JP6904296B2 - Polypropylene film, metal layer integrated polypropylene film, and film capacitors - Google Patents

Description

The present invention relates to a polypropylene film, a polypropylene film integrated with a metal layer, and a film capacitor.

The polypropylene film has excellent electrical characteristics such as high withstand voltage and low dielectric loss characteristics, and also has high moisture resistance. Therefore, it is widely used in electronic devices and electrical devices. Specifically, it is used as a film used for, for example, high-voltage capacitors, various switching power supplies, filter capacitors (for example, converters, inverters, etc.), smoothing capacitors, and the like.

In recent years, there has been a demand for further miniaturization and higher capacity of capacitors. In order to improve the capacitance without changing the volume of the capacitor, it is preferable to make the film as a dielectric thin. Therefore, there is a demand for a film having a thinner thickness.

Further, in recent years, polypropylene film has begun to be widely used as a capacitor for an inverter power supply device for controlling a drive motor of an electric vehicle, a hybrid vehicle, or the like. Capacitors for inverter power supply equipment used in automobiles and the like are required to have high withstand voltage over a long period of time in a wide temperature range (for example, -40 ° C to 90 ° C), with a small size, light weight, and high capacity. ..

Patent Document 1 discloses a polypropylene film in which polypropylene having a specific relationship between melt tension and melt flow rate (MFR) measured at 230 ° C. is contained in a polypropylene resin having high stereoregularity. (In particular, see claim 1 and claim 4). In addition, as an effect, it is excellent in stretchability, so that it is excellent in uniformity of thickness and various physical properties, and it can be uniformly stretched while using polypropylene resin with high regularity, and it is excellent in heat resistance, thermal dimensional stability, mechanical rigidity, and electrical insulation. It is stated that a polypropylene film can be provided (particularly, see paragraph [0011]).

Japanese Patent No. 4929923

The melt tension and melt flow rate described in Patent Document 1 are values obtained from raw material pellets. On the other hand, polypropylene film as a product undergoes a thermal history from raw material pellets to being molded into a film. Then, the values of the melt tension and the melt flow rate of the polypropylene film change due to the influence of the thermal history. Therefore, the polypropylene film of Patent Document 1 has a problem that the original sheet (film before stretching), which is the source of the polypropylene film, does not have sufficient stretchability and may not be suitably thinned.

Further, conventionally, there is also a method of adjusting the weight average molecular weight of the entire polypropylene and adjusting the molecular weight distribution so as to obtain the required molding processability (for example, stretchability). However, since these parameters are complicatedly related, it is difficult to derive a combination for satisfying the requirements, and there is room for improvement.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a polypropylene film having excellent moldability. Another object 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 present inventors have diligently studied polypropylene films. As a result, polypropylene having a specific coefficient within a predetermined range determined when the measurement results of the melt shear viscosity and the 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 has been found to be excellent in molding processability, and has completed the present invention.

That is, the polypropylene film according to the present invention is
The coefficient c representing the slope between the shear rate and the shear 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 the equation (1), is −200 or more −50. The thickness is as follows, and is characterized by having a thickness of 1 to 10 μm.

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 change in shear rate (the smaller the slope), and the smaller the coefficient c, the larger the change in shear viscosity with respect to the change in shear rate (the larger the slope). ).
In the present invention, the change in viscosity with respect to the change in shear rate is so large that the coefficient c is −50 or less. The present inventors explain that the reason why the formability of the polypropylene film is excellent when the coefficient c is -50 or less is that when the viscosity change with respect to the shear rate change is large, the fluidity of the resin in the high shear rate range in the extruder is large. It is presumed that this is because the extrusion moldability is improved.
On the other hand, even if the change in shear viscosity with respect to the change in shear rate is too large (that is, even if the coefficient c is smaller than -200), when the molten resin is extruded into a sheet, the viscosity changes significantly due to a slight change in speed. Therefore, stable extrusion becomes difficult, and it may be difficult to obtain a thin film. Therefore, in the present invention, the coefficient c is set to −200 or more and −50 or less. As a result, a thin polypropylene film having a thickness of 1 to 10 μm can be stably obtained.
According to the above configuration, since the coefficient c in the Carreau-Yasuda model represented by the formula (1) is −200 or more and −50 or less, the molding processability is good as can be seen from the examples. That is, since the present invention is a polypropylene film having a coefficient c of −200 or more and −50 or less, when the raw fabric sheet is stretched to obtain the polypropylene film, (i) there is no breakage during stretching of the raw fabric sheet. , (Ii) Thickness unevenness in the flow direction of the raw material sheet is suppressed, (iii) Thickness unevenness in the width direction of the raw material sheet is suppressed, and (iv) Thickness unevenness in the surface direction of the raw material sheet is suppressed. It is suppressed, and (v) the resin fluidity of the raw sheet is excellent.
As described above, the present invention is an invention based on the new finding by the present inventors that when the coefficient c is −200 or more and −50 or less, the molding processability of the polypropylene film is improved.
Further, according to the above configuration, the physical characteristics of the polypropylene film as an actual product, that is, the coefficient c is defined. That is, since it is defined by the actual physical properties of the polypropylene film after taking into account the heat history received in the film forming process, the polypropylene film satisfying the physical properties is surely improved in molding processability.
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 the shear rate of the produced polypropylene film. Therefore, a polypropylene film satisfying the required molding processability can be easily produced. 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, as the resin to be used, the extrusion molding conditions (sheet molding conditions, lip gap adjustment, etc.) at the time of film molding may be selected depending on whether a resin having a large change in viscosity during melt shear is selected or a resin having a small viscosity change is selected. 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 during melt shearing, the resin fluidity is low and the thickness variation tends to be large. , It is preferable to raise the molding temperature such as the transverse stretching temperature. Further, in the case of a resin having a wide molecular weight distribution and a large change in viscosity during melt shearing, the molding temperature such as the resin temperature, the longitudinal stretching temperature, and the transverse stretching temperature can be lowered within the range in which the film can be formed without uneven stretching, or the lip gap. It is preferable to spread the temperature.

The polypropylene film having the above constitution is a film made of polypropylene resin, melt-extruded from the polypropylene resin to form a raw sheet, and then biaxially stretched.
The rate of change between the melt flow rate of the polypropylene resin represented by the following formula (2) and the melt flow rate of the raw sheet is preferably 1.3 or less.
(Rate of change) = (melt flow rate of raw sheet) / (melt flow rate of polypropylene resin) Equation (2)

It is presumed that when the rate of change is 1.3 or less, the resin is less likely to deteriorate, 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 preferably for a capacitor.

Since the polypropylene film having a coefficient c of −200 or more and −50 or less is excellent in molding processability, it can be made thin and can be suitably used for a capacitor.

The polypropylene film having the above constitution contains a polypropylene resin and has a polypropylene resin.
Among the polypropylene resins, the polypropylene resin as the main component has a number average molecular weight Mn of 30,000 or more and 53,000 or less.
Among the polypropylene resins, the polypropylene resin as the main component has a weight average molecular weight Mw of 250,000 or more and 450,000 or less.
Among the polypropylene resins, the z average molecular weight Mz of the polypropylene resin as the main component is 500,000 or more and 2.1 million or less, and the molecular weight distribution of the polypropylene resin as the main component among the polypropylene resins [(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 polypropylene resin as the main component is preferably 10 or more and 70 or less.

As the polypropylene resin as the main component, the number average molecular weight Mn, the weight average molecular weight Mw, the z average molecular weight Mz, the molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)], and the molecular weight distribution [(z). If an average molecular weight Mz) / (number average molecular weight Mn)] is used within the above numerical range, it is easy to obtain a polypropylene film having the coefficient c of −200 or more and −50 or less.

The polypropylene film having the above constitution has a heptane-insoluble content (HI) of the polypropylene resin as the main component of 96.0% or more and 99.5% or less.
The melt flow rate (MFR) of the polypropylene resin as the main component is preferably 1.0 g / 10 min or more and 8.0 g / 10 min or less.

The higher the heptane insoluble content, the higher the stereoregularity of the resin. When 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 the moderately high stereoregularity. Moldability is improved. On the other hand, the rate of solidification (crystallization) at the time of molding the cast raw fabric sheet becomes appropriate, and the cast raw fabric has an appropriate stretchability.
Further, if a polypropylene resin having a melt flow rate (MFR) of 1.0 g / 10 min or more and 8.0 g / 10 min or less is used as the main component polypropylene resin, the coefficient c is −200 or more and -50 or less. Easy to get film.

Further, the polypropylene film integrated with a metal layer according to the present invention is
With the polypropylene film
It is characterized by having a metal layer laminated on one side or both sides of the polypropylene film.

According to the above configuration, since it has a metal layer laminated on one side or both sides of the polypropylene film, it can be used for a film capacitor in which the polypropylene film is a dielectric and the metal layer is an electrode. Further, since the polypropylene film having the coefficient c of −200 or more and −50 or less is provided, the molding processability is excellent and the thickness can be made thin.

Further, the film capacitor according to the present invention is characterized by having the wound metal layer integrated polypropylene film.

According to the present invention, it is possible to provide a polypropylene film having excellent molding processability and a thin thickness. Further, a metal layer-integrated polypropylene film having the polypropylene film and a film capacitor having the metal layer-integrated polypropylene film can be provided.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to these embodiments. Since the polypropylene film according to this embodiment is not a microporous film, it does not have a large number of pores. Further, the polypropylene film according to the present embodiment is preferably composed of a single layer.

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 regarding the melt shear viscosity and the shear rate are applied to the Carreau-Yasuda model shown in the equation (1), is −200 or more −50. It is as follows. The coefficient c is preferably −60 or less, and more preferably −70 or less. The coefficient c is preferably −180 or more, and more preferably −150 or more.

The Carreau-Yasuda model is a model that represents the shear viscosity curve of a non-Newtonian fluid, and is a model that can express both the characteristics of the zero shear region and the shear flow region.

Zero shear viscosity η ₀ represents the magnitude of the overall viscosity. Specifically, the larger the zero shear viscosity η ₀ , the larger the shear viscosity η. That is, when the shear rates are the same, the _{larger the zero shear viscosity η 0} , the larger the shear viscosity η.
The delay time λ is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the larger the coefficient λ, the smaller the change in shear viscosity with respect to the change in shear rate (the smaller the slope), and the smaller the coefficient λ, the larger the change in shear viscosity with respect to the change in shear rate (the larger the slope). ).
The coefficient b is a coefficient representing the slope between the temperature and the viscosity. Specifically, the smaller the coefficient b, the smaller the change in shear viscosity with respect to the temperature change (the slope becomes smaller), and the larger the coefficient b, the larger the change in the shear viscosity with respect to the temperature change (the slope 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 change in shear rate (the smaller the slope), and the smaller the coefficient c, the larger the change in shear viscosity with respect to the change in shear rate (the larger the slope). ).
The coefficient d is a coefficient representing the slope between the shear rate and the shear viscosity. Specifically, the larger the coefficient d, the smaller the change in shear viscosity with respect to the change in shear rate (the smaller the slope), and the smaller the coefficient d, the larger the change in shear viscosity with respect to the change in shear rate (the larger the slope). ).

Hereinafter, a method for obtaining the coefficient c will be described. Since each parameter (zero shear viscosity η ₀ , coefficient b, coefficient c, coefficient d, delay time λ) is obtained at the same time, a method for obtaining all parameters including the coefficient c will be described below.

<Method of determining each parameter in the Carreau-Yasuda model>
First, the relationship (flow curve) between the shear viscosity η and the shear rate γ at the measurement temperatures of 230 ° C., 240 ° C., and 250 ° C. is obtained by the following procedures (1) to (5). For the measurement, HAAKE MiniLab Rheomex CTW5 (microrheology compounder) manufactured by Thermo Fisher Scientific Co., Ltd. is used.
(1) Cut out a polypropylene film into strips, weigh 5 g, and charge the entire amount from the sample loading section.
(2) After stabilizing at a rotation speed of 10 rpm for 1 minute, the pressure loss dP at 10 points between the rotation speeds of 10 rpm and 360 rpm is measured, and the shear stress τ at each rotation speed is derived from the measured pressure loss dP. .. The 10 points to be measured are 10 points when evenly divided in logarithmic notation.
(3) Measure each resin amount Q discharged from the discharge port at rotation speeds 10, 20, 50, 100 rpm, derive the shear rate γ of each rotation speed from the measured resin amount Q, and γ and the rotation speed. Find the linear approximation formula of. From the obtained approximate expression, γ at the rotation speed of 10 points in (2) above is obtained.
(4) From the 10-point shear stress τ and shear velocity γ obtained in (1) to (3) above, the modified Hargen-Poisellle equation ([shear viscosity η] = [shear stress τ] / [shear velocity] γ]) is used to determine the shear viscosity η. From the above, the relationship (flow curve) between the shear viscosity η and the shear rate γ is obtained.
(5) The above operations (1) to (4) are carried out at the measurement temperatures of 230 ° C., 240 ° C., and 250 ° C. to obtain the relationship (flow curve) between the shear viscosity η and the shear rate γ at each measurement temperature.

Next, using the non-Newtonian pure viscosity model fit function of the analysis software (HASL Co., Ltd. analysis software Materialfit Ver. 3.0.0), the flow curve (η-γ curve) obtained in (5) above is obtained. A master curve is obtained by fitting to the Carreau-Yasuda model (viscosity formula) represented by the formula (1). From the above, each parameter (zero shear viscosity η ₀ , coefficient b, coefficient c, coefficient d, delay time λ) is obtained. The reference temperature Tr is set to 240 ° C. for fitting. The reference temperature Tr was set to 240 ° C. because the intermediate temperature of the measurement temperatures of 230 ° C., 240 ° C., and 250 ° C. was selected.

As described above, 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 change in shear rate (the smaller the slope), and the smaller the coefficient c, the larger the change in shear viscosity with respect to the change in shear rate (the larger the slope). ).
The polypropylene film according to the present embodiment has a large change in viscosity with respect to a change in shear rate to the extent that the coefficient c is −50 or less. The present inventors explain that the reason why the formability of the polypropylene film is excellent when the coefficient c is -50 or less is that when the viscosity change with respect to the shear rate change is large, the fluidity of the resin in the high shear rate range in the extruder is large. It is presumed that this is because the extrusion moldability is improved.
On the other hand, even if the change in shear viscosity with respect to the change in shear rate is too large (that is, even if the coefficient c is smaller than -200), when the molten resin is extruded into a sheet, the viscosity changes significantly due to a slight change in speed. Therefore, stable extrusion becomes difficult, and it may be difficult to obtain a thin film. Therefore, in the present embodiment, the coefficient c is set to −200 or more and −50 or less. As a result, a thin polypropylene film having a thickness of 1 to 10 μm can be stably obtained.
Since the polypropylene film according to the present embodiment has a coefficient c of −200 or more and −50 or less in the Carreau-Yasuda model represented by the formula (1), the molding processability is good as can be seen from the examples. That is, since the polypropylene film according to the present embodiment is a polypropylene film having a coefficient c of −200 or more and −50 or less, when the raw fabric sheet is stretched to obtain the polypropylene film, (i) the raw fabric sheet is stretched. There is no breakage at the time, (ii) thickness unevenness in the flow direction of the raw fabric sheet is suppressed, (iii) thickness unevenness in the width direction of the raw fabric sheet is suppressed, and (iv) the surface of the raw fabric sheet. The thickness unevenness in the direction is suppressed, and (v) the resin fluidity of the raw sheet is excellent.
Further, in the present embodiment, the physical characteristics of the polypropylene film as an actual product, that is, the coefficient c is defined. That is, since it is defined by the actual physical properties of the polypropylene film after taking into account the heat history received in the film forming process, the polypropylene film satisfying the physical properties is surely improved in molding processability.
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 the shear rate of the produced polypropylene film. Therefore, a polypropylene film satisfying the required molding processability can be easily produced. 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, as the resin to be used, the extrusion molding conditions (sheet molding conditions, lip gap adjustment, etc.) at the time of film molding may be selected depending on whether a resin having a large change in viscosity during melt shear is selected or a resin having a small viscosity change is selected. This can be achieved by optimally setting the stretching conditions, film forming equipment, and the like. Specifically, among the polypropylene resins constituting the polypropylene film according to the present embodiment, the polypropylene resin as the main component has a high molecular weight or a moderately narrow molecular weight distribution (for example, Mw / Mn is less than 8.5, 8. (4 or less, etc.) In the case of a resin with a small change in viscosity during melt shearing, the resin fluidity is low and the thickness variation tends to be large. It is preferable to raise the molding temperature such as. Further, among the polypropylene resins constituting the polypropylene film according to the present embodiment, the case of a resin having a wide molecular weight distribution of the polypropylene resin as a main component (for example, Mw / Mn of 8.5 or more) and a large change in viscosity 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 widen the lip gap within the range in which the film can be formed without uneven stretching.

In particular, the production of polypropylene film using a production machine (manufacturing equipment used in actual production) is performed at a high shear rate, but in a high shear rate region (for example, shear rate γ = 1000 (1 / s)). ) Is difficult to measure the shear viscosity η.
In the present embodiment, since the master curve is used, it is possible to obtain the relationship between the shear viscosity η and the shear rate γ at an arbitrary temperature. Then, by using the master curve, it is possible to know the tendency of the entire viscosity including the shear viscosity η in the high shear rate region, which is used in actual production and is difficult to actually measure. That is, in the present embodiment, how the tendency of the entire viscosity including the shear viscosity η in the high shear rate region, which is difficult to actually measure, affects the molding processability is grasped through the coefficient c to be sure. It guarantees the improvement of molding processability.

The dielectric breakdown strength ES of the polypropylene film at 27 ° C. is preferably 240 Vac / μm or more, more preferably 250 Vac / μm or more, and further preferably 260 Vac / μm or more. The higher the dielectric breakdown strength ES of the polypropylene film at 27 ° C. is, the more preferable, but for example, it is 500 Vac / μm or less, 450 Vac / μm or less, 400 Vac / μm or less.

The dielectric breakdown strength ES of the polypropylene film at 100 ° C. is preferably 235 Vac / μm or more, and more preferably 238 Vac / μm or more. The higher the dielectric breakdown strength ES of the polypropylene film at 100 ° C. is, the more preferable, but for example, it is 400 Vac / μm or less, 350 Vac / μm or less, and 300 Vac / μm or less.

The melting point of the polypropylene film is preferably 168.0 to 178.0 ° C, more preferably 171.0 to 175.0 ° C, and even more preferably 172.0 to 174.2 ° C. .. If the melting point of the polypropylene film is 168.0 ° C. or lower, the withstand voltage characteristics of the polypropylene film for capacitors may be inferior, which is not preferable. The method for measuring the melting point of the polypropylene film is as described in Examples.

As long as the coefficient c is −200 or more and −50 or less, the polypropylene film is not particularly limited in its use, but is preferably for a capacitor.

The polypropylene film having a coefficient c of −200 or more and −50 or less has good molding processability and can have a thin thickness. Therefore, it can be suitably used for capacitors.

The thickness of the polypropylene film is 1 to 10 μm from the viewpoint of ensuring the miniaturization and high capacity of the capacitor when used for the capacitor. Specifically, the thickness of the polypropylene film is 10 μm or less, preferably 6.0 μm or less, more preferably 4.0 μm or less, further preferably 3.5 μm or less, and particularly preferably 3.0 μm or less. The thickness of the polypropylene film is 1.0 μm or more from the viewpoint of manufacturing. The thickness of the polypropylene film can be 1.5 μm or more and 1.8 μm or more.

The thickness of the polypropylene film is a value measured according to JIS-C2330 using a micrometer (JIS-B7502).

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 total polypropylene film is 100% by mass). The upper limit of the content of the polypropylene resin is, for example, 100% by mass, 98% by mass, or the like with respect to the entire polypropylene film. The polypropylene resin may contain one kind of polypropylene resin alone, or may contain two or more kinds of polypropylene resins.

Here, when the polypropylene resin contains two or more kinds of polypropylene resin, the polypropylene resin having the larger content is referred to as "main component polypropylene resin" in the present specification. When the polypropylene resin contained in the polypropylene film is one kind, the polypropylene resin is referred to as "main component polypropylene resin" in the present specification.

Hereinafter, in the present specification, when the term "polypropylene resin" is used without specifying whether or not it is the main component, unless otherwise specified, the polypropylene resin as the main component and the polypropylene resin other than the main component are used. Means both. For example, when it is described that "the weight average molecular weight Mw of the polypropylene resin is preferably 250,000 or more and 450,000 or less", the weight average molecular weight Mw of the polypropylene resin as a main component is 250,000 or more and 450,000 or more. It means that the weight average molecular weight Mw of the polypropylene resin other than the main component is preferably 250,000 or more and 450,000 or less.

The polypropylene film may be a biaxially stretched film, a uniaxially stretched film, or a non-stretched film, but is preferably a biaxially stretched film. In the following, a 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. When the weight average molecular weight Mw of the polypropylene resin is 250,000 or more and 450,000 or less, the resin fluidity becomes appropriate. As a result, the thickness of the cast raw sheet can be easily controlled, and a thin stretched film can be easily produced. In addition, uneven thickness of the cast raw sheet and the stretched film is less likely to occur. In addition, it is possible to impart appropriate stretchability to the cast raw fabric sheet. When two or more kinds of polypropylene resins are used, it is preferable to use the polypropylene resin having Mw of 250,000 or more and less than 330,000 and the polypropylene resin having Mw of 330,000 or more and 450,000 or less in combination.

The number average molecular weight Mn of the polypropylene resin is preferably 30,000 or more and 53,000 or less, and more preferably 33,000 or more and 52,000 or less. When the number average molecular weight Mn of the polypropylene resin is 30,000 or more and 53,000 or less, it is easy to obtain a polypropylene film having the coefficient c of −200 or more and -50 or less.

The z average molecular weight Mz of the polypropylene resin is preferably 500,000 or more and 210000 or less, and more preferably 700,000 or more and 1700000 or less. When the z average molecular weight Mz of the polypropylene resin is 500,000 or more and 210000 or less, it is easy to obtain a polypropylene film having the coefficient c of −200 or more and −50 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 5 or more and 10 or less. It is more preferable, and it is particularly preferable that it is 5.5 to 9.5. When 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 c of −200 or more and -50 or less. When two or more kinds of polypropylene resins are used, it is preferable to use the polypropylene resin having a molecular weight distribution of 5 or more and less than 8.5 and the polypropylene resin having a molecular weight distribution of 8.5 or more and 11 or less in combination.

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 15 or more and 50 or less. Is even more preferable. When 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 c of −200 or more and -50 or less.

In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), the z average molecular weight, and the molecular weight distribution (Mw / Mn, and Mz / Mn) of the polypropylene resin are obtained by gel permeation chromatography (Mn). It is a value measured using a GPC) device. More specifically, it is a value measured using HLC-8121GPC-HT (trade name) of a high temperature GPC measuring machine with a built-in differential refractometer (RI) manufactured by Tosoh Corporation. As the GPC column, three TSKgel GMHHR-H (20) HTs manufactured by Tosoh Corporation are connected and used. The column temperature is set to 140 ° C., and trichlorobenzene is flowed as an eluent at a flow rate of 1.0 ml / 10 minutes to obtain measured values of Mw and Mn. A calibration curve with respect 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. Here, the logarithm of the base 10 of the molecular weight M of standard polystyrene is referred to as a logarithmic molecular weight (“Log (M)”).

In the molecular weight differential distribution curve, the polypropylene resin is the difference obtained by subtracting the differential distribution value when Log (M) = 6.0 from the differential distribution value when the logarithmic molecular weight Log (M) = 4.5 (hereinafter, The "differential distribution value difference _DM ") is preferably -5% or more and 14% or less, more preferably -4% or more and 12% or less, and -4% or more and 10% or less. Is even more preferable.
_{In addition, "the difference (differential distribution value difference DM} ) obtained by subtracting the differential distribution value when Log (M) = 6.0 from the differential distribution value when the logarithmic molecular weight Log (M) = 4.5 is-. "5% or more and 14% or less" is a typical distribution of components having a molecular weight of 10,000 to 100,000 on the low molecular weight side (hereinafter, also referred to as "low molecular weight components") based on the Mw value of the polypropylene resin. Log (M) as a typical distribution value of a component having a logarithmic molecular weight Log (M) = 4.5 as a value and a component having a molecular weight of about 1 million on the high molecular weight side (hereinafter, also referred to as “high molecular weight component”). When comparing the components around = 6.0, it can be understood that when the difference is positive, there are more low molecular weight components, and when the difference is negative, there are more high molecular weight components.

That is, even if the molecular weight distribution Mw / Mn is 5 to 12, it merely indicates the width of the molecular weight distribution, and the quantitative relationship between the high molecular weight component and the low molecular weight component in it is not known. Absent. Therefore, from the viewpoint of stable film forming property and thickness uniformity of the raw sheet, 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 low molecular weight components. It is preferable to use a polypropylene resin so that the difference in differential distribution value is -5% or more and 14% or less as compared with the component having a molecular weight of 1 million.

The differential distribution value is a value obtained as follows using GPC. A curve (generally also referred to as an "elution curve") indicating the intensity over time obtained by a GPC differential refractometer (RI) detector is used. Using a calibration curve obtained using standard polystyrene, the time axis is converted to a logarithmic molecular weight (Log (M)) to convert the elution curve into a curve showing the strength against 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, assuming that the total area of the curve showing the intensity is 100%. The differential distribution curve is obtained by differentiating this integral distribution curve with Log (M). Therefore, the "differential distribution" means the differential distribution of the concentration fraction with respect to the molecular weight. 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. The heptane insoluble content (HI) of the polypropylene resin is preferably 99.5% or less, more preferably 99.0% or less. Here, the larger the amount of heptane insoluble matter, the higher the stereoregularity of the resin. When the heptane insoluble content (HI) is 96.0% or more and 99.5% or less, the rate of solidification (crystallization) at the time of molding the cast raw fabric sheet becomes appropriate, and the cast raw fabric has an appropriate stretchability. The method for measuring heptane insoluble matter (HI) is as described in Examples.

The melt flow rate (MFR) of the polypropylene resin is 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. It is more preferably / 10 min. The method for measuring the melt flow rate of the polypropylene resin is as described in Examples.

When two or more kinds of polypropylene resins are contained in the polypropylene film, the polypropylene resin as the main component has the differential distribution value difference _DM of 8.0% or more and the heptane insoluble component (HI) of 98.5. % Or less, and the melt flow rate (MFR) is preferably 4 g / 10 min or more and 8 g / 10 min or less. Further, if the polypropylene resin contained in said polypropylene film is two or more, a polypropylene resin other than the main components, the less than the differential distribution value difference D _M is 8.0%, the heptane insolubles (HI) is It is preferably more than 98.5% and the previous melt flow rate (MFR) is 1 g / 10 min or more and 3.9 g / 10 min or less.

The polypropylene resin can be produced by using a generally known polymerization method. Examples of the polymerization method include a vapor phase polymerization method, a massive polymerization method and a slurry polymerization method.

The polymerization may be a single-stage (one-stage) polymerization using one polymerization reactor, or may be a multi-stage polymerization using two or more polymerization reactors. Further, the polymerization may be carried out by adding hydrogen or a comonomer as a molecular weight modifier in the reactor.

A generally known Ziegler-Natta catalyst can be used as the catalyst for the polymerization, and the polypropylene resin is not particularly limited as long as it can be obtained. The catalyst may include a co-catalyst component or a donor. By adjusting the catalyst and polymerization conditions, the molecular weight, molecular weight distribution, stereoregularity, etc. can be controlled.

The molecular weight distribution of the polypropylene resin and the like can be adjusted by resin mixing (blending). For example, a method of mixing two or more kinds of resins having different molecular weights and molecular weight distributions from each other can be mentioned. Generally, when the main resin is a resin having a higher average molecular weight or a resin having a lower average molecular weight, and the total amount of the resin is 100% by mass, the main resin is a mixture of two types of polypropylene having 55% by mass or more and 90% by mass or less. The system is preferable because the amount of low molecular weight components can be easily adjusted.

When the above-mentioned mixing adjustment method is adopted, the melt flow rate (MFR) may be used as a guideline for the average molecular weight. In this case, the difference in MFR between the main resin and the added resin is preferably about 1 to 30 g / 10 minutes from the viewpoint of convenience at the time of adjustment.

The method of mixing the resins is not particularly limited, but a method of dry-blending the polymer powder or pellets of the main resin and the additive resin using a mixer or the like, or the polymer powder or pellets of the main resin and the additive resin. Is supplied to a kneader and melt-kneaded to obtain a blended resin.

The mixer and the kneader are not particularly limited. The kneader may be a single-screw screw type, a double-screw screw type, or a multi-screw screw type. In the case of a screw type with two or more axes, either a kneading type that rotates in the same direction or that rotates in a different direction may be used.

In the case of blending by melt kneading, the kneading temperature is not particularly limited as long as a good kneaded product is obtained. Generally, the temperature is in the range of 200 ° C. to 300 ° C., preferably 230 ° C. to 270 ° C. from the viewpoint of suppressing deterioration of the resin. Further, in order to suppress deterioration during kneading and mixing of the resin, an inert gas such as nitrogen may be purged into the kneader. The melt-kneaded resin may be pelletized to an appropriate size using a generally known granulator. Thereby, the mixed polypropylene raw material resin pellets can be obtained.

The total ash content due to the polymerization catalyst residue and the like contained in the polypropylene raw material resin is preferably as small as possible in order to improve the 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 additives. The "additive" is an additive generally used for polypropylene resins, and is not particularly limited as long as a polypropylene film having a coefficient c of −200 or more and −50 or less can be obtained. Examples of the additive include antioxidants, chlorine absorbers, ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents and the like. The polypropylene resin may contain 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 not particularly limited as long as a polypropylene film having a coefficient c of −200 or more and −50 or less can be obtained, which is a resin other than the polypropylene resin which is regarded as a resin. Examples of the other resin include polyolefins other than polypropylene such as polyethylene, poly (1-butene), polyisobutene, poly (1-pentene), and poly (1-methylpentene); both ethylene-propylene copolymer and propylene-butene. Copolymers of α-olefins such as polymers and ethylene-butene copolymers; vinyl monomer-diene monomer random copolymers such as styrene-butadiene random copolymers; styrene-butadiene-styrene blocks Examples thereof include a vinyl monomer such as a polymer, a diene monomer, and a vinyl monomer random copolymer. The polypropylene film may contain the other resin in an amount within a range that does not adversely affect the polypropylene film.

The "cast raw fabric sheet before stretching" for producing the biaxially stretched polypropylene film according to the present embodiment can be suitably produced as follows. However, the "cast raw fabric sheet before stretching" for producing the biaxially stretched polypropylene film according to the present embodiment is not limited to the production method described below.

First, polypropylene resin pellets, dry-mixed polypropylene resin pellets, or mixed polypropylene resin pellets prepared by melt-kneading in advance are supplied to an extruder and heated and melted.
The number of revolutions of the extruder at the time of heating and melting is preferably 5 to 40 rpm, more preferably 14.5 to 30 rpm, and even more preferably 15 to 20 rpm. The set temperature of the extruder at the time of 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 ° C. 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 extruder set temperature during heat melting is significantly lower than 254 ° C and / or the resin temperature during heat melting is significantly lower than 251 ° C, uneven thickness in the flow direction and uneven thickness in the width direction of the raw sheet will occur. Therefore, it is difficult to obtain a thin polypropylene film having a thickness of 1 to 10 μm satisfactorily without breaking during stretching.
By appropriately selecting the extruder rotation speed, the extruder set temperature, and the resin temperature at the time of heating and melting within the above numerical ranges, a polypropylene film having the coefficient c of −200 or more and −50 or less can be obtained. The extruder rotation speed, extruder set temperature, and resin temperature at the time of heating and melting are selected in consideration of the physical characteristics of the polypropylene resin to be used. By keeping the resin temperature at the time of heating and melting within the above numerical range, deterioration of the resin can be suppressed. Increasing the extruder rotation speed tends to decrease the coefficient c, and decreasing the extruder rotation 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.

Next, the molten resin is extruded into a sheet using a T-die, and cooled and solidified with at least one metal drum to form an unstretched cast raw sheet. Here, 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 the position corresponding to the part to be the product of the cast raw sheet (the part excluding the part to be cut off instead of the product on both sides) is uniform. The method can be mentioned. Further, there is a method of adjusting each lip bolt so that the lip gap becomes wider or narrower toward the center in the width direction. The adjustment of the lip bolt can be determined according to the physical characteristics 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. The lip gap is preferably 0.4 mm or more, more preferably 0.5 mm or more. The thickness of the cast raw fabric sheet can be set by the extruder rotation speed and the lip gap, and if the lip gap is within the above numerical range, the cast raw fabric sheet thickness can be easily set to a uniform thickness. The value of the lip gap here means the average value of the gap at each lip bolt position. If the lip gap significantly exceeds 0.8 mm, it may break during stretching film formation. Increasing the lip gap tends to increase the coefficient c, and decreasing the lip gap tends to decrease the coefficient c.
The surface temperature of the metal drum (the temperature of the metal drum that first comes into contact with the metal drum after extrusion) is preferably 50 to 100 ° C, more preferably 60 to 100 ° C, and even more preferably 60 to 80. ℃. 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 good sheet formability of the raw sheet. Therefore, a thin film polypropylene film having a thickness of 1 to 10 μm without stretching unevenness or breakage during stretching film formation. It becomes difficult to obtain good results. By appropriately adjusting each lip bolt or appropriately setting the surface temperature of the metal drum, a polypropylene film having the coefficient c of −200 or more and −50 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 as described in Examples.

The rate of change between the melt flow rate of the polypropylene resin and the melt flow rate of the cast raw fabric sheet represented by the following formula (2) is preferably 1.3 or less, and preferably 1.2 or less. More preferable.
(Rate of change) = (melt flow rate of raw sheet) / (melt flow rate of polypropylene resin) Equation (2)

It is presumed that when the rate of change is 1.3 or less, the resin is less likely to deteriorate, the melt stability is excellent, and the thickness variation of the molded product is suppressed, so that the extrusion moldability is improved. The lower limit is 0 or more, 0.01 or more, 0.1 or more, and the like.

The thickness variation U _MD for each predetermined length of the cast raw sheet in the flow direction is preferably not 1.6μm or less, more preferably 1.5μm or less. The _{smaller the UMD} is, the more preferable it is, but for example, it is 0.01 μm or more.
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 the center position (position 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 at a position 10 mm from the end in the flow direction.
(3a) The average value A1 of the total thickness of 1001 points from the measurement start position to 0 mm to 2000 mm, the average value A2 of the total thickness of 1001 points from the 2000 mm to 4000 mm points, and the total 1001 points of the 4000 mm to 6000 mm points. The average value A3 of the thickness of the above and the average value A4 of the thickness of a total of 1001 points at the points of 6000 mm to 8000 mm are obtained.
(4a) The standard deviations of the average value A1, the average value A2, the average value A3, and the average value A4 are obtained, and this is referred to as _UMD .
More specifically, the method described in Examples is used.

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 0.01μm or more.
Maximum deviation of the _{U MD} is a value obtained by the following procedures (1b) ~ (2b).
(1b) The average value A1, the average value A2, the average value A3, and the average value B of the average value A4 are obtained.
(2b) of the difference between the thicknesses of the mean value B and all the measurement points, the one largest absolute value of the difference as the maximum deviation of the U _MD.
More specifically, the method described in Examples is used.

The thickness variation U _TD in the width direction of each flow direction a certain distance of the cast raw sheet is preferably not 1.2μm or less, more preferably 1.0μm or less. Further, the _{U TD} is preferably as small, preferably as small, for example 0.01μm or more.
The _UTD is a value obtained by the following procedures (1c) to (4c).
(1c) Prepare the sample of (1a) above.
(2c) The thickness of 181 points is measured at positions of 0 mm, 2000 mm, 4000 mm, 6000 mm, and 8000 mm in the flow direction at a pitch of 1 mm in the width direction. 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 10 mm from the end in the flow direction) of (2a) above (0 mm). ) Is the position.
(3c) The average value C1 of the total thickness of 181 points at the position of 0 mm in the flow direction, the average value C2 of the total thickness of 181 points at the position of 2000 mm in the flow direction, and the total value of 181 points at the position of 4000 mm in the flow direction. The average value C3 of the thickness, the average value C4 of the total thickness of 181 points at the position of 6000 mm in the flow direction, and the average value C5 of the total thickness of 181 points at the position of 8000 mm in the flow direction are obtained.
(4c) 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 are obtained, and this is referred to as _UTD .
More specifically, the method described in Examples is used.

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. The _{smaller the U TOTAL} , the more preferable, but for example, ^{it is 0.01 μm 2} or more. The U _TOTAL is a value obtained by the following formula.
U _TOTAL = U _MD x U _TD

Wherein _{U MD,} the _{U TD} and, at least one of said _{U TOTAL,} preferably, when all meets the numerical range, the overall thickness unevenness of the cast raw sheet can be said to be small. As a result, it is possible to suppress breakage during stretching and further suppress uneven thickness of the polypropylene film after stretching.
Incidentally, 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 preferred numerical range of the cast raw sheet produced using the production equipment is as follows.
The _{U MD} is preferably not 0.10μm or less, and more preferably not more than 0.08 .mu.m. The _{smaller the UMD} is, the more preferable it is, but for example, it is 0.01 μm or more.
Maximum deviation of the _{U MD} is preferably not 0.5μm or less, more preferably 0.3μm or less. The maximum deviation of the _{U MD} is preferably as small, for example 0.01μm or more.
The _UTD is preferably 0.5 μm or less, more preferably 0.3 μm or less. Further, the _{U TD} is preferably as small, preferably as small, for example 0.01μm or more.
The variation parameter U _TOTAL is preferably 0.05 μm ² or less, more preferably 0.03 μm ² or less. The _{smaller the U TOTAL} , the more preferable, but for example, ^{it is 0.01 μm 2} or more.
The preferable numerical range differs between the small research stretching device and the production equipment because the production equipment has less uneven thickness.

The thickness of the cast raw sheet is not particularly limited as long as the polypropylene film can be obtained, but it is usually preferably 0.05 mm to 2 mm, preferably 0.1 mm to 1 mm. Is more preferable.

The biaxially stretched polypropylene film according to the present embodiment can be suitably produced as follows. However, the biaxially stretched polypropylene film according to the present embodiment is not limited to the production method described below.

The polypropylene film can be produced by subjecting the polypropylene cast raw fabric sheet to a stretching treatment. The stretching is preferably biaxial stretching in which the orientation is biaxially oriented in the vertical and horizontal directions, and the sequential biaxial stretching method is preferable as the stretching method. As a sequential biaxial stretching method, for example, first, the cast raw sheet is kept at a temperature of preferably 110 to 170 ° C., more preferably 135 ° C. to 170 ° C., and passed between rolls provided with a speed difference in the flow direction. Stretch. The draw ratio in the flow direction is preferably 3.5 to 5.5 times, more preferably 4.2 to 5.4 times. Subsequently, the sheet is guided to the tenter and stretched in the lateral direction. The temperature during stretching in the lateral direction is preferably 150 ° C. to 165 ° C., and the stretching ratio in the lateral direction is preferably 9 to 11 times. After that, it is relaxed 2 to 10 times and heat-fixed. From the above, a biaxially stretched polypropylene film can be obtained. By appropriately setting the stretching ratio in the flow direction, the stretching ratio in the lateral direction, and the magnification after relaxation, a polypropylene film having the coefficient c of −200 or more and −50 or less can be obtained.

The polypropylene film may be subjected to a corona discharge treatment online or offline after the stretching and heat fixing steps are completed in order to improve the adhesive properties in a post-step such as a metal vapor deposition processing step. The corona discharge treatment can be performed by using a known method. It is preferable to use air, carbon dioxide gas, nitrogen gas, or a mixed gas thereof as the atmospheric gas.

In order to process it as a capacitor, a metal layer may be laminated on one side or both sides of the polypropylene film to form a polypropylene film integrated with a metal layer. The metal layer functions as an electrode. As the metal used for the metal layer, for example, a simple substance such as zinc, lead, silver, chromium, aluminum, copper, nickel, a mixture of a plurality of kinds thereof, an alloy thereof, or the like can be used, but the environment. , Zinc and aluminum are preferable in consideration of economy and condenser performance.

As a method of laminating a metal layer on one side or both sides of the polypropylene film, for example, a vacuum vapor deposition method or a sputtering method can be exemplified. The vacuum vapor deposition method is preferable from the viewpoint of productivity and economy. As the vacuum vapor deposition method, a crucible method, a wire method, or the like can be generally exemplified, but the method is not particularly limited, and the optimum method can be appropriately selected.

The margin pattern when laminating metal layers by vapor deposition is not particularly limited, but from the viewpoint of improving characteristics such as the safety of capacitors, a pattern including a so-called special margin such as a fishnet pattern or a T-margin pattern is used. It is preferably applied on one side of the film. It is effective in terms of improving security, destroying capacitors, preventing short circuits, and so on.

As a method for forming the margin, a generally known method such as a tape method or an oil method can be used without any limitation.

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. Such a film capacitor can be suitably used as a capacitor for an inverter power supply device that controls a drive motor of an electric vehicle, a hybrid vehicle, or the like. In addition, it can be suitably used for railway vehicles, wind power generation, solar power generation, general household appliances, and the like.

The metal layer-integrated polypropylene film can be laminated or wound by a conventionally known method to form a film capacitor.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[Polypropylene resin]
Table 1 shows the polypropylene resins used to produce the polypropylene films of Examples and Comparative Examples.
The polypropylene resin A shown in Table 1 is S802M manufactured by Korea Yuka Co., Ltd., and the polypropylene resin D is HPT-1. The polypropylene resin B is HC300BF manufactured by Borealis AG, 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. The resins A to H (polypropylene resins A to H) shown in Table 1 were purchased from Prime Polymer Co., Ltd., Korea Yuka Co., Ltd., or Borealis Co., Ltd.
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 measurement method is as follows.

<Measurement of 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 resin>
Using GPC (Gel Permeation Chromatography), 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 of polypropylene resin under the following conditions. (Mz / Mn), the differential distribution value of the distribution curve was measured.
The HLC-8121GPC-HT type, which is a high temperature GPC device with a built-in differential refractometer (RI) manufactured by Tosoh Corporation, was used. As a column, three TSKgel GMHR-H (20) HTs manufactured by Tosoh Corporation were connected and used. At a column temperature of 140 ° C., trichlorobenzene as an eluent was flowed at a flow rate of 1.0 ml / min for measurement. A calibration curve was prepared using standard polystyrene manufactured by Tosoh Corporation, and the measured molecular weight values were converted into polystyrene values to obtain the number average molecular weight (Mn), weight average molecular weight (Mw), and z-average. The molecular weight (Mz) was obtained. The molecular weight distribution (Mw / Mn) was obtained using the values of Mw and Mn. Moreover, the molecular weight distribution (Mz / Mn) was obtained using the values of Mz and Mn.

<Measurement of differential distribution value when logarithmic molecular weight log (M) = 4.5, differential distribution value when logarithmic molecular weight log (M) = 6.0, and difference in molecular weight differential distribution value>
Further, for the resins A to F, the differential distribution value when the logarithmic molecular weight log (M) = 4.5 and the differential distribution value when the logarithmic molecular weight log (M) = 6.0 are obtained by the following method. It was. First, the time curve (elution curve) of the intensity distribution detected by the RI detector is used as the distribution curve for the molecular weight M (Log (M)) of the standard polystyrene using the calibration curve prepared using the standard polystyrene. Converted. Next, after obtaining an integral distribution curve for Log (M) when the total area of the distribution curve is 100%, the differential distribution for Log (M) is obtained by differentiating this integral distribution curve with Log (M). I got a curve. From this differential distribution curve, the differential distribution values when Log (M) = 4.5 and Log (M) = 6.0 were read. Further, the difference between the differential distribution value when Log (M) = 4.5 and the differential distribution value when Log (M) = 6.0 was defined as the molecular weight differential distribution value difference. A series of operations until the differential distribution curve was obtained was performed using the analysis software built in the GPC measuring device used. As a result, the differential distribution values when the logarithmic molecular weight log (M) = 4.5 were 27.4% for resin A, 31.5% for resin B, 30.0% for resin C, and resin D. The ratio was 31.4%, the resin E was 33.6%, and the resin F was 30.3%. The differential distribution value when the logarithmic molecular weight log (M) = 6.0 is 30.8% for resin A, 26.5% for resin B, 21.2% for resin C, and resin D. , 27.6%, resin E was 24.4%, and resin F was 27.0%. The molecular weight differential distribution value difference _{(D M)} is the resin A, -3.4%, the resin B, 5.0%, in the resin C, 8.8%, the resin D, 3.8%, It was 9.2% for the resin E and 3.3% for the resin F.

<Measurement of heptane insoluble matter (HI)>
The resins A to G were press-molded to 10 mm × 35 mm × 0.3 mm to prepare a measurement sample of about 3 g. Next, about 150 mL of heptane was added and Soxhlet extraction was performed for 8 hours. The heptane insoluble content was calculated from the sample mass before and after extraction. As a result, 98.8% for resin A, 98.5% for resin B, 97.8% for resin C, 98.6% for resin D, 97.3% for resin E, and resin F. In the case of 97.2%, and in the case of resin G, it was 97.5%.

Using the above-mentioned polypropylene resin, polypropylene films of Examples and Comparative Examples were prepared and their physical characteristics were evaluated.

<Making polypropylene film with a small research stretching device>
(Example 1)
Pellets of polypropylene resin C were supplied to an extruder, the extruder rotation speed was set to 15 rpm, the extruder set temperature was set to 260 ° C., and the mixture was melted at a resin temperature of 257 ° C. Next, the molten resin was extruded into a sheet using a T-die with a width of 300 mm in which the lip gap was uniformly 0.70 mm in the width direction by adjusting 12 lip bolts arranged at equal intervals in the width direction, and the surface temperature was reached. Was wound around a metal drum held at 70 ° C. and solidified. At this time, polypropylene resin was sprayed onto the metal drum with an air knife. In this way, a cast raw sheet having a thickness of 200 μm was obtained. To adjust the lip gap, adjust the lip gap at the position corresponding to the part that will be the product of the cast raw sheet (the part excluding the part that is not cut off as a product on both sides), and make it uniform in the width direction. It was set to 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 (small research stretching device) manufactured by Brueckner, and then stretched 10 times in the lateral direction. Then, while being gripped with a clip, relaxation was applied to a lateral magnification of 9 times to obtain a biaxially stretched polypropylene film having a thickness of 5 μm.

(Example 2)
A biaxially stretched polypropylene film having a thickness of 5 μm 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 μm was obtained in the same manner as in Example 1 except that the polypropylene resin D was used.

(Example 4)
Polypropylene resin D and polypropylene resin E were dry-blended. The mixing ratio was (polypropylene resin D) :( polypropylene resin E) = 40: 60 in terms of mass ratio. Then, using the dry-blended resin, a biaxially stretched polypropylene film having a thickness of 5 μm was obtained in the same manner as in Example 1. However, the extrusion molding conditions (extruder rotation speed, resin temperature, lip gap) were as shown in Table 2.

(Example 5)
A biaxially stretched polypropylene film having a thickness of 5 μm was prepared in the same manner as in Example 1 except that the polypropylene resin A was used and the extrusion molding conditions (extruder rotation speed, resin temperature, lip gap) were as shown in Table 2. Obtained. The extruder set temperature in Example 5 was set to 265 ° C.

(Example 6)
Polypropylene resin A and polypropylene resin E were dry-blended. The mixing ratio was (polypropylene resin A) :( polypropylene resin E) = 35:65 in terms of mass ratio. Then, using the dry-blended resin, a biaxially stretched polypropylene film having a thickness of 4 μm was obtained in the same manner as in Example 1. However, the extrusion molding conditions (extruder rotation speed, resin temperature, lip gap) were as shown in Table 2. The extruder set temperature in Example 6 was set to 265 ° C.

(Example 7)
Polypropylene resin A and polypropylene resin C were dry-blended. The mixing ratio was (polypropylene resin A) :( polypropylene resin C) = 25: 75 in terms of mass ratio. Then, using the dry-blended resin, a biaxially stretched polypropylene film having a thickness of 4 μm was obtained in the same manner as in Example 1. However, the extrusion molding conditions (extruder rotation speed, resin temperature, lip gap) were as shown in Table 2. The extruder set temperature in Example 7 was set to 265 ° C.

(Comparative Example 1)
A biaxially stretched polypropylene film having a thickness of 5 μm was obtained in the same manner as in Example 1 except that polypropylene resin A was used.

(Comparative Example 2)
A biaxially stretched polypropylene film having a thickness of 5 μm was obtained in the same manner as in Example 1 except that polypropylene resin B was used.

(Comparative Example 3)
A biaxially stretched polypropylene film having a thickness of 5 μm was obtained in the same manner as in Example 1 except that the polypropylene resin F was used.

(Comparative Example 4)
A biaxially stretched polypropylene film having a thickness of 5 μm was obtained in the same manner as in Example 1 except that the polypropylene resin G was used.

(Comparative Example 5)
Polypropylene resin E and polypropylene resin H were dry-blended. The mixing ratio was (polypropylene resin E) :( polypropylene resin H) = 90:10 in terms of mass ratio. Then, using the dry-blended resin, a biaxially stretched polypropylene film having a thickness of 5 μm was obtained in the same manner as in Example 1.

(Comparative Example 6)
An attempt was made to obtain a biaxially stretched polypropylene film in the same manner as in Example 1 except that the polypropylene resin E was used and the extrusion molding conditions (extruder rotation speed, resin temperature, lip gap) were as shown in Table 2. However, the molten resin fluctuated and the thickness unevenness of the raw sheet became remarkably large, and breakage occurred frequently during stretching and film forming. The extruder set temperature in Comparative Example 6 was set to 250 ° C.
In Comparative Example 6, for the reason described above, the viscosity parameters described later were not measured.

<Determination of each parameter in the Carreau-Yasuda model>
First, the relationship (flow curve) between the shear viscosity η and the shear rate γ at the measurement temperatures of 230 ° C., 240 ° C., and 250 ° C. was obtained by the following procedures (1) to (5). For the measurement, HAAKE MiniLab Rheomex CTW5 (microrheology compounder) manufactured by Thermo Fisher Scientific Co., Ltd. was used.
(1) The polypropylene films obtained in Examples and Comparative Examples were cut into strips, weighed 5 g, and the entire amount was charged from the sample charging section.
(2) After stabilizing at a rotation speed of 10 rpm for 1 minute, the pressure loss dP at 10 points between the rotation speeds of 10 rpm and 360 rpm was measured, and the shear stress τ at each rotation speed was derived from the measured pressure loss dP. .. The measured 10 points are 10 points when evenly divided in logarithmic notation.
(3) Measure each resin amount Q discharged from the discharge port at rotation speeds 10, 20, 50, 100 rpm, derive the shear rate γ of each rotation speed from the measured resin amount Q, and γ and the rotation speed. The linear approximation formula of was obtained. From the obtained approximate expression, γ at the rotation speed of 10 points in (2) above was obtained.
(4) From the 10-point shear stress τ and shear velocity γ obtained in (1) to (3) above, the modified Hargen-Poisellle equation ([shear viscosity η] = [shear stress τ] / [shear velocity] γ]) was used to determine the shear viscosity η. From the above, the relationship (flow curve) between the shear viscosity η and the shear rate γ was obtained.
(5) The above operations (1) to (4) were carried out at the measurement temperatures of 230 ° C., 240 ° C., and 250 ° C., and the relationship (flow curve) between the shear viscosity η and the shear rate γ at each measurement temperature was obtained. ..

Next, using the non-Newtonian pure viscosity model fit function of the analysis software (HASL Co., Ltd. analysis software Materialfit Ver. 3.0.0), the flow curve (η-γ curve) obtained in (5) above is obtained. A master curve was obtained by fitting to the Carreau-Yasuda model (viscosity formula) represented by the formula (1). From the above, each parameter (zero shear viscosity η ₀ , coefficient b, coefficient c, coefficient d, delay time λ) was obtained. The reference temperature Tr was set to 240 ° C. for fitting. The reference temperature Tr was set to 240 ° C. because the intermediate temperature of the measurement temperatures of 230 ° C., 240 ° C., and 250 ° C. was selected. Table 2 shows each model parameter obtained.

<Measurement of 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 fabric sheets (sheets 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 having a test temperature of 230 ° C., and preheated for 3.5 minutes under a load of 2.16 kg. Then, the weight of the sample extruded from the bottom hole was measured in 30 seconds to determine the MFR (g / 10 min). The above measurement was repeated 3 times, and the average value was taken as the measured value of MFR.
Moreover, the rate of change of MFR was calculated by the following formula (2). The results are shown in Table 2.
(Rate of change) = (melt flow rate of raw sheet) / (melt flow rate of polypropylene resin) Equation (2)

<Measurement of melting point of biaxially stretched polypropylene film>
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 type DSC Diamond DSC manufactured by PerkinElmer. First, about 5 mg of a biaxially stretched polypropylene film was weighed, packed in an aluminum sample holder, and set in a DSC device. The temperature was raised from 30 ° C. to 280 ° C. at a rate of 20 ° C./min under nitrogen flow, 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. and 190 ° C., and the peak top temperature of the melting peak curve on the highest temperature side was evaluated as the melting point.
As a result, 174.1 ° C. in Example 1, 174.0 ° C. in Example 2, 174.1 ° C. in Example 3, 174.2 ° C. in Example 4, and 174.1 ° C. in Example 5. 9 ° C., 174.6 ° C. in Example 6, 174.5 ° C. in Example 7, 175.0 ° C. in Comparative Example 1, 174.3 ° C. in Comparative Example 2, 170. It was 0 ° C., and in Comparative Example 4, it was 171.0 ° C.

<Evaluation of uneven thickness>
Example, the thickness variation for each predetermined length in the flow direction of the cast raw sheet after extrusion according to the comparative example (biaxially before stretching) U _MD, the maximum deviation of the U _MD, in the width direction of each flow direction a predetermined distance The thickness variation _UTD 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) First, cast raw fabric sheets according to Examples and Comparative Examples were prepared. The extrusion molding conditions of the cast raw sheet were the same as the extrusion molding conditions in each Example and each Comparative Example. The width of the prepared cast material sheet was 260 mm in both Examples and Comparative Examples.
Next, a sample having a width of 180 mm and a flow direction of 8020 mm was taken by cutting off the portions 0 to 40 mm and 220 to 260 mm at the end of the cast raw sheet in the width direction.
From the above, a sample of a cast raw sheet having a width of 180 mm and a flow direction of 8020 mm was prepared.
(2a) The thickness of 4001 points was measured at the center position (position 90 mm from both ends) in the width direction of the sample at a pitch of 2 mm in the flow direction. The measurement was started from a position 10 mm from the end in the flow direction.
(3a) The average value A1 of the total thickness of 1001 points from the measurement start position to 0 mm to 2000 mm, the average value A2 of the total thickness of 1001 points from the 2000 mm to 4000 mm points, and the total 1001 points of the 4000 mm to 6000 mm points. The average value A3 of the thickness of the above and the average value A4 of the thickness of a total of 1001 points at the points of 6000 mm to 8000 mm were obtained.
(4a) The standard deviations of the average value A1, the average value A2, the average value A3, and the average value A4 were obtained and used as _UMD.

Maximum deviation of the _{U MD} was obtained by the following procedures (1b) ~ (2b).
(1b) The average value A1, the average value A2, the average value A3, and the average value B of the average value A4 were obtained.
(2b) of the difference between the thicknesses of the mean value B and all the measurement points, the one largest absolute value of the difference was the largest deviation of U _MD.

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 positions of 0 mm, 2000 mm, 4000 mm, 6000 mm, and 8000 mm in the flow direction at a pitch of 1 mm in the width direction. 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 10 mm from the end in the flow direction) of (2a) above (0 mm). ) Is the position.
(3c) The average value C1 of the total thickness of 181 points at the position of 0 mm in the flow direction, the average value C2 of the total thickness of 181 points at the position of 2000 mm in the flow direction, and the total value of 181 points at the position of 4000 mm in the flow direction. The average value C3 of the thickness, the average value C4 of the total thickness of 181 points at the position of 6000 mm in the flow direction, and the average value C5 of the total thickness of 181 points at the position of 8000 mm in the flow direction were obtained.
(4c) 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 _UTD.

The thickness variation parameter U _TOTAL during continuous film formation of the cast raw sheet was obtained by the following formula.
U _TOTAL = U _MD x U _TD

The results are shown in Table 3.

<Evaluation of fracture during stretching>
Biaxial stretching of the cast raw sheet was carried out three times and evaluated according to the following criteria. The conditions for biaxial stretching were the same as those for biaxial stretching in each Example and each Comparative Example. The results are shown in Table 3.
A: No tear occurred during stretching.
B: There was a case where a small tear of about 1 cm square occurred in the vicinity of the clip during stretching.
C: The film could not be formed due to tearing in the entire width.
When there is no tear as in the examples, the stable film forming property is high.

<Evaluation of edge fluidity during extrusion>
The width length of the ear at the end of the cast raw sheet after extrusion molding was measured, and the average value at both ends was calculated as the ear width. The case where the ear width was 5 mm or less was evaluated as 0, and the case where the ear width exceeded 5 mm was evaluated as ×. The results are shown in Table 3. The endmost portion means a portion of 0 to 4% and 96% to 100% of the position in the width direction. In Examples and Comparative Examples, the portions of 0 to 10.4 mm and 249.6 to 260 mm from the end are referred to. Further, the "ear" means a portion thicker than the thickness at the center position in the width direction by 150% or more.
The ear width indicates the fluidity of the resin during extrusion molding, and it can be said that the wider the ear width, the lower the fluidity. If the fluidity is low, the thickness unevenness of the cast raw sheet becomes large, and the film forming property at the time of biaxial stretching becomes unstable. Further, if the fluidity of the resin is low, the thickness of the end portion of the product becomes thick, the product cannot be produced, and the yield also decreases.

<Making polypropylene film with production equipment>
(Example 8)
A biaxially stretched polypropylene film having a thickness of 2.0 μm was obtained in the same manner as in Example 4 except that the production equipment was used instead of the small research stretching apparatus.

(Comparative Example 7)
A biaxially stretched polypropylene film having a thickness of 2.0 μm was obtained in the same manner as in Comparative Example 1 except that a production facility was used instead of the small research stretching apparatus.

<Determination of each parameter in the Carreau-Yasuda model>
In the same manner as in Examples 1 to 7 and Comparative Examples 1 to 5, each parameter in the Carreau-Yasuda model was determined for Example 8 and Comparative Example 7. The results are shown in Table 4.

<Measurement of melt flow rate (MFR)>
The melt flow rate (MFR) was measured for Examples 8 and 7 in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 5. The results are shown in Table 4.

<Measurement of melting point of biaxially stretched polypropylene film>
When the melting point of the biaxially stretched polypropylene film was measured in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 5, Example 8 was 172.0 ° C. and Comparative Example 7 was 172.5. It was ° C.

<Evaluation of uneven thickness>
In the same manner as in Examples 1 to 7 and Comparative Examples 1 to 5, the cast raw sheet (before biaxial stretching) after extrusion molding according to Examples 8 and 7 is for each fixed length in the flow direction. the thickness variation _{U MD, U MD} maximum deviation, the thickness variation in the width direction of each flow direction a predetermined distance _{U TD,} and to obtain a thickness fluctuation parameter _{U TOTAL} during continuous film. The results are shown in Table 5.

<Evaluation of fracture during stretching>
For Example 8 and Comparative Example 7, biaxial stretching of the cast raw fabric sheet was carried out once and evaluated according to the following criteria. As the cast raw sheet, a sheet that was continuously extruded was used. The conditions for biaxial stretching were the same as those for biaxial stretching when producing the biaxially stretched polypropylene film in Example 8 and Comparative Example 7. The results are shown in Table 5.
A: No tear occurred over 75,000 m during stretching.
B: During stretching, no tear occurred up to 30,000 m, but tear occurred at a portion of 30,000 m or more and less than 75,000 m.
C: During stretching, a tear occurred at a position less than 30,000 m.

<Evaluation of edge fluidity during extrusion>
In the same manner as in Examples 1 to 7 and Comparative Examples 1 to 5, the edge fluidity during extrusion molding was evaluated for Examples 8 and 7. The results are shown in Table 5.

Claims (7)

Contains polypropylene resin
The weight average molecular weight Mw of the polypropylene resin is 250,000 or more and 450,000 or less.
The number average molecular weight Mn of the polypropylene resin is 30,000 or more and 53,000 or less.
The z average molecular weight Mz of the polypropylene resin is 500,000 or more and 210000 or less.
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.
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.
The heptane insoluble content (HI) of the polypropylene resin is 96.0% or more, and is
The melt flow rate (MFR) of the polypropylene resin is 1.0 to 8.0 g / 10 min.
The coefficient c representing the slope between the shear rate and the shear 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 the equation (1), is −200 or more −50. A polypropylene film having the following, and having a thickness of 1 to 10 μm.

The pre-Symbol polypropylene resin and melt extrusion to raw sheet, then, a film obtained by biaxially stretching,
The polypropylene film according to claim 1, wherein the rate of change between the melt flow rate of the polypropylene resin and the melt flow rate of the raw sheet, which is represented by the following formula (2), is 1.3 or less. ..
(Rate of change) = (melt flow rate of raw sheet) / (melt flow rate of polypropylene resin) Equation (2) The polypropylene film according to claim 1 or 2, wherein the polypropylene film is for a capacitor. Among previous SL polypropylene resin, the number average molecular weight Mn of the polypropylene resin of the main component is, is from 30,000 to 53000 or less,
Among the polypropylene resins, the polypropylene resin as the main component has a weight average molecular weight Mw of 250,000 or more and 450,000 or less.
Among the polypropylene resins, the polypropylene resin as the main component has a z average molecular weight Mz of 500,000 or more and 2.1 million or less.
Among the polypropylene resins, the molecular weight distribution [(weight average molecular weight Mw) / (number average molecular weight Mn)] of the polypropylene resin as the main component is 5 or more and 12 or less.
Any of claims 1 to 3, wherein the polypropylene resin as the main component has a molecular weight distribution [(z average molecular weight Mz) / (number average molecular weight Mn)] of 10 or more and 70 or less. The polypropylene film according to 1. The heptane insoluble content (HI) of the polypropylene resin as the main component is 96.0% or more and 99.5% or less.
The polypropylene film according to claim 4, wherein 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. The polypropylene film according to any one of claims 1 to 5, and the polypropylene film.
A polypropylene film integrated with a metal layer, which has a metal layer laminated on one side or both sides of the polypropylene film. A film capacitor having a wound metal layer-integrated polypropylene film according to claim 6.