JP2020132882A - Polypropylene film, and metal film laminated film and film capacitor using the same - Google Patents

Abstract

To provide a polypropylene film, that has excellent long-term use reliability in high-temperature environments when used in high-voltage capacitors, and that is suitable for such capacitor applications and has excellent structural stability against heat, and to provide a metal film laminated film and film capacitor using the same.SOLUTION: A polypropylene film, having the sum of F5 values at 130°C in the longitudinal and width directions of 15 MPa or more, and in which, in the dielectric breakdown test at 130°C, the dielectric breakdown voltage (B150) (V/μm) when heat-treated at 150°C for 1 minute and the dielectric breakdown voltage (B0) (V/μm) when not heat-treated satisfy the following relationship. (B150)/(B0)≥0.80.SELECTED DRAWING: None

Description

The present invention relates to polypropylene films that are particularly suitable for capacitor applications.

Since polypropylene film is excellent in transparency, mechanical properties, electrical properties, etc., it is used in various applications such as packaging applications, tape applications, cable wrapping, and electrical applications such as capacitors.

Among these, polypropylene films are particularly preferably used for high-voltage capacitors, not limited to direct current and alternating current, because of their excellent withstand voltage and low loss characteristics in capacitor applications.

Recently, various electric devices are being converted to inverters, and along with this, there is an increasing demand for smaller capacitors and larger capacities. In response to demands from such fields, especially automobile applications (including hybrid car applications), solar power generation, and wind power generation applications, polypropylene films have thinning properties, improved breakdown voltage, and long-term use in high-temperature environments. It is becoming an essential situation to have excellent reliability that can maintain the power generation.

Polypropylene film is said to have high heat resistance and dielectric breakdown voltage among polyolefin films. On the other hand, when applied to the above fields, it is important to exhibit excellent dimensional stability at the operating environment temperature and stable electrical performance such as electric resistance even in a region 10 to 20 ° C higher than the operating environment temperature. Is. Here, from the viewpoint of heat resistance, it is said that the operating environment temperature will be higher when considering power semiconductor applications using silicon carbide (SiC) in the future. Due to the demand for higher heat resistance and higher withstand voltage as a capacitor, improvement of the dielectric breakdown voltage of a film in a high temperature environment exceeding 110 ° C. is required. However, as described in Non-Patent Document 1, it is said that the upper limit of the operating temperature of the polypropylene film is about 110 ° C., and it is extremely difficult to stably maintain the dielectric breakdown voltage in such a temperature environment. .. In addition, it is thought that the heat history received by the film itself in the process of vapor deposition processing of the film is up to around 150 ° C. It was difficult to fully demonstrate it.

So far, as a method for obtaining excellent performance in a high temperature environment when a polypropylene film is a thin film and used as a capacitor, for example, by controlling the stress at 125 ° C. in the longitudinal elongation of 50%, at a high temperature. Proposal of a film with improved capacitor characteristics and reliability (for example, Patent Document 1), and by adding a melt-type nucleating agent to polypropylene having a high melting point, the stretchability was improved and the mechanical strength of the film at 125 ° C. was improved. A film has been proposed (for example, Patent Document 2). Furthermore, a proposal for a film in which the crystal orientation of the film is improved by forming a meso phase on a cast sheet by quenching the highly stereoregular polypropylene raw material after melt extrusion (for example, Patent Document 3), a highly stereoregular polypropylene resin Has been proposed for a film in which the insulation breakdown voltage is improved by reducing the oxygen concentration in the extrusion hopper, optimizing the amount of antioxidant added, and improving the filtration accuracy of the filter (for example, Patent Document 4). ).

Japanese Unexamined Patent Publication No. 2016-033211 International Publication No. 2016/043172 Pamphlet International Publication No. 2016/182003 Pamphlet International Publication No. 2017/159103 Pamphlet

Motonobu Kawai, "Film Capacitor Breakthrough, From Car to Energy", Nikkei Electronics, Nikkei BP, September 17, 2012, p.57-62

However, the polypropylene films described in Patent Documents 1 to 4 do not sufficiently improve the dielectric breakdown voltage in a high temperature environment exceeding 110 ° C., and are more reliable in long-term use in a high temperature environment when used as a capacitor. Even so, it was hard to say that it was enough.

Therefore, the present invention provides a polypropylene film having excellent long-term use reliability in a high temperature environment, suitable for capacitor applications used under high temperature and high voltage, and excellent in structural stability against heat. An object of the present invention is to provide a metal film laminated film and a film capacitor using the same.

The present inventors have made extensive studies to solve the above problems, and have reached the following invention.

The sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction is 15 MPa or more.
In the dielectric breakdown test at 130 ° C., the dielectric breakdown voltage (B150) (V / μm) when the heat treatment was performed at 150 ° C. for 1 minute and the dielectric breakdown voltage (B0) (V / μm) when the heat treatment was not performed were A polypropylene film that meets the following relationships.
(B150) / (B0) ≧ 0.80

INDUSTRIAL APPLICABILITY The present invention provides a polypropylene film having excellent long-term use reliability in a high temperature environment, suitable for capacitor applications used under high temperature and high voltage, and excellent structural stability against heat. Further, a metal film laminated film and a film capacitor using the same are provided.

The present inventors have made extensive studies to solve the above-mentioned problems, and the polypropylene films described in Patent Documents 1 to 4 have an insulation breakdown voltage in a high temperature environment and a long time in a high temperature environment when used as a capacitor. The reason why the usage reliability is not sufficient is considered as follows.

That is, the polypropylene films described in Patent Documents 1 and 2 can be said to have sufficient withstand voltage resistance and reliability in a 105 ° C. environment as a capacitor, but when further assuming the withstand voltage resistance in a high temperature environment, It was considered that the stretching ratio in film forming, preheating and heat treatment at the time of transverse stretching were not always sufficient, and there was a problem that the amorphous structure of the film was relaxed and the breakdown voltage was lowered at a higher temperature. As for Patent Document 3, assuming the withstand voltage in a high temperature environment, the preheating and heat treatment at the time of lateral stretching in the film forming film are not always sufficient, and the slow cooling treatment is performed at the heat treatment temperature after the lateral stretching. Since there are many movable amorphous components in the film, it is considered that the breakdown voltage at high temperature may be low, and Patent Document 4 is an idea of controlling the cold xylene soluble portion (CXS) contained in the raw material. In addition, since the stretching ratio and the lateral stretching slow cooling in the film forming were not sufficient, the crystallinity was not sufficiently improved, and thus the withstand voltage resistance at high temperature was sometimes inferior.

Based on the above considerations, the present inventors further studied the relationship between the sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction of the polypropylene film and the breakdown voltage before and after the heat treatment at 150 ° C. for 1 minute. It was found that the above-mentioned problems can be solved by using a film having a value equal to or higher than a certain value.

That is, in the present invention, the sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction is 15 MPa or more, and in the dielectric breakdown test at 130 ° C., the dielectric breakdown voltage (B150) when heat treatment is performed at 150 ° C. for 1 minute. ) (V / μm) and the dielectric breakdown voltage (B0) (V / μm) when no heat treatment is performed satisfy the following relationship.
(B150) / (B0) ≥ 0.80.

In the present specification, the polypropylene film may be simply referred to as a film below. Since the polypropylene film of the present invention is not a microporous film, it does not have a large number of pores. That is, the polypropylene film of the present invention means a polypropylene film other than the microporous film. Here, the microporous film penetrates both surfaces of the film and uses a JIS P 8117 (1998) B-type Garley tester at 23 ° C. and a relative humidity of 65% at a permeation time of 100 ml of air. It is defined as a film having a pore structure having an air permeability of 000 seconds / 100 ml or less.

The polypropylene film of the present invention has a sum of F5 values at 130 ° C. in the longitudinal direction and the width direction of the film of 15 MPa or more, and in an dielectric breakdown test at 130 ° C., dielectric breakdown occurs when heat treatment is performed at 150 ° C. for 1 minute. It is necessary that the voltage (B150) (V / μm) and the dielectric breakdown voltage (B0) (V / μm) when no heat treatment is performed satisfy the following relationship.
(B150) / (B0) ≥ 0.80.

That is, the present inventors diligently studied to obtain a polypropylene film that exhibits long-term reliability in a high temperature environment in capacitor applications, and as a result, the sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction of the film, and In the dielectric breakdown test at 130 ° C., the dielectric breakdown voltage (B150) (V / μm) when the film was heat-treated at 150 ° C. for 1 minute and the dielectric breakdown voltage (B0) (V /) when the film was not heat-treated. It was found that the relationship of μm), (B150) / (B0), has a high correlation with the long-term reliability of the capacitor at high temperature. In the case of polypropylene films that can exhibit long-term reliability in high-temperature environments in capacitor applications, it is particularly long to control the change in the breakdown voltage before and after heating the film at a temperature higher than the operating environment temperature. It is the present invention that has been found to be important in the long-term reliability of time capacitors.

Here, in the dielectric breakdown test at 130 ° C., the dielectric breakdown voltage (B150) when the film is heat-treated at 150 ° C. for 1 minute and the dielectric breakdown voltage (B0) (V / μm) when the film is not heat-treated are Satisfying the relationship of (B150) / (B0) ≥ 0.80 suggests that the structural change is small even when the film is heated, and the film has a very stable structure especially in a high temperature environment. Means. The value of (B150) / (B0) is preferably 0.83 or more, more preferably 0.86 or more, and most preferably 0.89 or more. The higher this value is, the higher the breakdown voltage is exhibited even at high temperatures, and when a capacitor is used, long-term reliability can be exhibited in a high temperature environment.

In order to satisfy (B150) / (B0) ≥ 0.80, for example, a polypropylene raw material having a high mesopentad fraction and a cold xylene-soluble portion (CXS) of less than 1.5% by mass is used, as described later. Before the filter, after the filter, the melt extrusion temperature in the mouthpiece is lowered in multiple stages, the area stretching ratio is 60 times or more at the time of biaxial stretching, the stretching ratio in the width direction is 10.5 times or more, and after uniaxial stretching in the longitudinal direction. The preheating temperature immediately before the biaxial stretching in the width direction is set to + 5 to + 15 ° C. in the width direction, and in the heat treatment and relaxation treatment steps after the biaxial stretching, first, the temperature is lower than the stretching temperature in the width direction. The relaxation treatment is performed while performing the heat treatment in the first stage (first stage), and then the heat treatment at 135 ° C. or higher (second stage) at a temperature lower than the heat treatment temperature of the first stage while maintaining the tension in the width direction, and further 80. It can be obtained by appropriately applying a multi-stage heat fixing treatment and a relaxation treatment in which the heat treatment (third stage) is performed at a temperature of ° C. or higher and lower than the heat treatment temperature of the second stage.

On the other hand, when the value of (B150) / (B0) is less than 0.80, when it is used as a capacitor in a high temperature environment where a high voltage is applied, especially when it is placed in a high temperature state for a long time. , The molecular chain relaxation of the film progresses, the withstand voltage is lowered, the capacitance of the capacitor is reduced, short-circuit fracture is caused, and the capacitor becomes inferior in reliability. Further, the upper limit of the above relational expression (B150) / (B0) is not particularly limited, but it is practical that it is 0.99 or less. If (B150) / (B0) is to be made larger than 0.99, it is necessary to increase the stretching ratio at the time of film formation, which may cause tearing.

The polypropylene film of the present invention preferably has a film dielectric breakdown voltage (B0) at 130 ° C. of 350 V / μm or more. It is more preferably 375 V / μm or more, still more preferably 400 V / μm or more, particularly preferably 420 V / μ m or more, and most preferably 440 V / μ m or more, but the upper limit is not particularly limited, but is about 800 V / μ m. When (B0) is 350 V / μm or more, when a capacitor is used, short circuit failure is unlikely to occur even when used for a long time especially in a high temperature environment, withstand voltage resistance is maintained, and high reliability can be obtained. In order to control (B0) to the above range (350 V / μm or more), for example, a polypropylene raw material having a high mesopentad fraction and a cold xylene-soluble portion (CXS) of less than 1.5% by mass is used as described later. It is obtained by lowering the melt extrusion temperature in the mouthpiece before, after, and after the filter by a multi-stage low temperature, and setting the area stretching ratio to 60 times or more and the stretching ratio in the width direction to 10.5 times or more at the time of biaxial stretching. It is possible.

The polypropylene film of the present invention needs to have a sum of F5 values of 15 MPa or more at 130 ° C. in the longitudinal direction and the width direction of the film. When the sum of the F5 values at 130 ° C. is 15 MPa or more, it means that sufficient film strength is maintained even at high temperatures, and especially when used as a capacitor in a high temperature environment for a long time, short circuit failure is unlikely to occur and withstand voltage resistance. Can be maintained and high reliability can be obtained. The sum of the F5 values at 130 ° C. is preferably 18 MPa or more, more preferably 20 MPa or more. In order to make the sum of the F5 values at 130 ° C. 15 MPa or more, for example, a polypropylene raw material having a high mesopentad fraction and a cold xylene-soluble portion (CXS) of less than 1.5% by mass is used, as described later. At the time of biaxial stretching, the area stretching ratio is 60 times or more, the stretching ratio in the width direction is 10.5 times or more, and the preheating temperature immediately after biaxial stretching in the longitudinal direction and immediately before biaxial stretching is set in the width direction. In the stretching temperature of + 5 to + 15 ° C., and in the heat fixing treatment and relaxation treatment step after biaxial stretching, first, the relaxation treatment is performed while performing heat treatment (first stage) at a temperature lower than the stretching temperature in the width direction. Heat treatment of 135 ° C. or higher (second stage) at a temperature lower than the heat treatment temperature of the first stage while maintaining tension in the width direction of the film, and further heat treatment at 80 ° C. or higher and lower than the heat treatment temperature of the second stage (3). It can be obtained by appropriately applying a multi-stage heat treatment and relaxation treatment to the film.

On the other hand, when the sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction of the film is less than 15 MPa, the capacitor is inferior in withstand voltage because the mechanical strength at high temperature is low. The upper limit of the sum of the F5 values at 130 ° C. is not particularly limited, but it is practical that the sum is 50 MPa or less. If the sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction of the film is to be larger than 50 MPa, it is necessary to increase the draw ratio during film formation, which may cause tearing.

Here, in the polypropylene film of the present invention, the "longitudinal direction" is the direction corresponding to the flow direction in the film manufacturing process (hereinafter, may be referred to as "MD"), and the "width direction" is the above-mentioned film. It is a direction orthogonal to the flow direction in the manufacturing process (hereinafter, may be referred to as "TD"). When the film sample has a shape such as a reel or a roll, the film winding direction can be said to be the longitudinal direction. On the other hand, in the case of a film in which it is not clear from the appearance of the film which direction corresponds to the flow direction in the film manufacturing process, for example, a line is drawn in 15 ° increments based on an arbitrary straight line on the film plane. A slit-shaped film piece is sampled parallel to each line, the breaking strength is obtained with a tensile tester, and the direction that gives the maximum breaking strength is regarded as the film width direction, and the direction orthogonal to the film width direction. Is considered to be the longitudinal direction. Details will be described later, but if the width of the sample is less than 50 mm and the breaking strength cannot be determined with a tensile tester, the crystal orientation of the α crystal (110) plane of the polypropylene film by wide-angle X-ray is measured as follows. , The film length and width directions are based on the following criteria. That is, X-rays (CuKα rays) are incident in the direction perpendicular to the film surface, and the crystal peak at 2θ = about 14 ° (α crystal (110) plane) is scanned in the circumferential direction, and the obtained diffraction intensity distribution is obtained. The direction in which the diffraction intensity is highest is the film width direction, and the direction orthogonal to it is the longitudinal direction.

The polypropylene film of the present invention preferably has a heat shrinkage stress value (SF130MD) (MPa) of 2.0 MPa or less, more preferably 1.5 MPa, which is obtained by using a thermomechanical analyzer at 130 ° C. in the longitudinal direction of the film. Below, it is more preferably 1.0 MPa or less. When the thermal shrinkage stress value (SF130MD) (MPa) obtained using a thermomechanical analyzer at 130 ° C. in the longitudinal direction of the film is 2.0 MPa or less, the shrinkage of the film itself is suppressed by the heat of the capacitor manufacturing process and the use process. Since the element is not tightly wound, the self-healing function (self-healing) operates by maintaining an appropriate gap between the film layers, suppressing the penetration short-circuit fracture accompanied by a rapid capacitance decrease, and improving the reliability as a capacitor. Can be enhanced. The lower limit of the heat shrinkage stress value (SF130MD) (MPa) obtained by using a thermomechanical analyzer at 130 ° C. in the longitudinal direction of the film is not particularly limited, but it is practically set to about 0.1 MPa. If the shrinkage stress is lower than 0.1 MPa, the shrinkage of the film itself becomes insufficient due to the heat of the capacitor manufacturing process and the use process, and there is a possibility that a sufficient capacity is not developed with respect to the design capacity. In order to control the heat shrinkage stress value (SF130MD) (MPa) obtained by using a thermomechanical analyzer in the longitudinal direction of the film at 130 ° C. within a preferable range, for example, a high mesopentad fraction and a cold xylene-soluble portion ( A polypropylene raw material having a CXS) of less than 1.5% by mass is used, the stretching ratio in the width direction is set to 10.5 times or more during biaxial stretching, and preheating immediately before biaxial stretching after uniaxial stretching in the longitudinal direction. The temperature is set to the stretching temperature in the width direction + 5 to + 15 ° C., and in the heat fixing treatment and the relaxation treatment step after the biaxial stretching, first, while performing the heat treatment (first step) at a temperature lower than the stretching temperature in the width direction. After the relaxation treatment, the film is heat-treated at a temperature lower than the heat treatment temperature of the first stage at 135 ° C. or higher (second stage) while maintaining tension in the width direction, and further at 80 ° C. or higher and lower than the heat treatment temperature of the second stage. It is possible to obtain the film by appropriately performing a multi-stage heat fixing treatment and a relaxation treatment in which heat treatment (third stage) is performed under the above conditions.

The polypropylene film of the present invention has the sum of storage elastic moduli (E'135 (MD + TD)) (GPa) obtained by fixed viscoelasticity measurement at 135 ° C. in the longitudinal direction and the width direction of the film, and the longitudinal direction and the width direction. It is preferable that the relationship of the sum of storage elastic moduli (E'125 (MD + TD)) (GPa) obtained by the fixed viscoelasticity measurement at 125 ° C. satisfies the following equation.
(E'135 (MD + TD) / E'125 (MD + TD))> 0.80.

The value of E'135 (MD + TD) / E'125 (MD + TD) is more preferably 0.83 or more, still more preferably 0.86 or more, and most preferably 0.89 or more. The fact that the ratio of the sum of the storage elastic moduli at 135 ° C. and the sum of the storage elastic moduli at 125 ° C. satisfies the above relationship (E'135 (MD + TD) / E'125 (MD + TD)> 0.80) means that the storage elastic modulus It means that the temperature dependence at high temperature of the modulus is small, and it means that the film has a structure that is very stable to heat by suppressing the movement and loosening of the film molecular chains, especially in a high temperature environment. means. That is, it exhibits a high dielectric breakdown voltage even at high temperatures, and can exhibit long-term reliability in a high-temperature environment when used as a capacitor. The upper limit of the above relational expression is not particularly limited, but it is practical that it is 0.99 or less.

The ratio of the sum of the storage elasticity at 135 ° C. and the sum of the storage elasticity at 125 ° C. satisfies the above relationship (E'135 (MD + TD) / E'125 (MD + TD)> 0.80), as will be described later. In addition, for example, a polypropylene raw material having a high mesopentad fraction and a cold xylene-soluble portion (CXS) of less than 1.5% by mass is used, and the area stretching ratio is 60 times or more during biaxial stretching and the stretching ratio in the width direction. Is 10.5 times or more, and the preheating temperature immediately before biaxial stretching in the width direction after uniaxial stretching in the longitudinal direction is set to the stretching temperature + 5 to + 15 ° C in the width direction, heat treatment after biaxial stretching, and heat treatment. In the relaxation treatment step, first, the relaxation treatment is performed while performing the heat treatment (first stage) at a temperature lower than the stretching temperature in the width direction, and then the temperature is lower than the heat treatment temperature of the first stage while maintaining the tension in the width direction. The film is appropriately subjected to a multi-stage heat fixing treatment and relaxation treatment in which heat treatment at 135 ° C. or higher (second stage) and further heat treatment at 80 ° C. or higher and lower than the heat treatment temperature of the second stage (third stage) are performed. It is possible by that.

The polypropylene film of the present invention has few surface dents and has an appropriate slipperiness, so that the element processability and the withstand voltage can be improved. Therefore, on at least one surface of the film, 1,252 μm × The total valley-side volume, which is the sum of the volumes of valleys having a depth of 20 nm or more in the region of 939 μm, is preferably 1 to 12,000 μm ³ . From the viewpoint of the lower limit, the total valley side volume is more preferably 300 μm ³ or more, and further preferably 600 μm ³ or more. The total valley volume, more preferably to 5,000 .mu.m ³ or less in terms of the upper limit, it is particularly preferable to be 1,000 .mu.m ³ or less. If the total valley side volume is less than 1 μm ³ , the surface is not uneven and tends to be flat. In that case, the slip of the film is extremely reduced, the handleability is lowered, and wrinkles are likely to occur, which affects the element workability. May appear. In addition, when used as a capacitor for a long time, the capacitance change becomes large due to the influence of wrinkles, etc., and when a capacitor with laminated films is used, there is no appropriate gap between the films, so the self-healing function (self-recovery function) Healing) is difficult to operate and the reliability of the capacitor may decrease. On the other hand, when it exceeds 12,000 μm ³ , there are many locally thin parts, which may cause dielectric breakdown from the parts, and the withstand voltage of the film is lowered, especially for high voltage capacitor applications. At that time, the withstand voltage and reliability in a high temperature environment may be impaired. The total valley volume by the preferred ranges described above (the total valley volume 1 [mu] m ³ or more 12,000 ³ or less), dent less surface reduces the risk of breakdown at a low voltage is generated, the withstand voltage of the film The properties are improved, and especially when used for high-voltage capacitors, the withstand voltage and reliability in a high-temperature environment are improved, and the capacitance change when used as a capacitor for a long time can be suppressed. Further, in the case of a capacitor in which films are laminated, an appropriate gap can be formed between the films, so that a self-healing function can be operated and the reliability of the capacitor can be improved. As a method for controlling the total valley side volume, for example, a polypropylene raw material having a high mesopentad fraction and a cold xylene-soluble portion (CXS) of less than 1.5% by mass is used, and the stretching temperature in the longitudinal direction is within a preferable range. It can be obtained by controlling and setting the area stretching ratio to 60 times or more and the stretching ratio in the width direction to 10.5 times or more at the time of biaxial stretching.

The polypropylene film of the present invention preferably satisfies the following equation in the relationship between the F5 value (F5MD) (MPa) in the longitudinal direction and the F5 value (F5TD) (MPa) in the width direction at room temperature.
(F5TD) / (F5MD) ≧ 1.5.

The value of (F5TD) / (F5MD) is more preferably 1.7 or more, further preferably 1.9 or more, and most preferably 2.1 or more. The higher this value is, the higher the degree of orientation to TD is, and the higher the breakdown voltage can be exhibited even at a high temperature. In order to satisfy (F5TD) / (F5MD) ≧ 1.5, for example, the area stretching ratio should be 60 times or more at the time of biaxial stretching, and the stretching ratio in the width direction should be 10.5 times or more. It is possible to obtain by. The upper limit of the value of (F5TD) / (F5MD) is not particularly limited, and is not particularly limited as long as it is 1.5 or more, but a realistically achievable value is considered to be about 4.0.

The polypropylene film of the present invention preferably has a heat shrinkage stress value (SF130TD) (MPa) obtained by using a thermomechanical analyzer at 130 ° C. in the film width direction of 2.0 MPa or less, more preferably 1.5 MPa. Below, it is more preferably 1.1 MPa or less. When the thermal shrinkage stress value (SF130TD) (MPa) obtained using a thermomechanical analyzer at 130 ° C. in the film width direction is 2.0 MPa or less, the vapor-deposited film electrode portion is used in the aging process after the metallikon spraying in the capacitor manufacturing process. It is possible to prevent poor contact between the metallikon electrode portion and obtain a capacitor element as designed, and it is possible to suppress deformation of the element during high temperature use for a long time, and to prevent capacity decrease and short-circuit breakage. The lower limit of the heat shrinkage stress value (SF130TD) (MPa) obtained by using a thermomechanical analyzer at 130 ° C. in the film width direction is not particularly limited, but it is practically set to about 0.1 MPa. If the heat shrinkage stress is lower than 0.1 MPa, the film itself may not shrink sufficiently due to the heat of the capacitor manufacturing process and the use process, and a sufficient capacity may not be developed with respect to the design capacity. In order to control the heat shrinkage stress value (SF130TD) (MPa) obtained by using a thermomechanical analyzer in the film width direction at 130 ° C. within a preferable range, for example, a high mesopentad fraction and a cold xylene-soluble portion (CXS) ) Is less than 1.5% by mass, the area stretching ratio is 60 times or more at the time of biaxial stretching, the stretching ratio in the width direction is 10.5 times or more, and the width after uniaxial stretching in the longitudinal direction. It can be obtained by setting the preheating temperature immediately before biaxial stretching in the direction to the stretching temperature in the width direction of +5 to + 15 ° C. The detailed measurement method of the heat shrinkage stress value (SF130TD) (MPa) obtained by using a thermomechanical analyzer at 130 ° C. is as described below.

The polypropylene film of the present invention has a ratio of heat shrinkage stress values (SF130MD) / (SF130TD) obtained by using a thermomechanical analyzer at 130 ° C. in the longitudinal direction and the width direction of the film to be 0.5 or more and 1.7. The following is preferable. When the ratio of the heat shrink stress values is in this range, that is, 0.5 or more and 1.7 or less, the balance of the heat shrink stress is good in the film surface, and the uniformity of the film interlayer gap when used as a capacitor is improved. Life and reliability are improved. The lower limit of the ratio of heat shrinkage stress values (SF130MD) / (SF130TD) is more preferably 0.8 or more, still more preferably 1.0 or more, and most preferably 1.2 or more. On the other hand, the upper limit of the value of the ratio of heat shrinkage stress values (SF130MD) / (SF130TD) is more preferably 1.5 or less, further preferably 1.4 or less, and most preferably 1.3 or less.

In order to control the ratio of heat treatment stress values (SF130MD) / (SF130TD) within a preferable range, that is, 0.5 or more and 1.7 or less, for example, a high mesopentad fraction and a cold xylene-soluble portion, as described later. After using a polypropylene raw material having (CXS) of less than 1.5% by mass, the area stretching ratio is 60 times or more during biaxial stretching, the stretching ratio in the width direction is 10.5 times or more, and uniaxial stretching is performed in the longitudinal direction. The preheating temperature immediately before the biaxial stretching in the width direction is set to + 5 to + 15 ° C. in the width direction, and in the heat treatment and relaxation treatment steps after the biaxial stretching, first, the temperature is lower than the stretching temperature in the width direction. The relaxation treatment is performed by 2 to 20% while performing the heat treatment in the first stage (first stage), and then the heat treatment at 135 ° C. or higher (second stage) at a temperature lower than the heat treatment temperature of the first stage while maintaining the tension in the width direction of the film. It can be obtained by appropriately performing a multi-stage heat fixing treatment and relaxation treatment in which heat treatment (third stage) is performed at 80 ° C. or higher and lower than the heat treatment temperature of the second stage.

In the polypropylene film of the present invention, with respect to the relaxation time T2 of the amorphous component obtained by the pulse NMR method, the relaxation time (T2A) (μs) after the film is heat-treated at 150 ° C. for 1 minute and the relaxation time (μs) before the heat treatment ( It is preferable that the relationship of T2B) (μs) satisfies the following equation.
(T2B) / (T2A) ≧ 0.90.

The value of (T2B) / (T2A) is more preferably 0.92 or more, further preferably 0.95 or more, and most preferably 0.97 or more. The higher this value is, the higher the breakdown voltage is exhibited even at high temperatures, and when a capacitor is used, long-term reliability can be exhibited in a high temperature environment.

As a method for controlling the value of (T2B) / (T2A), for example, a polypropylene raw material having a mesopentad fraction of 0.970 or more and a cold xylene-soluble portion (CXS) of less than 1.5% by mass is used and a filter is used. Before, after filtering, the melt extrusion temperature in the mouthpiece is lowered in multiple stages, the area stretching ratio is 60 times or more at the time of biaxial stretching, and the stretching ratio in the width direction is 10.5 times or more, and after uniaxial stretching in the longitudinal direction. The preheating temperature immediately before the biaxial stretching in the width direction is set to the stretching temperature of + 5 to + 15 ° C. in the width direction, and in the heat treatment and relaxation treatment steps after the biaxial stretching, first, the temperature is lower than the stretching temperature in the width direction. Relaxation treatment is performed while performing heat treatment (first stage), then heat treatment at 135 ° C. or higher (second stage) at a temperature lower than the heat treatment temperature of the first stage while maintaining tension in the width direction, and further 80 ° C. or higher. (T2B) / (T2A) ≧ 0.90 can be easily applied to the film by appropriately performing a multi-stage heat fixing treatment and relaxation treatment in which the heat treatment (third stage) is performed under the condition of being lower than the heat treatment temperature of the second stage. It is possible to obtain a heat-treated polypropylene film.

The polypropylene film of the present invention has a relaxation time (T2A) (μs) of 29.0 μs or less after the film is heat-treated at 150 ° C. for 1 minute with respect to the relaxation time T2 of the amorphous component obtained by the pulse NMR method. Is preferable, and (T2A) (μs) is more preferably 28.0 μs or less, still more preferably 27.0 μs or less. The relaxation time (T2B) (μs) before the heat treatment is preferably 26.0 μs or less, and (T2B) (μs) is more preferably 25.6 μs or less, still more preferably 25.3 μs or less. The lower the value of the relaxation time T2 of the amorphous component, the more the mobility of the amorphous molecular chain is suppressed, indicating that the structure is stable and difficult to move.

In order to control (T2A) (μs) and (T2B) (μs) to preferable ranges, for example, a high mesopentad fraction and a cold xylene-soluble portion (CXS) of less than 1.5% by mass are described later. The melt extrusion temperature of the base before, after, and after the filter is reduced to a multi-stage low temperature, and the area stretch ratio is 60 times or more during biaxial stretching and the stretch ratio in the width direction is 10.5 times or more. The preheating temperature immediately before biaxial stretching in the width direction after uniaxial stretching in the longitudinal direction is set to the stretching temperature + 5 to + 15 ° C. in the width direction. In the heat fixing treatment and relaxation treatment step after biaxial stretching, first, The relaxation treatment is performed while performing the heat treatment at a temperature lower than the stretching temperature in the width direction (first stage), and then the heat treatment at 135 ° C. or higher lower than the heat treatment temperature of the first stage while maintaining the tension in the width direction (first stage). The film can be obtained by appropriately performing a multi-stage heat fixing treatment and relaxation treatment in which the heat treatment (third stage) is performed at 80 ° C. or higher and lower than the heat treatment temperature of the second stage. is there.

In the polypropylene film of the present invention, when the polypropylene film is completely dissolved with xylene and then precipitated at room temperature, the polypropylene component (CXS, also referred to as cold xylene-soluble portion) dissolved in xylene is 1. It is preferably less than 5% by mass. Here, it is considered that the cold xylene soluble portion (CXS) corresponds to a component that is difficult to crystallize due to reasons such as low stereoregularity and low molecular weight. By making the CXS less than 1.5% by mass, the absolute value of the storage elastic modulus at high temperature of the film is increased, and the temperature dependence is improved, the dielectric breakdown voltage is increased, and the thermal dimensional stability is improved. Can be done. On the other hand, when CXS is 1.5% by mass or more, the temperature dependence of the storage elastic modulus at high temperature of the film is inferior, the absolute value of the storage elastic modulus at high temperature becomes low, and the breakdown voltage decreases. This may cause problems such as a decrease in thermal dimensional stability and an increase in leakage current. Therefore, CXS is more preferably 1.3% by mass or less, further preferably 1.1% by mass or less, particularly preferably less than 1.0% by mass, and most preferably less than 0.9% by mass.

In order to obtain such a CXS content (CXS is less than 1.5% by mass), a method of increasing the catalytic activity when obtaining the polypropylene resin to be used, a method of washing the obtained polypropylene resin with a solvent or the propylene monomer itself. Etc. can be used. The lower limit of CXS is not particularly limited, but it is practical that it is 0.1% by mass. If the CXS is set to less than 0.1% by mass, the stretchability during film formation may deteriorate and tearing may occur.

The polypropylene used in the polypropylene film of the present invention preferably has a melt flow rate (MFR) of 1 to 10 g / 10 minutes (230 ° C., 21.18 N load), more preferably 2 to 5 g / from the viewpoint of film forming property. It takes 10 minutes (230 ° C., 21.18 N load). In order to set the melt flow rate (MFR) to the above value, a method of controlling the average molecular weight or the molecular weight distribution is adopted.

The polypropylene used in the polypropylene film of the present invention is mainly composed of a homopolymer of propylene, but a copolymerization component using other unsaturated hydrocarbons may be used as long as the object of the present invention is not impaired, or propylene. A polymer that is not a homopolymer may be blended. Examples of monomer components other than propylene constituting such copolymerization components and blends include ethylene, 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene and 4-. Examples thereof include methylpentene-1,5-ethylhexene-1,1-octene, 1-decene, 1-dodecene, vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene, 5-methyl-2-norbornene and the like.

The copolymerization amount or blend amount other than the propylene component is preferably less than 1 mol% as the copolymerization amount from the viewpoint of insulation breakdown voltage and heat resistance, and the blend amount constitutes the film as the amount of the component other than propylene. It is preferably less than 1% by mass of the total resin.

The polypropylene film of the present invention may contain a branched-chain polypropylene resin. Specifically, LyondellBasell's "Protax" (registered trademark) (PF-814, etc.), Borealis's "Daploy" (WB130HMS, WB135HMS, etc.), Japan Polypropylene Corporation, "WAYMAX" (MFX8, etc.) Commercially available products (MFX6, MFX3, etc.) can be appropriately selected and used.

There are several commercially available branched chain polypropylene resins such as Ziegler-Natta catalyst system and metallocene catalyst system, but the metallocene catalyst system with few low molecular weight components and high molecular weight components and narrow molecular weight distribution increases the withstand voltage of the film. It is more preferable from the viewpoint of improving the capacitor characteristics. The melt tension of the branched chain polypropylene resin is preferably 2 cN or more and 40 cN or less from the viewpoint of stretching uniformity. The lower limit of the melt tension is more preferably 3 cN or more, and further preferably 5 cN or more. The upper limit is more preferably 30 cN or less, and further preferably 20 cN or less. In order to set the melt tension to the above value, a method of controlling the average molecular weight, the molecular weight distribution, the degree of branching in the polypropylene resin, or the like is adopted. The content of the branched-chain polypropylene resin is preferably 0.1 to 10% by mass in the entire film. The lower limit of the content of the branched chain polypropylene resin is more preferably 0.15% by mass, further preferably 0.2% by mass, and particularly preferably 0.5% by mass. On the other hand, the upper limit is more preferably 9% by mass and even more preferably 8% by mass. By setting the content of the separator chain polypropylene resin within the above range, the size of spherulite generated in the cooling process of the melt-extruded resin sheet can be easily controlled to be small, and the generation of insulation defects generated in the stretching process can be suppressed to a small value. , A polypropylene film having excellent high temperature withstand voltage can be obtained.

The polypropylene resin used in the polypropylene film of the present invention has various additives such as organic particles, inorganic particles, crystal nucleating agents, antioxidants, heat stabilizers, chlorine trapping agents, and slips, as long as the object of the present invention is not impaired. It may contain an agent, an antistatic agent, an antiblocking agent, a filler, a viscosity modifier, and an anticoloring agent.

When an antioxidant is contained among these, the selection of the type and amount of the antioxidant is important from the viewpoint of long-term heat resistance. That is, the antioxidant is preferably a phenolic agent having steric hindrance, and at least one of them is a high molecular weight type having a molecular weight of 500 or more. Specific examples thereof include various examples. For example, 1,3,5-trimethyl-2,4,6-with 2,6-di-t-butyl-p-cresol (BHT: molecular weight 220.4). Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (eg, BASF's Irganox® 1330: molecular weight 775.2) or tetrakis [methylene-3 (3,5-di-t) -Butyl-4-hydroxyphenyl) propionate] methane (for example, Irganox (registered trademark) 1010 manufactured by BASF Corporation: molecular weight 1,177.7) and the like are preferably used in combination. The total content of these antioxidants is preferably in the range of 0.1 to 1.0% by mass with respect to the total amount of polypropylene. If the amount of antioxidant is too small, long-term heat resistance may be poor. If there is too much antioxidant, blocking at high temperature due to bleeding out of these antioxidants may adversely affect the capacitor element. A more preferable total content is 0.2 to 0.7% by mass, and particularly preferably 0.2 to 0.4% by mass, based on the total mass of the resin.

The polypropylene film of the present invention preferably has a mesopentad fraction of the film of 0.970 or more. The mesopentad fraction is more preferably 0.975 or more, further preferably 0.980 or more, and most preferably 0.983 or more.

The mesopentad fraction is an index showing the stereoregularity of the polypropylene crystal phase measured by the nuclear magnetic resonance method (NMR method). In the present invention, when it is 0.970 or more, the crystallinity is high and the melting point is high. It is preferable because it has the effect of increasing the storage elastic modulus at high temperature and can improve the insulation breakdown voltage in a high temperature environment. The upper limit of the mesopentad fraction is not specified. In the present invention, the polypropylene resin having a high mesopentad molecular weight is preferably made by a so-called Ziegler-Natta catalyst, and a method of appropriately selecting an electron donating component in the catalyst is preferably adopted. The molecular weight distribution (Mw / Mn) can be 3.0 or more, and the <2,1> erythro site defect can be 0.1 mol% or less, and it is preferable to use such a polypropylene resin.

The melting point of the polypropylene resin used in the polypropylene film of the present invention is preferably 164 ° C. or higher, more preferably 165 ° C. or higher, still more preferably 166 ° C. or higher. When the melting point of the polypropylene resin is less than 164 ° C, the crystallinity is low, so that the storage elastic modulus at high temperature is low, the insulation breakdown voltage of the film is lowered in the high temperature environment, and the thermal dimensional stability is lowered. In the process of forming a metal film by vapor deposition or in the process of winding a capacitor element, the film may break during film transfer.

The polypropylene film of the present invention has a melting peak temperature (Tmβ) (° C.) observed by measuring DSC at a heating rate β (° C./min) for each of a film heat-treated at 150 ° C. for 1 minute and an untreated film. Is the Y-axis, and the temperature rise rate β (° C / min) is raised to the 0.5th power (β ^0.5 ), and the linear function ((Tmβ) = xβ ^0.5 + y) obtained from the relationship with the X-axis. The relationship between the y-intercept (H1y) (° C.) of the linear function in the film heat-treated at 150 ° C. for 1 minute and the y-intercept (H0y) (° C.) of the linear function in the untreated film satisfies the following relationship. Is preferable.
(H1y) / (H0y) ≧ 0.90.

The value of (H1y) / (H0y) is more preferably 0.92 or more, further preferably 0.94 or more, and most preferably 0.96 or more. The higher this value is, the higher the breakdown voltage is exhibited even at high temperatures, and when a capacitor is used, long-term reliability can be exhibited in a high temperature environment.

In order to control the value of (H1y) / (H0y) to a preferable range (0.90 or more), for example, a high mesopentad fraction and a cold xylene-soluble portion (CXS) are 1.5% by mass, as described later. Using less than polypropylene raw material, the melt extrusion temperature before, after, and after the filter is reduced to a multi-stage low temperature, the area stretching ratio is 60 times or more during biaxial stretching, and the stretching ratio in the width direction is 10.5 times or more. The preheating temperature immediately before the biaxial stretching in the width direction after the uniaxial stretching in the longitudinal direction is set to the stretching temperature + 5 to + 15 ° C. in the width direction. In the heat treatment and relaxation treatment steps after the biaxial stretching, first , The relaxation treatment is performed while performing the heat treatment (first stage) at a temperature lower than the stretching temperature in the width direction, and then the heat treatment at 135 ° C. or higher lower than the heat treatment temperature of the first stage while maintaining the tension in the width direction. (2nd stage) Further, it is possible to obtain the film by appropriately performing a multi-stage heat fixing treatment and relaxation treatment in which the heat treatment (3rd stage) is performed under the condition of 80 ° C. or higher and lower than the heat treatment temperature of the 2nd stage. Is.

The polypropylene film of the present invention preferably has a y-intercept (H1y) (° C.) of the linear function of 155 ° C. or higher in the film heat-treated at 150 ° C. for 1 minute. The high temperature of the y-intercept (H1y) (° C.) means that the melting temperature of the film is high and the heat resistance is high, so that short-circuit fracture is unlikely to occur especially when the film is used for a long time in a high temperature environment. Withstand voltage is maintained and high reliability can be obtained. The y-intercept (H1y) (° C.) is more preferably 157 ° C. or higher, further preferably 159 ° C. or higher.

The polypropylene film of the present invention has a film thickness of 0.5 μm or more and less than 10 μm from the viewpoint that it is particularly suitable for a thin film heat-resistant film capacitor required for automobile applications (including hybrid car applications) used in a high temperature environment. It is preferable to have. It is more preferably 0.6 μm or more and 8 μm or less, still more preferably 0.8 μm or more and 6 μm or less, and for the above heat resistant film capacitor application, 0.8 μm or more and 4 μm or less is most preferable from the balance between characteristics and the capacitor size due to thinning.

The polypropylene film of the present invention is preferably in the form of a single-layer film, but may be in the form of a laminated film.

The polypropylene film of the present invention is preferably used as a dielectric film for a capacitor, but the type of the capacitor is not limited. Specifically, from the viewpoint of the electrode configuration, it may be either a combined winding capacitor of a metal foil and a film or a metal-deposited film capacitor, and no oil-immersed type capacitor impregnated with insulating oil or insulating oil is used. It is also preferably used for dry capacitors. However, due to the characteristics of the film of the present invention, it is particularly preferably used as a metal-deposited film capacitor. From the viewpoint of shape, it may be a winding type or a laminated type.

Since polypropylene film usually has a low surface energy and it is difficult to stably apply metal vapor deposition, it is preferable to perform surface treatment before vapor deposition for the purpose of improving the adhesiveness with the metal film. Specific examples of the surface treatment include corona discharge treatment, plasma treatment, glow treatment, and flame treatment. Normally, the surface wetting tension of a polypropylene film is about 30 mN / m, but by these surface treatments, the wetting tension is preferably 37 to 75 mN / m, more preferably 39 to 65 mN / m, and most preferably 41 to 55 mN / m. The degree is preferable because it has excellent adhesiveness to the metal film and good safety.

The polypropylene film of the present invention can be obtained by biaxial stretching, heat treatment and relaxation treatment using a raw material capable of imparting the above-mentioned properties. The biaxial stretching method can be obtained by any of the inflation simultaneous biaxial stretching method, the tenter simultaneous biaxial stretching method, and the tenter sequential biaxial stretching method. Among them, the film formation stability and crystal / amorphous method are used. It is preferable to adopt the tenter sequential biaxial stretching method in terms of controlling the mechanical properties and thermal dimensional stability while increasing the structure and surface characteristics, particularly the stretching ratio in the width direction of the present invention.

Next, the method for producing the polypropylene film of the present invention will be described as an example. First, the polypropylene resin is melt-extruded onto the support to obtain an unstretched polypropylene film. This unstretched polypropylene film is stretched in the longitudinal direction, then stretched in the width direction, and sequentially biaxially stretched. Then, heat treatment and relaxation treatment are performed to produce a biaxially oriented polypropylene film. Hereinafter, the present invention will be described in more detail, but the present invention is not necessarily construed as being limited to this.

First, the CXS is less than 1.5% by mass from the viewpoint of suppressing the change in the relaxation time T2 of the amorphous component before and after heating the film, structural stability against insulation breakdown voltage and heat at high temperature, and reducing leakage current. After passing the polypropylene resin through a melt extrusion filtration filter from a single-screw extruder in which the extrusion temperature is preferably set to 220 to 280 ° C., more preferably 230 to 270 ° C., the polypropylene resin is preferably 200 to 260 ° C., more preferably 210 to 240 ° C. Extrude from the slit-shaped mouthpiece at the temperature of. Here, during melt extrusion, the resin is sufficiently melted to prevent cutting of the molecular chain length due to shearing due to screw rotation, so that the film structure can be stabilized without being relaxed even at high temperatures. Is preferably set to a low temperature, and the base temperature immediately before ejection is preferably set to a temperature at which a further lowered multi-stage low temperature can be achieved. The molten sheet extruded from the slit-shaped mouthpiece is solidified on a casting drum (cooling drum) controlled to a temperature of 40 to 110 ° C. to obtain an unstretched polypropylene film. As a method of adhering the molten sheet to the casting drum, any of the methods such as electrostatic application method, adhesion method using surface tension of water, air knife method, press roll method, underwater casting method, and air chamber method is used. However, the air knife method having good flatness and capable of controlling the surface roughness is preferable. Further, it is preferable to appropriately adjust the position of the air knife so that air flows to the downstream side of the film formation so as not to cause vibration of the film. The temperature of the casting drum is preferably 60 to 110 ° C., more preferably 80 to 110, from the viewpoint of improving element workability and withstand voltage by having few dents on the surface and having appropriate slipperiness. ℃.

Next, the unstretched polypropylene film is biaxially stretched and biaxially oriented. The unstretched polypropylene film is preheated by passing it between rolls kept at preferably 70 to 150 ° C., more preferably 80 to 145 ° C., and subsequently the unstretched polypropylene film is preferably 70 ° C. to 150 ° C., more preferably 80 ° C. The temperature is maintained at ~ 145 ° C., and the film is stretched preferably 2 to 15 times, more preferably 4.5 to 12 times, still more preferably 5.5 to 10 times in the longitudinal direction, and then cooled to room temperature.

Next, the end of the film stretched uniaxially in the longitudinal direction is held by a clip and guided to the tenter. Here, in the present invention, it is uniaxial that the temperature of the preheating step immediately before stretching in the width direction is preferably the stretching temperature in the width direction + 5 to + 15 ° C, more preferably + 5 to + 12 ° C, and further preferably + 5 to + 10 ° C. The fibril structure highly oriented in the longitudinal direction can be further strengthened by stretching, and the change in the insulation breakdown voltage before and after heating the film can be suppressed. Further, after uniaxial stretching, it is preferable from the viewpoint that the thermal dimensional stability can be improved by stabilizing the molecular chain having insufficient orientation by high temperature preheating. If the preheating temperature is less than the stretching temperature + 5 ° C, the change in the breakdown voltage before and after the film heating cannot be suppressed, and the thermal dimensional stability may not be improved. On the other hand, the preheating temperature is the stretching temperature +15. If the temperature is higher than ℃, the film may be torn during the stretching process.

Next, the temperature at which the end of the film is stretched in the width direction while being gripped by the clip (stretching temperature in the width direction) is preferably 150 to 170 ° C, more preferably 155 to 165 ° C.

From the viewpoint of suppressing the change in the dielectric breakdown voltage before and after heating the film, the draw ratio in the width direction is preferably 10.5 to 20 times, more preferably 11 to 19 times, and most preferably 11.5 to 18 times. .. If the stretching ratio in the width direction is less than 10.5 times, the orientation contribution of the highly oriented fibril structure in the longitudinal direction remains largely in the uniaxial stretching, so that the film cannot suppress the change in the dielectric breakdown voltage before and after heating the film. Increasing the stretch ratio in the width direction gives orientation in the width direction while maintaining a high orientation state in the longitudinal direction, which increases in-plane molecular chain tension and further improves structural stability against heat, which is a trade-off. It is preferable from the viewpoint of considering that the effect of improving the heat shrinkage characteristics can be obtained. On the other hand, if the draw ratio in the width direction exceeds 20 times, the film may be easily torn during film formation and the productivity may be inferior.

Here, it is preferable that the area stretching ratio is 60 times or more from the viewpoint of suppressing the change in the dielectric breakdown voltage before and after heating the film and making the capacitor excellent in long-term use reliability in a high temperature environment. .. In the present invention, the area stretching ratio is obtained by multiplying the stretching ratio in the longitudinal direction by the stretching ratio in the width direction. The area stretch ratio is more preferably 64 times or more, further preferably 68 times or more, and most preferably 72 times or more.

In the production of the polypropylene film of the present invention, in the subsequent heat treatment and relaxation treatment steps, while tension-grasping the width direction with a clip and giving 2 to 20% relaxation in the width direction, the temperature is 145 ° C. or higher and 165 ° C. or lower and in the width direction. After heat-fixing (first-stage heat treatment) at a temperature lower than the stretching temperature (first-stage heat treatment temperature), the heat-fixing temperature (first-stage heat treatment temperature) is 135 ° C. or higher while the width direction is tightly gripped with the clip again. Multi-stage heat treatment under the condition of less than (2nd stage heat treatment), and further heat-fixing (3rd stage heat treatment) under the condition of 80 ° C. or higher and less than the above-mentioned heat fixing temperature (2nd stage heat treatment temperature) while holding the tension. It is preferable to perform the heat treatment of the method from the viewpoint of suppressing the change in the insulation breakdown voltage before and after heating the film, improving the structural stability against heat, and obtaining the withstand voltage resistance and reliability when the capacitor is used.

In the relaxation treatment, the relaxation rate is preferably 2 to 20%, more preferably 5 to 18%, and even more preferably 8 to 15% from the viewpoint of enhancing the structural stability against heat. If it exceeds 20%, the film may loosen too much inside the tenter, causing wrinkles in the product and causing unevenness during vapor deposition, or deterioration of mechanical properties. On the other hand, if the relaxation rate is less than 2%, it is sufficient. Structural stability against heat cannot be obtained, which may cause capacitance reduction or short-circuit failure in a high-temperature environment when used as a capacitor.

After undergoing a multi-stage low temperature heat treatment, the film is guided to the outside of the tenter, the clip at the edge of the film is released in a room temperature atmosphere, the edge of the film is slit in the winder process, and the film thickness is 0.5 μm or more and less than 10 μm. Take up the product roll. Here, in order to improve the adhesiveness of the vapor-deposited metal on the surface to be vapor-deposited before winding the film, it is preferable to perform the corona discharge treatment in air, nitrogen, carbon dioxide gas, or a mixed gas thereof.

Specific examples of the production conditions to be focused on in order to obtain the polypropylene film of the present invention are as follows.
-The melt extrusion temperature should be lowered in multiple stages before, after, and after the filter.
-The polypropylene resin has a mesopendat fraction of 0.970 or more.-The polypropylene resin has a CXS of less than 1.5% by mass.
-Area of stretching The stretching ratio is 60 times or more.
-The stretching ratio in the width direction is 10.5 times or more.
-The preheating temperature before stretching in the width direction is the stretching temperature in the width direction + 5 to + 15 ° C.
-The heat treatment temperature of the first stage is 145 ° C. or higher and 165 ° C. or lower, and is lower than the stretching temperature in the width direction.
-The heat treatment temperature of the second stage is 135 ° C or higher and lower than the heat treatment temperature of the first stage.
-The heat treatment temperature of the third stage is 80 ° C. or higher and lower than the heat treatment temperature of the second stage.
-In the first heat treatment step, 2 to 20% relaxation treatment is applied in the width direction.

Subsequently, a metal film laminated film made of the polypropylene film of the present invention, a film capacitor made of the same, and a method for manufacturing them will be described.

The metal film laminated film of the present invention has a metal film on at least one side of the polypropylene film of the present invention. This metal film laminated film can be obtained by providing a metal film on at least one side of the polypropylene film according to the present invention.

In the present invention, the method of applying the metal film is not particularly limited, but for example, a metal such as a vapor-deposited film which is an internal electrode of a film capacitor by depositing aluminum or an alloy of aluminum and zinc on at least one surface of a polypropylene film. A method of providing a film is preferably used. At this time, other metal components such as nickel, copper, gold, silver, and chromium can be vapor-deposited simultaneously or sequentially with aluminum. Further, a protective layer may be provided on the vapor-deposited film with oil or the like. When the surface roughness of the polypropylene film is different on the front and back sides, it is preferable to provide a metal film on the surface side having a smooth roughness to form a metal film laminated film from the viewpoint of enhancing withstand voltage.

In the present invention, if necessary, after forming the metal film, the metal film laminated film can be annealed at a specific temperature or heat-treated. Further, for insulation or other purposes, at least one side of the metal film laminated film may be coated with a resin such as polyphenylene sulfide.

The film capacitor of the present invention is made by using the metal film laminated film of the present invention. That is, the film capacitor of the present invention has the metal film laminated film of the present invention.

For example, the film capacitor of the present invention can be obtained by laminating or winding the above-mentioned metal film laminated film of the present invention by various methods. An example of a preferable manufacturing method of the wound film capacitor is as follows.

Aluminum is deposited on one side of a polypropylene film under reduced pressure. At that time, the film is deposited in a striped shape having a margin portion running in the longitudinal direction. Next, a blade is inserted into the center of each vapor deposition portion and the center of each margin portion on the surface to slit the reel, and a tape-shaped take-up reel having a margin on one side of the surface is created. A tape-shaped take-up reel having a margin on the left or right is wound by stacking two tape-shaped take-up reels having a left margin and a right margin so that the vapor-deposited portion protrudes from the margin portion in the width direction. To get.

When vapor deposition is performed on both sides, vapor deposition is performed in a striped shape having a margin portion running in the longitudinal direction of one surface, and the other surface is striped so that the margin portion in the longitudinal direction is located in the center of the back surface side vapor deposition portion. Deposit in the form. Next, a blade is inserted in the center of each of the front and back margins to make a slit, and a tape-shaped take-up reel having a margin on one side of each side (for example, if there is a margin on the right side of the front surface, a margin on the left side on the back surface) is produced. Two reels and one undeposited laminated film are laminated and wound so that the metallized film protrudes from the laminated film in the width direction to obtain a wound body.

A wound film capacitor can be obtained by removing the core material from the wound body prepared as described above, pressing the core material, spraying metallicon on both end surfaces to form an external electrode, and welding a lead wire to the metallicon. The applications of film capacitors are wide-ranging, such as for railway vehicles, automobiles (hybrid cars, electric vehicles), solar power generation / wind power generation, and general household appliances, and the film capacitors of the present invention are also suitable for these applications. Can be used. In addition, it can be used for various purposes such as packaging film, mold release film, process film, sanitary goods, agricultural goods, construction goods, and medical goods.

The method for measuring the characteristic value and the method for evaluating the effect in the present invention are as follows.

(1) Film Thickness The thickness of an arbitrary 10 points of the polypropylene film was measured using a contact type electronic micrometer (K-312A type) manufactured by Anritsu Co., Ltd. in an atmosphere of 23 ° C. and 65% RH. The arithmetic mean value of the thickness at the 10 points was taken as the film thickness (unit: μm) of the polypropylene film.

(2) Sum of F5 values in the longitudinal direction and the width direction of the film at 130 ° C. A rectangular polypropylene film cut out with the trial length direction (longitudinal direction or width direction) of the film as the long side direction (width (short side) 10 mm × length (width (short side)) The long side) 150 mm) was used as the measurement sample. Next, the film was set in a sample tensile tester (Tensilon UCT-100 manufactured by Orientec) with an initial chuck distance of 20 mm, and the film was subjected to a tensile test at a tensile speed of 300 mm / min in a temperature-controlled oven at 130 ° C. Was done. At this time, the position of the sample in the length direction was adjusted so that the center of the sample was near the center between the chucks. The load applied to the film when the sample elongation is 5% is read, and the value obtained by dividing by the cross section (film thickness x width (10 mm)) of the sample before the test is the stress (F5 value, unit: MPa) when the elongation is 5%. ). The measurement was performed 5 times for each of the samples for measurement in the longitudinal direction and the width direction, and the F5 value in the longitudinal direction or the width direction was obtained as the arithmetic mean value, and the sum was obtained by adding them.

As the film thickness used for calculating the F5 value, the value measured in (1) above was used.

(3) Dielectric breakdown voltage (B0) (V / μm) at 130 ° C. without heat treatment
The film was heated for 1 minute in an oven kept at 130 ° C., and then measured in the atmosphere according to JIS C2330 (2001) 7.4.11.2 B method (plate electrode method). However, for the lower electrode, "Conductive rubber E-100 <65>" manufactured by Togawa Rubber Co., Ltd. of the same size is placed on the metal plate described in Method B of JIS C2330 (2001) 7.4.11.2. Was used as an electrode. The insulation breakdown voltage test was performed 30 times, and the obtained value was divided by the film thickness (measured in (1) above) and converted to (V / μm), out of a total of 30 measured values (calculated values). The average value of 20 points excluding 5 points in descending order from the maximum value and 5 points in ascending order from the minimum value was defined as the breakdown voltage (B0) (V / μm) when no heat treatment was performed.

(4) Ratio of dielectric breakdown voltage at 130 ° C. (B150) / (B0)
The method of heat-treating the film at 150 ° C. for 1 minute uses a square metal frame having a thickness of 2 mm, an outer dimension of 300 mm × 300 mm, and an inner dimension of 280 mm × 280 mm and a width of 20 mm, and both sides of the frame surface have both sides. A tape (Nichiban's "Nystack" NW-H15 adhesive strength 02) is attached, the film is attached so that the film covers the entire surface of the metal frame, and the film is sandwiched between metal frames of the same size. At this time, attach the film so that it does not wrinkle. Next, in the state of a metal frame / double-sided tape / film / metal frame, a sample was prepared by sandwiching the four sides of the frame with clips and fixed, and left in an oven heated to 150 ° C. for 1 minute. After 1 minute, the sample was taken out, left at room temperature for 5 minutes, and then a film was cut out along the inner frame of the metal frame to obtain a film after heat treatment at 150 ° C. for 1 minute. When the film could not be obtained with a size of 300 mm × 300 mm, a metal frame having a size that could be attached was used. Dielectric breakdown voltage (B150) (V /) when a film heat-treated at 150 ° C. for 1 minute was subjected to a dielectric breakdown test in an atmosphere of 130 ° C. in the same manner as in (3) and heat-treated at 150 ° C. for 1 minute. μm) was calculated. Next, the ratio of the dielectric breakdown voltage (B0) (V / μm) to (B150) (V / μm) obtained in (3) when the heat treatment was not performed was calculated, and the value of (B150) / (B0) was obtained. ..

(5) Ratio of sum of storage elastic moduli ((E'135 (MD + TD)) / (E'125 (MD + TD)))
Under the equipment and conditions shown below, a rectangular polypropylene film (width (short side) 10 mm x length (long side) 50 mm) cut out with the film trial length direction (longitudinal direction or width direction) as the long side direction is formed. The film was attached to the chuck portion of the apparatus in an atmosphere of ° C., and the temperature was raised from 23 ° C. to 260 ° C. for measurement. A viscoelasticity-temperature curve was drawn by the dynamic viscoelasticity method, and the storage elastic modulus (E'125) (GPa) at 125 ° C. and the storage elastic modulus (E'135) (GPa) at 135 ° C. were read. The number of measurement tests was set to n = 5, and the average value of the remaining n = 3 excluding the maximum and minimum values was taken as the storage elastic modulus in that direction, and each direction of the film in the longitudinal direction and the width direction. Measured in. From the results obtained, the sum of the storage elastic moduli at 125 ° C. in the longitudinal direction and the width direction (E'125 (MD + TD)) (GPa) and the sum of the storage elastic moduli at 135 ° C. in the longitudinal direction and the width direction (E). '135 (MD + TD)) (GPa) was calculated, and ((E'135 (MD + TD)) / (E'125 (MD + TD))) was calculated.

Equipment: EXSTAR DMS6100 (manufactured by Seiko Instruments Inc.)
Test mode: Tension mode Chuck distance: 20 mm
Frequency: 1Hz
Strain amplitude: 10.0 μm
Gain: 1.5
Initial value of force amplitude: 400 mN
Temperature range: 23-260 ° C
Temperature rise rate: 2 ° C./min Measurement atmosphere: Measured thickness in nitrogen: The film thickness was determined by the method (1) above.

(6) Ratio of heat shrinkage stress (SF130MD) (MPa) and (SF130TD) (MPa), 130 ° C. heat shrinkage stress at 130 ° C. in the longitudinal direction and width direction of the film ((SF130MD) / (SF130TD))
The polypropylene film was cut into a rectangular sample having a width of 4 mm and a length of 50 mm with the measurement direction (longitudinal direction) of the film as the long side, and the film was sandwiched between metal chucks so as to have a trial length of 20 mm. The sample sandwiched between the chucks was set in the following device, and the stress curves in the longitudinal direction and the width direction of the film in which the test length was kept constant were obtained by the following temperature program. From the obtained stress curve, the shrinkage stress (SF130MD) (MPa) and (SF130TD) (MPa) of the film at 130 ° C. were read. The ratio of the heat shrinkage stress at 130 ° C. ((SF130MD) / (SF130TD)) was calculated from the ratio of the longitudinal direction (SF130MD) (MPa) and the width direction (SF130TD) (MPa).

Equipment: Thermomechanical analyzer TMA / SS6000 (manufactured by Seiko Instruments Inc.)
Test mode: L control mode Test length: 20 mm
Temperature range: 23-200 ° C
Temperature rise rate: 10 ° C./min SS program: 0.1 μm / min Measurement atmosphere: Measurement thickness in nitrogen: The film thickness was determined by the method (1) above.

(7) Total volume of valleys with a depth of 20 nm or more on the film surface (total valley side volume)
The measurement was performed using VertScan2.0 R5300GL-Lite-AC of Ryoka System Co., Ltd., and the analysis was performed using the bearing function, which is an analysis tool of the attached analysis software. In order to specify a valley-side void having a depth of 20 nm or more, the valley-side height threshold was set to −20 nm in the height region designation. Next, the analyzed valley-side void volume value was read and rounded to two significant figures.

When both sides of the film are measured and the total valley side volume is within the range of 1 to 12,000 μm ³ , the value of the side surface within the range (when both sides are within the range). The value of the surface on the side having a small value), and the value of the surface on the side where the total valley side volume is close to the range of 1 to 12,000 μm ³ when both sides are not within the range.

The measurement conditions are as follows.
Manufacturer: Ryoka System Co., Ltd. Device name: VertScan2.0 R5300GL-Lite-AC
Measurement conditions: CCD camera SONY HR-57 1/2 inch (1.27 cm)
Objective lens 10x
Intermediate lens 0.5x
Wavelength filter 520nm white
Measurement mode: Phase
Measurement software: VS-Measure Version 5.5.1
Analysis software: VS-Viewer Version 5.5.1
Measuring area: 1.252 x 0.939 mm ² .

(8) Cold xylene-soluble portion (CXS) of the film
For polypropylene resin in the case of raw material and film sample in the case of film, 0.5 g is dissolved in 100 ml of xylene at 135 ° C., allowed to cool, recrystallized in a constant temperature water bath at 20 ° C. for 1 hour, and then dissolved in a filtrate. The polypropylene component was quantified by the liquid chromatograph method. The following formula CXS (%) = (X / X0) × 100, where the amount of polypropylene-based component dissolved in the filtrate is X (g) and the precision value of 0.5 g of sample is X0 (g).
Calculated from.

(9) Mesopentad fraction A polypropylene resin was used as a raw material, and a film sample was made into a powder by freeze pulverization in the case of a film, and extracted with n-heptane at 60 ° C. for 2 hours to remove impurities and additives in polypropylene. Then, a sample which was dried under reduced pressure at 130 ° C. for 2 hours or more was used as a sample. The sample was dissolved in a solvent, and the mesopentad fraction (mm mm) was determined under the following conditions using ¹³ C-NMR.

Measurement conditions / equipment: Bruker DRX-500
-Measurement nucleus: ¹³ C nucleus (resonance frequency: 125.8 MHz)
-Measured concentration: 10% by mass
-Solvent: Benzene: Dichlorobenzene = 1: 3 mixed solution (volume ratio)
・ Measurement temperature: 130 ℃
・ Spin rotation speed: 12Hz
・ NMR sample tube: 5 mm tube ・ Pulse width: 45 ° (4.5 μs)
・ Pulse repetition time: 10 seconds ・ Data point: 64K
・ Number of integrations: 10,000 times ・ Measurement mode: complete decoupling
The Fourier transform was performed with the analysis condition LB (line broadening factor) as 1, and the mmmm peak was set to 21.86 ppm. Peak splitting was performed using WINFIT software (manufactured by Bruker). At that time, the peak is divided from the peak on the high magnetic field side as follows, and the software is automatically fitted to optimize the peak division, and then the total of the peak fractions of mm mm is the mesopentad fraction. It was set to (mm mm).
(1) mrrm
(2) (3) rrrm (divided into two peaks)
(4) rrrrr
(5) mrmr
(6) mrmm + rmrr
(7) mmrr
(8) rmmr
(9) mmml
(10) mmmm
The same measurement was performed 5 times for the same sample, and the average value of the obtained mesopentad fractions was taken as the mesopentad fraction of the sample.

(10) Melting Point of Polypropylene Resin Using a differential scanning calorimeter (EXSTAR DSC6220 manufactured by Seiko Instruments Inc.), a temperature of 3 mg of polypropylene chips is raised from 30 ° C. to 260 ° C. at 20 ° C./min in a nitrogen atmosphere. Then, after holding at 260 ° C. for 5 minutes, the temperature is lowered to 30 ° C. under the condition of 20 ° C./min. Further, after holding at 30 ° C. for 5 minutes, the temperature is raised from 30 ° C. to 260 ° C. under the condition of 20 ° C./min. The peak temperature of the endothermic curve obtained at the time of this temperature rise was defined as the melting point of the polypropylene resin. When a plurality of peak temperatures could be observed, the highest temperature was defined as the melting point (unit: ° C.) of the polypropylene resin.

(11) Ratio of F5 values (F5TD) / (F5MD)
A rectangular polypropylene film (width (short side) 10 mm × length (long side) 150 mm) cut out with the film trial length direction (longitudinal direction or width direction) as the long side direction was used as a measurement sample. Next, the film was set in a sample tensile tester (Tensilon UCT-100 manufactured by Orientec) with an initial chuck distance of 20 mm, and a tensile test of the film was performed at a tensile speed of 300 mm / min in an environment at room temperature. At this time, the position of the sample in the length direction was adjusted so that the center of the sample was near the center between the chucks. The load applied to the film when the sample elongation is 5% is read, and the value obtained by dividing by the cross section (film thickness x width (10 mm)) of the sample before the test is divided by the stress (F5 value, unit:) when the elongation is 5%. It was calculated as MPa). The measurement was performed 5 times for each of the samples for measurement in the longitudinal direction and the width direction, and the F5 values (F5MD) (MPa) and (F5TD) (MPa) in the longitudinal direction and the width direction were obtained as the arithmetic mean values. The ratio of F5TD) / (F5MD) was determined.

As the film thickness used for calculating the F5 value, the value measured in (1) above was used.

(12) Evaluation of film capacitor characteristics (reliability at 120 ° C)
On one side of the film (if the wet tension is different on both the front and back sides, the side with the higher wet tension) is aluminum with a vacuum vapor deposition machine manufactured by ULVAC Co., Ltd. with a film resistance of 10 Ω / sq and vertical in the longitudinal direction. A thin-film deposition pattern with a so-called T-shaped margin (longitudinal pitch (cycle) of 17 mm and fuse width of 0.5 mm due to masking oil) is provided with a margin in each direction, and after slitting, the film width is 50 mm (edge). A thin-film deposition reel (part margin width 2 mm) was obtained.

Next, using this reel, a capacitor element was wound by a device winding machine (KAW-4NHB) manufactured by Minato Seisakusho Co., Ltd., a metallikon was applied, and then heat treatment was performed at a temperature of 130 ° C. for 8 hours under reduced pressure. The lead wire was attached and finished as a capacitor element.

Using the 10 capacitor elements thus obtained, a voltage of 250 VDC is applied to the capacitor element at a high temperature of 120 ° C., and after 10 minutes have passed at the voltage, the applied voltage is gradually increased at 50 VDC / 1 minute in steps. A so-called step-up test was performed in which the above steps were repeated.

<Reliability>
After increasing the voltage until the capacitance decreased to 12% or less of the initial value, the capacitor element was disassembled and the state of failure was examined, and the reliability was evaluated as follows.
⊚: There is no change in the element shape, and no penetrating fracture is observed.
◯: There is no change in the element shape, and penetrating fracture within 5 layers of the film is observed.
F: There is no change in the element shape, and penetrating fracture within 6 to 10 layers of the film is observed.
Δ: A change is observed in the element shape, or a penetrating fracture of more than 10 layers is observed.
×: The element shape changes significantly and is destroyed. ◎ can be used without any problem, and ○ and F can be used depending on the conditions. Δ and × are inferior in practical performance.

Hereinafter, the present invention will be described in more detail with reference to examples.

(Example 1)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.984, a melting point of 168 ° C., a melt flow rate (MFR) of 2.5 g / 10 minutes, and a cold xylene soluble part (CXS) of 0.8% by mass. The polypropylene resin is supplied to an extruder having a temperature of 255 ° C. to be melted, passed through a pipe set at 250 ° C. after passing through a filtration filter, and melt-extruded into a sheet from a T-shaped slit die set at 245 ° C., and the molten sheet is melted. Was brought into close contact with an air knife on a casting drum maintained at 77 ° C. and cooled and solidified to obtain an unstretched polypropylene film. The unstretched polypropylene film was preheated stepwise to 142 ° C. in a plurality of roll groups, passed as it was between rolls provided with a peripheral speed difference, and stretched 6.3 times in the longitudinal direction. Subsequently, the film was led to a tenter, preheated at a temperature of 169 ° C. (TD stretching temperature + 8 ° C.) while holding both ends of the film width with clips, and then stretched 12.3 times in the width direction at a temperature of 161 ° C. .. Further, as the first-stage heat treatment and relaxation treatment, heat treatment was performed at 158 ° C. while giving 11% relaxation in the width direction, and further, as the second-stage heat treatment, heat treatment was performed at 143 ° C. while gripping in the width direction with a clip. Finally, as the third stage heat treatment, the film is guided to the outside of the tenter through a heat treatment at 114 ° C., the clip at the end of the film is released, and then the film surface (casting drum contact surface side) is exposed to the atmosphere at a processing strength of 25 W / min / m ^2. A corona discharge treatment was performed inside, and a film having a film thickness of 2.2 μm was wound up as a film roll. The characteristics of the polypropylene film and the capacitor characteristics of this example are as shown in the table. For the film, the sum of the F5 values in the longitudinal and width directions of the film at 130 ° C. and the ratio of the dielectric breakdown strength before and after heating at 150 ° C. for 1 minute ( The relationship of B150) / (B0) was extremely good, and the reliability as a capacitor was also excellent.

(Examples 2 and 3)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.981, a melting point of 166 ° C., a melt flow rate (MFR) of 3.0 g / 10 minutes, and a cold xylene soluble part (CXS) of 1.4% by mass. Examples were the same as in Example 1 except that the temperature of the casting drum for cooling the melt-extruded sheet using polypropylene resin, the draw ratio during biaxial stretching, TD preheating, TD stretching and heat treatment were set as the conditions in the table. In No. 2, a polypropylene film having a thickness of 2.1 μm was obtained, and in Example 3, a polypropylene film having a thickness of 2.2 μm was obtained. The characteristics of the polypropylene film and the capacitor characteristics of Examples 2 and 3 are as shown in the table, and the film has a good relationship of dielectric breakdown strength ratio (B150) / (B0) before and after heating at 150 ° C. for 1 minute, and is actually used as a capacitor. There was no problem with the reliability of use.

(Example 4)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.982, a melting point of 167 ° C., a melt flow rate (MFR) of 3.0 g / 10 minutes, and a cold xylene soluble part (CXS) of 0.8% by mass. Examples were the same as in Example 1 except that the temperature of the casting drum for cooling the melt-extruded sheet using polypropylene resin, the draw ratio during biaxial stretching, TD preheating, TD stretching and heat treatment were set as the conditions in the table. No. 4 obtained a polypropylene film having a thickness of 2.1 μm. The characteristics of the polypropylene film and the capacitor characteristics of this example are as shown in the table. For the film, the sum of the F5 values in the longitudinal and width directions of the film at 130 ° C. and the ratio of the dielectric breakdown strength before and after heating at 150 ° C. for 1 minute ( The relationship of B150) / (B0) was good, and there was no problem in the reliability in actual use as a capacitor.

(Example 5)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.981, a melting point of 166 ° C., a melt flow rate (MFR) of 3.0 g / 10 minutes, and a cold xylene soluble part (CXS) of 1.4% by mass. A branched chain polypropylene resin (high melt tension polypropylene Profax PF-814) manufactured by Basell was blended with the polypropylene resin in an amount of 1.0% by mass and supplied to an extruder at a temperature of 260 ° C. to obtain a melt extrusion sheet. Example 5 is a polypropylene film having a thickness of 2.2 μm in the same manner as in Example 2 except that the temperature of the casting drum to be cooled, the stretching ratio during biaxial stretching, TD preheating, TD stretching and heat treatment are set as the conditions in the table. Obtained. The characteristics of the polypropylene film and the capacitor characteristics of Example 5 are as shown in the table, and the film is the sum of the F5 values in the longitudinal direction and the width direction of the film at 30 ° C. and the ratio of the dielectric breakdown strength before and after heating at 150 ° C. for 1 minute ( The relationship of B150) / (B0) was good, and there was no problem in the reliability in actual use as a capacitor.

(Example 6)
The unstretched sheet obtained in the same manner as in Example 1 was simultaneously biaxially stretched to MD and TD at the TD preheating stretching temperature and the TD stretching temperature shown in Table 1, except that the heat treatment conditions were set as the conditions in the table. In the same manner as in No. 1, a polypropylene film having a thickness of 2.4 μm was obtained in Example 6. The characteristics of the polypropylene film of Example 6 and the characteristics of the capacitor are as shown in the table, and the film has a good relationship of dielectric breakdown strength ratio (B150) / (B0) before and after heating at 150 ° C. for 1 minute, and is actually used as a capacitor. There was no problem with the reliability of.

(Example 7)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.984, a melting point of 168 ° C., a melt flow rate (MFR) of 2.5 g / 10 minutes, and a cold xylene-soluble part (CXS) of 0.8% by mass. 3.0% by mass of a branched chain polypropylene resin ("WAYMAX" MFX3) manufactured by Japan Polypropylene Corporation is blended with polypropylene resin, supplied to an extruder at 255 ° C to melt it, and a pipe set to 250 ° C after passing through a filtration filter is installed. A melt-extruded sheet was obtained in the form of a sheet from a T-shaped slit die set at 245 ° C. The temperature of the casting drum for cooling the melt-extruded sheet, the draw ratio during biaxial stretching, TD preheating, TD stretching and heat treatment conditions were the same as in Example 1, and Example 9 obtained a polypropylene film having a thickness of 2.2 μm. .. The characteristics of the polypropylene film and the capacitor characteristics of this example are as shown in the table. For the film, the sum of the F5 values in the longitudinal and width directions of the film at 130 ° C. and the ratio of the dielectric breakdown strength before and after heating at 150 ° C. for 1 minute ( The relationship of B150) / (B0) was extremely good, and the reliability as a capacitor was also excellent.

(Comparative Example 1)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.981, a melting point of 166 ° C., a melt flow rate (MFR) of 4.0 g / 10 minutes, and a cold xylene soluble part (CXS) of 1.8% by mass. Polypropylene resin is supplied to an extruder with a temperature of 255 ° C. to melt it, and the resin temperature after passing through a filtration filter is set to 255 ° C., and then melt-extruded into a sheet from a T-shaped slit die to cool the melt-extruded sheet. A polypropylene film having a thickness of 2.2 μm was obtained in Comparative Example 1 in the same manner as in Example 1 except that the temperature of the casting drum, the draw ratio during biaxial stretching, TD preheating, TD stretching and heat treatment conditions were set as the conditions in the table. .. The characteristics of the polypropylene film of Comparative Example 1 and the characteristics of the capacitor are as shown in the table.

Since the polypropylene film of Comparative Example 1 has no gradient in extrusion temperature, has a large amount of CXS as a raw material, and has a low dielectric breakdown ratio, the film has a sum of F5 values in the longitudinal and width directions of the film at 130 ° C. and 150 ° C. for 1 minute. The relationship between the dielectric breakdown strength before and after heating (B150) / (B0) was insufficient, and the reliability of the capacitor was broken due to a change in the element shape, which was a problematic level in actual use.

(Comparative Examples 2, 3, 4)
Comparative Examples 2, 3, and 4 were the same as in Example 1 except that the temperature of the casting drum for cooling the melt-extruded sheet, the draw ratio during biaxial stretching, TD preheating, TD stretching, and heat treatment were set as the conditions in the table. Then, a polypropylene film having a thickness of 2.3 μm was obtained.

As shown in the table, the polypropylene film of Comparative Example and the capacitor characteristic of the polypropylene film of Comparative Example 2 have the same TD preheating temperature and TD stretching temperature, and are not subjected to multi-stage heat treatment. The relationship of dielectric breakdown strength ratio (B150) / (B0) before and after heating at 150 ° C for 1 minute is insufficient, and the reliability of the capacitor has changed in the element shape, which is a problematic level in actual use. It was.

Further, the polypropylene film of Comparative Example 3 has a high MD stretching ratio and a low TD stretching ratio, so that the ratio of F5 values is small, and the film thermal shrinkage stress of MD is high, and the storage elastic moduli at 135 ° C. and 125 ° C. The ratio of insulation breakdown strength (B150) / (B0) before and after heating at 150 ° C for 1 minute is insufficient, and the reliability of the capacitor changes in the element shape. It was destroyed and destroyed, and it was a problematic level in actual use.

Further, since the polypropylene film of Comparative Example 4 is a two-stage heat treatment in which the preheating temperature for TD stretching is low and the heat treatment conditions are low temperature 130 ° C./high temperature 140 ° C., the film thermal breakdown stress is high in both MD and TD, and is 135 ° C. The ratio of the storage elasticity at 125 ° C and the dielectric breakdown voltage at 130 ° C is insufficient and the thermal stability is inferior, and the relationship between the dielectric breakdown strength before and after heating at 150 ° C for 1 minute (B150) / (B0) is unclear. Since it was sufficient, the reliability of the capacitor was broken due to a change in the element shape, which was a problem in actual use.

(Comparative Example 5)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.972, a melting point of 165 ° C., a melt flow rate (MFR) of 4.0 g / 10 minutes, and a cold xylene-soluble portion (CXS) of 2.4% by mass. Comparative Example in the same manner as in Example 1 except that the temperature of the casting drum for cooling the melt-extruded sheet using polypropylene resin, the draw ratio during biaxial stretching, TD preheating, TD stretching and heat treatment were set as the conditions in the table. In No. 5, a polypropylene film having a thickness of 2.2 μm was obtained. As shown in the table, the polypropylene film characteristics and capacitor characteristics of this comparative example are as shown in the table. Since the cold xylene-soluble portion (CXS) of the polypropylene resin used is large and the cold xylene-soluble portion (CXS) of the film is large, the heat shrinkage stress The relationship between the sum of the F5 values in the longitudinal direction and the width direction of the film at 130 ° C. and the ratio of dielectric breakdown strength (B150) / (B0) before and after heating at 150 ° C. for 1 minute was insufficient. The reliability was broken due to a change in the element shape, which was a problem in actual use.

(Comparative Example 6)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.979, a melting point of 167 ° C., a melt flow rate (MFR) of 2.6 g / 10 minutes, and a cold xylene soluble part (CXS) of 1.8% by mass. Using polypropylene resin, the temperature of the casting drum that cools the melt extruded sheet, the stretching ratio during biaxial stretching, TD preheating, TD stretching and heat treatment conditions are set as the conditions in the table, and the first stage heat treatment and relaxation treatment are performed in the width direction. A polypropylene film having a thickness of 2.3 μm was obtained in Comparative Example 6 in the same manner as in Example 1 except that the relaxation was 25%. As shown in the table, the polypropylene film characteristics and capacitor characteristics of this comparative example have a large cold xylene-soluble portion (CXS) of the film, the TD preheating temperature and the TD stretching temperature are the same, the area stretching ratio is low, and the relaxation treatment is performed. Because it was large, the ratio of the storage elasticity at 135 ° C and 125 ° C and the dielectric breakdown voltage at 130 ° C were insufficient, resulting in poor thermal stability, and the ratio of dielectric breakdown strength before and after heating at 150 ° C for 1 minute (B150) / (B0). ) Was insufficient, so the reliability of the capacitor was broken due to a change in the element shape, which was a problem in actual use.

(Comparative Example 7)
Made by Prime Polymer Co., Ltd., which has a mesopentad fraction of 0.975, a melting point of 165 ° C., a melt flow rate (MFR) of 4.6 g / 10 minutes, and a cold xylene soluble part (CXS) of 1.4% by mass. Polypropylene resin 80% by mass, mesopentad fraction 0.970, melting point 164 ° C., melt flow rate (MFR) 0.4g / 10min, cold xylene soluble part (CXS) 1.4% by mass. Using 20% by mass of polypropylene resin manufactured by Japan Polypropylene Corporation, the temperature of the casting drum for cooling the melt-extruded sheet, the stretching ratio during biaxial stretching, TD preheating, TD stretching and heat treatment conditions are set as the conditions in the table. A polypropylene film having a thickness of 2.2 μm was obtained. As shown in the table, the polypropylene film characteristics and capacitor characteristics of this comparative example have the same TD preheating temperature and TD stretching temperature, have a low dielectric breakdown ratio, and have not been heat-treated. Therefore, the storage elasticity at 135 ° C. and 125 ° C. The ratio and the dielectric breakdown voltage at 130 ° C are insufficient and the thermal stability is inferior. The sum of the F5 values in the longitudinal and width directions of the film at 130 ° C and the ratio of the dielectric breakdown strength before and after heating at 150 ° C for 1 minute ( Since the relationship of B150) / (B0) was insufficient, the reliability of the capacitor was broken due to a change in the element shape, which was a problematic level in actual use.

(Comparative Example 8)
The temperature of the casting drum for cooling the melt-extruded sheet was set to 25 ° C., and the same as in Example 1 except that the draw ratio during biaxial stretching, TD stretching, and heat treatment conditions were set as the conditions in the table, and in Comparative Example 8, the thickness was 2. A 3 μm polypropylene film was obtained. As shown in the table, the polypropylene film characteristics and capacitor characteristics of this comparative example are as low as 25 ° C for the casting drum, the same TD preheating temperature and TD stretching temperature, and the heat treatment conditions are low temperature 130 ° C / high temperature 140 ° C. Since it is a two-stage heat treatment, the sum of the F5 values in the longitudinal direction and the width direction of the film at 130 ° C. is insufficient, so that the reliability of the capacitor is changed in the element shape, which is a problem in actual use. It was a level.

Claims (8)

The sum of the F5 values at 130 ° C. in the longitudinal direction and the width direction is 15 MPa or more.
In the dielectric breakdown test at 130 ° C., the dielectric breakdown voltage (B150) (V / μm) when the heat treatment was performed at 150 ° C. for 1 minute and the dielectric breakdown voltage (B0) (V / μm) when the heat treatment was not performed were A polypropylene film that meets the following relationships.
(B150) / (B0) ≧ 0.80 The polypropylene film according to claim 1, wherein the heat shrinkage stress value (SF130MD) (MPa) obtained by using a thermomechanical analyzer at 130 ° C. in the longitudinal direction is 2.0 MPa or less. The polypropylene film according to claim 1 or 2, wherein the polypropylene component (CXS) dissolved in xylene is less than 1.5% by mass when it is completely dissolved in xylene and then precipitated at room temperature. For the sum of storage elastic moduli (E'135 (MD + TD)) (GPa) obtained by the fixed viscoelasticity measurement at 135 ° C. in the longitudinal direction and the width direction, and the fixed viscoelasticity measurement at 125 ° C. in the longitudinal direction and the width direction. The polypropylene film according to any one of claims 1 to 3, wherein the relationship of the sum of the storage elastic moduli (E'125 (MD + TD)) (GPa) obtained is satisfied by the following equation.
(E'135 (MD + TD)) / (E'125 (MD + TD))> 0.8 The method according to any one of claims 1 to 4, wherein the total valley-side volume, which is the sum of the volumes of valleys having a depth of 20 nm or more in the region of 1,252 μm × 939 μm on at least one surface, is 1 to 12,000 μm ³ . Polypropylene film. The polypropylene film according to any one of claims 1 to 5, wherein the relationship between the F5 value (F5MD) (MPa) in the longitudinal direction and the F5 value (F5TD) (MPa) in the width direction at room temperature satisfies the following equation.
(F5TD) / (F5MD) ≧ 1.5 A metal film laminated film having a metal film on at least one side of the polypropylene film according to any one of claims 1 to 6. A film capacitor using the metal film laminated film according to claim 7.