm)とした。
なお、表面粗さはそれぞれの主面を測定し、それぞれの値を記載した。 (9) Surface roughness Using a non-contact type three-dimensional roughness meter (manufactured by Kosaka Laboratory, ET-30HK) with a semiconductor laser having a wavelength of 780 nm, a measuring length (Lx) of 1 mm with an optical probe having a beam diameter of 1.6 μm, Film surface under the conditions of sampling pitch 2 μm, cut-off 0.25 mm, thickness direction enlargement magnification 10,000 times, lateral direction enlargement magnification 200 times, scanning line number 100 (accordingly, measurement length Ly = 0.2 mm in Y direction) The protrusion profile was measured. In addition, it measured about the surface of each roll inner surface and outer surface of a film. When the roughness curved surface was represented by Z = f (x, y), the value obtained by the following formula was defined as the center line average surface roughness (Ra, unit: nm) of the film.
In addition, the surface roughness measured each main surface, and described each value.
熱機械分析装置(SII Technology社製、TMA6000)を用い、3.14mN/μmの荷重をかけながら、30℃から180℃まで5℃/minの速度で昇温し、30℃~160℃の寸法変化割合を算出した。このときサンプル長は測定方向30mm×幅方向4mm(チャック間20mm)とした。なおフィルムの幅方向のみ測定した。
TMAの伸びが30000ppm以上・・・×
TMAの伸びが10000ppm~30000ppm未満・・・△
TMAの伸びが3000ppm~10000ppm未満・・・○
TMAの伸びが3000ppm未満・・・◎ (10) Wrinkle evaluation Using a thermomechanical analyzer (manufactured by SII Technology, TMA6000), while applying a load of 3.14 mN / μm, the temperature was increased from 30 ° C. to 180 ° C. at a rate of 5 ° C./min. The dimensional change rate of ˜160 ° C. was calculated. At this time, the sample length was 30 mm in the measurement direction × 4 mm in the width direction (20 mm between chucks). Only the width direction of the film was measured.
The elongation of TMA is 30000 ppm or more.
The elongation of TMA is 10,000ppm to less than 30000ppm ・ ・ ・ △
The elongation of TMA is 3000ppm to less than 10,000ppm.
The elongation of TMA is less than 3000 ppm ...
得られた二軸配向フィルムを用い、JIS規格C2151に記載のDC試験のうち平板電極法に準拠して、東京精電株式会社製ITS-6003を用いて、0.1kV/secの昇圧速度で測定し、破壊時の電圧を絶縁破壊電圧として測定した。測定はn=50で行い、平均値を絶縁破壊電圧とし、標準偏差を絶縁破壊電圧のばらつきとした。なお測定は20℃の室温で実施した。 (11) Breakdown voltage (BDV)
Using the obtained biaxially oriented film, in accordance with the plate electrode method in the DC test described in JIS standard C2151, using an ITS-6003 made by Tokyo Seiden Co., Ltd., at a boosting rate of 0.1 kV / sec. The voltage at the time of breakdown was measured as a dielectric breakdown voltage. The measurement was performed at n = 50, the average value was the breakdown voltage, and the standard deviation was the variation in breakdown voltage. The measurement was performed at room temperature of 20 ° C.
重量平均分子量3.0×105であり、13C-NMR測定でほぼ完全なシンジオタクチック構造であることが観察されるポリスチレン67.9質量部と、熱可塑性非晶樹脂として、ポリ(2,6-ジメチル-1,4-フェニレン)エーテル(クロロホルム中で測定された固有粘度が0.32dl/g、ガラス転移温度が210℃)30質量部と、酸化防止剤(C1)として、ペンタエリスリトールテトラキス〔3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート〕(チバ・スペシャルティ・ケミカルズ社製:商品名IRGANOX1010、融点120℃、熱分解温度335℃)2質量部と、滑剤として多孔質シリカ粒子(平均粒径=2.7μm、圧縮率=66%、細孔容積=1.5ml/g、細孔平均径=10nm)0.1重量部とを混練し、樹脂組成物を得た。
(配向フィルムの製膜)
得られた樹脂組成物を120℃で7時間乾燥し、次いで押出機に供給し、300℃で溶融し、ダイスリットから押出し後、50℃に冷却されたキャスティングドラム上で冷却固化し、未延伸シートを作成した。 [Example 1]
67.9 parts by mass of polystyrene, which has a weight average molecular weight of 3.0 × 10 5 and is observed to have a nearly complete syndiotactic structure by 13 C-NMR measurement, and poly (2 , 6-dimethyl-1,4-phenylene) ether (inherent viscosity measured in chloroform is 0.32 dl / g, glass transition temperature is 210 ° C.) and 30 parts by weight as an antioxidant (C1), pentaerythritol 2 parts by mass of tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals: trade name IRGANOX 1010, melting point 120 ° C., thermal decomposition temperature 335 ° C.) Porous silica particles (average particle diameter = 2.7 μm, compressibility = 66%, pore volume = 1.5 ml / g, average pore diameter = 10 n as a lubricant m) 0.1 part by weight was kneaded to obtain a resin composition.
(Oriented film production)
The obtained resin composition was dried at 120 ° C. for 7 hours, then fed to an extruder, melted at 300 ° C., extruded from a die slit, solidified by cooling on a casting drum cooled to 50 ° C., and unstretched Created a sheet.
表1に記載の通り、フィルム組成、製膜条件、最終のフィルム厚みを変更する以外は実施例1と同様な操作を繰り返した。得られた配向フィルムの評価結果を、実施例と比較例は表1に示す。 [Examples 2 to 11, Comparative Examples 1 to 4]
As shown in Table 1, the same operation as in Example 1 was repeated except that the film composition, film forming conditions, and final film thickness were changed. The evaluation results of the obtained oriented film are shown in Table 1 for Examples and Comparative Examples.
Claims (7)
- シンジオタクチック構造のスチレン系重合体を主たる樹脂成分として含み、ガラス転移温度が130℃以上である熱可塑性非晶樹脂を含む樹脂組成物からなり、130℃で30分熱処理した時の面内方向における熱収縮率が5.0%以下、200℃で10分熱処理したときの面内方向における少なくとも1方向の熱収縮率が6.5%以上であることを特徴とする配向フィルム。 In-plane direction when a resin composition containing a thermoplastic amorphous resin having a glass transition temperature of 130 ° C. or higher, including a styrene polymer having a syndiotactic structure as a main resin component, and heat-treated at 130 ° C. for 30 minutes An oriented film having a heat shrinkage rate of 5.0% or less at a heat shrinkage rate of 6.5% or more in at least one direction in the in-plane direction when heat-treated at 200 ° C. for 10 minutes.
- 振動周波数10Hzでの損失弾性率(E’’)のピーク温度が125℃以上でかつ破断強度が90MPa以上である請求項1記載の配向フィルム。 2. The oriented film according to claim 1, wherein the peak temperature of the loss elastic modulus (E ″) at a vibration frequency of 10 Hz is 125 ° C. or higher and the breaking strength is 90 MPa or higher.
- 200℃で10分熱処理したときの製膜方向および幅方向の熱収縮率の平均値が6.5以上15.0%以下である請求項1記載の配向フィルム。 The oriented film according to claim 1, wherein an average value of heat shrinkage in the film forming direction and the width direction when heat-treated at 200 ° C for 10 minutes is from 6.5 to 15.0%.
- 130℃で30分熱処理したときの面内方向における熱収縮率が0.0%以上5.0%以下である請求項1記載の配向フィルム。 The oriented film according to claim 1, wherein the heat shrinkage in the in-plane direction when heat-treated at 130 ° C for 30 minutes is 0.0% or more and 5.0% or less.
- 熱可塑性非晶樹脂がポリフェニレンエーテルである請求項1に記載の配向フィルム。 The oriented film according to claim 1, wherein the thermoplastic amorphous resin is polyphenylene ether.
- フィルムの厚みが0.3~30μmである請求項1記載の配向フィルム。 The oriented film according to claim 1, wherein the film has a thickness of 0.3 to 30 µm.
- 蒸着加工に用いられる請求項1記載の配向フィルム。 The oriented film according to claim 1, which is used for vapor deposition.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016560215A JP6346301B2 (en) | 2014-11-18 | 2015-11-16 | Oriented film |
CN201580062749.1A CN107001661B (en) | 2014-11-18 | 2015-11-16 | Alignment film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014233560 | 2014-11-18 | ||
JP2014-233560 | 2014-11-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016080356A1 true WO2016080356A1 (en) | 2016-05-26 |
Family
ID=56013893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/082141 WO2016080356A1 (en) | 2014-11-18 | 2015-11-16 | Alignment film |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6346301B2 (en) |
CN (1) | CN107001661B (en) |
WO (1) | WO2016080356A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021070863A1 (en) * | 2019-10-11 | 2021-04-15 | 王子ホールディングス株式会社 | Resin composition suitable for use as film for film capacitor |
JP2021063215A (en) * | 2019-10-11 | 2021-04-22 | 王子ホールディングス株式会社 | Resin composition suitable for film application for film capacitor |
JP2021063216A (en) * | 2019-10-11 | 2021-04-22 | 王子ホールディングス株式会社 | Resin composition suitable for film application for film capacitor |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114555694A (en) * | 2019-10-11 | 2022-05-27 | 王子控股株式会社 | Resin composition suitable for film applications for film capacitors |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01182346A (en) * | 1988-01-14 | 1989-07-20 | Idemitsu Kosan Co Ltd | Molded body of styrene based resin and production thereof |
JPH02218724A (en) * | 1988-09-30 | 1990-08-31 | Idemitsu Kosan Co Ltd | Draw molded body of styrene-based resin and production thereof |
WO2008156210A1 (en) * | 2007-06-21 | 2008-12-24 | Teijin Limited | Insulating film |
WO2012147777A1 (en) * | 2011-04-26 | 2012-11-01 | 帝人株式会社 | High-insulating film |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5801532B2 (en) * | 2009-11-30 | 2015-10-28 | 帝人株式会社 | High insulation film |
KR101986868B1 (en) * | 2012-01-24 | 2019-06-07 | 도요보 가부시키가이샤 | Stretched polypropylene film |
-
2015
- 2015-11-16 CN CN201580062749.1A patent/CN107001661B/en active Active
- 2015-11-16 WO PCT/JP2015/082141 patent/WO2016080356A1/en active Application Filing
- 2015-11-16 JP JP2016560215A patent/JP6346301B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01182346A (en) * | 1988-01-14 | 1989-07-20 | Idemitsu Kosan Co Ltd | Molded body of styrene based resin and production thereof |
JPH02218724A (en) * | 1988-09-30 | 1990-08-31 | Idemitsu Kosan Co Ltd | Draw molded body of styrene-based resin and production thereof |
WO2008156210A1 (en) * | 2007-06-21 | 2008-12-24 | Teijin Limited | Insulating film |
WO2012147777A1 (en) * | 2011-04-26 | 2012-11-01 | 帝人株式会社 | High-insulating film |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021070863A1 (en) * | 2019-10-11 | 2021-04-15 | 王子ホールディングス株式会社 | Resin composition suitable for use as film for film capacitor |
JP2021063215A (en) * | 2019-10-11 | 2021-04-22 | 王子ホールディングス株式会社 | Resin composition suitable for film application for film capacitor |
JP2021063216A (en) * | 2019-10-11 | 2021-04-22 | 王子ホールディングス株式会社 | Resin composition suitable for film application for film capacitor |
JP7439721B2 (en) | 2019-10-11 | 2024-02-28 | 王子ホールディングス株式会社 | Resin composition suitable for film use in film capacitors |
JP7439722B2 (en) | 2019-10-11 | 2024-02-28 | 王子ホールディングス株式会社 | Resin composition suitable for film use in film capacitors |
Also Published As
Publication number | Publication date |
---|---|
CN107001661B (en) | 2020-03-17 |
JPWO2016080356A1 (en) | 2017-07-27 |
CN107001661A (en) | 2017-08-01 |
JP6346301B2 (en) | 2018-06-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5801532B2 (en) | High insulation film | |
JP5149240B2 (en) | Biaxially oriented polypropylene film for capacitors, metal-deposited film thereof, and cast raw sheet | |
JP6304470B1 (en) | Biaxially oriented polypropylene film, metallized film for capacitors, and capacitors | |
JP6346301B2 (en) | Oriented film | |
JP5110604B2 (en) | Finely roughened polypropylene film and method for producing the same | |
WO1998006776A1 (en) | Polypropylene film and capacitor made by using the same as the dielectric | |
JP6314509B2 (en) | Capacitor element manufacturing method | |
JP2007169595A (en) | Polypropylene film for capacitor | |
JP5358111B2 (en) | High insulation film | |
WO2016043172A1 (en) | Polypropylene film and film capacitor | |
JP5771068B2 (en) | High insulation film | |
US9617407B2 (en) | Highly insulating film | |
WO2021162021A1 (en) | Polypropylene film, polypropylene film integrated with metal layer, and film capacitor | |
JP2020132882A (en) | Polypropylene film, and metal film laminated film and film capacitor using the same | |
JP5629235B2 (en) | High insulation film | |
JP2022001638A (en) | Polypropylene film, metal layer-integrated polypropylene film, film capacitor and film roll | |
JP5684873B2 (en) | High insulation film | |
WO2024058078A1 (en) | Biaxially stretched polypropylene film, metallized film, and capacitor | |
JP6309838B2 (en) | Oriented film | |
JP7020394B2 (en) | Polypropylene film, metal layer integrated polypropylene film, film capacitor, and film roll | |
JP2022046339A (en) | Amorphous resin stretched porous material | |
WO2022190838A1 (en) | Film suitable for capacitor use | |
JP2022140299A (en) | Film suitable for use in capacitor | |
JP2023113106A (en) | Film suitable for capacitor use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15861204 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016560215 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 16/08/2017) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15861204 Country of ref document: EP Kind code of ref document: A1 |