Stretched film, metal laminated film, and film capacitor

Abstract

The present invention provides a stretched film having a high dielectric breakdown strength even under a high temperature environment of 120°C or higher, and having little change in the dielectric breakdown strength under the high temperature environment with respect to the dielectric breakdown strength at room temperature (for example, 25°C).　The present invention is a stretched film containing a polypropylene resin, wherein the loss tangent tan δ at 100°C is 0.15 or less in temperature dispersion data in the TD direction at a frequency of 1 Hz obtained from dynamic viscoelasticity measurement, or the loss tangent tan δ has a peak in a region of 140°C or higher in temperature dispersion data in the TD direction at a frequency of 1 Hz obtained from dynamic viscoelasticity measurement.

Description

Stretched films, metal laminated films, and film capacitors

[0001] The present invention relates to a stretched film formed from a polypropylene resin, a metal laminated film having the stretched film, and a film capacitor.

[0002] Stretched films primarily composed of polypropylene are used in film capacitor applications due to their excellent electrical properties. In electronic and electrical equipment, film capacitors made from stretched polypropylene are used, for example, as high-voltage capacitors, various switching power supplies, filter capacitors in converters and inverters, and smoothing capacitors. Film capacitors are also increasingly used in automobiles, such as electric vehicles and hybrid vehicles, where demand has been growing in recent years, for example, in inverters and converters that control drive motors.

[0003] Film capacitors, particularly automotive film capacitors, are increasingly being used in high-temperature environments. For example, in devices that control automotive drive motors (inverters, converters, etc.), the use of highly heat-resistant semiconductors (such as silicon carbide semiconductors) has increased in recent years. Consequently, capacitors used in these devices are required to have high heat resistance, such as 120°C or higher, preferably 130°C or higher. Conventional capacitors using polypropylene film are said to have an upper limit of operating temperature of about 110°C, and it is extremely difficult to stably maintain electrical insulation in high-temperature environments exceeding this.

[0004] One example of a resin film with high heat resistance is a film made of a resin composition containing a polyolefin mainly composed of polypropylene and a hydrogenated block copolymer, which is excellent in heat resistance and especially in its ability to block water vapor (Patent Document 1).

[0005] Japanese Patent Publication No. 2014-37532

[0006] Polypropylene-based resin films tend to exhibit a decrease in physical properties, such as reduced rigidity and reduced electrical insulation, as the operating temperature increases. In this regard, stretching a polypropylene-based resin film in at least one direction, preferably two directions, improves rigidity and electrical insulation, allowing these properties to be maintained even in high-temperature regions exceeding 110°C. However, at operating temperatures above 120°C, and even above 130°C, maintaining rigidity and electrical insulation becomes difficult even with stretched films.

[0007] The present invention has been made in view of the above, and aims to provide a stretched film that has high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and moreover, that shows little change in dielectric breakdown strength in high-temperature environments compared to dielectric breakdown strength at room temperature (for example, 25°C). The present invention also aims to provide a metal laminated film and a film capacitor comprising the stretched film.

[0008] The inventors of the present invention conducted extensive research to achieve the above objectives and, as a result, discovered that the objectives can be achieved by including a polypropylene resin and adjusting a predetermined loss tangent (tanδ) at 100°C to a specific range, thereby completing the present invention.

[0009] In other words, the present invention encompasses, for example, the subject matter described in the following sections: Section 1 A stretched film comprising a polypropylene resin, wherein, in temperature dispersion data in the TD direction at a frequency of 1 Hz obtained from dynamic viscoelasticity measurement, the loss tangent tanδ at 100°C is 0.15 or less. Section 2 A stretched film comprising a polypropylene resin, wherein, in temperature dispersion data in the TD direction at a frequency of 1 Hz obtained from dynamic viscoelasticity measurement, the loss tangent tanδ peak is in the region of 140°C or higher. Section 3 The stretched film according to Section 1, wherein, in the temperature dispersion data, the loss tangent tanδ peak is in the region of 140°C or higher. Section 4 The stretched film according to any one of Sections 1 to 3, wherein, in measurement by differential scanning calorimeter, when the temperature is increased at 20°C / min, the stretched film has a first melting peak at 170-175°C and a second melting peak at 165-170°C. Item 5: A stretched film according to any one of items 1 to 4, wherein, in X-ray diffraction intensity measurement, the interplanar spacing d of the diffraction lines of the (040) plane originating from the α-crystal of isotactic polypropylene is 5.10 to 5.23 Å. Item 6: In infrared absorption spectrum measurement, 880 to 890 cm⁻¹ －１ Absorption peaks are observed in the range, and at 1450 cm. －１A stretched film according to any one of claims 1 to 5, having at least one of the shoulder peaks due to absorption in the vicinity. Claim 7 A stretched film according to any one of claims 1 to 6, wherein in the temperature dispersion data, the value of E'(135) / E'(25), which is the ratio of the storage modulus E'(135) at 135°C to the storage modulus E'(25) at 25°C, is 0.15 or more. Claim 8 A stretched film according to any one of claims 1 to 7, wherein the polypropylene resin contains 55% by mass or more and 99% by mass or less isotactic polypropylene resin and 1% by mass or more and 45% by mass or less of a polymer having an alicyclic structure, and is stretched in at least one direction. Claim 9 A stretched film according to claim 8, wherein the polymer having an alicyclic structure contains two or more polymers with different glass transition temperatures. Item 10 The stretched film according to item 8 or 9, wherein the polymer having an alicyclic structure comprises polymer B1 having an alicyclic structure with a glass transition temperature of 133°C to 155°C and polymer B2 having an alicyclic structure with a glass transition temperature of 70°C to less than 133°C. Item 11 The stretched film according to item 10, wherein the mass ratio B2 / B1 of polymer B2 to polymer B1 is less than 0.85. Item 12 The stretched film according to any one of items 8 to 11, wherein the polymer having an alicyclic structure contains hydrogenated polystyrene. Item 13 The stretched film according to item 12, wherein the hydrogenated polystyrene has an atactic structure and a hydrogenation rate of 95% or more. Item 14 The stretched film according to any one of items 1 to 13, wherein the thickness is 1.8 μm to 10 μm and the total light transmittance is 80% or more. Item 15 A metal laminated film having a metal layer on one or both sides of the stretched film according to any one of items 1 to 14. Item 16 A film capacitor comprising the metal laminated film described in Item 15.

[0010] The stretched film of the present invention has high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and moreover, the change in dielectric breakdown strength in high-temperature environments compared to room temperature (e.g., 25°C) is small.

[0011] The results of dynamic viscoelasticity measurements of the stretched films obtained in the examples and comparative examples are shown, with temperature dispersion data for the stretched film in the TD direction at a frequency of 1 Hz, where the X axis is temperature, the first Y axis is the logarithm of the storage modulus E' (logE'(Pa)), and the second Y axis is the loss tangent tanδ. The results of the infrared absorption spectrum of the stretched film are shown, where (a) shows the infrared absorption spectrum measurement at 850-950 cm⁻¹. －１ (b) is within the range of 1400-1500 cm. －１ This indicates the range.

[0012] Embodiments of the present invention will be described in detail below. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of."

[0013] In the numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. Furthermore, in this specification, numbers connected by "~" mean a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0014] 1. Stretched Film The stretched film of the present invention includes the following stretched film A and stretched film B. Stretched film A: Contains a polypropylene resin, and in the temperature dispersion data in the TD direction at a frequency of 1 Hz obtained from dynamic viscoelasticity measurement of the stretched film, the loss tangent (i.e., tanδ) at 100°C is 0.15 or less. Stretched film B: Contains a polypropylene resin, and in the temperature dispersion data in the TD direction at a frequency of 1 Hz obtained from dynamic viscoelasticity measurement of the stretched film, the loss tangent (i.e., tanδ) has a peak in the region of 140°C or higher.

[0015] The stretched film A of the present invention can have high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and specifically, it has high dielectric breakdown strength even in high-temperature environments of 140°C. Moreover, the stretched film A of the present invention exhibits little change in dielectric breakdown strength in high-temperature environments (e.g., 140°C environment) compared to room temperature (e.g., 25°C environment).

[0016] Similarly, the stretched film B of the present invention can have high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and specifically, it has high dielectric breakdown strength even in high-temperature environments of 140°C. Moreover, the stretched film B of the present invention exhibits little change in dielectric breakdown strength under high-temperature environments (e.g., 140°C environment) compared to dielectric breakdown strength at room temperature (e.g., 25°C).

[0017] Here, in a stretched film, a small change in dielectric breakdown strength under high-temperature conditions relative to dielectric breakdown strength at room temperature (e.g., 25°C) means that, specifically, if the dielectric breakdown strength of the stretched film at 25°C is V25 (Vdc / μm) and the dielectric breakdown strength at 140°C is V140 (Vdc / μm), then the value of the strength ratio "V140 / V25" is close to 1. In particular, in stretched film A and stretched film B of the present invention, the value of V140 / V25 is preferably 0.75 or higher, more preferably 0.78 or higher, even more preferably 0.79 or higher, and particularly preferably 0.80 or higher. The value of V140 / V25 is usually 1 or less, preferably 0.99 or less, and more preferably 0.95 or less.

[0018] In the following, the value "V140 / V25," which represents the degree of change in dielectric breakdown strength at 140°C (high temperature) compared to room temperature (e.g., 25°C), may be simply abbreviated as "dielectric breakdown strength ratio."

[0019] In the present invention, the ratio of dielectric breakdown strengths can be measured by the method described in the examples below.

[0020] In the stretched film A and stretched film B of the present invention, temperature dispersion data can be obtained by dynamic viscoelasticity measurement of each stretched film.

[0021] Specifically, for example, if the stretched film is stretched film A of the present invention, temperature dispersion data can be obtained by performing dynamic viscoelasticity measurements in accordance with JIS-K7244-1 and -4 (1999 edition) using test pieces cut from the stretched film A in strip form. The conditions for such dynamic viscoelasticity measurements are tensile mode, vibration frequency of 1 Hz, chuck distance of 20 mm, strain amplitude of 10 μm, minimum tension of 20 mN, and heating rate of 2 °C / min. The tensile direction of the stretched film is perpendicular to the flow direction (MD direction) of the stretched film, i.e., the TD direction. By performing dynamic viscoelasticity measurements of stretched film A in this way, the relationship between temperature (X axis) and storage modulus E' (Y axis) and / or loss tangent tanδ (Y axis) can be obtained as temperature dispersion (also called temperature dependence) data.

[0022] The temperature dispersion data for the stretched film B of the present invention can also be obtained by the same method as described above. That is, by using a test specimen of the stretched film B of the present invention instead of a test specimen of the stretched film A of the present invention, the temperature dispersion (temperature dependence) data of the dynamic viscoelasticity of the stretched film B of the present invention can be obtained.

[0023] In the stretched film A of the present invention, the loss tangent (tanδ) at 100°C obtained based on the temperature dispersion data is 0.15 or less. As a result, the stretched film A can have high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and the change in dielectric breakdown strength is small (the V140 / V25 ratio becomes larger). In the stretched film A of the present invention, if the loss tangent (tanδ) at 100°C exceeds 0.15, the dielectric breakdown strength in high-temperature environments of 120°C or higher decreases, and the change in dielectric breakdown strength becomes large, that is, the V140 / V25 value mentioned above decreases.

[0024] In the stretched film A of the present invention, the loss tangent (tanδ) at 100°C is preferably 0.145 or less, more preferably 0.140 or less, even more preferably 0.135 or less, and particularly preferably 0.130 or less. In the stretched film A of the present invention, the loss tangent (tanδ) at 100°C is, for example, 0.05 or more, preferably 0.08 or more, more preferably 0.10 or more, and even more preferably 0.11 or more.

[0025] Here, in the stretched film A of the present invention, a loss tangent (tanδ) of 0.15 or less at 100°C means that the temperature dispersion (temperature dependence) data of the tanδ value described above does not substantially have a peak at 100°C. The absence of a substantially peak at 100°C means that, in the loss tangent tanδ temperature dispersion data, there is almost no fluctuation in the value of the loss tangent tanδ around 100°C (for example, in the range of 80 to 120°C), and the characteristic increase in the tanδ value in this temperature range due to the movement based on the lattice relaxation of polypropylene does not occur. In other words, the movement of lattice relaxation is suppressed, and for example, in the range of 80 to 120°C, there is a simple increase towards the main dispersion peak of tanδ.

[0026] The method for adjusting the 100°C loss tangent (tanδ) of the stretched film A of the present invention to 0.15 or less is not particularly limited. For example, known methods that can be used to suppress the lattice relaxation motion of isotactic polypropylene can be widely employed. In particular, it is easier to adjust the 100°C loss tangent (tanδ) to 0.15 or less by manufacturing the stretched film A with a polypropylene resin containing an isotactic polypropylene resin. In particular, as will be described later, when the stretched film A is manufactured using a polypropylene resin containing an isotactic polypropylene resin and a polymer having an alicyclic structure, it becomes even easier to adjust the 100°C loss tangent (tanδ) to 0.15 or less.

[0027] In the stretched film B of the present invention, the temperature dispersion data has a peak in the loss tangent (tanδ) in the region of 140°C or higher. Specifically, in this specification, "having a peak in the loss tangent (tanδ) in the region of 140°C or higher" means that in the temperature dispersion data (also called temperature-dependent data) of dynamic viscoelasticity, the loss tangent (tanδ) has a clear principal dispersion peak (i.e., the peak with the largest tanδ value) in the region of 140°C or higher.

[0028] Here, "having a clear principal dispersion peak in the region above 140°C" can mean, for example, that in the temperature range of 140 to 160°C of the temperature dispersion data (also called temperature-dependent data) of the dynamic viscoelasticity, the difference between the maximum and minimum values ​​of the tanδ (range of change in the temperature range) is ±0.03 or more, preferably ±0.04 or more, more preferably ±0.05 or more, and particularly preferably ±0.06 or more.

[0029] In the stretched film B of the present invention, the method for having a loss tangent (tanδ) peak in the region of 140°C or higher is not particularly limited. For example, known methods for raising the glass transition temperature or methods using resin blends can be widely employed. In particular, a method of producing the stretched film B with a polypropylene resin containing an isotactic polypropylene resin is preferred. Among these, as described below, when the stretched film B is produced with a polypropylene resin containing an isotactic polypropylene resin and a polymer having an alicyclic structure, it is easy to obtain a loss tangent (tanδ) peak in the region of 140°C or higher.

[0030] The above-described features of the stretched film B of the present invention may also be present in the stretched film A of the present invention. That is, similar to the stretched film B, it is also preferable that the stretched film A of the present invention has a peak in the loss tangent (tanδ) in the region of 140°C or higher in the temperature dispersion data.

[0031] Hereinafter, the characteristics common to the stretched film A and the stretched film B of the present invention will be described in detail. In the following description, the stretched film A and the stretched film B of the present invention will be collectively referred to as "the stretched film of the present invention".

[0032] In the measurement of the differential scanning calorimeter (DSC) of the stretched film of the present invention, when the temperature is raised at 20 ° C. / min, it preferably has a first melting peak at 170 to 175 ° C and a second melting peak at 165 to 170 ° C. In this case, the stretched film has two stable crystal regions, namely, metastable crystal lamellae derived from the second melting peak and the most stable crystal lamellae derived from the first melting peak with higher crystallinity, so that it can have a higher dielectric breakdown strength even in a high-temperature environment of 120 ° C or higher, and the change in the dielectric breakdown strength is also more likely to be smaller. To have the first melting peak and the second melting peak, the polypropylene-based resin may contain a polymer having an alicyclic structure described later in addition to isotactic polypropylene.

[0033] In the X-ray diffraction intensity measurement of the stretched film of the present invention, the interplanar spacing value d of the diffraction line of the (040) plane derived from the α-crystal of isotactic polypropylene is preferably 5.10 to 5.23 Å. In this case, the stretched film can have a higher dielectric breakdown strength even in a high-temperature environment of 120 ° C or higher, and the change in the dielectric breakdown strength is also more likely to be smaller. Therefore, the polypropylene-based resin for forming the stretched film preferably contains at least isotactic polypropylene as described later. In particular, to adjust the interplanar spacing value d within the above range, the polypropylene-based resin may contain a polymer having an alicyclic structure described later in addition to isotactic polypropylene. By the polypropylene-based resin containing the polymer having an alicyclic structure, the lattice spacing of the (040) plane derived from the α-crystal of isotactic polypropylene can vary within the range of the above interplanar spacing value.

[0034] In the infrared absorption spectrum measurement of the stretched film of the present invention, an absorption peak in the range of 880 to 890 cm －１ and, 1450 cm－１ Preferably, it has at least one of the shoulder peaks due to absorption in the vicinity. In this case, the stretched film can have a higher dielectric breakdown strength even in a high-temperature environment of 120 ° C. or higher, and the change in the dielectric breakdown strength is also more likely to be smaller. In the infrared absorption spectrum measurement of the stretched film of the present invention, 880 to 890 cm －１ There is an absorption peak in the range of, and a shoulder peak due to absorption around 1450 cm －１ It is more preferable to have both.

[0035] There is an absorption peak in the range of 880 to 890 cm －１ And / or, to have a shoulder peak due to absorption around 1450 cm －１ For example, the composition ratio of each component in the polypropylene-based resin for forming the stretched film may be adjusted. For example, the characteristic peak of infrared absorption of the polymer having an alicyclic structure described later is in the range of 880 to 890 cm －１ And / or, since it exists around 1450 cm －１ The polypropylene-based resin preferably contains a polymer component having the alicyclic structure. For example, the content ratio of the polymer component having the alicyclic structure described later in the polypropylene-based resin for forming the stretched film may be adjusted to 6% by mass or more, preferably 10% by mass or more.

[0036] In the temperature dispersion data of the stretched film of the present invention, the value of E'(135) / E'(25), which is the ratio of the storage elastic modulus E'(135) at 135 ° C. to the storage elastic modulus E'(25) at 25 ° C., is preferably 0.15 or more. In this case, the stretched film can have a higher dielectric breakdown strength even in a high-temperature environment of 120 ° C. or higher, and the change in the dielectric breakdown strength is also more likely to be smaller. The value of E'(135) / E'(25) is more preferably 0.16 or more, further preferably 0.18 or more, and preferably 0.5 or less. The value of E'(135) / E'(25) can be controlled, for example, by adjusting the content ratio of the polymer component having the alicyclic structure described later in the polypropylene-based resin for forming the stretched film.

[0037] Incidentally, the storage elastic modulus E'(135) and the storage elastic modulus E'(25) can be obtained by the same method as the method for obtaining the temperature dispersion data described above. That is, by performing dynamic viscoelasticity measurement under the same measurement conditions as described above, the relationship between the temperature (X-axis) and the storage elastic modulus (Y-axis) can be obtained as temperature dispersion data.

[0038] The thickness of the stretched film of the present invention can be adjusted to an appropriate range according to the use, and for example, it can be in the same range as the thickness of the stretched film used for capacitor applications. For example, the thickness of the stretched film of the present invention is preferably 1.8 μm or more and 10 μm or less. The thickness of the stretched film is measured in accordance with JIS-C2330:2014, except that it was measured at 100 ± 10 kPa using a paper thickness gauge MEI-11 manufactured by Citizen Seimitsu Co., Ltd.

[0039] From the viewpoint that the stretched film of the present invention can have high transparency, the total light transmittance is preferably 80% or more. In particular, the stretched film of the present invention preferably has a thickness of 1.8 μm or more and 10 μm or less, and a total light transmittance of 80% or more. In this case, the stretched film of the present invention can be particularly preferably used for capacitor applications.

[0040] The stretched film of the present invention may have a single-layer structure or a multilayer structure in which a plurality of layers are laminated. When the stretched film has a multilayer structure, a part or all of each layer may be a different layer. In this case, at least one layer is a layer containing the polypropylene-based resin.

[0041] (Polypropylene-based resin) Next, the polypropylene-based resin contained in the stretched film of the present invention will be described. The stretched film of the present invention is formed using a polypropylene-based resin.

[0042] A wide variety of polypropylene resins can be included in the stretched film. In particular, it is preferable that the polypropylene resin contains at least an isotactic polypropylene resin and a heat-resistant resin having a high glass transition temperature, given that the stretched film tends to satisfy the aforementioned 100°C loss tangent (tanδ) of 0.15 or less, or that it tends to have a peak in the loss tangent (tanδ) in the region of 140°C or higher. The heat-resistant resin having a high glass transition temperature can be crystalline or amorphous, but it is preferable that it be an amorphous resin in order to better demonstrate the effect of having a high glass transition temperature. In particular, it is preferable that the polypropylene resin contains an isotactic polypropylene resin and a polymer having an alicyclic structure. In this case, the loss tangent (tanδ) at 100°C tends to be 0.15 or less, or the loss tangent (tanδ) tends to have a peak in the region above 140°C, and even in high-temperature environments above 120°C, it is possible to have a higher dielectric breakdown strength, and the change in dielectric breakdown strength tends to be smaller.

[0043] As described above, in the stretched film of the present invention, the polypropylene resin is preferably a resin (so-called blended resin) that includes an isotactic polypropylene resin and a polymer having an alicyclic structure.

[0044] <Isotactic Polypropylene Resin> For the isotactic polypropylene resin, for example, known isotactic polypropylenes can be widely used.

[0045] The melt mass flow rate (MFR) of the isotactic polypropylene resin is preferably 0.5 g / 10 min or more and 6 g / 10 min or less, more preferably 1 g / 10 min or more and 5 g / 10 min or less, and even more preferably 1.5 g / 10 min or more and 4 g / 10 min or less, as measured at 230°C and 2.16 kgf. In this case, appropriate resin fluidity is obtained when stretching the film, and the stretchability is improved.

[0046] The melting point of the isotactic polypropylene resin is preferably 155°C or higher. In this case, the electrical insulation and stretchability at high temperatures are improved. The melting point is more preferably 160°C to 180°C, and even more preferably 164°C to 175°C.

[0047] The mesopentad fraction of the isotactic polypropylene resin is preferably 95 mol% or more and 99.9 mol% or less. A fraction of 95 mol% or more tends to improve the rigidity and electrical insulation of the stretched film of the present invention, while a fraction of 99.9 mol% or less tends to improve the stretchability. The mesopentad fraction is more preferably 96 mol% or more and 99.5 mol%, even more preferably 96 mol% or more and 99 mol%, and particularly preferably 97 mol% or more and 98 mol%.

[0048] The heptane-insoluble content (HI) of the isotactic polypropylene resin is preferably 94% by mass or more and 99.9% by mass or less. If it is 94% by mass or more, the rigidity and electrical insulation of the stretched film tend to improve, and if it is 99.9% by mass or less, the stretchability tends to improve. The heptane-insoluble content is more preferably 96% by mass or more and 99.5% by mass or less, even more preferably 97% by mass or more and 99.2% by mass or less, and particularly preferably 98% by mass or more and 99% by mass or less.

[0049] The number-average molecular weight (Mn) of the isotactic polypropylene resin is preferably between 30,000 and 70,000, and more preferably between 35,000 and 65,000. In this case, the rigidity, electrical insulation, and stretchability of the stretched film of the present invention tend to improve.

[0050] The weight-average molecular weight (Mw) of the isotactic polypropylene resin is preferably between 250,000 and 500,000, and more preferably between 300,000 and 450,000. In this case, the rigidity, electrical insulation, and stretchability of the stretched film of the present invention tend to improve.

[0051] The molecular weight distribution (Mw / Mn) of the isotactic polypropylene resin is preferably 3 or more and 12 or less, more preferably 5 or more and 10 or less, and even more preferably 6 or more and 9.5 or less. In this case, the rigidity, electrical insulation, and stretchability of the stretched film of the present invention are easily improved.

[0052] The z-average molecular weight (Mz) of the isotactic polypropylene resin is preferably between 700,000 and 3,000,000, and more preferably between 1,000,000 and 2,500,000. In this case, the rigidity, electrical insulation, and stretchability of the stretched film of the present invention tend to improve.

[0053] The Mz / Mw of the isotactic polypropylene resin is preferably 2 to 7, more preferably 2.5 to 6, and even more preferably 3 to 5. In this case, the rigidity, electrical insulation, and stretchability of the stretched film of the present invention tend to improve.

[0054] Isotactic polypropylene resin can be manufactured, for example, by known methods, or it can be obtained from the market.

[0055] Polymerization methods for obtaining isotactic polypropylene resins include, for example, gas-phase polymerization, bulk polymerization, and slurry polymerization. Polymerization may be a single-step polymerization using one polymerization reactor, or a multi-step polymerization using two or more polymerization reactors. Alternatively, hydrogen or comonomers may be added to the reactor as molecular weight modifiers during polymerization. Conventional known Ziegler-Natta catalysts or metallocene catalysts can be used as polymerization catalysts, and the polymerization catalysts may contain co-catalyst components or donors. The mesopentade fraction, melt mass flow rate, molecular weight, and molecular weight distribution of the polypropylene resin can be controlled by appropriately adjusting the polymerization catalyst and other polymerization conditions.

[0056] The polypropylene resin may contain one or more isotactic polypropylene resins.

[0057] Furthermore, when the polypropylene resin includes isotactic polypropylene resin, the X-ray diffraction intensity measurement of the stretched film shows diffraction peaks from the (040) plane originating from the α-crystal of the isotactic polypropylene mentioned above.

[0058] <Polymers with Alicyclic Structures> Polymers with alicyclic structures are polymers that have alicyclic structures in their main chain or side chains. Typically, the alicyclic structure exists covalently bonded to the main chain or side chains.

[0059] An alicyclic structure is defined as comprising one or more saturated and / or unsaturated carbon ring structures that do not possess aromaticity. There may be two or more such carbon ring structures. The carbon ring structures may have branching aliphatic hydrocarbon structures. The carbon ring structures are bonded directly or via hydrocarbon chains to the hydrocarbon chains of the polymer backbone.

[0060] Examples of the aforementioned carbocyclic structures include cycloalkane structures such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane, as well as cycloalkene structures such as cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, and cyclooctene. Examples of bicyclic structures include bicyclic alkane structures such as bicycloundecane, and bicyclic alkene structures such as norbornene and norbornadiene, which can be suitably used. In particular, having a carbocyclic structure with 4 to 8 carbon atoms is preferred from the viewpoint of extensibility, having a monocyclic carbocyclic structure with 4 to 8 carbon atoms is more preferred, having a monocyclic cycloalkane carbocyclic structure with 4 to 8 carbon atoms is even more preferred, and having a cyclohexane structure is particularly preferred.

[0061] The main chain of a polymer having an alicyclic structure can be mainly composed of aliphatic hydrocarbons. The aliphatic hydrocarbons in the polymer main chain may have branches of aliphatic hydrocarbon structures and / or aromatic hydrocarbon structures. The main chain of a polymer having an alicyclic structure may further contain the alicyclic structure, but it is preferable that the main chain does not have an alicyclic structure, and that it is contained in the side chains, in order to easily maintain high dielectric breakdown strength even in high-temperature environments of 120°C or higher. Therefore, it is preferable that a polymer having an alicyclic structure is a polymer in which the side chain has an alicyclic structure.

[0062] A polymer having an alicyclic structure in its side chain may be a homopolymer whose constituent units are structures having an alicyclic structure in its side chain. For example, it may be a polyvinylcycloolefin obtained by homopolymerizing vinylcycloolefins. Examples of polyvinylcycloolefins include polyvinylcyclopropane, polyvinylcyclobutane, polyvinylcyclopentane, polyvinylcyclohexane, polyvinylcycloheptane, polyvinylcyclooctane, polyvinylcyclononane, polyvinylcyclodecane, polyvinylcycloundecane, and polyvinylcyclododecane. In the case of a homopolymer, it is preferable that rigidity and electrical insulation properties tend to be high in high-temperature environments. Among these, polyvinylcyclopentane, polyvinylcyclohexane, and polyvinylcycloheptane are preferred, with polyvinylcyclohexane being the most preferred.

[0063] Another example of a polymer having an alicyclic structure in its side chain is a hydrogenated block copolymer. The type of hydrogenated block copolymer is not particularly limited, and for example, known hydrogenated block copolymers can be broadly mentioned. A hydrogenated block copolymer can be, for example, a copolymer obtained by hydrogenating a block copolymer having at least a vinyl aromatic polymer block and a conjugated diene polymer block. That is, a hydrogenated block copolymer is a copolymer having at least a hydrogenated vinyl aromatic polymer block and a hydrogenated conjugated diene polymer block. Hydrogenated block copolymers will be described below.

[0064] ≪Hydrogenated Vinyl Aromatic Polymer Block≫ The hydrogenated vinyl aromatic polymer block contains constituent units derived from vinyl aromatic compounds, which have been hydrogenated. The hydrogenated vinyl aromatic polymer block contains 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass, constituent units derived from vinyl aromatic compounds. By having 50% by mass or more of constituent units derived from vinyl aromatic compounds, rigidity and electrical insulation properties in high-temperature environments are easily improved.

[0065] Examples of vinyl aromatic compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, vinyltoluene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The vinyl aromatic compound is preferably selected from styrene and α-methylstyrene, and more preferably styrene.

[0066] The hydrogenated vinyl aromatic polymer block may consist of only one of the vinyl aromatic compounds, or it may consist of two or more. The hydrogenated vinyl aromatic polymer block may contain other constituent units other than those derived from the vinyl aromatic compounds. Examples of other constituent units include those derived from isoprene, butadiene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, and the like.

[0067] The content of the vinyl hydrogenated aromatic polymer block is preferably 50% by mass or more and less than 100% by mass, relative to 100% by mass of the total of the vinyl hydrogenated aromatic polymer block and the hydrogenated conjugated diene polymer block. A content of 50% by mass or more tends to increase rigidity and electrical insulation at high temperatures. More preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

[0068] ≪Hydrogenated Conjugated Diene Polymer Block≫ The hydrogenated conjugated diene polymer block contains constituent units derived from a conjugated diene, which has been hydrogenated. The hydrogenated conjugated diene polymer block contains 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass of constituent units derived from a conjugated diene.

[0069] Examples of conjugated dienes include butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The conjugated diene is preferably selected from butadiene and isoprene, and more preferably butadiene.

[0070] The hydrogenated conjugated diene polymer block may contain structural units derived from a conjugated diene without side chains. Examples of conjugated dienes without side chains include butadiene, 1,3-pentadiene, and 1,3-hexadiene. Butadiene is preferred as the conjugated diene without side chains.

[0071] In hydrogenated conjugated diene polymer blocks, the bonding configuration of the conjugated dienes, i.e., the microstructure, is not particularly limited. For example, butadiene can have 1,2-bonds and 1,4-bonds. Isoprene can have 1,2-bonds, 3,4-bonds, and 1,4-bonds. Only one of these bonding configurations may be present, or two or more may be present. If two or more bonding configurations are present, the proportion of each configuration is not particularly limited.

[0072] Hydrogenated conjugated diene polymer blocks may contain other constituent units besides those derived from conjugated dienes. Examples of other constituent units include those derived from styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, vinyltoluene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like.

[0073] The content of the hydrogenated conjugated diene polymer block is preferably more than 0% by mass (e.g., 1% by mass or more) and 50% by mass or less, based on 100% by mass of the total of the hydrogenated vinyl aromatic polymer block and the hydrogenated conjugated diene polymer block. A content of 50% by mass or less is preferable because it tends to increase rigidity and electrical insulation at high temperatures. More preferably, it is 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[0074] ≪Hydrogenation Rate≫ In the hydrogenated vinyl aromatic polymer block according to this embodiment, the hydrogenation rate of the aromatic ring of the hydrogenated vinyl aromatic polymer block is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, particularly preferably 90 mol% or more, and even more preferably 95 mol% or more. The hydrogenation rate may be 100 mol%. Furthermore, the hydrogenation rate of the carbon-carbon double bond derived from the conjugated diene in the hydrogenated conjugated diene polymer block is preferably 90 mol% or more, more preferably 95 mol% or more. The hydrogenation rate may be 100 mol%.

[0075] By setting the hydrogenation rate of the aromatic rings in the vinyl hydrogenated aromatic polymer block and / or the hydrogenation rate of the carbon-carbon double bonds derived from the conjugated diene in the hydrogenated conjugated diene polymer block within the above-mentioned range, the stretchability is improved, and the glass transition temperature (Tg) tends to be 100°C or higher, which is preferable.

[0076] ≪Bonding patterns of hydrogenated block copolymers≫ The bonding patterns of polymer blocks in hydrogenated block copolymers may be linear, branched, or radial, or a combination thereof.

[0077] For example, if we represent a hydrogenated vinyl aromatic polymer block as "X" and a hydrogenated conjugated diene polymer block as "Y", the bonding modes include diblock copolymers (X-Y), triblock copolymers (X-Y-X), tetrablock copolymers (X-Y-X-Y), and pentablock copolymers (X-Y-X-Y-X, or Y-X-Y-X-Y). From the viewpoint of ease of manufacture, the bonding modes are preferably diblock copolymers, triblock copolymers, or tetrablock copolymers.

[0078] Specific examples of hydrogenated block copolymers include hydrogenated block copolymers obtained by hydrogenating styrene-isoprene diblock copolymer (SI), styrene-butadiene diblock copolymer (SB), styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene / isoprene-styrene triblock copolymer (SB / IS), and styrene-butadiene-styrene triblock copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), and styrene-butylene-butadiene-styrene copolymer (SBBS). Among these, hydrogenated block copolymers obtained by hydrogenating styrene-butadiene diblock copolymer (SB) are particularly preferred.

[0079] ≪Method for Producing Hydrogenated Block Copolymers≫ The method for producing hydrogenated block copolymers is not particularly limited, and known methods such as anionic polymerization can be used. Specifically, hydrogenated block copolymers can be produced by a polymerization reaction using an alkyllithium compound as an initiator to sequentially polymerize a vinyl aromatic compound and a conjugated diene; a method using an alkyllithium compound as an initiator to sequentially polymerize a vinyl aromatic compound and a conjugated diene, and then adding a coupling agent for coupling; or a method using a dilithium compound as an initiator to sequentially polymerize a conjugated diene, and then a vinyl aromatic compound, followed by a hydrogenation reaction.

[0080] Examples of alkyllithium compounds include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium.

[0081] Examples of coupling agents include polyvalent epoxy compounds such as divinylbenzene, epoxidized 1,2-polybutadiene, epoxidized soybean oil, and 1,3-bis(N,N-glycidylaminomethyl)cyclohexane; halogen compounds such as dimethyldichlorosilane, dimethyldibromosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, and tetrachlorotin; ester compounds such as methyl benzoate, ethyl benzoate, phenyl benzoate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dimethyl isophthalate, and dimethyl terephthalate; carbonate ester compounds such as dimethyl carbonate, diethyl carbonate, and diphenyl carbonate; and alkoxysilane compounds such as dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, bis(trimethoxysilyl)hexane, and bis(triethoxysilyl)ethane.

[0082] Examples of dilithium compounds include naphthalenedithium and dilithiohexylbenzene.

[0083] The polymerization reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it is inert to the initiator and does not adversely affect the reaction. Examples include saturated aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, and decane; and aromatic hydrocarbons such as toluene, benzene, and xylene. The polymerization reaction temperature is usually preferably 0 to 100°C, more preferably 30 to 90°C, even more preferably 40 to 80°C, and particularly preferably 50 to 80°C, from the viewpoint of microstructure control. The polymerization reaction time is preferably 0.5 to 50 hours, from the viewpoint of microstructure control.

[0084] Furthermore, Lewis bases may be used as co-catalysts during polymerization reactions. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; and amines such as triethylamine, N,N,N',N'-tetramethylethylenediamine, and N-methylmorpholine. These Lewis bases may be used individually or in combination of two or more.

[0085] The hydrogenation reaction may be carried out immediately after the polymerization reaction, or it may be carried out after the block copolymer has been isolated following the polymerization reaction.

[0086] To isolate a block copolymer after a polymerization reaction, the polymerization reaction solution obtained after the polymerization reaction can be poured into a poor solvent for the block copolymer, such as methanol, to solidify the block copolymer. Alternatively, the polymerization reaction solution can be poured into hot water along with steam to remove the solvent by azeotropic removal (steam stripping), and then the block copolymer can be isolated by drying.

[0087] The hydrogenation reaction of block copolymers can be carried out, for example, by reacting them for 0.1 to 100 hours under conditions of a reaction temperature of 20 to 200°C and a hydrogen pressure of 0.1 to 20 MPa in the presence of a hydrogenation catalyst.

[0088] Examples of hydrogenation catalysts include Raney nickel; heterogeneous catalysts in which metals such as platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), and nickel (Ni) are supported on carriers such as carbon, alumina, and diatomaceous earth; Ziegler catalysts consisting of combinations of transition metal compounds (nickel octoate, nickel naphthenate, nickel acetylacetonate, cobalt octoate, cobalt naphthenate, cobalt acetylacetonate, etc.) and organoaluminum compounds such as triethylaluminum and triisobutylaluminum, or organolithium compounds; and metallocene catalysts consisting of combinations of bis(cyclopentadienyl) compounds of transition metals such as titanium, zirconium, and hafnium and organometallic compounds consisting of lithium, sodium, potassium, aluminum, zinc, or magnesium.

[0089] When the hydrogenation reaction is carried out immediately following the polymerization reaction, the hydrogenated block copolymer can be isolated by pouring the hydrogenation reaction solution into a poor solvent for the hydrogenated block copolymer, such as methanol, and allowing it to solidify, or by pouring the hydrogenation reaction solution into hot water with steam to remove the solvent by azeotrope (steam stripping), followed by drying.

[0090] <Polymers having an alicyclic structure in the main chain> In polymers having an alicyclic structure, the alicyclic structure may be present in the main chain. As polymers having an alicyclic structure in the main chain, known cycloolefin copolymers (so-called COCs) can be widely applied, for example. Specifically, a polymer in which an alkylene skeleton is the main chain and a part of the alkylene is replaced with an alicyclic structure can be given as an example. The alkylene skeleton may be, for example, an ethylene unit (-CH ２ -CH ２ -) is one example.

[0091] A specific example of a polymer having an alicyclic structure in its main chain is a polymer of norbornene and ethylene. In this case, the polymer having an alicyclic structure in its main chain is a polymer in which an alicyclic structure derived from norbornene is introduced into the polyethylene main chain. Polymers having an alicyclic structure in their main chain can be manufactured by known methods or obtained from commercially available products. Examples of commercially available polymers having an alicyclic structure in their main chain include the "Topas (registered trademark) COC" series from Polyplastics Co., Ltd., such as "COC6013F-04" (glass transition temperature Tg of 137°C) and "COC8007F-04" (Tg of 76°C).

[0092] <Preferred Embodiments of Polymers Having an Alicyclic Structure> As described above, polymers having an alicyclic structure may be homopolymers or copolymers. When the polymer having an alicyclic structure is a homopolymer, it is preferable that such polymer is a hydrogenated polymer, a so-called hydrogenated polymer. When the polymer having an alicyclic structure is a hydrogenated polymer, specifically, hydrogenated polystyrene (for example, polyvinylcyclohexane) can be mentioned. The stereoregularity of the hydrogenated polystyrene may be isotactic, syndiotactic, or atactic, but in order to better demonstrate the effect of having a high glass transition temperature, it is more preferable that it be an atactic amorphous resin.

[0093] When the polymer having the alicyclic structure contains hydrogenated polystyrene, it can have particularly high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and the change in dielectric breakdown strength tends to be particularly small. Preferably, the hydrogenated polystyrene has an atactic structure and a hydrogenation rate of 95% or more.

[0094] When the polymer having an alicyclic structure is a copolymer, a block copolymer having at least a vinyl aromatic polymer block and a conjugated diene polymer block is preferred, and a hydrogenated block copolymer obtained by hydrogenating a styrene-butadiene diblock copolymer (SB) is particularly preferred.

[0095] The glass transition temperature (Tg) of a polymer having an alicyclic structure is preferably, for example, 100°C to 180°C. Setting the glass transition temperature to 100°C or higher tends to increase rigidity and electrical insulation at high temperatures, while setting it to 180°C or lower can improve stretchability. The glass transition temperature is more preferably 120°C to 165°C, more preferably 130°C to 160°C, and particularly preferably 140°C to 155°C.

[0096] In particular, polymers having an alicyclic structure preferably contain two or more polymers with different glass transition temperatures.

[0097] In this case, it is preferable that the polymer having an alicyclic structure includes polymer B1 having an alicyclic structure with a glass transition temperature of 133°C to 155°C and polymer B2 having an alicyclic structure with a glass transition temperature of 70°C to less than 133°C. In this case, heat resistance is improved by B1, and compatibility between polypropylene and B1 is increased by B2, resulting in particularly high dielectric breakdown strength even in high-temperature environments of 120°C or higher, and the change in dielectric breakdown strength tends to be particularly small. Hereinafter, polymer B1 having an alicyclic structure with a glass transition temperature of 133°C to 155°C will be abbreviated as "polymer B1", and polymer B2 having an alicyclic structure with a glass transition temperature of 70°C to less than 133°C will be abbreviated as "polymer B2".

[0098] The glass transition temperature of polymer B1 is preferably 135°C or higher. Furthermore, the glass transition temperature of polymer B2 is preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and particularly preferably 110°C or higher.

[0099] The mass ratio of polymer B2 to polymer B1, B2 / B1 (where B2 represents the content (parts by mass) of polymer B2 in a polymer having an alicyclic structure, and B1 represents the content (parts by mass) of polymer B1 in a polymer having an alicyclic structure), is not particularly limited. For example, the mass ratio of polymer B2 to polymer B1, B2 / B1, is preferably less than 0.85. In this case, the compatibility between polymer B1 and polymer B2 is increased, which tends to result in a particularly high dielectric breakdown strength at room temperature and a particularly small change in dielectric breakdown strength. B2 / B1 is preferably 0.80 or less, more preferably 0.75 or less, even more preferably 0.70 or less, particularly preferably 0.65 or less, and also preferably 0.10 or more, more preferably 0.20 or more, even more preferably 0.25 or more, and particularly preferably 0.30 or more.

[0100] Even when the polymer having an alicyclic structure includes polymer B1 and / or polymer B2, it is preferable that both polymer B1 and polymer B2 are the aforementioned hydrogenated polystyrene, block copolymer, etc. For example, a combination can be given in which polymer B1 is hydrogenated polystyrene and polymer B2 is a block copolymer (for example, a hydrogenated block copolymer obtained by hydrogenating a styrene-butadiene diblock copolymer).

[0101] The Vicat softening point (1 kg, 50°C / hr) of polymers having an alicyclic structure is preferably between 100°C and 170°C. Setting the Vicat softening point above 100°C tends to increase rigidity and electrical insulation at high temperatures, while setting it below 170°C improves stretchability. A Vicat softening point of 120°C to 165°C is more preferable, 130°C to 160°C is even more preferable, and 140°C to 155°C is particularly preferable.

[0102] The glass transition temperature (Tg) and Vicat softening point of polymers having an alicyclic structure can be adjusted by the type of constituent unit having an alicyclic structure in the side chain, or by the type and ratio of one or more other constituent units.

[0103] The weight-average molecular weight (Mw) of the polymer having an alicyclic structure is preferably, for example, 50,000 to 400,000. In this case, the rigidity, electrical insulation, and stretchability of the stretched film of the present invention are easily improved.

[0104] The melt mass flow rate (MFR) of a polymer having an alicyclic structure is preferably 1 g / 10 min or more and 40 g / 10 min or less, more preferably 2 g / 10 min or more and 20 g / 10 min or less, and even more preferably 3 g / 10 min or more and 15 g / 10 min or less, as measured at 260°C and 2.16 kgf. In this case, appropriate resin fluidity is obtained when stretching the film, and the stretchability is easily improved.

[0105] Polymers having an alicyclic structure can be manufactured, for example, by known methods, or can be obtained from the market. An example of a commercially available product is ViviOn® (manufactured by USI Corporation).

[0106] Polypropylene resins may contain polymers having one or more alicyclic structures.

[0107] <Method for producing polymers having an alicyclic structure> The method for producing polymers having an alicyclic structure is not particularly limited and can be produced using known methods such as radical polymerization, ionic polymerization (anionic polymerization, coordination anionic polymerization, etc.), bulk polymerization, solution polymerization, suspension polymerization, etc. Specifically, polymers having an alicyclic structure can be produced by carrying out a polymerization reaction using known initiators such as alkyllithium compounds and dilithium compounds to sequentially polymerize monomers having an alicyclic structure (e.g., vinylcycloolefins); or by sequentially polymerizing monomers having an alicyclic structure and then adding a coupling agent to perform coupling.

[0108] In particular, polymers having an alicyclic structure in their side chains can be produced by polymerizing a monomer having an aromatic ring structure (e.g., styrene) by a known method, followed by a hydrogenation reaction. The hydrogenation reaction can be carried out, for example, by the method described later in the method for producing hydrogenated block copolymers.

[0109] When a hydrogenation reaction is carried out, the hydrogenation rate to the aromatic ring structure is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, particularly preferably 90 mol% or more, and even more preferably 95 mol% or more. The hydrogenation rate may also be 100 mol%. It is preferable to set the hydrogenation rate within the above range because it improves the stretchability while also tending to result in a glass transition temperature (Tg) of 100°C or higher.

[0110] A polymer having an alicyclic structure may be, for example, a copolymer having structural units with an alicyclic structure in their side chains and one or more other structural units. The copolymer may be a random copolymer or a block copolymer having at least two polymer blocks. From the viewpoint of stretchability, copolymers are preferred, and block copolymers are more preferred. Examples of other structural units include ethylene, propylene, butene, pentene, hexene, heptene, octene, etc., and may or may not have side chains. It may also contain both structural units with side chains and structural units without side chains. Examples of structural units with side chains include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc. The other structural units may be unsaturated hydrocarbons, but saturated hydrocarbons are preferred from the viewpoint of electrical insulation.

[0111] When a polymer having an alicyclic structure contains propylene as another constituent unit, the propylene content in the polymer is less than 50% by mass, preferably 20% by mass or less, and more preferably 10% by mass or less, based on 100% by mass of the polymer.

[0112] Polymers having an alicyclic structure can be obtained, for example, by polymerizing monomers having their respective constituent units using known methods. Furthermore, if the side chain has an aromatic ring structure, a polymer with an alicyclic structure in the side chain can be obtained by hydrogenation. Hydrogenation of polymers with aromatic ring structures in the side chain allows for the industrially inexpensive production of polymers with an alicyclic structure in the side chain.

[0113] <Polypropylene Resin> The polypropylene resin contained in the stretched film of the present invention preferably contains the isotactic polypropylene resin described above and the polymer having the alicyclic structure described above, more preferably containing the isotactic polypropylene resin and hydrogenated polystyrene (e.g., polyvinylcyclohexane), and even more preferably containing the isotactic polypropylene resin and hydrogenated polystyrene (polyvinylcyclohexane) having an atactic structure and a hydrogenation rate of 95% or more. Furthermore, the polypropylene resin contained in the stretched film of the present invention may contain the isotactic polypropylene resin and the block copolymer, or it may contain the isotactic polypropylene resin and the polymer B1 and the polymer B2.

[0114] When the polypropylene resin contains an isotactic polypropylene resin and a polymer having the aforementioned alicyclic structure, it is preferable that the isotactic polypropylene resin is present in an amount of 55% to 99% by mass and the polymer having the alicyclic structure is present in an amount of 1% to 45% by mass, relative to the total mass of the polypropylene resin. In this case, particularly high dielectric breakdown strength can be achieved even in high-temperature environments of 120°C or higher, and the change in dielectric breakdown strength tends to be particularly small.

[0115] The polypropylene resin more preferably contains 60% by mass or more of isotactic polypropylene resin, even more preferably 65% ​​by mass or more, particularly preferably 70% by mass or more, more preferably 97% by mass or less, even more preferably 95% by mass or less, and particularly preferably 93% by mass or less.

[0116] The polypropylene resin more preferably contains 3% by mass or more of a polymer having an alicyclic structure, even more preferably 5% by mass or more, particularly preferably 7% by mass or more, more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less. In these cases as well, the polymer having an alicyclic structure may preferably be, for example, hydride polystyrene (polyvinylcyclohexane) or the block copolymer, or the polymer having an alicyclic structure may include polymer B1 and polymer B2.

[0117] Polypropylene resins may include other resins besides isotactic polypropylene resins and polymers having an alicyclic structure. Examples of other resins include polyolefin resins and copolymer resins thereof, such as polyethylene, poly(1-butene), polyisobutene, poly(1-pentene), and poly(4-methyl-1-pentene), such as ethylene-propylene copolymers, propylene-butene copolymers, ethylene-butene copolymers, and ethylene-(4-methyl-1-pentene) copolymers, such as copolymers of α-olefins. Other examples include polystyrene resins, elastomers, polyvinyl resins, polyester resins, polyurethane resins, nylon resins, and copolymers thereof. Commercially available resins may be used as other resins, for example, Tuffmer® (manufactured by Mitsui Chemicals, Inc.) is an example of a copolymer of α-olefins and can be suitably used for the aforementioned purposes.

[0118] The polypropylene resin preferably contains 90% by mass or more of isotactic polypropylene resin and polymers having an alicyclic structure, more preferably 95% by mass or more, and even more preferably 99% by mass or less. The polypropylene resin also preferably does not contain any resins other than isotactic polypropylene resin and polymers having an alicyclic structure.

[0119] When the polypropylene resin includes isotactic polypropylene resin and polymers having an alicyclic structure, the aforementioned loss tangent (tanδ) at 100°C tends to satisfy 0.15 or less, or the loss tangent (tanδ) tends to have a peak in the region of 140°C or higher.

[0120] For example, when a polypropylene resin contains isotactic polypropylene resin and a polymer having an alicyclic structure, it may have a clear peak in the loss tangent (tanδ) in the region above 140°C. Such a peak is the main dispersion peak and may correspond to the glass transition temperature (Tg) of the polymer having an alicyclic structure (e.g., hydride polystyrene). This peak becomes clearer as the content of the polymer having an alicyclic structure (e.g., hydride polystyrene) increases. At the same time, the gentle swelling around 100°C present in polypropylene (100% polypropylene) (which may correspond to lattice relaxation of typical isotactic polypropylene) is lost with the addition of the polymer having an alicyclic structure because the molecular mobility caused by lattice relaxation is suppressed. That is, the loss tangent (tanδ) at 100°C becomes 0.15 or less.

[0121] While we do not necessarily desire a restrictive interpretation, the fact that the loss tangent (tanδ) at 100°C is easily less than 0.15, or that there is a peak in the loss tangent (tanδ) in the region above 140°C, may indicate that the isotactic polypropylene resin and the polymer having an alicyclic structure have a phase-separated structure upon mixing. The structure consisting of the isotactic polypropylene resin and the polymer having an alicyclic structure is by no means a brittle phase-separated structure, and this can be judged from the fact that the film is not cloudy, that it maintains a high Tg (the presence of the aforementioned main dispersion peak), that the loss tangent (tanδ) at 100°C is small, that the lattice relaxation motion of polypropylene is contained (motion suppression effect), and that the temperature dependence of the storage modulus is small and flat with respect to temperature.

[0122] When a polypropylene resin contains isotactic polypropylene resin and polymers having an alicyclic structure, the presence of polymers having an alicyclic structure can be confirmed, for example, by changes in the infrared absorption spectrum. In particular, changes in the infrared absorption spectrum are more likely to occur when the polymer having an alicyclic structure contains hydrogenated polystyrene.

[0123] The fact that isotactic polypropylene resins made from polymers with alicyclic structures possess a phase-separated structure while maintaining polypropylene crystals can be observed from X-ray diffraction measurements. Specifically, in the X-ray diffraction intensity measurement of stretched films, the diffraction peaks originating from the crystals (α-crystals) of isotactic polypropylene are shifted to the wide-angle side (the interplanar spacing value (d value) originating from the (040) plane is shifted to a lower value), which confirms that the lattice is dense. For example, as mentioned above, in the X-ray diffraction intensity measurement, the interplanar spacing value d of the diffraction line of the (040) plane originating from the α-crystal of isotactic polypropylene is 5.10 to 5.23 Å, which confirms phase separation and high packing of polypropylene molecular chains.

[0124] When a polypropylene resin contains isotactic polypropylene resin and polymers having an alicyclic structure, differential scanning calorimeter (DSC) measurements of the stretched film show a characteristic double peak due to the presence of polymers with an alicyclic structure, which is associated with the melting of isotactic polypropylene crystals. That is, as mentioned above, differential scanning calorimeter measurements of the stretched film tend to show a first melting peak at 170-175°C and a second melting peak at 165-170°C when the temperature is increased at 20°C / min. For example, since hydride polystyrene is amorphous, both of these melting peaks can be said to be based on melting originating from isotactic polypropylene crystals. One peak (the high-temperature side) (the first melting peak) is attributed to stable polypropylene crystals, while the subpeak (the second melting peak) is attributed to metastable crystals due to the influence of the hydride polystyrene blend.

[0125] When the polypropylene resin contains isotactic polypropylene resin and polymers having an alicyclic structure, dynamic viscoelasticity measurements suggest that a "phase separation structure" is formed. By forming such a "phase separation structure," the relaxation motion (molecular chain motion) of polypropylene that occurs at high temperatures can be suppressed. As a result, the decrease in dielectric strength at high temperatures can be suppressed, and the stretched film of the present invention has high dielectric strength even in high-temperature environments of 120°C or higher, and moreover, the change in dielectric strength at high temperatures compared to room temperature (e.g., 25°C) is small.

[0126] When the polypropylene resin contains isotactic polypropylene resin and polymers having an alicyclic structure, the ratio of dielectric breakdown strength (V140 / V25) can be closer to 1, and when it contains 10% by mass or more of polymers having an alicyclic structure, the V140 / V25 value becomes particularly close to 1.

[0127] While it is preferable in one embodiment that the polypropylene resin includes isotactic polypropylene resin and polymers having an alicyclic structure, the polypropylene resin may be composed of other resins, for example, propylene homopolymers such as syndiotactic polypropylene; copolymers of propylene and other olefins (e.g., ethylene, 1-butene, etc.) (the copolymer may be a random copolymer or a block copolymer having at least two polymer blocks); long-chain branched polypropylene; or polypropylene resin produced from plant-derived raw materials. In this case, the MFR, melting point, mesopentade fraction, heptane insoluble matter (HI), Mn, Mw, Mw / Mn, Mz, and Mz / Mw of the polypropylene resin can all be within the same range as the isotactic polypropylene resin described above.

[0128] (Other features of the stretched film of the present invention) The stretched film of the present invention can be obtained using the polypropylene resin described above. The stretched film of the present invention is stretched in at least one direction. Preferably, the stretched film of the present invention is a biaxially oriented film stretched in two directions. Preferably, such a biaxially oriented film is stretched in the MD (flow) direction and the TD (width) direction, respectively.

[0129] The stretched film of the present invention may also contain various additives, to the extent that the effects of the present invention are not impaired. Examples of additives include those found in stretched films used in known capacitor applications, such as antioxidants, necessary stabilizers such as chlorine absorbers and ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents, and colorants.

[0130] Examples of antioxidants include hindered phenol antioxidants. Among hindered phenol antioxidants, examples of hindered phenol antioxidants having a carbonyl group include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: Irganox 245), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259), pentaerythrultyl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1010), 2,2- Examples include o-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1035), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: Irganox 1076), and N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide) (trade name: Irganox 1098), but pentaerythrutyl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which has excellent heat resistance, is particularly preferred. All Irganox® products are manufactured by BASF Japan Ltd.

[0131] When the stretched film of the present invention contains an antioxidant, the amount is preferably 1,000 ppm by mass or more and 7,000 ppm by mass or less, and more preferably 2,000 ppm by mass or more and 6,000 ppm by mass or less, relative to the total mass of the stretched film. In general, the amount of the hindered phenol antioxidant remaining after the extrusion process during the stretched film formation process is 60 to 80% by mass of the above-mentioned content, as some of it is oxidized and decomposed during the extrusion process.

[0132] The stretched film of the present invention can be applied to capacitor applications, as well as various other applications such as packaging and separator applications. In particular, the stretched film of the present invention can be suitably used in capacitor applications, and is suitable for use in high-temperature environments of 120°C or higher, and is extremely suitable for small and high-capacitance capacitors (for example, 5 μF or more, preferably 10 μF or more, and even more preferably 20 μF or more).

[0133] The method for producing the stretched film of the present invention is not particularly limited. For example, the stretched film of the present invention can be produced by manufacturing a cast raw material sheet (unstretched film) using the polypropylene resin and then stretching the cast raw material sheet.

[0134] If the polypropylene resin includes an isotactic polypropylene resin and a polymer having an alicyclic structure, it can be obtained by mixing each resin in a predetermined ratio. For example, melt blending can be used as a mixing method. The polypropylene resin may be subjected to drying treatment or the like as needed.

[0135] The method for manufacturing the cast raw material sheet (unstretched film) is not particularly limited, and a wide range of known methods can be employed. For example, the cast raw material sheet can be manufactured by melt-kneading a polypropylene resin and then extruding it. As for the melt-kneading method, a single-screw type, twin-screw type, or multi-screw type melt-kneader can be used. The temperature during melt-kneading is preferably 200°C to 300°C, and more preferably 220°C to 280°C, considering the balance between suppressing resin degradation and the quality of the kneading. During melt-kneading, it is preferable to purge the kneader with an inert gas such as nitrogen in order to suppress resin degradation.

[0136] The extrusion molding method is not particularly limited; for example, a cast raw material sheet (unstretched film) can be obtained by extruding a molten and kneaded polypropylene resin into a film extruder. The extrusion molding method is not particularly limited, and known extrusion molding methods can be used. The molten and kneaded polypropylene resin may be filtered beforehand. The temperature during extrusion molding is not particularly limited, for example, 200 to 300°C, preferably 210 to 280°C, more preferably 215 to 270°C, and even more preferably 220 to 260°C.

[0137] The extruded, molten polypropylene resin can be cooled using a cooling roll. The surface temperature of the cooling roll is, for example, 30 to 130°C, preferably 35 to 120°C, and more preferably 40 to 110°C. This yields a cast raw material sheet. The thickness of the cast raw material sheet is not particularly limited, but is, for example, 20 to 300 μm.

[0138] The stretched film of the present invention can be obtained by stretching a cast raw material sheet. The stretching method is not particularly limited, and examples include: a method of stretching the cast raw material sheet in the longitudinal direction (flow direction, MD) by heating it with a heating roll (longitudinal uniaxial roll stretching method); a method of stretching the cast raw material sheet in the transverse direction (width direction, TD) in an oven at a predetermined temperature (generally called a tenter) (transverse uniaxial stretching method); a method of performing transverse uniaxial stretching after longitudinal uniaxial roll stretching (sequential biaxial stretching method); a method of performing transverse uniaxial stretching after longitudinal uniaxial roll stretching, and then longitudinal uniaxial (roll or tenter method) stretching (multi-stage sequential biaxial stretching method); a method of sequentially stretching the cast raw material sheet longitudinally and transversely in a tenter at a predetermined temperature (tenter method sequential biaxial stretching method); a method of simultaneously stretching the cast raw material sheet longitudinally and transversely in a tenter (simultaneous biaxial stretching method); and so on. As for the stretching method, a method in which longitudinal uniaxial roll stretching is followed by transverse uniaxial stretching (sequential biaxial stretching method) is preferable because it provides excellent rigidity, electrical insulation, and stretchability of the stretched film.

[0139] One example of a sequential biaxial stretching method is to maintain a cast raw material sheet at a temperature of approximately 100 to 180°C (longitudinal stretching temperature), pass it between rolls with a speed difference to stretch it 3 to 7 times (longitudinal stretching ratio) in the flow direction, and immediately cool it to room temperature. After cooling, the stretched film is guided to a tenter and stretched at a stretching angle of 5 to 17° (transverse stretching angle) at a temperature of 150°C or higher (transverse stretching temperature) to approximately 3 to 11 times (transverse stretching ratio) in the width direction, after which it can be relaxed, heat-set, and wound up. The wound film can be aged in an atmosphere of approximately 20 to 45°C and then cut to the desired product width. The transverse stretching angle is defined as the angle between a straight line Lx connecting one edge Px in the width direction of the stretched film at the start of the transverse stretching process and the other edge Py (on the same side as Px) in the width direction of the stretched film at the end of the transverse stretching process, and a straight line Ly that starts at Px and is parallel to the extrusion direction.

[0140] The resulting stretched film may be subjected to corona treatment, electrostatic discharge treatment, heating treatment, etc. Appropriate implementation of corona treatment, electrostatic discharge treatment, heating treatment, etc. can improve passability to the vapor deposition process. The heating treatment temperature is preferably 20°C to 80°C, more preferably 25°C to 60°C, and even more preferably 30°C to 55°C. The heating treatment time is preferably 3 hours to 50 hours, and more preferably 6 hours to 30 hours.

[0141] 2. Metal Laminate Film / Film Capacitor The stretched film of the present invention may have a metal layer on one or both sides thereof. That is, a metal laminate film having a metal layer on one or both sides of the stretched film can be obtained using the stretched film of the present invention.

[0142] In a metal laminated film, the metal film can act as an electrode. Examples of the metal film include metal foil, paper with at least one side metallized, and plastic film with at least one side metallized. The metal can be a single metal such as zinc, lead, silver, chromium, aluminum, copper, and nickel, a mixture of several of these, or an alloy thereof. However, considering the environment, economy, and capacitor performance, zinc and aluminum are preferred.

[0143] The metal film can be formed, for example, by vacuum deposition and sputtering, and vacuum deposition is preferred from the viewpoint of productivity and economic efficiency. Vacuum deposition methods generally include the crucible method and the wire method.

[0144] The film resistance of the metal film is preferably about 1 to 100 Ω / □, more preferably 5 Ω / □ or higher, and even more preferably 10 Ω / □ or higher, from the viewpoint of the electrical characteristics of the capacitor. Furthermore, from the viewpoint of safety as a capacitor, the film resistance of the metal film is more preferably 50 Ω / □ or lower, and even more preferably 30 Ω / □ or lower. The film resistance of the metal film can be measured during metal deposition, for example, by the four-terminal method known to those skilled in the art. The film resistance of the metal film can be adjusted, for example, by adjusting the output of the evaporation source to adjust the evaporation rate. For the sake of clarity, in this specification, the unit "Ω / □" means "Ω / square".

[0145] When forming a metal film on one side of the film, an insulating margin is formed from one end of the film without deposition for a certain width, so that the film acts as a capacitor when wound. Furthermore, to strengthen the bond between the metal laminated film and the metallicon electrode, it is preferable to form a heavy edge structure at the end opposite the insulating margin. The film resistance of the heavy edge is usually about 1 to 8 Ω / □, and preferably about 1 to 5 Ω / □. The thickness of the metal film is not particularly limited, but for example, 1 to 200 nm is preferred.

[0146] There are no particular restrictions on the margin pattern, and from the standpoint of improving characteristics such as the safety of the capacitor, patterns including so-called special margins such as fishnet patterns and T-margin patterns can be used. As for the method of forming the margin, any known method can be used without any restrictions, such as the tape method, which involves masking with tape during vapor deposition, or the oil method, which involves masking by applying oil.

[0147] The metal laminated film can be processed into the capacitor of the present invention, as described later, by winding it along the longitudinal direction of the film. Specifically, two metal laminated films are stacked as a pair, with the metal vapor-deposited film and polypropylene film alternately laminated and wound together. Then, a pair of metal-coated electrodes are formed on both end surfaces by thermal spraying to produce a film capacitor.

[0148] A capacitor can be manufactured using the above-mentioned multilayer metal film for capacitors. As long as the capacitor includes the above-mentioned multilayer metal film for capacitors, its other components are not particularly limited; for example, it can have a configuration similar to that of a known capacitor.

[0149] Since the capacitor described above is equipped with the stretched film of the present invention, it can have a high dielectric breakdown voltage, and moreover, the change in dielectric breakdown strength under high-temperature environments is small compared to the dielectric breakdown strength at room temperature (e.g., 25°C). Therefore, even when a voltage of, for example, 200 (Vdc / μm) is continuously applied to the capacitor at a high temperature of 135°C or higher, it will not short circuit and can maintain its insulation and capacitance for more than 500 hours. In other words, the capacitor does not short circuit at 135°C and exhibits little decrease in capacitance even under continuous voltage load.

[0150] The capacitor of the present invention, utilizing the stretched film of the present invention, is suitable for use in high-temperature environments and can be made into a small and high-capacitance capacitor (for example, 5 μF or more, preferably 10 μF or more, and even more preferably 20 μF or more). Therefore, the capacitor of the present invention can be used in electronic equipment, electrical equipment, etc., as a high-voltage capacitor; various switching power supplies; filter capacitors and smoothing capacitors for converters, inverters, etc. Furthermore, the capacitor of the present invention can be suitably used as an inverter capacitor and converter capacitor for controlling drive motors in electric vehicles, hybrid vehicles, etc., for which demand has been increasing in recent years.

[0151] In specifying the inventions contained herein, the components (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. That is, this disclosure encompasses all subject matter consisting of any combination of the combinatable components described herein.

[0152] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0153] (1) Measurement Methods The various measurement methods are as follows:

[0154] (1-1) Mn, Mw, Mz, Mw / Mn, and Mz / Mw of isotactic polypropylene resin 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 / Mw) of isotactic polypropylene resin were measured using GPC (gel permeation chromatography) under the following conditions.

[0155] Specifically, a high-temperature GPC instrument with a built-in differential refractometer (RI), the HLC-8121GPC-HT model, manufactured by Tosoh Corporation, was used. Three TSKgel GMHHR-H(20)HT columns, also manufactured by Tosoh Corporation, were used in conjunction. Measurements were taken at a column temperature of 140°C, with trichlorobenzene flowing as the eluent at a flow rate of 1.0 ml / min. A calibration curve for the molecular weight M was created using standard polystyrene manufactured by Tosoh Corporation, and the measured values ​​were converted to the molecular weight of polypropylene using the Q-factor to obtain the number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz). The molecular weight distribution (Mw / Mn) was obtained using the Mw and Mn values. The molecular weight distribution (Mz / Mw) was also obtained using the Mz and Mw values.

[0156] (1-2) Mesopentad fraction of isotactic polypropylene resin The isotactic polypropylene resin was dissolved in a solvent and measured using a high-temperature Fourier transform nuclear magnetic resonance spectrometer (high-temperature FT-NMR) under the following conditions. High-temperature nuclear magnetic resonance (NMR) spectrometer: JEOL Ltd., high-temperature Fourier transform nuclear magnetic resonance spectrometer (high-temperature FT-NMR), JNM-ECP500 Observed nucleus: 13C (125 MHz) Measurement temperature: 135°C Solvent: Ortho-dichlorobenzene (ODCB: mixed solvent of ODCB and deuterated ODCB (mixing ratio = 4 / 1)) Measurement mode: Single pulse proton broadband decoupling Pulse width: 9.1 μsec (45° pulse) Pulse interval: 5.5 sec Number of integrations: 4,500 Shift reference: CH3 (mmmm) = 21.7 ppm The mesopentad fraction, which represents the degree of stereoregularity, was calculated as a percentage (%) from the integral intensity values ​​of each signal derived from combinations of five pentads (mmmm, mrrm, etc.) consisting of pentads arranged in the same direction ("meso (m)") and pentads arranged in opposite directions ("racemo (r)"). For the assignment of each signal derived from mmmm, mrrm, etc., spectral descriptions such as "T. Hayashi et al., Polymer, Vol. 29, p. 138 (1988)" were consulted.

[0157] (1-3) Melt Mass Flow Rate (MFR) The melt flow rate (MFR) was measured in accordance with JIS K 7210-1:2014 using a melt indexer from Toyo Seiki Co., Ltd. Specifically, first, 4 g of raw material was inserted into a cylinder heated to the test temperature (230°C for isotactic polypropylene resin, and 260°C for polymers with an alicyclic structure), and preheated for 3.5 minutes under a load of 2.16 kgf. Then, the weight of the resin extruded from the bottom hole in 30 seconds was measured, and the MFR (g / 10 min) was determined. The above measurement was repeated three times, and the average value was taken as the measured value of MFR.

[0158] (1-4) Melting point and glass transition temperature The melting point and glass transition temperature were calculated using a Perkin-Elmer input-compensated DSC, DiamondDSC, following the procedure below. 5 mg of each resin was weighed out, packed into an aluminum sample holder, and set in the DSC apparatus. The temperature was increased from 30°C to 230°C at a rate of 20°C / min under a nitrogen flow, held at 230°C for 5 minutes, cooled to 30°C at a rate of 20°C / min, and held at 30°C for 5 minutes. The melting point and glass transition temperature were then determined from the DSC curve when the temperature was increased again to 230°C at a rate of 20°C / min. Specifically, the melting peak (the largest melting peak if multiple melting peaks are shown) as defined in JIS-K7121:1987 9.1(1) was used as the melting point, and the midpoint glass transition temperature as defined in JIS-K7121:1987 9.3(1) was used as the glass transition temperature.

[0159] (1-5) Heptane-insoluble content (HI) of polypropylene resin A sample of approximately 3 g was prepared for measurement by press-molding polypropylene resin to 10 mm x 35 mm x 0.3 mm. Next, approximately 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.

[0160] (2) In order to prepare the polypropylene resin for obtaining the stretched raw material film, the following isotactic polypropylene resin and polymer having an alicyclic structure were prepared. [A1; Isotactic Polypropylene Resin A1] As isotactic polypropylene resin A1, an isotactic polypropylene resin "Prime Polypro (registered trademark); manufactured by Prime Polymer Co., Ltd." having the following physical properties was prepared. In addition, 3500 ppm by mass of "Irganox 1010" manufactured by BASF Japan Ltd. was pre-mixed into isotactic polypropylene resin A1 as an antioxidant. MFR: 3.5 g / 10 min (measurement temperature 230°C, 2.16 kgf) Melting point: 164°C Mesopentadione fraction: 98.6 mol% Heptane insoluble matter: 98.1 mass% Number average molecular weight (Mn): 49000 Weight average molecular weight (Mw): 390000 Z average molecular weight (Mz): 1,520000 Molecular weight distribution (Mw / Mn): 8.0 Molecular weight distribution (Mz / Mw): 3.9

[0161] [B1; Polymer B1 having an alicyclic structure] As polymer B1 having an alicyclic structure, hydrogenated polystyrene "Vivion® 0645; manufactured by USI Corporation" having the following physical properties was prepared. Glass transition temperature: 143°C (measured by DSC) MFR: 5.5 g / 10 min (measurement temperature 260°C, 2.16 kgf) Such polymer is a polymer having an alicyclic structure with a cyclohexane structure in the side chain, and the cyclohexane structure is formed by hydrogenation of the aromatic ring structure, with a hydrogenation rate of 99 mol% or more.

[0162] [B2; Polymer B2 having an alicyclic structure] As polymer B1 having an alicyclic structure, "Vivion® 1325; manufactured by USI Corporation" having the following physical properties was prepared. Glass transition temperature: 128°C MFR: 13 g / 10 min (measurement temperature 260°C, 2.16 kgf) Polymer B2 is a polymer having an alicyclic structure with a cyclohexane structure in its side chain, and is a hydrogenated block copolymer obtained by hydrogenating a styrene-butadiene diblock copolymer, and is not a hydrogenated polystyrene polymer. The cyclohexane structure is formed by hydrogenation of the aromatic ring structure derived from styrene, and the other structures are formed by hydrogenation of the carbon-carbon double bond derived from butadiene, with a hydrogenation rate of 99 mol% or more.

[0163] (Example 1) The isotactic polypropylene resin A1 and the polymer B1 having an alicyclic structure were blended and mixed in amounts of 95% by mass and 5% by mass, respectively (i.e., A1:B1 = 95:5 by mass ratio) to prepare a raw material. After dry blending this raw material, it was supplied to a single-screw type film extruder (GM-50, L / D = 32, manufactured by GM Engineering Co., Ltd.) and melted at 260°C. The molten raw material was extruded using a T-die, and then wrapped around a metal drum with a surface temperature of 100°C to solidify, producing a cast raw material sheet (unstretched film) with a thickness of approximately 75 μm. Subsequently, this cast raw material sheet was stretched 3.5 times in the flow direction at a temperature of 160°C, immediately cooled to room temperature, and then stretched 7 times in the transverse direction at a temperature of 165°C using a tenter to obtain a biaxially oriented film with a thickness of 3 μm.

[0164] (Example 2) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that the isotactic polypropylene resin A1 and the polymer B1 having the alicyclic structure were blended in amounts of 90% by mass and 10% by mass, respectively (i.e., the mass ratio A1:B1 = 90:10).

[0165] (Example 3) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that the isotactic polypropylene resin A1 and the polymer B1 having the alicyclic structure were blended in amounts of 85% by mass and 15% by mass, respectively (i.e., the mass ratio A1:B1 = 85:15).

[0166] (Example 4) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that the isotactic polypropylene resin A1 and the polymer B1 having the alicyclic structure were blended in amounts of 75% by mass and 25% by mass, respectively (i.e., the mass ratio A1:B1 = 75:25).

[0167] (Example 5) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that the isotactic polypropylene resin A1 and the polymers B1 and B2 having the alicyclic structure were blended in amounts of 86% by mass, 10% by mass, and 4% by mass, respectively (i.e., the mass ratio A1:B1:B2 = 86:10:4).

[0168] (Example 6) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that the isotactic polypropylene resin A1 and the polymers B1 and B2 having the alicyclic structure were blended in amounts of 84% by mass, 7.2% by mass, and 8.8% by mass, respectively (i.e., the mass ratio A1:B1:B2 = 84:7.2:8.8).

[0169] (Comparative Example 1) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that a cast raw material sheet was made using only isotactic polypropylene resin A1 without using polymer B1 having the alicyclic structure.

[0170] (Comparative Example 2) A biaxially oriented film with a thickness of 3 μm was obtained in the same manner as in Example 1, except that the isotactic polypropylene resin A1 and the polymer B2 having the alicyclic structure were blended in amounts of 86% by mass and 14% by mass, respectively (i.e., the mass ratio A1:B2 = 86:14).

[0171] (Evaluation Method) <Dynamic Viscoelasticity Measurement> A "Viscoelasticity Measuring Device (Model: DMS6100)" manufactured by Seiko Instruments was used as the dynamic viscoelasticity measuring instrument. As a measurement sample, the stretched film was cut into strips of 50 mm in the vertical direction and 10 mm in the horizontal direction, with the TD direction being perpendicular to the film flow direction (MD direction), i.e., with the TD direction as the long axis. The temperature dependence of the dynamic viscoelasticity of the film (temperature dispersion data) was measured according to JIS-K7244 (1999 edition) under the measurement conditions shown below. Test mode: Tensile mode Chuck distance: 20 mm Vibration frequency: 1 Hz Strain amplitude: 10 μm Minimum tension: 20 mN Tension gain: 1.2 Initial force amplitude: 100 mN Temperature range: -30 to 180 °C Heating rate: 2 °C / min Measurement atmosphere: Air Measurement thickness: Approximately 3.0 μm From the measurement results using the above measurement method, temperature dispersion data of the dynamic viscoelasticity of the stretched film was obtained. From this temperature dispersion data, the temperature of the main dispersion peak of the loss tangent (tanδ), the loss tangent (tanδ) value at 100 °C, and the storage modulus (E') at 25 °C and 135 °C were determined. An example of the measurement results of the logarithmic value of the storage modulus (log E') and the temperature dependence of the loss tangent (tanδ) is shown in Figure 1.

[0172] <Differential Scanning Calorimeter (DSC): Melting Peak Measurement> A 5 ​​mg sample was cut from the stretched film, sealed in an aluminum pan, and input-compensated differential scanning calorimetry was performed using a differential scanning calorimeter (Diamond DSC, Perkin-Elmer). During the measurement, the temperature was increased from -50°C to 280°C at a rate of 20°C / min under a nitrogen atmosphere. The melting peak temperature was determined from the results of the initial temperature increase.

[0173] <X-ray Diffraction Intensity Measurement (XRD)> The X-ray diffraction intensity of the stretched film was measured using an XRD (wide-angle X-ray diffraction) device (manufactured by Rigaku Corporation) under the following conditions. Measurement device: Rigaku Corporation, X-ray diffractometer Mini-FLEX300 X-ray source: CuKα monometer wave (wavelength: 0.15418 nm) Irradiation output: 30 KV - 10 mA Scattering slit: 1.25 deg Receiving slit: 1.25 deg Scanning axis: 2θ / θ Scanning speed: 0.5 deg / min From the obtained data, the interplanar spacing value d of the diffraction lines of the α-crystal (040) plane was calculated using an analysis computer and the integrated powder X-ray analysis software PDXL (Ver. 2.1.3.4) included as standard with the device.

[0174] <Infrared Absorption Spectrum Measurement (IR)> The infrared absorption spectrum of the stretched film was measured using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation). A prism was placed in close contact with the stretched film (sample), and the absorbance spectrum against wavenumber was measured using the ATR method under the following conditions: Measurement device: JASCO Corporation, Fourier transform infrared spectrophotometer FT / IR-4000 ATR unit: ATR-PRO410-M Prism: ZnSe Incident angle: 45° Scanning range: 4000 cm －１ ~650cm －１ Integration number: Auto (121 times) Resolution: 4cm －１ Gain: Auto Aperture: Auto Scan Speed: Auto Filter: Auto

[0175] <Film Thickness> The thickness of the stretched film was measured in accordance with JIS-C2330:2014, except that it was measured at 100 ± 10 kPa using a Citizen Seimitsu MEI-11 paper thickness gauge.

[0176] <Total Light Transmittance> The total light transmittance of the stretched film was measured using a haze meter NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS-K7361:1997.

[0177] <Method for Calculating the Ratio of Dielectric Breakdown Strength (V140 / V25)> The ratio of the dielectric breakdown strength of the stretched films obtained in the examples and comparative examples at high temperature (140°C) and 25°C was evaluated as follows. First, a measuring apparatus conforming to JIS C2151:2006 17.2.2 (flat plate electrode method) was prepared. However, instead of the elastic material described in JIS C2151:2006 17.2.2, conductive rubber (E12S10 manufactured by Seiwa Electric Co., Ltd.) was used as the lower electrode, and no aluminum foil wrapping was performed. The measurement environment was a forced-circulation oven with a set temperature of 140°C or 25°C. The electrodes and films were used after being conditioned in the oven for 30 minutes. The voltage increase was started from 0V and increased at a rate of 100V / second, and the voltage when the current value exceeded 5mA was defined as the dielectric breakdown voltage. The dielectric breakdown voltage was measured 20 times. Each dielectric breakdown voltage value Vdc was divided by the thickness of the stretched film (μm), and the average of the 16 values ​​obtained by excluding the top 2 and bottom 2 values ​​from the 20 calculations was taken as the dielectric breakdown strength (Vdc / μm). The obtained dielectric breakdown strength was taken as the dielectric breakdown strength of the stretched film, and the dielectric breakdown strength V140 (Vdc / μm) of the stretched film at high temperature (140°C environment) was divided by the dielectric breakdown strength of the stretched film at room temperature (25°C) to calculate the dielectric breakdown strength ratio "V140 / V25".

[0178] (Evaluation Results) Figure 1 shows an example of temperature dispersion data for dynamic viscoelasticity obtained by dynamic viscoelasticity measurement. This temperature dispersion (temperature dependence) data shows the relationship between temperature (X axis) and tanδ (second Y axis), and the relationship between temperature (X axis) and the logarithm of the storage modulus (first Y axis). In Figure 1, the solid line represents the storage modulus LogE' (Pa), and the dashed line represents the loss tangent tanδ.

[0179] As shown in Figure 1, the stretched film obtained in the example has a loss tangent tanδ of 0.15 or less at 100°C, and a clear main dispersion peak of the loss tangent (tanδ) is observed in the region above 140°C.

[0180] Figure 2 shows the results of the infrared absorption spectrum of the stretched film, where (a) shows the infrared absorption spectrum measurement at 850–950 cm⁻¹. －１(b) is within the range of 1400-1500 cm. －１ This indicates the range.

[0181] Figure 2 shows that the infrared absorption spectrum of the stretched film obtained in the example was 880–890 cm⁻¹. －１ Absorption peaks are observed in the range, and at 1450 cm. －１ It can be seen that there is a shoulder peak due to absorption in the vicinity.

[0182] Table 1 shows the physical properties and evaluation results of the stretched film. In Table 1, A1 refers to isotactic polypropylene resin A1, A2 refers to "isotactic polypropylene resin A2", B1 refers to "polymer B1 having an alicyclic structure", and B2 refers to "polymer B2 having an alicyclic structure". In Table 1, blank spaces indicate 0% by mass (i.e., the corresponding resin was not used).

[0183] In Table 1, "temperature at which the main dispersion peak was observed" refers to the loss tangent (taaδ) peak clearly observed in the region above 140°C, and "tanδ at 100°C" refers to the loss tangent (tanδ) at 100°C obtained based on the temperature dispersion data. Furthermore, the first melting peak temperature (DSC) and the second melting peak temperature (DSC) refer to the peak top temperatures observed at 170–175°C and 165–170°C, respectively, in the DSC measurement. In Table 1, the infrared absorption spectrum is 880–890 cm⁻¹. －１ Absorption peaks are observed in the range, and at 1450 cm. －１ If a shoulder peak due to absorption was observed in the vicinity, it was indicated as "present," and if not observed, it was indicated as "absent."

[0184] Table 1 shows that stretched films with a loss tangent tanδ of 0.15 or less at 100°C (i.e., stretched film A) or stretched films with a peak in the loss tangent (tanδ) in the region above 140°C (i.e., stretched film B) have high dielectric breakdown strength even in high-temperature environments. In other words, the stretched films of the examples have a high ratio of dielectric breakdown strength at 140°C to that at room temperature (e.g., 25°C) "V140 / V25" (close to "1"), and the change in dielectric breakdown strength between high and room temperature is small, indicating that the dielectric breakdown strength is maintained.

[0185] Capacitors using the stretched film obtained in the examples as a dielectric film do not short-circuit even when a voltage of, for example, 200 (Vdc / μm) is continuously applied at a high temperature of 140°C, and can maintain their insulation and capacitance for more than 500 hours. In other words, the above capacitor does not short-circuit even at 140°C, and the decrease in capacitance is small even under continuous voltage load.

[0186]

Claims

1. A stretched film containing a polypropylene resin, wherein the loss tangent tanδ at 100°C in the temperature dispersion data in the TD direction at a frequency of 1 Hz, obtained from dynamic viscoelasticity measurement, is 0.15 or less.

2. A stretched film containing a polypropylene resin, wherein the temperature dispersion data in the TD direction at a frequency of 1 Hz, obtained from dynamic viscoelasticity measurement, has a peak in the loss tangent tanδ in the region of 140°C or higher.

3. The stretched film according to claim 1, wherein the temperature dispersion data has a peak in the loss tangent tanδ in the region of 140°C or higher.

4. The stretched film according to claim 1 or 2, wherein, when measured by differential scanning calorimeter, it has a first melting peak at 170-175°C and a second melting peak at 165-170°C when the temperature is increased at 20°C / min.

5. The stretched film according to claim 1 or 2, wherein, in X-ray diffraction intensity measurement, the interplanar spacing d of the diffraction lines of the (040) plane originating from the α-crystal of isotactic polypropylene is 5.10 to 5.23 Å.

6. In infrared absorption spectroscopy, 880–890 cm⁻¹ －１ Absorption peaks are observed in the range, and at 1450 cm. －１ The stretched film according to claim 1 or 2, having at least one of the shoulder peaks due to absorption in the vicinity.

7. The stretched film according to claim 1 or 2, wherein in the temperature dispersion data, the value of E'(135) / E'(25), which is the ratio of the storage modulus E'(135) at 135°C to the storage modulus E'(25) at 25°C, is 0.15 or greater.

8. The stretched film according to claim 1 or 2, wherein the polypropylene resin contains 55% by mass or more and 99% by mass or less isotactic polypropylene resin and 1% by mass or more and 45% by mass or less a polymer having an alicyclic structure.

9. The stretched film according to claim 8, wherein the polymer having the alicyclic structure comprises two or more polymers with different glass transition temperatures.

10. The stretched film according to claim 8, wherein the polymer having an alicyclic structure comprises polymer B1 having an alicyclic structure with a glass transition temperature of 133°C or more and 155°C or less, and polymer B2 having an alicyclic structure with a glass transition temperature of 70°C or more and less than 133°C.

11. The stretched film according to claim 10, wherein the mass ratio B2 / B1 of polymer B2 to polymer B1 is less than 0.

85.

12. The stretched film according to claim 8, wherein the polymer having the alicyclic structure contains hydrogenated polystyrene.

13. The stretched film according to claim 12, wherein the hydrogenated polystyrene has an atactic structure and a hydrogenation rate of 95% or more.

14. The stretched film according to claim 1 or 2, wherein the thickness is 1.8 μm or more and 10 μm or less, and the total light transmittance is 80% or more.

15. A metal laminated film having a metal layer on one or both sides of the stretched film according to claim 1 or 2.

16. A film capacitor comprising the metal laminated film described in claim 15.

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