WO2018181938A1 - Film de polypropylène, film de polypropylène intégré à une couche métallique et condensateur à film - Google Patents

Film de polypropylène, film de polypropylène intégré à une couche métallique et condensateur à film Download PDF

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Publication number
WO2018181938A1
WO2018181938A1 PCT/JP2018/013727 JP2018013727W WO2018181938A1 WO 2018181938 A1 WO2018181938 A1 WO 2018181938A1 JP 2018013727 W JP2018013727 W JP 2018013727W WO 2018181938 A1 WO2018181938 A1 WO 2018181938A1
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Prior art keywords
polypropylene
resin
polypropylene film
molecular weight
less
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PCT/JP2018/013727
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English (en)
Japanese (ja)
Inventor
佳宗 奥山
立治 石田
明洋 筧
中田　将裕
忠和 石渡
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王子ホールディングス株式会社
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Priority claimed from JP2018060433A external-priority patent/JP6904296B2/ja
Priority claimed from JP2018060198A external-priority patent/JP6904295B2/ja
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Publication of WO2018181938A1 publication Critical patent/WO2018181938A1/fr

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/32—Wound capacitors

Definitions

  • the present invention (the first invention and the second invention) relates to a polypropylene film, a metal layer integrated polypropylene film, and a film capacitor.
  • Polypropylene film has excellent electrical characteristics such as high voltage resistance and low dielectric loss characteristics, and also has high moisture resistance. Therefore, it is widely used for electronic equipment and electrical equipment. Specifically, it is used as a film used for, for example, a high voltage capacitor, various switching power supplies, a filter capacitor (for example, a converter, an inverter, etc.), a smoothing capacitor, and the like.
  • Inverter power supply capacitors used in automobiles and the like are small, light and have high capacity, and are required to have high voltage resistance over a long period of time in a wide temperature range (eg, -40 ° C to 90 ° C). .
  • Patent Document 1 discloses a polypropylene film in which a polypropylene resin having a high stereoregularity contains polypropylene satisfying a specific relationship between melt tension when measured at 230 ° C. and melt flow rate (MFR). (See especially claim 1 and claim 4). In addition, as an effect, it has excellent stretchability, excellent uniformity in thickness and various physical properties, and can be stretched uniformly while using a highly regular polypropylene resin, with excellent heat resistance, thermal dimensional stability, mechanical rigidity, and electrical insulation. (See paragraph [0011] in particular).
  • the melt tension and melt flow rate described in Patent Document 1 are values obtained from raw material pellets.
  • a polypropylene film as a product undergoes a thermal history until it is formed into a film from raw material pellets. And the value of the melt tension and the melt flow rate of a polypropylene film changes with the influence of a heat history.
  • the first aspect of the present invention has been made in view of the above-described problems, and an object thereof is to provide a polypropylene film having good voltage resistance at high temperatures. Moreover, 1st this invention is providing the film capacitor which has the metal layer integrated polypropylene film which has the said polypropylene film, and the said metal layer integrated polypropylene film.
  • the second aspect of the present invention has been made in view of the above-described problems, and an object thereof is to provide a polypropylene film having excellent moldability.
  • the second aspect of the present invention is to provide a metal layer integrated polypropylene film having the polypropylene film and a film capacitor having the metal layer integrated polypropylene film.
  • the polypropylene film according to the first invention is The coefficient b representing the gradient between temperature and viscosity, determined when the measurement results relating to the melt shear viscosity and the shear rate are applied to the Carreau-Yasuda model shown in Equation (1) is 0.005 or more and 0.013 The thickness is 1 to 10 ⁇ m.
  • the coefficient b is a coefficient representing the gradient between temperature and viscosity. Specifically, the smaller the coefficient b, the smaller the change in the shear viscosity with respect to the temperature change (the inclination becomes smaller), and the larger the coefficient b, the larger the change in the shear viscosity with respect to the temperature change (the inclination becomes larger).
  • the change in the shear viscosity with respect to the temperature change is small to the extent that the coefficient b is 0.013 or less. The inventors of the present invention have found that when the coefficient b is 0.013 or less, the voltage resistance of the polypropylene film at a high temperature is good.
  • the 1st present invention is an invention based on the new knowledge by the present inventors that when the coefficient b is 0.013 or less, the voltage resistance of the polypropylene film at a high temperature is improved. .
  • the physical property of the polypropylene film as an actual product ie, the coefficient b
  • regulated the physical property of the polypropylene film as an actual product. That is, since the physical properties of the actual polypropylene film after the heat history received in the film formation process are defined, the polypropylene film satisfying the physical properties has improved withstand voltage characteristics.
  • the coefficient b is preferably smaller from the viewpoint of voltage resistance at high temperatures. However, if the change in shear viscosity with respect to temperature change is too small (that is, if the coefficient b is too small), the molten resin is formed into a sheet. When extruding, it may be difficult to stably extrude, and it may be difficult to obtain a thin film.
  • the coefficient b is set to 0.005 or more.
  • a thin polypropylene film having a thickness of 1 to 10 ⁇ m can be stably obtained.
  • the condition that the coefficient b is 0.005 or more and 0.013 or less may be determined by measuring the melt shear viscosity and the shear rate of the produced polypropylene film. Therefore, a polypropylene film satisfying the required voltage resistance can be easily produced.
  • a polypropylene film having a coefficient b of 0.013 or less can be achieved by selecting a resin or a manufacturing method.
  • the polypropylene film according to the first aspect of the present invention achieves the above-described problem when the thickness is very small (thin) of 1 to 10 ⁇ m.
  • the polypropylene film according to the first aspect of the present invention has a thickness of 1 to 10 ⁇ m, and ensures good voltage resistance at high temperatures while ensuring miniaturization and high capacity of the capacitor when used in a capacitor. Prepare.
  • the polypropylene film having the above configuration is for a capacitor.
  • the polypropylene film having the coefficient b of 0.005 or more and 0.013 or less can be used as a capacitor because it can be made thin and has excellent voltage resistance at high temperatures.
  • the polypropylene film having the above structure contains a polypropylene resin, Among the polypropylene resins, the number average molecular weight Mn of the main component polypropylene resin is 30000 or more and 53000 or less, Among the polypropylene resins, the weight average molecular weight Mw of the main component polypropylene resin is 250,000 to 450,000, Among the polypropylene resins, the z-average molecular weight Mz of the main component polypropylene resin is 500,000 to 2.1 million, Among the polypropylene resins, the molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)] of the main component polypropylene resin is 5 or more and 12 or less, Among the polypropylene resins, the molecular weight distribution [(z average molecular weight Mz) / (number average molecular weight Mn)] of the main component polypropylene resin is preferably 10 or more and 70 or less.
  • the main component polypropylene resin has a heptane-insoluble content (HI) of 96.0% or more and 99.5% or less
  • the melt flow rate (MFR) of the main component polypropylene resin is preferably 1.0 g / 10 min or more and 8.0 g / 10 min or less.
  • the stereoregularity of the resin increases.
  • a polypropylene resin having a heptane insoluble content (HI) of 96.0% or more and 99.5% or less is used as the main component polypropylene resin, the crystallinity of the resin is appropriately improved due to a reasonably high stereoregularity.
  • the withstand voltage at high temperature is improved.
  • the rate of solidification (crystallization) at the time of forming the cast original fabric sheet becomes moderate, and it has moderate stretchability.
  • the polypropylene resin as the main component has a melt flow rate (MFR) of 1.0 g / 10 min or more and 8.0 g / 10 min or less
  • MFR melt flow rate
  • the coefficient b is 0.005 or more and 0.013 or less. It is easy to obtain a certain polypropylene film.
  • the polypropylene film having the above-described structure has a crystallite size of 16.0 nm or less obtained from the half-value width of the reflection peak of the ⁇ crystal (040) plane measured by a wide-angle X-ray diffraction method using the Scherrer equation. Is preferred.
  • the coefficient b When the coefficient b is kept at 0.013 or less and the crystallite size is made 16.0 nm or less, the leakage current becomes small and the structural breakdown due to Joule heat generation hardly occurs. Is preferably improved.
  • the metal layer integrated polypropylene film according to the first aspect of the present invention has the metal layer laminated
  • the polypropylene film since the polypropylene film has the metal layer laminated on one side or both sides of the polypropylene film, it can be used for a film capacitor using the polypropylene film as a dielectric and the metal layer as an electrode. Moreover, since it has the said polypropylene film whose coefficient b is 0.005 or more and 0.013 or less, it can be set as thin thickness and the withstand voltage property under high temperature improves.
  • the film capacitor according to the first aspect of the present invention is characterized by having the metal layer integrated polypropylene film wound.
  • the first invention has been described above.
  • ⁇ Second Invention> In order to solve the second problem, the present inventors have intensively studied a polypropylene film. As a result, polypropylene having a specific coefficient within a predetermined range determined when the measurement results of melt shear viscosity and shear rate are applied to the Carreau-Yasuda model, which is a model representing the shear viscosity curve of a non-Newtonian fluid. The film was found to be excellent in moldability, and the second invention was completed.
  • the polypropylene film according to the second invention is
  • the coefficient c representing the slope between the shear rate and the shear viscosity, which is determined when the measurement results relating to the melt shear viscosity and the shear rate are applied to the Carreau-Yasuda model shown in Formula (1), is ⁇ 200 or more and ⁇ 50
  • the thickness is 1 to 10 ⁇ m.
  • the coefficient c is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the larger the coefficient c, the smaller the change in shear viscosity with respect to the shear rate change (the slope becomes smaller), and the smaller the coefficient c, the greater the change in shear viscosity with respect to the shear rate change (the slope becomes larger). ).
  • the change in viscosity with respect to the change in shear rate is so large that the coefficient c is ⁇ 50 or less.
  • the reason why the processability of the polypropylene film is excellent is as follows.
  • the coefficient c is set to -200 or more and -50 or less.
  • the second aspect of the present invention is a polypropylene film satisfying a coefficient c of ⁇ 200 or more and ⁇ 50 or less.
  • the second aspect of the present invention is based on the new finding by the present inventors that when the coefficient c is ⁇ 200 or more and ⁇ 50 or less, the moldability of the polypropylene film is improved.
  • the physical property of the polypropylene film as an actual product ie, the coefficient c
  • regulated the physical property of the polypropylene film as an actual product.
  • the coefficient c Whether or not the coefficient c satisfies the condition of ⁇ 200 or more and ⁇ 50 or less may be determined by measuring the melt shear viscosity and shear rate of the produced polypropylene film. Therefore, it is possible to easily produce a polypropylene film that satisfies the required moldability.
  • a polypropylene film having a coefficient c of ⁇ 200 or more and ⁇ 50 or less can be achieved by selecting a resin or a manufacturing method. For example, depending on whether a resin having a large viscosity change at the time of melt shear or a small resin is selected as the resin to be used, the extrusion molding conditions (sheet molding conditions, lip gap adjustment, etc.) during film molding, This can be achieved by optimally setting the stretching conditions. Specifically, in the case of a resin having a high molecular weight and a small change in viscosity at the time of melt shearing, the resin temperature and the longitudinal stretching temperature are within a range where film formation can be performed without uneven stretching because the resin flowability is low and the thickness variation tends to increase.
  • the molding temperature such as the transverse stretching temperature.
  • the molding temperature such as the resin temperature, the longitudinal stretching temperature, the transverse stretching temperature, etc. can be lowered or the lip gap within the range where the film can be formed without uneven stretching. It is preferable to widen.
  • the polypropylene film having the above-described structure is a film obtained by using a polypropylene resin as a material, melt-extrusion of the polypropylene resin into a raw sheet, and then biaxially stretching, It is preferable that the rate of change between the melt flow rate of the polypropylene resin and the melt flow rate of the raw sheet shown in the following formula (2) is 1.3 or less.
  • (Change rate) (Melt flow rate of raw sheet) / (Melt flow rate of polypropylene resin) Formula (2)
  • the rate of change is 1.3 or less, the resin is hardly deteriorated and the melt stability is excellent, and the thickness variation of the molded product is suppressed, so that the extrusion moldability is improved.
  • the polypropylene film having the above configuration is for a capacitor.
  • the polypropylene film having a coefficient c of ⁇ 200 or more and ⁇ 50 or less is excellent in molding processability, and thus can be made thin and can be suitably used for a capacitor.
  • the polypropylene film having the above structure contains a polypropylene resin, Among the polypropylene resins, the number average molecular weight Mn of the main component polypropylene resin is 30000 or more and 53000 or less, Among the polypropylene resins, the weight average molecular weight Mw of the main component polypropylene resin is 250,000 to 450,000, Among the polypropylene resins, the z-average molecular weight Mz of the main component polypropylene resin is 500,000 to 2.1 million, and among the polypropylene resins, the molecular weight distribution of the main component polypropylene resin [(weight average molecular weight Mw) / ( Number average molecular weight Mn)] is 5 or more and 12 or less, Among the polypropylene resins, the molecular weight distribution [(z average molecular weight Mz) / (number average molecular weight Mn)] of the main component polypropylene resin is preferably 10 or more and 70 or less.
  • the main component polypropylene resin has a heptane-insoluble content (HI) of 96.0% or more and 99.5% or less
  • the melt flow rate (MFR) of the main component polypropylene resin is preferably 1.0 g / 10 min or more and 8.0 g / 10 min or less.
  • the stereoregularity of the resin increases.
  • a polypropylene resin having a heptane insoluble content (HI) of 96.0% or more and 99.5% or less is used as the main component polypropylene resin, the crystallinity of the resin is appropriately improved due to a reasonably high stereoregularity. Molding processability is improved.
  • the rate of solidification (crystallization) at the time of forming the cast original fabric sheet becomes moderate, and it has moderate stretchability.
  • the coefficient c is ⁇ 200 or more and ⁇ 50 or less. Easy to get a film.
  • the metal layer integrated polypropylene film according to the second aspect of the present invention has the metal layer laminated
  • the polypropylene film since the polypropylene film has the metal layer laminated on one side or both sides of the polypropylene film, it can be used for a film capacitor using the polypropylene film as a dielectric and the metal layer as an electrode.
  • the polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less is provided, the moldability is excellent and the thickness can be reduced.
  • the film capacitor according to the second aspect of the present invention is characterized by having the metal layer integrated polypropylene film wound.
  • the metal layer integrated polypropylene film which has the said polypropylene film, and the film capacitor which has the said metal layer integrated polypropylene film can be provided.
  • the metal layer integrated polypropylene film which has the said polypropylene film, and the film capacitor which has the said metal layer integrated polypropylene film can be provided.
  • the first embodiment of the present invention will be described below. However, the first present invention is not limited to these embodiments.
  • the polypropylene film which concerns on this embodiment is not a microporous film, it does not have many holes. Moreover, it is preferable that the polypropylene film which concerns on this embodiment is comprised by the single layer.
  • the polypropylene film according to the present embodiment has a coefficient b representing the gradient between temperature and viscosity, which is determined when the measurement results regarding the melt shear viscosity and the shear rate are applied to the Carreau-Yasuda model shown in Equation (1). Is 0.013 or less.
  • the coefficient b is preferably 0.0125 or less, more preferably 0.012 or less, and still more preferably 0.0115 or less.
  • the coefficient b is 0.005 or more from the viewpoint that a stable thin film can be obtained.
  • the coefficient b is preferably as small as possible from the viewpoint of withstand voltage at high temperatures, but from the viewpoint of obtaining a stable thin film, it is preferably 0.007 or more, more preferably 0.010 or more, and 0.011 or more. Further preferred.
  • the Carreau-Yasuda model is a model that represents a shear viscosity curve of a non-Newtonian fluid, and is a model that can express both characteristics of a zero shear region and a shear flow region.
  • Zero shear viscosity ⁇ 0 represents the magnitude of the overall viscosity. Specifically, the shear viscosity ⁇ increases as the zero shear viscosity ⁇ 0 increases. That is, when the shear rate is the same, the shear viscosity ⁇ increases as the zero shear viscosity ⁇ 0 increases.
  • the delay time ⁇ is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the larger the coefficient ⁇ , the smaller the change in shear viscosity with respect to the change in shear rate (the slope becomes smaller), and the smaller the coefficient ⁇ , the greater the change in shear viscosity with respect to the change in shear rate (the slope becomes larger). ).
  • the coefficient b is a coefficient representing the gradient between temperature and viscosity. Specifically, the smaller the coefficient b, the smaller the change in the shear viscosity with respect to the temperature change (the inclination becomes smaller), and the larger the coefficient b, the larger the change in the shear viscosity with respect to the temperature change (the inclination becomes larger).
  • the coefficient c is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the larger the coefficient c, the smaller the change in shear viscosity with respect to the shear rate change (the slope becomes smaller), and the smaller the coefficient c, the greater the change in shear viscosity with respect to the shear rate change (the slope becomes larger). ).
  • the coefficient d is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the greater the coefficient d, the smaller the change in shear viscosity with respect to the shear rate change (the slope becomes smaller), and the smaller the coefficient d, the greater the change in shear viscosity with respect to the shear rate change (the slope becomes larger). ).
  • the flow curve ( ⁇ - ⁇ curve) obtained in the above (5) is obtained using the non-Newtonian pure viscosity model fitting function of the analysis software (HASL analysis software Materialfit Ver. 3.0.0).
  • a master curve is obtained by fitting to the Carreau-Yasuda model (viscosity formula) shown in formula (1).
  • each parameter zero shear viscosity ⁇ 0 , coefficient b, coefficient c, coefficient d, delay time ⁇
  • the fitting is performed at a reference temperature Tr of 240 ° C.
  • the reason why the reference temperature Tr is set to 240 ° C. is that an intermediate temperature among the measurement temperatures 230 ° C., 240 ° C., and 250 ° C. is selected.
  • the coefficient b is a coefficient representing the gradient between temperature and viscosity. Specifically, the smaller the coefficient b, the smaller the change in the shear viscosity with respect to the temperature change (the inclination becomes smaller), and the larger the coefficient b, the larger the change in the shear viscosity with respect to the temperature change (the inclination becomes larger).
  • the polypropylene film according to the present embodiment has a small change in shear viscosity with respect to a change in temperature such that the coefficient b is 0.013 or less. The inventors of the present invention have found that when the coefficient b is 0.013 or less, the voltage resistance of the polypropylene film at a high temperature is good.
  • the coefficient b in the Carreau-Yasuda model shown in the equation (1) is 0.013 or less, and therefore, as can be seen from the examples, the voltage resistance of the polypropylene film at a high temperature is high. It is good.
  • the polypropylene film which concerns on this embodiment further suppresses the temperature dependence of withstand voltage property in a high temperature range. This point is also apparent from the examples. Moreover, since b is 0.013 or less, the polypropylene film which concerns on this embodiment is excellent also in the withstand voltage property in normal temperature. This point is also apparent from the examples. Further, if the coefficient b is 0.013 or less, the internal structure of the film becomes a regular structure, and it is difficult to form a defect structure, and it is easy to be uniformly stretched. The polypropylene film further suppresses unevenness (stretching unevenness) when the cast raw sheet is stretched.
  • the physical properties of a polypropylene film as an actual product that is, the coefficient b is defined. That is, since the physical properties of the actual polypropylene film after taking into account the thermal history received in the film formation process are specified, the polypropylene film satisfying the physical properties has improved characteristics such as withstand voltage.
  • the coefficient b is preferably smaller from the viewpoint of voltage resistance at high temperatures. However, if the change in shear viscosity with respect to temperature change is too small (that is, if the coefficient b is too small), the molten resin is formed into a sheet. When extruding, it may be difficult to stably extrude, and it may be difficult to obtain a thin film.
  • the coefficient b is set to 0.005 or more.
  • a thin polypropylene film having a thickness of 1 to 10 ⁇ m can be stably obtained.
  • the condition that the coefficient b is 0.005 or more and 0.013 or less may be determined by measuring the melt shear viscosity and the shear rate of the produced polypropylene film. Therefore, a polypropylene film satisfying the required voltage resistance can be easily produced.
  • a polypropylene film having a coefficient b of 0.013 or less can be achieved by selecting a resin or a manufacturing method.
  • the extrusion molding conditions sheet molding conditions, lip gap adjustment, etc.
  • the main component polypropylene resin has a high molecular weight or a moderately narrow molecular weight distribution (for example, Mw / Mn is less than 8.5, 8.
  • the molding temperature such as temperature, longitudinal stretching temperature, and transverse stretching temperature.
  • the molecular weight distribution of the main component polypropylene resin is wide (for example, Mw / Mn is 8.5 or more), and the resin has a large viscosity change during melt shearing.
  • the molding temperature such as resin temperature, longitudinal stretching temperature, transverse stretching temperature, etc. is lowered to such an extent that large stretching unevenness is not possible, the lip gap is widened, and the rotational speed of the extruder Is preferably lowered.
  • the coefficients (zero shear viscosity ⁇ 0 , coefficient b, coefficient c, coefficient d, delay time ⁇ ) in the Carreau-Yasuda model are the actual physical properties of the polypropylene film. It is a coefficient calculated after being influenced by the shear rate change and temperature change received in the molding process.
  • the master curve since the master curve is used, the relationship between the shear viscosity ⁇ and the shear rate ⁇ at an arbitrary temperature can be obtained. And if the said master curve is used, the tendency of the whole viscosity including the shear viscosity (eta) in the high shear rate area
  • the dielectric breakdown strength ES that serves as an index of withstand voltage refers to the dielectric breakdown strength measured by applying an AC voltage with an AC power supply.
  • the dielectric breakdown strength ES at 120 ° C. of the polypropylene film is preferably 226 Vac / ⁇ m or more, more preferably 228 Vac / ⁇ m or more, and further preferably 230 Vac / ⁇ m or more.
  • the dielectric breakdown strength ES at 120 ° C. of the polypropylene film is preferably as high as possible. For example, it is 300 Vac / ⁇ m or less, 280 Vac / ⁇ m or less, or 250 Vac / ⁇ m or less.
  • the dielectric breakdown strength ES at 27 ° C. of the polypropylene film is preferably 240 Vac / ⁇ m or more, more preferably 250 Vac / ⁇ m or more, and further preferably 260 Vac / ⁇ m or more.
  • the dielectric breakdown strength ES at 27 ° C. of the polypropylene film is preferably as high as possible. For example, it is 500 Vac / ⁇ m or less, 450 Vac / ⁇ m or less, or 400 Vac / ⁇ m or less.
  • the dielectric breakdown strength ES at 100 ° C. of the polypropylene film is preferably 235 Vac / ⁇ m or more, and more preferably 238 Vac / ⁇ m or more.
  • the dielectric breakdown strength ES at 100 ° C. of the polypropylene film is preferably as high as possible, but is, for example, 400 Vac / ⁇ m or less, 350 Vac / ⁇ m or less, or 300 Vac / ⁇ m or less.
  • the dielectric breakdown strength ES at 110 ° C. of the polypropylene film is preferably 230 Vac / ⁇ m or more, and more preferably 235 Vac / ⁇ m or more.
  • the dielectric breakdown strength ES at 110 ° C. of the polypropylene film is preferably as high as possible.
  • the measuring method of the dielectric breakdown strength ES at 27 ° C., 100 ° C., 110 ° C., and 120 ° C. of the polypropylene film is based on the method described in the examples.
  • the slope of the dielectric breakdown strength ES with respect to the temperature of the polypropylene film (100 ° C., 110 ° C., 120 ° C.) when the temperature is on the horizontal axis and the dielectric breakdown strength ES is on the vertical axis is preferably closer to 0 (zero).
  • the dielectric breakdown strength ES decreases as the temperature increases. Accordingly, it can be inferred that the closer the slope is to 0, the less the insulation failure at the time of temperature change at high temperature, and thus the higher withstand voltage at higher temperature.
  • the inclination is preferably ⁇ 1.0 or more, more preferably ⁇ 0.9 or more, and further preferably ⁇ 0.8 or more. The inclination is preferably closer to 0, but can be set to, for example, -0.01 or less, -0.1 or less, -0.3 or less, or -0.5 or less.
  • the melting point of the polypropylene film is preferably 174.1 ° C. or higher.
  • the voltage resistance and thermal dimensional stability at high temperatures are excellent.
  • fusing point of the said polypropylene film is based on the method of an Example description.
  • the use of the polypropylene film is not particularly limited as long as the coefficient b is 0.005 or more and 0.013 or less, but it is preferably used for a capacitor.
  • the polypropylene film having the coefficient b of 0.005 or more and 0.013 or less has good voltage resistance at high temperatures, the temperature dependence of the voltage resistance at high temperatures is suppressed, and the resistance at room temperature is low. It is excellent in voltage property, and stretching unevenness of the stretched film is suppressed. Moreover, it can be set as thin thickness. Therefore, it can be suitably used for a capacitor.
  • the thickness of the polypropylene film is 1 to 10 ⁇ m from the viewpoint of ensuring miniaturization and high capacity of the capacitor when used in a capacitor.
  • the thickness of the polypropylene film is 10 ⁇ m or less, preferably 6.0 ⁇ m or less, more preferably 4.0 ⁇ m or less, further preferably 3.5 ⁇ m or less, and particularly preferably 3.0 ⁇ m or less.
  • the thickness of the said polypropylene film is 1.0 micrometer or more from a viewpoint on manufacture.
  • the polypropylene film may have a thickness of 1.5 ⁇ m or more and 1.8 ⁇ m or more.
  • the thickness of the polypropylene film is a value measured according to JIS-C2330 using a micrometer (JIS-B7502).
  • the polypropylene film has a crystallite size obtained by using the Scherrer equation (the following equation (2)) from the half-value width of the reflection peak of the ⁇ crystal (040) plane measured by a wide-angle X-ray diffraction method. It is preferably 0 nm or less, more preferably 15.0 nm or less, still more preferably 14.5 nm or less, even more preferably 14.0 nm or less, particularly preferably 13.9 nm or less, and particularly preferably 13.7 nm or less. Is preferable.
  • the crystallite size is, for example, 10.0 nm or more, 11.0 nm or more, 11.5 nm or more, etc. in view of mechanical strength and the like and the lamella (folded crystal) thickness of the polymer chain.
  • the polypropylene film contains a polypropylene resin as described later.
  • the crystallite size is not only affected by the blending amount and molecular weight of the polypropylene resin, but also the conditions during stretching (for example, the temperature of longitudinal stretching, the speed of longitudinal stretching, the lateral stretching) Temperature, lateral stretching speed, etc.).
  • the crystallite size tends to decrease as the temperature of longitudinal stretching decreases.
  • the slower the longitudinal stretching speed the larger the crystallite size.
  • the crystallite size decreases as the temperature of transverse stretching decreases.
  • the slower the transverse stretching speed the larger the crystallite size.
  • the polypropylene film preferably has the coefficient b satisfying at least 0.005 or more and 0.013 or less, and the coefficient c described later or later is preferably ⁇ 200 or more and ⁇ 50 or less, more preferably ⁇ 180 or more and ⁇ 60 or less.
  • the coefficient c satisfies the numerical value range, the molding processability described in the section “Embodiment according to the second aspect of the present invention” is also excellent.
  • the polypropylene film contains a polypropylene resin.
  • the content of the polypropylene resin is preferably 90% by mass or more, more preferably 95% by mass or more, based on the entire polypropylene film (when the entire polypropylene film is 100% by mass).
  • the upper limit of the content of the polypropylene resin is, for example, 100% by mass or 98% by mass with respect to the entire polypropylene film.
  • the polypropylene resin may include a single type of polypropylene resin, or may include two or more types of polypropylene resins.
  • the polypropylene resin having the larger content is referred to as “main component polypropylene resin” in the present specification.
  • the polypropylene resin contained in the said polypropylene film is 1 type, the said polypropylene resin is called "the main component polypropylene resin" in this specification.
  • polypropylene resin when it is referred to as “polypropylene resin” without particularly specifying whether or not it is a main component, unless otherwise specified, a polypropylene resin as a main component, and a polypropylene resin other than the main component, Means both.
  • the weight average molecular weight Mw of the polypropylene resin is preferably 250,000 to 450,000
  • the weight average molecular weight Mw of the polypropylene resin as a main component is 250,000 to 450,000. It means that the following is preferable and that the weight average molecular weight Mw of the polypropylene resin other than the main component is preferably 250,000 to 450,000.
  • the polypropylene film may be a biaxially stretched film, a uniaxially stretched film, or an unstretched film, but is preferably a biaxially stretched film.
  • the case where the polypropylene film is a biaxially stretched film will be described.
  • the weight average molecular weight Mw of the polypropylene resin is preferably 250,000 or more and 450,000 or less, and more preferably 250,000 or more and 400,000 or less.
  • the resin fluidity becomes appropriate.
  • moderate stretchability can be given to the cast raw fabric sheet.
  • the number average molecular weight Mn of the polypropylene resin is preferably 30000 or more and 53000 or less, and more preferably 33000 or more and 52000 or less.
  • Mn of the polypropylene resin is 30000 or more and 53000 or less, it is easy to obtain a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less.
  • the z-average molecular weight Mz of the polypropylene resin is preferably 500000 or more and 2100000 or less, and more preferably 700000 or more and 1700000 or less.
  • the z average molecular weight Mz of the polypropylene resin is 500000 or more and 2100000 or less, it is easy to obtain a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less.
  • the molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)] of the polypropylene resin is preferably 5 or more and 12 or less, more preferably 5 or more and 11 or less, and more preferably 5 or more and 10 or less. More preferably, it is particularly preferably 5.5 to 9.5.
  • the molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)] of the polypropylene resin is 5 or more and 12 or less, it is easy to obtain a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less.
  • polypropylene resin whose molecular weight distribution is 5 or more and less than 8.5 and the polypropylene resin whose molecular weight distribution is 8.5 or more and 11 or less.
  • the molecular weight distribution [(z average molecular weight Mz) / (number average molecular weight Mn)] of the polypropylene resin is preferably 10 or more and 70 or less, more preferably 15 or more and 60 or less, and more preferably 15 or more and 50 or less. More preferably.
  • the molecular weight distribution [(z average molecular weight Mz) / (number average molecular weight Mn)] of the polypropylene resin is 10 or more and 70 or less, it is easy to obtain a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), z average molecular weight (Mz), and molecular weight distribution (Mw / Mn and Mz / Mn) of the polypropylene resin are gel permeation. It is the value measured using the chromatograph (GPC) apparatus. More specifically, it is a value measured using an HLC-8121 GPC-HT (trade name), a high-temperature GPC measuring machine with a built-in differential refractometer (RI) manufactured by Tosoh Corporation. As GPC columns, three TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation are connected and used.
  • GPC chromatograph
  • the column temperature is set to 140 ° C., and trichlorobenzene is allowed to flow as an eluent at a flow rate of 1.0 ml / 10 minutes to obtain measured values of Mw and Mn.
  • a calibration curve related to the molecular weight M is prepared using standard polystyrene manufactured by Tosoh Corporation, and the measured values are converted into polystyrene values to obtain Mw, Mn and Mz.
  • the logarithm of the bottom 10 of the molecular weight M of standard polystyrene is referred to as logarithmic molecular weight (“Log (M)”).
  • the “differential distribution value difference D M ” is preferably ⁇ 5% to 14%, more preferably ⁇ 4% to 12%, and more preferably ⁇ 4% to 10%. Is more preferable.
  • high molecular weight component a component having a molecular weight of about 1 million on the high molecular weight side
  • the polypropylene resin has a wide molecular weight distribution and at the same time has a molecular weight of 10,000 to 100,000 in order to appropriately contain a low molecular weight component. It is preferable to use a polypropylene resin so that the component has a differential distribution value difference of -5% or more and 14% or less compared to a component having a molecular weight of 1,000,000.
  • the differential distribution value is a value obtained as follows using GPC.
  • a curve (generally also referred to as “elution curve”) showing the intensity with respect to time obtained by a differential refraction (RI) detector of GPC is used.
  • the elution curve is converted into a curve showing the intensity with respect to Log (M) by converting the time axis into logarithmic molecular weight (Log (M)). Since the RI detection intensity is proportional to the component concentration, an integral distribution curve with respect to the logarithmic molecular weight Log (M) can be obtained when the total area of the curve indicating the intensity is 100%.
  • the differential distribution curve is obtained by differentiating the integral distribution curve with Log (M). Therefore, “differential distribution” means a differential distribution with respect to the molecular weight of the concentration fraction. From this curve, the differential distribution value at a specific Log (M) is read.
  • the heptane insoluble content (HI) of the polypropylene resin is preferably 96.0% or more, more preferably 97.0% or more. Further, the heptane-insoluble content (HI) of the polypropylene resin is preferably 99.5% or less, more preferably 99.0% or less.
  • the heptane-insoluble content indicates that the greater the stereoregularity of the resin, the greater the amount.
  • the heptane-insoluble content (HI) is 96.0% or more and 99.5% or less, the crystallinity of the resin is moderately improved due to a reasonably high stereoregularity, and the withstand voltage at high temperature is improved. To do. On the other hand, the rate of solidification (crystallization) at the time of forming the cast original fabric sheet becomes moderate, and it has moderate stretchability.
  • the method for measuring heptane-insoluble matter (HI) is according to the method described in the examples.
  • the polypropylene resin has a melt flow rate (MFR) of preferably 1.0 to 8.0 g / 10 min, more preferably 1.5 to 7.0 g / 10 min, and 2.0 to 6.0 g. More preferably, it is / 10 min.
  • MFR melt flow rate
  • the method for measuring the melt flow rate of the polypropylene resin is according to the method described in the examples.
  • the main component polypropylene resin has the differential distribution value difference DM of 8.0% or more, and the heptane insoluble matter (HI) is 98.5. It is preferable that the melt flow rate (MFR) is 4 g / 10 min or more and 8 g / 10 min or less.
  • the said differential distribution value difference DM is less than 8.0%
  • the said heptane insoluble content (HI) is It is preferably over 98.5%
  • the previous melt flow rate (MFR) is preferably 1 g / 10 min or more and 3.9 g / 10 min or less.
  • the polypropylene resin can be produced using a generally known polymerization method.
  • the polymerization method include a gas phase polymerization method, a bulk polymerization method, and a slurry polymerization method.
  • the polymerization may be single-stage (one-stage) polymerization using one polymerization reactor or multi-stage polymerization using two or more polymerization reactors.
  • the polymerization may be performed by adding hydrogen or a comonomer as a molecular weight modifier in the reactor.
  • the catalyst for polymerization generally known Ziegler-Natta catalysts can be used, and there is no particular limitation as long as the polypropylene resin can be obtained.
  • the catalyst may contain a promoter component and a donor.
  • the molecular weight, molecular weight distribution, stereoregularity, etc. can be controlled by adjusting the catalyst and polymerization conditions.
  • the molecular weight distribution of the polypropylene resin can be adjusted by resin blending. For example, a method of mixing two or more types of resins having different molecular weights or molecular weight distributions.
  • a resin having a higher average molecular weight or a lower resin is used as the main resin and the resin as a whole is 100% by mass
  • the main resin is mixed in two types of polypropylene having a main resin content of 55% by mass or more and 90% by mass or less.
  • the system is preferable because it is easy to adjust the amount of low molecular weight components.
  • melt flow rate MFR
  • the difference in MFR between the main resin and the additive resin is preferably about 1 to 30 g / 10 minutes from the viewpoint of convenience during adjustment.
  • the method of mixing the resin is not particularly limited, but the method is a method of dry blending the main resin and additive resin polymer powder or pellets using a mixer or the like, or the main resin and additive resin polymer powder or pellets. Is supplied to a kneader and melt-kneaded to obtain a blend resin.
  • the mixer and the kneader are not particularly limited.
  • the kneader may be either a single screw type, a twin screw type, or a multi-screw type of higher. In the case of a screw type with two or more axes, either a kneading type rotating in the same direction or rotating in a different direction may be used.
  • the kneading temperature is not particularly limited as long as a good kneaded product is obtained. Generally, it is in the range of 200 ° C. to 300 ° C., and is preferably 230 ° C. to 270 ° C. from the viewpoint of suppressing deterioration of the resin. Further, an inert gas such as nitrogen may be purged into the kneader in order to suppress deterioration during resin kneading and mixing.
  • the melt-kneaded resin may be pelletized to an appropriate size using a generally known granulator. Thereby, a mixed polypropylene raw material resin pellet can be obtained.
  • the total ash due to the polymerization catalyst residue and the like contained in the polypropylene raw resin is as small as possible in order to improve electrical characteristics.
  • the total ash content is preferably 50 ppm or less, more preferably 40 ppm or less, and particularly preferably 30 ppm or less, based on the polypropylene resin (100 parts by weight).
  • the polypropylene resin may contain an additive.
  • the “additive” is generally an additive used for a polypropylene resin, and is not particularly limited as long as a polypropylene film having the coefficient b of 0.013 or less can be obtained.
  • the additive include an antioxidant, a chlorine absorbent, an ultraviolet absorbent, a lubricant, a plasticizer, a flame retardant, and an antistatic agent.
  • the polypropylene resin may include the additive in an amount that does not adversely affect the polypropylene film.
  • the polypropylene film may contain a resin other than the polypropylene resin (hereinafter also referred to as “other resin”).
  • the “other resin” is generally a resin other than a polypropylene resin, and is not particularly limited as long as a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less can be obtained. .
  • the other resin examples include polyolefins other than polypropylene, such as polyethylene, poly (1-butene), polyisobutene, poly (1-pentene), and poly (1-methylpentene); ethylene-propylene copolymer, propylene-butene copolymer Polymers, copolymers of ⁇ -olefins such as ethylene-butene copolymer; vinyl monomers-diene monomer random copolymers such as styrene-butadiene random copolymer; styrene-butadiene-styrene block copolymer And vinyl monomer-diene monomer-vinyl monomer random copolymer such as a polymer.
  • the polypropylene film may include the other resin in an amount that does not adversely affect the polypropylene film.
  • the “cast raw sheet before stretching” for producing the biaxially stretched polypropylene film according to the present embodiment can be suitably produced as follows.
  • the “cast raw fabric sheet before stretching” for producing the biaxially stretched polypropylene film according to this embodiment is not limited to the production method described below.
  • polypropylene resin pellets, dry-mixed polypropylene resin pellets, or mixed polypropylene resin pellets prepared by melting and kneading in advance are supplied to an extruder and melted by heating.
  • the rotation speed of the extruder during heating and melting is preferably 5 to 40 rpm, more preferably 10.0 to 16.5 rpm, and further preferably 13.5 to 16.0 rpm.
  • the set temperature of the extruder at the time of heating and melting is preferably 235 to 280 ° C, more preferably 250 to 280 ° C, further preferably 260 to 280 ° C, and particularly preferably 260 to 270 ° C.
  • the resin temperature at the time of heating and melting is preferably 232 to 277 ° C, more preferably 247 to 277 ° C, further preferably 257 to 277 ° C, and particularly preferably 257 to 267 ° C.
  • the resin temperature at the time of heating and melting is a value measured by a thermometer inserted in an extruder. If the set temperature of the extruder during heat melting is significantly lower than 235 ° C. and / or the resin temperature during heat melting is significantly lower than 232 ° C., a thickness of 1 to It becomes difficult to obtain a thin film polypropylene film having a thickness of 10 ⁇ m.
  • a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less can be obtained by appropriately selecting the number of revolutions of the extruder at the time of heating and melting, the extruder set temperature, and the resin temperature within the above numerical ranges.
  • the number of revolutions of the extruder at the time of heating and melting, the extruder set temperature, and the resin temperature are selected in consideration of the physical properties of the polypropylene resin to be used.
  • deterioration of resin can also be suppressed by making the resin temperature at the time of heat-melting into the said numerical range. Increasing the extruder rotational speed tends to increase the coefficient b, and decreasing the extruder rotational speed tends to decrease the coefficient b. Further, when the resin temperature at the time of heating and melting is increased, the coefficient b tends to increase, and when the resin temperature at the time of heating and melting is decreased, the coefficient b tends to decrease.
  • the molten resin is extruded into a sheet shape using a T die, and cooled and solidified with at least one metal drum to form an unstretched cast raw sheet.
  • the lip gap of the T die is adjusted by a plurality of lip bolts arranged at regular intervals in the width direction. Specifically, for example, each lip bolt is adjusted so that the lip gap at a position corresponding to a portion (a portion excluding a portion to be cut off without being a product on both sides) of a cast raw sheet is uniform.
  • a method is mentioned.
  • the method of adjusting each lip bolt so that a lip gap may become wide or narrow as it goes to the center in the width direction is mentioned.
  • the adjustment of the lip bolt can be determined according to the physical properties of the polypropylene resin used.
  • the lip gap is preferably less than 0.8 mm, more preferably 0.75 mm or less, and even more preferably 0.70 mm or less. Further, the lip gap is preferably 0.4 mm or more, and more preferably 0.5 mm or more.
  • the thickness of the cast original sheet can be set by the number of revolutions of the extruder and the lip gap. If the lip gap is within the above numerical range, the desired thickness of the cast original sheet can be obtained. Easy to make uniform thickness.
  • the value of the lip gap means an average value of the gap at each lip bolt position. If the lip gap is significantly greater than 0.8 mm, there is a risk of breaking during stretching.
  • the surface temperature of the metal drum (the temperature of the metal drum that first contacts after extrusion) is preferably 50 to 100 ° C., more preferably 60 to 100 ° C., and still more preferably 60 to 80 ° C. ° C.
  • the surface temperature of the metal drum can be determined according to the physical properties of the polypropylene resin used. When the surface temperature of the metal drum is significantly lower than 50 ° C., it is difficult to obtain a good sheet formability of the original fabric sheet. It is difficult to obtain a favorable value.
  • a polypropylene film having the coefficient b of 0.013 or less can be obtained.
  • the melt flow rate (MFR) of the cast raw sheet is preferably 1.0 to 9.0 g / 10 min, more preferably 2.0 to 8.0 g / 10 min, and 3.0 to 7 More preferably, it is 0.0 g / 10 min.
  • the method for measuring the melt flow rate of the polypropylene film is according to the method described in the examples.
  • the thickness of the cast original sheet is not particularly limited as long as the polypropylene film can be obtained, but is usually preferably 0.05 mm to 2 mm, and preferably 0.1 mm to 1 mm. Is more preferable.
  • the biaxially stretched polypropylene film according to this embodiment can be suitably produced as follows.
  • the biaxially stretched polypropylene film according to this embodiment is not limited to the production method described below.
  • the polypropylene film can be produced by subjecting the original polypropylene cast sheet to stretching.
  • the stretching is preferably biaxial stretching that is biaxially oriented in the longitudinal and lateral directions, and the sequential biaxial stretching method is preferred as the stretching method.
  • the sequential biaxial stretching method for example, first, the cast raw fabric sheet is maintained at a temperature of 110 to 170 ° C. (preferably 135 to 170 ° C.), and is stretched in the flow direction through rolls provided with a speed difference.
  • the draw ratio in the flow direction is preferably 3.5 to 5.5 times, more preferably 4.2 to 5.4 times.
  • the sheet is guided to a tenter and stretched in the transverse direction.
  • the temperature during stretching in the transverse direction is preferably 150 ° C.
  • the draw ratio in the transverse direction is preferably 9 to 11 times. Thereafter, relaxation and heat fixation are performed 2 to 10 times. As described above, a biaxially stretched polypropylene film is obtained.
  • a polypropylene film having the coefficient b of 0.005 or more and 0.013 or less can be obtained.
  • the polypropylene film may be subjected to a corona discharge treatment on-line or off-line after completion of the stretching and heat-setting steps in order to enhance the adhesive properties in a later step such as a metal vapor deposition step.
  • the corona discharge treatment can be performed using a known method. It is preferable to use air, carbon dioxide gas, nitrogen gas, or a mixed gas thereof as the atmospheric gas.
  • a metal layer may be laminated on one or both sides of the polypropylene film to form a metal layer integrated polypropylene film.
  • the metal layer functions as an electrode.
  • a simple metal such as zinc, lead, silver, chromium, aluminum, copper, nickel, a mixture of plural kinds thereof, an alloy thereof or the like can be used. In view of economy and capacitor performance, zinc and aluminum are preferable.
  • Examples of the method of laminating a metal layer on one or both sides of the polypropylene film include a vacuum deposition method and a sputtering method. From the viewpoint of productivity and economy, the vacuum deposition method is preferable. Examples of the vacuum deposition method generally include a crucible method and a wire method, but are not particularly limited, and an optimum one can be selected as appropriate.
  • the margin pattern when the metal layer is laminated by vapor deposition is not particularly limited, but a pattern including a so-called special margin such as a fish net pattern or a T margin pattern is used in order to improve characteristics such as the security of the capacitor. It is preferable to apply on one side of the film. Security is enhanced, and it is effective in terms of capacitor destruction and prevention of short circuit.
  • a generally known method such as a tape method or an oil method can be used without any limitation.
  • the metal layer-integrated polypropylene film can be laminated by a conventionally known method or wound to form a film capacitor.
  • the film capacitor of the present embodiment may have a configuration in which a plurality of metal layer integrated polypropylene films are laminated, or may have a wound metal layer integrated polypropylene film.
  • a film capacitor can be suitably used as a capacitor for an inverter power supply device that controls a drive motor of an electric vehicle or a hybrid vehicle.
  • it can also be suitably used for railway vehicles, wind power generation, solar power generation, general household appliances, and the like.
  • the second embodiment of the present invention will be described below.
  • the second invention is not limited to these embodiments.
  • the polypropylene film which concerns on this embodiment is not a microporous film, it does not have many holes.
  • the polypropylene film which concerns on this embodiment is comprised by the single layer.
  • the polypropylene film which concerns on this embodiment does not need to be the coefficient b 0.005 or more and 0.013 or less like embodiment of 1st this invention.
  • the polypropylene film according to the present embodiment does not have to have the dielectric strength ES at 120 ° C. satisfying the numerical range as in the first embodiment of the present invention.
  • the polypropylene film which concerns on this embodiment does not need the dielectric breakdown strength ES in 110 degreeC satisfy
  • the polypropylene film according to this embodiment is The coefficient c representing the slope between the shear rate and the shear viscosity, which is determined when the measurement results relating to the melt shear viscosity and the shear rate are applied to the Carreau-Yasuda model shown in Formula (1), is ⁇ 200 or more and ⁇ 50 It is as follows.
  • the coefficient c is preferably ⁇ 60 or less, more preferably ⁇ 65 or less, and further preferably ⁇ 70 or less.
  • the coefficient c is preferably ⁇ 180 or more, more preferably ⁇ 160 or more, and further preferably ⁇ 150 or more.
  • the coefficient c is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the larger the coefficient c, the smaller the change in shear viscosity with respect to the shear rate change (the slope becomes smaller), and the smaller the coefficient c, the greater the change in shear viscosity with respect to the shear rate change (the slope becomes larger). ).
  • the polypropylene film according to this embodiment has a large change in viscosity with respect to a change in shear rate so that the coefficient c is ⁇ 50 or less. When the coefficient c is ⁇ 50 or less, the reason why the processability of the polypropylene film is excellent is as follows.
  • the coefficient c is set to ⁇ 200 or more and ⁇ 50 or less.
  • the polypropylene film according to this embodiment has good moldability as can be seen from the examples. That is, the polypropylene film according to the present embodiment is a polypropylene film having a coefficient c satisfying ⁇ 200 or more and ⁇ 50 or less.
  • the physical property of the polypropylene film as an actual product that is, the coefficient c is defined.
  • the coefficient c is defined.
  • Whether or not the coefficient c satisfies the condition of ⁇ 200 or more and ⁇ 50 or less may be determined by measuring the melt shear viscosity and shear rate of the produced polypropylene film. Therefore, it is possible to easily produce a polypropylene film that satisfies the required moldability.
  • a polypropylene film having a coefficient c of ⁇ 200 or more and ⁇ 50 or less can be achieved by selecting a resin or a manufacturing method.
  • the extrusion molding conditions sheet molding conditions, lip gap adjustment, etc.
  • the main component polypropylene resin has a high molecular weight or a moderately narrow molecular weight distribution (for example, Mw / Mn is less than 8.5, 8.
  • the resin temperature, the longitudinal stretching temperature, and the transverse stretching temperature are within a range in which the film can be formed without uneven stretching because the resin fluidity is low and the thickness variation tends to be large. It is preferable to increase the molding temperature.
  • the molecular weight distribution of the main component polypropylene resin is wide (for example, Mw / Mn is 8.5 or more), and the resin has a large viscosity change during melt shearing. It is preferable to lower the molding temperature such as the resin temperature, the longitudinal stretching temperature, and the transverse stretching temperature or to widen the lip gap as long as the film can be formed without uneven stretching.
  • the master curve since the master curve is used, the relationship between the shear viscosity ⁇ and the shear rate ⁇ at an arbitrary temperature can be obtained. And if the said master curve is used, the tendency of the whole viscosity including the shear viscosity (eta) in the high shear rate area
  • the dielectric breakdown strength ES at 27 ° C. of the polypropylene film and the dielectric breakdown strength ES at 100 ° C. of the polypropylene film are within the numerical ranges described in the section “Embodiment according to the first aspect of the present invention”. It is preferable.
  • the melting point of the polypropylene film is preferably 168.0 to 178.0 ° C, more preferably 171.0 to 175.0 ° C, and further preferably 172.0 to 174.2 ° C. . If the melting point of the polypropylene film is 168.0 ° C. or lower, it may be inferior to the withstand voltage characteristics as a capacitor polypropylene film, which is not preferable.
  • fusing point of the said polypropylene film is based on the method of an Example description.
  • the use of the polypropylene film is not particularly limited as long as the coefficient c is ⁇ 200 or more and ⁇ 50 or less, but it is preferably used for a capacitor.
  • the polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less has good moldability and can be made thin. Therefore, it can be suitably used for a capacitor.
  • the thickness of the polypropylene film is preferably within the numerical range described in the section “Embodiment 1 of the present invention”.
  • the polypropylene film preferably has a coefficient b of 0.005 or more and 0.013 or less, more preferably 0.007 or more and 0.013 or less after the coefficient c satisfies at least ⁇ 200 or more and ⁇ 50 or less.
  • it is 0.010 or more and 0.013 or less, more preferably 0.011 or more and 0.013 or less.
  • the voltage resistance described in the section “Embodiment 1 of the present invention” (voltage resistance at an AC power source at a high temperature (120 ° C.)) is also used. Excellent.
  • Examples of the upper limit value of the coefficient b include 0.013, 0.0125, 0.012, 0.0115, and the like.
  • the polypropylene film contains a polypropylene resin.
  • the polypropylene resin having the larger content is referred to as “ The main component is called a polypropylene resin.
  • the polypropylene resin contained in the said polypropylene film is 1 type, the said polypropylene resin is called "the main component polypropylene resin" in this specification.
  • each characteristic of the polypropylene resin (weight average molecular weight Mw, number average molecular weight Mn, z average molecular weight Mz, molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)], molecular weight distribution [(Z average molecular weight Mz) / (number average molecular weight Mn)], differential distribution value difference D M , heptane insoluble matter (HI), melt flow rate (MFR)) are “embodiments according to the first aspect of the present invention”. It is preferable to be within the numerical range described in the section.
  • the weight average molecular weight Mw of the polypropylene resin is within the numerical range, it is easy to control the thickness of the cast original fabric sheet, and it becomes easy to produce a thin stretched film. Moreover, it becomes difficult to generate
  • the number average molecular weight Mn of the polypropylene resin is within the numerical range, it is easy to obtain a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less.
  • the molecular weight distribution [(z average molecular weight Mz) / (number average molecular weight Mn)] of the polypropylene resin is within the numerical range, it is easy to obtain a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less.
  • D M of the polypropylene resin is within the above range, preferred for the same reason as described in the section "the first embodiment of the present invention.
  • the heptane-insoluble content (HI) of the polypropylene resin is within the above numerical range, the rate of solidification (crystallization) at the time of forming the cast original fabric sheet becomes moderate, and it has moderate stretchability.
  • the melt flow rate (MFR) of the polypropylene resin is within the numerical range, it is easy to obtain a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less.
  • the main component polypropylene resin has the differential distribution value difference DM of 8.0% or more, and the heptane insoluble matter (HI) is 98.5. It is preferable that the melt flow rate (MFR) is 4 g / 10 min or more and 8 g / 10 min or less.
  • the said differential distribution value difference DM is less than 8.0%
  • the said heptane insoluble content (HI) is It is preferably over 98.5%
  • the previous melt flow rate (MFR) is preferably 1 g / 10 min or more and 3.9 g / 10 min or less.
  • the method described in the section “Embodiment according to the first aspect of the present invention” can be employed.
  • the additive is not particularly limited as long as a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less can be obtained.
  • the polypropylene resin contains other resin described in the section “Embodiment according to the first aspect of the present invention”, the other resin obtains a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less. It is not particularly limited as long as it can.
  • the “cast raw sheet before stretching” for producing the biaxially stretched polypropylene film according to the present embodiment can be suitably produced as follows.
  • the “cast raw fabric sheet before stretching” for producing the biaxially stretched polypropylene film according to this embodiment is not limited to the production method described below.
  • polypropylene resin pellets, dry-mixed polypropylene resin pellets, or mixed polypropylene resin pellets prepared by melting and kneading in advance are supplied to an extruder and melted by heating.
  • the rotation speed of the extruder during heating and melting is preferably 5 to 40 rpm, more preferably 14.5 to 30 rpm, and further preferably 15 to 20 rpm.
  • the set temperature of the extruder during heating and melting is preferably 254 to 280 ° C, more preferably 258 ° C to 280 ° C, further preferably 260 to 280 ° C, and particularly preferably 260 to 270 ° C.
  • the resin temperature at the time of heating and melting is preferably 251 to 277 ° C., more preferably 255 to 277 ° C., further preferably 257 to 277 ° C., and particularly preferably 257 to 267 ° C.
  • the resin temperature at the time of heating and melting is a value measured by a thermometer inserted in an extruder.
  • a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less can be obtained by appropriately selecting the number of revolutions of the extruder during heating and melting, the set temperature of the extruder, and the resin temperature within the above numerical ranges.
  • the number of revolutions of the extruder at the time of heating and melting, the extruder set temperature, and the resin temperature are selected in consideration of the physical properties of the polypropylene resin to be used.
  • deterioration of resin can also be suppressed by making the resin temperature at the time of heat-melting into the said numerical range. Increasing the extruder rotational speed tends to decrease the coefficient c, and decreasing the extruder rotational speed tends to increase the coefficient c. Further, when the resin temperature at the time of heating and melting is increased, the coefficient c tends to decrease, and when the resin temperature at the time of heating and melting is decreased, the coefficient c tends to increase.
  • the molten resin is extruded into a sheet shape using a T die, and cooled and solidified with at least one metal drum to form an unstretched cast raw sheet.
  • the lip gap of the T die is adjusted by a plurality of lip bolts arranged at regular intervals in the width direction. Specifically, for example, each lip bolt is adjusted so that the lip gap at a position corresponding to a portion (a portion excluding a portion to be cut off without being a product on both sides) of a cast raw sheet is uniform.
  • a method is mentioned.
  • the method of adjusting each lip bolt so that a lip gap may become wide or narrow as it goes to the center in the width direction is mentioned.
  • the adjustment of the lip bolt can be determined according to the physical properties of the polypropylene resin used.
  • the lip gap is preferably less than 0.8 mm, more preferably 0.75 mm or less, and even more preferably 0.70 mm or less. Further, the lip gap is preferably 0.4 mm or more, and more preferably 0.5 mm or more.
  • the thickness of the cast original sheet can be set by the number of revolutions of the extruder and the lip gap. If the lip gap is within the above numerical range, the thickness of the cast original sheet can be easily made uniform.
  • the value of the lip gap means an average value of the gap at each lip bolt position. If the lip gap is significantly greater than 0.8 mm, there is a risk of breaking during stretching.
  • the surface temperature of the metal drum (the temperature of the metal drum that first contacts after extrusion) is preferably 50 to 100 ° C., more preferably 60 to 100 ° C., and still more preferably 60 to 80 ° C. ° C.
  • the surface temperature of the metal drum can be determined according to the physical properties of the polypropylene resin used. When the surface temperature of the metal drum is significantly lower than 50 ° C., it is difficult to obtain a good sheet formability of the original fabric sheet. It is difficult to obtain a favorable value.
  • a polypropylene film having the coefficient c of ⁇ 200 or more and ⁇ 50 or less can be obtained by appropriately adjusting each lip bolt or appropriately setting the surface temperature of the metal drum.
  • melt flow rate (MFR) of the cast original sheet is preferably within the numerical range described in the section “Embodiment 1 of the present invention”.
  • the rate of change between the melt flow rate of the polypropylene resin and the melt flow rate of the cast original sheet shown in the following formula (2) is preferably 1.3 or less, and preferably 1.2 or less. More preferred.
  • (Change rate) (Melt flow rate of raw sheet) / (Melt flow rate of polypropylene resin) Formula (2)
  • the rate of change is 1.3 or less, the resin is hardly deteriorated and the melt stability is excellent, and the thickness variation of the molded product is suppressed, so that the extrusion moldability is improved.
  • they are 0 or more, 0.01 or more, 0.1 or more, etc.
  • the thickness variation U MD for each predetermined length of the cast raw sheet in the flow direction is preferably not 1.6 ⁇ m or less, more preferably 1.5 ⁇ m or less. Moreover, although the said UMD is so preferable that it is small, it is 0.01 micrometer or more, for example.
  • the UMD is a value obtained by the following procedures (1a) to (4a).
  • (1a) A sample of a cast raw sheet having a width of 180 mm and a flow direction of 8020 mm is prepared.
  • (2a) The thickness of 4001 points is measured at a central position (position of 90 mm from both ends) in the width direction of the sample at a pitch of 2 mm in the flow direction. The measurement starts from a position 10 mm from the end in the flow direction.
  • Maximum deviation of the U MD is preferably not more than 7.0 .mu.m, and more preferably not more than 6.0 .mu.m.
  • the maximum deviation of the U MD is preferably as small, for example 0.01 ⁇ m or more.
  • Maximum deviation of the U MD is a value obtained by the following procedures (1b) ⁇ (2b).
  • (1b) An average value B of the average value A1, the average value A2, the average value A3, and the average value A4 is obtained.
  • the thickness variation U TD in the width direction of each flow direction a certain distance of the cast raw sheet is preferably not 1.2 ⁇ m or less, more preferably 1.0 ⁇ m or less.
  • the U TD is preferably as small as possible, but is preferably as small as possible, but is 0.01 ⁇ m or more, for example.
  • the U TD is a value obtained by the following procedures (1c) to (4c).
  • (1c) Prepare the sample of (1a) above.
  • (2c) At a position of 0 mm, 2000 mm, 4000 mm, 6000 mm, and 8000 mm in the flow direction, the thickness of 181 points is measured at a 1 mm pitch in the width direction.
  • positions of 0 mm, 2000 mm, 4000 mm, 6000 mm, and 8000 mm in the flow direction are based on the measurement start position (position of 10 mm from the end in the flow direction) of (2a) (0 mm ).
  • An average value C3 of thickness, an average value C4 of a total of 181 points at a position of 6000 mm in the flow direction, and an average value C5 of a total of 181 points at a position of 8000 mm in the flow direction are obtained.
  • a standard deviation of the average value C1, the average value C2, the average value C3, the average value C4, and the average value C5 is obtained, and this is defined as U TD . More specifically, according to the method described in the examples.
  • the thickness fluctuation parameter U TOTAL during continuous film of the cast raw sheet is preferably not 1.0 .mu.m 2 or less, more preferably 0.9 .mu.m 2 or less, more preferably 0.8 [mu] m 2 or less. Moreover, although the said U TOTAL is so preferable that it is small, it is 0.01 micrometer ⁇ 2 > or more, for example.
  • the U MD, the maximum deviation of the U MD, the U TD and, preferable numerical ranges of the U TOTAL is a cast raw preferable range of anti sheet prepared using laboratory small stretching device.
  • the preferable numerical range of the cast original fabric sheet produced using the production equipment is as follows.
  • the U MD is preferably not 0.10 ⁇ m or less, and more preferably not more than 0.08 .mu.m.
  • the said UMD is so preferable that it is small, it is 0.01 micrometer or more, for example.
  • Maximum deviation of the U MD is preferably not 0.5 ⁇ m or less, more preferably 0.3 ⁇ m or less.
  • the maximum deviation of the U MD is preferably as small, for example 0.01 ⁇ m or more.
  • the U TD is preferably 0.5 ⁇ m or less, and more preferably 0.3 ⁇ m or less.
  • the U TD is preferably as small as possible, but is preferably as small as possible, but is 0.01 ⁇ m or more, for example.
  • the variation parameter U TOTAL is preferably 0.05 ⁇ m 2 or less, more preferably 0.03 ⁇ m 2 or less.
  • the said U TOTAL is so preferable that it is small, it is 0.01 micrometer ⁇ 2 > or more, for example.
  • the reason why the preferable numerical range is different between the research small stretching apparatus and the production facility is that the production facility has less thickness unevenness.
  • the thickness of the cast original sheet is preferably within the numerical range described in the section “Embodiment 1 of the present invention”.
  • the biaxially stretched polypropylene film according to this embodiment can be suitably produced by the method described in the section “Embodiment according to the first invention”.
  • the biaxially stretched polypropylene film according to this embodiment is not limited to this production method.
  • a metal layer may be laminated on one or both sides of the polypropylene film to form a metal layer integrated polypropylene film.
  • the contents described in the section “Embodiment according to the first aspect of the present invention” can be adopted.
  • Polypropylene resin Table 1 shows the polypropylene resins used for producing the polypropylene films of Examples and Comparative Examples.
  • the polypropylene resin A shown in Table 1 is S802M manufactured by Korea Oil Chemical Co., Ltd., and the polypropylene resin D is HPT-1.
  • the polypropylene resin B is HC300BF manufactured by Borealis, the polypropylene resin F is HC318BF, and the polypropylene resin H is WB135HMS.
  • Polypropylene resin C, polypropylene resin E, and polypropylene resin G are products manufactured by Prime Polymer Co., Ltd.
  • Resins A to H (polypropylene resins A to H) shown in Table 1 were purchased from Prime Polymer Co., Korea Oil Chemical Co., Ltd., or Borealis Co. Table 1 shows the number average molecular weight (Mn), weight average molecular weight (Mw), z average molecular weight (Mz), molecular weight distribution (Mw / Mn), and molecular weight distribution (Mz / Mn) of polypropylene resins A to H. It was. These values are values in the form of raw material resin pellets. The measuring method is as follows.
  • HLC-8121GPC-HT type a high-temperature GPC device with a built-in differential refractometer (RI), manufactured by Tosoh Corporation was used.
  • RI differential refractometer
  • As a column three TSKgel GMHHR-H (20) HT manufactured by Tosoh Corporation were connected and used. At a column temperature of 140 ° C., measurement was performed by flowing trichlorobenzene as an eluent at a flow rate of 1.0 ml / min.
  • a calibration curve was prepared using standard polystyrene manufactured by Tosoh Corporation, and the measured molecular weight value was converted to a polystyrene value to obtain a number average molecular weight (Mn), a weight average molecular weight (Mw), and a z average.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz z average.
  • Mw molecular weight distribution
  • Mz / Mn was obtained using the values of Mz and Mn.
  • the molecular weight differential distribution value difference (D M ) is ⁇ 3.4% for Resin A, 5.0% for Resin B, 8.8% for Resin C, 3.8% for Resin D, For Resin E, it was 9.2%, and for Resin F, it was 3.3%.
  • polypropylene films of Examples and Comparative Examples were produced and their physical properties were evaluated.
  • Example 1 The pellets of polypropylene resin A were supplied to the extruder, the extruder rotation speed was set to 15 rpm, the extruder set temperature was set to 260 ° C., and the resin was melted at a resin temperature of 257 ° C. Next, the molten resin was extruded into a sheet using a 300-mm wide T-die having a lip gap of 0.70 mm that is uniform in the width direction by adjusting twelve lip bolts arranged at equal intervals in the width direction, and the surface temperature Was wound around a metal drum maintained at 70 ° C. and solidified. At this time, polypropylene resin was sprayed onto the metal drum with an air knife.
  • a cast raw sheet having a thickness of 200 ⁇ m was obtained.
  • the lip gap is adjusted by adjusting the lip gap at a position corresponding to the portion of the cast original fabric sheet product (the portion excluding the portion to be discarded without being a product on both sides), and uniformly in the width direction. 70 mm.
  • This sheet was stretched 4.6 times in the flow direction at 165 ° C. using a batch type biaxial stretching machine KARO IV manufactured by Brueckner Co. Relaxation was performed at a magnification of 9 times in the direction to obtain a biaxially stretched polypropylene film having a thickness of 5 ⁇ m.
  • Example 2 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 1 except that the polypropylene resin B was used.
  • Example 3 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 1 except that the polypropylene resin C was used.
  • Example 4 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 1 except that the polypropylene resin D was used.
  • Example 6 A biaxially oriented polypropylene film having a thickness of 5 ⁇ m was used in the same manner as in Example 1 except that the polypropylene resin E was used and the extrusion molding conditions (extruder rotational speed, resin temperature, lip gap) were as shown in Table 2. Obtained. In addition, the extruder preset temperature in Example 6 was 250 degreeC.
  • Example 1 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 1 except that the polypropylene resin F was used.
  • Example 2 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 1 except that the polypropylene resin E was used.
  • Example 3 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 1 except that the polypropylene resin G was used.
  • Example 5 A biaxially stretched polypropylene film was obtained in the same manner as in Example 1 except that the polypropylene resin E was used and the extrusion molding conditions (extruder speed, resin temperature, lip gap) were as shown in Table 2. However, the melted resin fluctuated, and the thickness unevenness of the original fabric sheet became remarkably large, and breakage occurred frequently during stretch film formation. In addition, the extruder preset temperature in the comparative example 5 was 250 degreeC. About the comparative example 5, the viscosity parameter mentioned later, the measurement of the crystallite size of a biaxially stretched polypropylene film, etc. were not able to be performed for the reason mentioned above.
  • Example 6 A biaxially oriented polypropylene film having a thickness of 7 ⁇ m was used in the same manner as in Example 1 except that the polypropylene resin E was used and the extrusion molding conditions (extruder rotational speed, resin temperature, lip gap) were as shown in Table 2. Obtained.
  • the flow curve ( ⁇ - ⁇ curve) obtained in the above (5) is obtained using the non-Newtonian pure viscosity model fitting function of the analysis software (HASL analysis software Materialfit Ver. 3.0.0). Fitting to the Carreau-Yasuda model (viscosity formula) shown in formula (1), a master curve was obtained. Thus, each parameter (zero shear viscosity ⁇ 0 , coefficient b, coefficient c, coefficient d, delay time ⁇ ) was obtained. The fitting was performed at a reference temperature Tr of 240 ° C. The reason why the reference temperature Tr is set to 240 ° C. is that an intermediate temperature among the measurement temperatures 230 ° C., 240 ° C., and 250 ° C. is selected. The obtained model parameters are shown in Table 2.
  • melt flow rate (MFR) Melt flow rate (MFR) in the form of raw material resin pellets used in Examples and Comparative Examples, and melt flow rate (MFR) of raw sheet (sheet before biaxial stretching) obtained in Examples and Comparative Examples was measured according to the condition M of JIS K 7210 using a melt indexer manufactured by Toyo Seiki Co., Ltd. Specifically, first, a sample weighed to 4 g was inserted into a cylinder set at a test temperature of 230 ° C., and preheated for 3.5 minutes under a load of 2.16 kg. Thereafter, the weight of the sample extruded from the bottom hole in 30 seconds was measured to obtain MFR (g / 10 min). The above measurement was repeated three times, and the average value was taken as the MFR measurement value. The results are shown in Table 2.
  • the melting points of the biaxially stretched polypropylene films obtained in Examples and Comparative Examples were obtained by the following procedure using an input compensation DSC Diamond DSC manufactured by Perkin Elmer. First, about 5 mg of a biaxially stretched polypropylene film was weighed, packed in an aluminum sample holder, and set in a DSC apparatus. Under a nitrogen flow, the temperature was raised from 30 ° C. to 280 ° C. at a rate of 20 ° C./min, and the melting curve was measured. As a result of DSC measurement, at least one or more melting peaks could be obtained between 100 ° C.
  • Example 1 175.0 ° C. in Example 1, 174.3 ° C. in Example 2, 174.1 ° C. in Example 3, 174.1 ° C. in Example 4, 174. 2 ° C., Example 6 at 174.2 ° C., Example 7 at 174.6 ° C., Example 8 at 174.5 ° C., Comparative Example 1 at 170.0 ° C., Comparative Example 2 at 174.
  • the half width of the diffraction reflection peak of the ⁇ crystal (040) plane was calculated using an analysis computer and integrated powder X-ray analysis software PDXL attached to the equipment standard. From the half-value width, the crystallite size was determined using Scherrer's formula (the following formula (2)). The results are shown in Table 2.
  • the polypropylene film of the Example whose coefficient b is 0.013 or less has high withstand voltage property in the alternating current power supply under high temperature (120 degreeC). Further, it was also confirmed that the polypropylene films of the examples had a withstand voltage with an AC power source that could withstand practical use as a capacitor film even at 27 ° C, 100 ° C, 110 ° C, and 120 ° C. It was also confirmed that stretching unevenness was suppressed. On the other hand, it can be seen that the polypropylene film of the comparative example having a coefficient b larger than 0.013 is inferior in voltage resistance at an AC power source at a high temperature (120 ° C.). In addition, stretching unevenness occurred.
  • Example 9 The pellets of polypropylene resin C were supplied to the extruder, the extruder rotation speed was set to 15 rpm, the extruder set temperature was set to 260 ° C., and the resin was melted at a resin temperature of 257 ° C. Next, the molten resin was extruded into a sheet using a 300-mm wide T-die having a lip gap of 0.70 mm that is uniform in the width direction by adjusting twelve lip bolts arranged at equal intervals in the width direction, and the surface temperature Was wound around a metal drum maintained at 70 ° C. and solidified. At this time, polypropylene resin was sprayed onto the metal drum with an air knife.
  • a cast raw sheet having a thickness of 200 ⁇ m was obtained.
  • the lip gap is adjusted by adjusting the lip gap at a position corresponding to the portion of the cast original fabric sheet product (the portion excluding the portion to be discarded without being a product on both sides), and uniformly in the width direction. 70 mm.
  • This sheet was stretched 4.6 times in the flow direction at 165 ° C. and then 10 times in the transverse direction at 165 ° C. using a batch type biaxial stretching machine KARO IV manufactured by Brueckner. Thereafter, the film was relaxed to 9 times the horizontal magnification while being held by a clip, to obtain a biaxially stretched polypropylene film having a thickness of 5 ⁇ m.
  • Example 10 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 9 except that the polypropylene resin E was used.
  • Example 11 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 9 except that the polypropylene resin D was used.
  • Example 13 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was used in the same manner as in Example 9 except that the polypropylene resin A was used and the extrusion molding conditions (extruder rotational speed, resin temperature, lip gap) were as shown in Table 4. Obtained.
  • the extruder set temperature in Example 13 was 265 ° C.
  • Example 9 A biaxially stretched polypropylene film having a thickness of 5 ⁇ m was obtained in the same manner as in Example 9 except that the polypropylene resin F was used.
  • Comparative Example 12 A biaxially stretched polypropylene film was obtained in the same manner as in Example 9 except that the polypropylene resin E was used and the extrusion molding conditions (extruder rotational speed, resin temperature, lip gap) were as shown in Table 4. However, the melted resin fluctuated, and the thickness unevenness of the original fabric sheet became remarkably large, and breakage occurred frequently during stretch film formation. In addition, the extruder preset temperature in the comparative example 12 was 250 degreeC. About the comparative example 12, the viscosity parameter mentioned later etc. could not be measured for the above-mentioned reason.
  • melt flow rate (MFR) in the form of raw material resin pellets used in Examples and Comparative Examples, and Examples, The melt flow rate (MFR) of the raw sheet (sheet before biaxial stretching) obtained in the comparative example was measured. Moreover, the change rate of MFR was calculated
  • (Change rate) (Melt flow rate of raw sheet) / (Melt flow rate of polypropylene resin) Formula (2)
  • Thickness variation UMD UMD maximum deviation in the flow direction of the cast raw fabric sheet (before biaxial stretching) after extrusion molding according to Examples and Comparative Examples, the maximum deviation of UMD, the width direction at regular intervals in the flow direction
  • the thickness variation U TD and the thickness variation parameter U TOTAL during continuous film formation were calculated by the following procedure.
  • the UMD was obtained by the following procedures (1a) to (4a).
  • (1a) a cast original fabric sheet according to Examples and Comparative Examples was prepared.
  • the extrusion conditions of the cast raw sheet were the same as the extrusion conditions in each example and each comparative example.
  • variety of the prepared cast original fabric sheet was 260 mm in both the Example and the comparative example.
  • a sample having a width of 180 mm and a flow direction of 8020 mm was sampled by cutting off the 0-40 mm position and 220-260 mm position in the width direction end of the cast raw sheet.
  • a sample of a cast raw sheet having a width of 180 mm and a flow direction of 8020 mm was prepared.
  • the thickness of 4001 points was measured at a center position (position of 90 mm from both ends) in the width direction of the sample at a pitch of 2 mm in the flow direction. The measurement started from a position 10 mm from the end in the flow direction.
  • the average value A3 of the thickness and the average value A4 of the total thickness of 1001 points from the points of 6000 mm to 8000 mm were obtained.
  • a standard deviation of the average value A1, the average value A2, the average value A3, and the average value A4 was determined and used as UMD .
  • the thickness variation U TD in the width direction of each flow direction a certain distance of the cast raw sheet was obtained by the following procedures (1c) ⁇ (4c).
  • (1c) The sample of (1a) above was prepared.
  • (2c) The thickness of 181 points was measured at a pitch of 1 mm in the width direction at positions of 0 mm, 2000 mm, 4000 mm, 6000 mm, and 8000 mm in the flow direction. Note that the “positions of 0 mm, 2000 mm, 4000 mm, 6000 mm, and 8000 mm in the flow direction” in (2c) are based on the measurement start position (position of 10 mm from the end in the flow direction) of (2a) (0 mm ).
  • An average value C3 of thickness, an average value C4 of a total of 181 points at a position of 6000 mm in the flow direction, and an average value C5 of a total of 181 points at a position of 8000 mm in the flow direction were obtained.
  • the standard deviations of the average value C1, the average value C2, the average value C3, the average value C4, and the average value C5 were obtained and used as U TD .
  • the thickness variation parameter U TOTAL during continuous film formation of the cast raw sheet was obtained by the following equation.
  • U TOTAL U MD ⁇ U TD
  • the biaxial stretching of the cast original fabric sheet was performed 3 times and evaluated according to the following criteria.
  • the biaxial stretching conditions were the same as the biaxial stretching conditions in each example and each comparative example. The results are shown in Table 5.
  • ⁇ Evaluation of end fluidity during extrusion> The widths of the ears at the extreme end of the cast raw sheet after extrusion were measured, and the average value at both ends was calculated as the ear width. A case where the ear width was 5 mm or less was evaluated as A, and a case where the ear width exceeded 5 mm was evaluated as B. The results are shown in Table 5. Note that the extreme end portions refer to the portions in the width direction position of 0 to 4% and 96% to 100%. In the examples and comparative examples, it refers to the portions of 0 to 10.4 mm and 249.6 to 260 mm from the end. The “ear” refers to a portion that is 150% or more thicker than the thickness at the center in the width direction.
  • the ear width indicates the fluidity of the resin during extrusion molding, and it can be said that the fluidity is low when the ear width is wide.
  • the fluidity is low, the thickness unevenness of the cast raw sheet becomes large, and the film forming property at the biaxial stretching becomes unstable.
  • liquidity of resin is low, the thickness of a product edge part will become thick, it cannot be set as a product, and a yield will also fall.
  • Example 16 A biaxially stretched polypropylene film having a thickness of 2.0 ⁇ m was obtained in the same manner as in Example 12 except that the production equipment was used instead of the small stretching apparatus for research.
  • Comparative Example 13 A biaxially stretched polypropylene film having a thickness of 2.0 ⁇ m was obtained in the same manner as in Comparative Example 7 except that production equipment was used instead of the small stretching apparatus for research.
  • melt flow rate (MFR) was measured for Example 16 and Comparative Example 13. The results are shown in Table 6.
  • Example 16 and Comparative Example 13 the biaxial stretching of the cast original fabric sheet was performed once and evaluated according to the following criteria. In addition, the cast raw fabric sheet used what was continuously extruded. The biaxial stretching conditions were the same as the biaxial stretching conditions in producing the biaxially stretched polypropylene film in Example 16 and Comparative Example 13. The results are shown in Table 7. A: No tearing occurred for 75000 m or more during stretching. B: At the time of stretching, no tearing occurred up to 30000 m, but tearing occurred at a location of 30000 m or more and less than 75000 m. C: At the time of stretching, tearing occurred at a location less than 30000 m.
  • Example in which coefficient b satisfies 0.005 or more and 0.013 or less and coefficient c satisfies ⁇ 200 or more and ⁇ 50 or less means an example in the case of (1) below, This means an embodiment in the case of (2).
  • Example in which the polypropylene film according to the first aspect of the present invention further satisfies the coefficient c of ⁇ 200 or more and ⁇ 50 or less.
  • Example 3 and Example 9 are the same polypropylene film, but in Example 3, in the withstand voltage (high temperature (120 ° C.) at the high temperature (120 ° C.) described in the first embodiment of the present invention. In Example 9, it is shown that the molding processability described in the section “Embodiment according to the second aspect of the present invention” is excellent.
  • Example 3 and Example 9 are regarded as one example, when the coefficient b satisfies 0.005 or more and 0.013 or less and the coefficient c satisfies ⁇ 200 or more and ⁇ 50 or less, Excellent in voltage resistance (voltage resistance at an AC power source at a high temperature (120 ° C.)) described in the section “Embodiment 1 of the present invention” and of “Embodiment 2 of the present invention” It is shown that the molding processability described in the section is excellent.
  • Example 4 and Example 11 are taken as one example. What was taken, Example 5 and Example 12 were taken as one example, Example 7 and Example 14 were taken as one example, Example 8 and Example 15 were taken as one example What was captured as.

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Abstract

La présente invention concerne un film de polypropylène qui a une épaisseur de 1 à 10 µm et dans lequel le coefficient b, qui représente le gradient entre la température et la viscosité et est déterminé lors de l'application de résultats de mesure concernant la viscosité de cisaillement de fusion et la vitesse de cisaillement au modèle de Carreau-Yasuda, est égal à 0,005-0,013.
PCT/JP2018/013727 2017-03-31 2018-03-30 Film de polypropylène, film de polypropylène intégré à une couche métallique et condensateur à film WO2018181938A1 (fr)

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JP2018-055403 2018-03-23
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JP2018060433A JP6904296B2 (ja) 2017-07-20 2018-03-27 ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ
JP2018060198A JP6904295B2 (ja) 2017-03-31 2018-03-27 ポリプロピレンフィルム、金属層一体型ポリプロピレンフィルム、及び、フィルムコンデンサ
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022107706A1 (fr) * 2020-11-17 2022-05-27 王子ホールディングス株式会社 Film de polypropylène, film de polypropylène intégré avec une couche métallique et condensateur à film
WO2022220248A1 (fr) * 2021-04-12 2022-10-20 王子ホールディングス株式会社 Film de polypropylène métallisé
WO2023162557A1 (fr) * 2022-02-25 2023-08-31 王子ホールディングス株式会社 Film de polypropylène biorienté, film métallisé et condensateur

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105552A1 (fr) * 2012-01-11 2013-07-18 王子ホールディングス株式会社 Film de polypropylène à orientation biaxiale pour condensateurs
JP2014055276A (ja) * 2012-01-24 2014-03-27 Toyobo Co Ltd 延伸ポリプロピレンフィルム
WO2015151591A1 (fr) * 2014-03-31 2015-10-08 王子ホールディングス株式会社 Film de polypropylène à orientation biaxiale pour condensateurs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013105552A1 (fr) * 2012-01-11 2013-07-18 王子ホールディングス株式会社 Film de polypropylène à orientation biaxiale pour condensateurs
JP2014055276A (ja) * 2012-01-24 2014-03-27 Toyobo Co Ltd 延伸ポリプロピレンフィルム
WO2015151591A1 (fr) * 2014-03-31 2015-10-08 王子ホールディングス株式会社 Film de polypropylène à orientation biaxiale pour condensateurs

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022107706A1 (fr) * 2020-11-17 2022-05-27 王子ホールディングス株式会社 Film de polypropylène, film de polypropylène intégré avec une couche métallique et condensateur à film
WO2022220248A1 (fr) * 2021-04-12 2022-10-20 王子ホールディングス株式会社 Film de polypropylène métallisé
WO2023162557A1 (fr) * 2022-02-25 2023-08-31 王子ホールディングス株式会社 Film de polypropylène biorienté, film métallisé et condensateur

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